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NPTEL Online - IIT Bombay

Course Name Engine Emissions

Department Mechanical
Engineering
IIT Kanpur
Instructor

Prof. BP Pundir

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 1:Introduction to IC Engines and Air Pollution

The Lecture Contains:


Historical Overview of IC Engine Development
IC Engine Classification Based on Combustion Process
Main Events in Four-Stroke SI Engine Cycle
Main Events in Four-Stroke CI Engine Cycle

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 1: Introduction to IC Engines and Air Pollution
Historical Overview of IC Engine Development
The modern reciprocating internal combustion engines have their origin in the Otto and Diesel Engines
invented in the later part of 19th century. The main engine components comprising of piston, cylinder,
crank-slider crankshaft, connecting road, valves and valve train, intake and exhaust system remain
functionally overall similar since those in the early engines although great advancements in their design
and materials have taken place during the last 100 years or so. An historical overview of IC engine
development with important milestones since their first production models were built, is presented in
Table 1.1

Table 1.1
Historical Overview and Milestones in IC
Engine Development
Year

Milestone

1860-1867

J. E. E. Lenoir and
Nikolaus Otto developed atmospheric engine wherein
combustion of fuel-air charge during first half of outward stroke of a free piston
accelerating the piston which was connected to a rack assembly. The free piston
would produce work during second half of the stroke creating vacuum in the cylinder
and the atmospheric pressure then would push back the piston.

1876

Nikolaus Otto developed 4-stroke SI engine where in the


compressed before being ignited.

1878

Dougald Clerk developed the first 2-stroke engine

1882

Atkinson develops an engine having lower expansion stroke than the compression
stroke for improvement in engine thermal efficiency at cost of specific engine power.
The Atkinson cycle is finding application in the modern hybrid electric vehicles (HEV)

1892

Rudolf Diesel takes patent on engine having combustion by direct injection of fuel in
the cylinder air heated solely by compression , the process now known as
compression ignition (CI)

1896

Henry Ford develops first automobile powered by the IC engine

1897

Rudolph Diesel developed CI engine prototype, also called as the Diesel engine

1923

Antiknock additive tetra ethyl lead discovered by the General Motors became
commercially available which provided boost to development of high compression
ratio SI engines

1957

Felix Wankel developed rotary internal combustion engine

1981

Multipoint port fuel injection introduced on production gasoline cars

1988

Variable valve timing and lift control introduced on gasoline cars

1989-1990

Electronic fuel injection on heavy duty diesel introduced

1990

Carburettor was replaced by port fuel injection on all US production cars

1994

Direct injection stratified charge (DISC) engine powered cars came in production by
Mitsubishi and Toyota

fuel-air charge was

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 1: Introduction to IC Engines and Air Pollution
IC Engine Classification based on Combustion Process
IC Engines may be classified based on the state of air-fuel mixture present at the time of ignition in the
engine cycle, the type of ignition employed and the nature of combustion process subsequent to ignition
of the air-fuel mixture.
A. Physical State of Mixture
Homogeneous Charge
Premixed outside( conventional gasoline and gas engines with fuel inducted in the
intake manifold)
Premixed in-cylinder: In- cylinder direct injection and port fuel injection
Heterogeneous Charge
B. Ignition Type
Positive source of Ignition e.g., spark ignition
Compression ignition
C. Mode of Combustion
Flame propagation
Spray combustion
This course primarily deals with combustion generated engine emissions and approaches the subject
from the point of fundamentals of engine combustion processes. The engines are therefore, categorized
based on the mode of ignition employed viz., Spark Ignition (SI) Engines and Compression
Ignition (CI) Engines.
Method of ignition has been adopted as the main criterion of classification as in the conventional
type IC engines it governs
Fuel type
Mixture preparation methods
Progression of combustion process
Combustion chamber design
Engine load control, and
Operating and emission characteristics
More advanced and newer combustion systems are dealt as special variations of the IC engines. For
example the direct injection stratified charge (DISC) engine is taken as a special variant of SI engine.
The homogeneous charge compression ignition engines are being developed around the conventional SI
and CI engines and are discussed accordingly.

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 1: Introduction to IC Engines and Air Pollution
Main Events in Four-Stroke SI Engine Cycle
Figure 1.1 shows typical pressure crank angle (P-) history for a four-stroke SI engine cycle. The
sequence of main events in the cycle are given in Table 1.2

Figure
1.1

Sequence of Events in 4-Stroke SI Engine


Cycles

Table 1.2
Sequence of Events in 4-Stroke SI
Engine Cycle
Event

Time of Occurrence, Crank angle

Intake valve opens (IO)

20 - 5 CA bTDC at the end of exhaust stroke

Exhaust valve closes (EC)

8 to 20 CA aTDC in the beginning of intake stroke

Intake valve closes (IC)

60 -40
stroke

CA aBDC in the beginning of compression

Spark ignition

45 -15
stroke

CA

bTDC towards the end of compression

Combustion by turbulent Begins shortly after ignition up to 15 to 30 CA aTDC


flame propagation
Early in the expansion stroke

Exhaust valve opens (EC)

50 -30 CA bBDC Shortly before the end of expansion


stroke

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CA: Crank Angle, ATDC: After Top Dead Centre; BTDC: Before Top Dead Centre; ABDC: After
Bottom Dead Centre;
BBDC:Before Bottom Dead Centre;

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 1: Introduction to IC Engines and Air Pollution
Main Events in Four-Stroke CI Engine Cycle
Figure 1.2 shows typical pressure crank angle (P-) history for a four-stroke CI engine cycle. The
sequence of main events in the cycle are given in Table 1.3

Figure 1.2 Main Events in Four-Stroke CI Engine Cycle

Table 1.3
Sequence of Events in 4-Stroke CI
Engine Cycle
Event

Time of occurrence, Crank angle

Intake valve opens (IO)

5 -20 CA bTDC at the end of exhaust stroke

Exhaust valve closes (EC)

8 to 20 CA aTDC in the beginning of intake stroke

Intake valve closes (IC)

40 -20 CA aBDC in the beginning of compression stroke

Start of Injection (SOI)

15-5 CA bTDC towards the end of compression stroke. Injection


duration at full engine load about 15 to 25 CA

Start of combustion (SOC)

5 -0 CA bTDC, (considering ignition delay after injection)

End of combustion (EOC)


Exhaust valve opens (EC)

20 to 30 CA aTDC in expansion stroke


40 to 30 CA bBDC Shortly before the end of expansion stroke

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 2: Engine Emissions and Air Pollution
Engine Emissions and Air Pollution
The Lecture Contains:
Principal Engine Emissions
Sources of Engine/Vehicle Emissions
Emissions and Pollutants
Photochemical Smog
Photochemical Reactivity of Hydrocarbons
Health Effects of Air Pollutants
Historical Overview: Engine and Vehicle Emission Control

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 2: Engine Emissions and Air Pollution
Principal Engine Emissions
SI Engines

CO, HC and NOx

CI Engines

CO, HC, NOx and PM

CO = Carbon monoxide, HC = Unburned hydrocarbons, NO x = Nitrogen oxides mainly mixture of NO and


NO 2 ,
PM = Particulate matter
Other engine emissions include aldehydes such as formaldehyde and acetaldehyde primarily from the alcohol
fuelled engines, benzene and polyaromatic hydrocarbons (PAH).

Sources of Engine/Vehicle Emissions


Figure 1.3 shows the sources of emissions from a gasoline fuelled SI engine viz., exhaust, crankcase blow by
and fuel evaporation from fuel tank and fuel system

Figure. 1.3

Emission sources
fuelled car

in

gasoline

From a diesel engine powered vehicle the emission sources are shown in Fig. 1.4.

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Figure 1.4

Emission sources in a diesel engine powered


bus.

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 2: Engine Emissions and Air Pollution
Emissions and Pollutants
Engine emissions undergo chemical reactions in atmosphere known largely as photochemical reactions
and give rise to other chemical species which are hazardous to health and environment. Linkage of
engine emissions and air pollutants is shown in Fig. 1.5.

TSP = Total suspended particulate matter in air


PAN = Peroxy- acetyl nitrate
Figure. 1.5

Air
pollutants
emissions

resulting

from

engine

Photochemical Smog
Photochemical smog is a brownish-gray haze resulting from the reactions caused by solar ultraviolet
radiations between hydrocarbons and oxides of nitrogen in the atmosphere. The air pollutants such as
ozone, nitric acid, organic compounds like peroxy- acetylnitrates or PAN ( CH3 CO-OO-NO 2 ) are
trapped near the ground by temperature inversion experienced especially during winter months. These
chemical substances can effect human health and cause damage to plants. The photochemical reactions
are initiated by nitrogen oxides emitted by vehicles into atmosphere. A simple set of reactions leading to
photochemical smog formation is as follows:

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is energy of a photon and UV is ultraviolet light radiations .

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 2: Engine Emissions and Air Pollution

The above reactions form NO 2 photolytic cycle. However, if only these reactions are involved then, NO 2
concentration in the atmosphere would remain constant. But, volatile organic compounds (VOCs) that
include unburned hydrocarbons and their volatile derivatives also react with NO and O 2 to form NO 2 .
The reactions between HC and NO do not necessarily involve ozone and provide another route to form
NO 2 and thus, the concentration of ozone and NO 2 in the urban air rises. The most reactive VOCs in
atmosphere are olefins i.e., the hydrocarbons with C=C bond. The general reaction between
hydrocarbons (RH) and NO may be written as

The overall global reaction is

Main processes in photochemical smog formation are shown in Fig. 1.6.

Main processes in photochemical smog formation


from http://mtsu32.mtsu.edu:11233/SmogAtm1.htm)

Figure1.6 (adapted

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 2: Engine Emissions and Air Pollution
The harmful constituents of photochemical smog are, NO 2 , O 3 , PAN and aldehydes. The PAN and
aldehydes cause eye irritation. NO 2 and ozone are strong oxidants and cause damage to elastomeric/
rubber materials and plants.

Photochemical Reactivity of Hydrocarbons


The exhaust gases of gasoline engines contain more than 150 different hydrocarbons and their
derivatives. Some hydrocarbons are more reactive than the others. The photochemical reactivity of
hydrocarbons has been measured in terms of the rate at which the specific hydrocarbon causes
oxidation of NO to NO 2 . To determine the rate of photo-oxidation, NO in presence of the specific
hydrocarbon is irradiated by ultra violet radiations in a reaction chamber and the buildup of NO 2 in
terms parts per billion/per minute is recorded. Another photochemical reactivity scale has been defined
in terms of ozone formation. Reactivity of different classes of hydrocarbons based on formation of NO 2
is given in Table 1.4
It has been noted that the reactivity of a given hydrocarbon depends also on the initial concentrations of
pollutants in the environment in which a particular hydrocarbon is added when emitted. A reactivity
termed as incremental activity has been determined in terms of ozone formed. It is defined as the
change in ozone formation rate when specific VOC is added to the base reactive organic gas mixture
in the environment divided by the amount of the specific VOC added. This reactivity is considered to
bge of more practical relevance.

Table 1.4
Photochemical Reactivity of
Hydrocarbons (General Motor Scale)
Hydrocarbon

Relative Reactivity*

C1-C4 paraffins AcetyleneBenzene

C4 and higher paraffins Monoalkyl benzenes Ortho- and


para-dialkyl benzenes Cyclic paraffins

Ethylene Meta- dialkyl benzenes Aldehydes

1-olefins (except ethylene) Diolefins Tri- and tetraalkyl


benzenes

10

Internally bonded olefins

30

Internally bonded
bondCyclo-olefins

olefins

with

substitution

at double

100

*based on NO 2 formation rate for the specific hydrocarbon relative to that for 2,3 dimethyl-2-benzene

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 2: Engine Emissions and Air Pollution
Health Effects of Air Pollutants
The effect of pollutants on human health depends on pollutant concentration in the ambient air and the
duration to which the human beings are exposed. Adverse health effects of different pollutants on
human health are given in Table 1.5 for short term and long term exposures. Carbon monoxide on
inhalation is known to combine with haemoglobin at a rate 200 to 240 times faster than oxygen thus
reducing oxygen supply to body tissues and results in CO intoxication. Nitrogen oxides get dissolved in
mucous forming nitrous and nitric acids causing irritation of nose throat and respiratory tract. Long term
exposure causes nitrogen oxides to combine with haemoglobin and destruction of red blood cells. Long
term exposure resulting in more than 10% of haemoglobin to combine with nitrogen oxides causes
bluish colouration of skin, lips fingers etc

Table 1.5
Adverse Health Effects of IC Engine
Generated Air Pollutants

Pollutants

Short-term health
effects

Carbon
monoxide

Effects on brain and central nervous system,


Headache, shortness of breath,
nausea, vomiting, cardiac and pulmonary
dizziness, impaired judgment,
functional changes, loss of consciousness and
lack of motor coordination
death

Nitrogen
dioxide

Development of cyanosis especially at lips, fingers


Soreness, coughing, chest
and toes, adverse changes in cell structure of
discomfort, eye irritation
lung wall

Oxidants

Difficulty in breathing, chest Impaired lung function, increased susceptibility to


tightness, eye irritation
respiratory function

Ozone
Sulfates

Long-term health effects

Similar to those of NO 2 but at


a lower concentration
Increased asthma attacks

TSP/Respirable
Increased
susceptibility
suspended
other pollutants
particulate

Development of emphysema, pulmonary edema


Reduced lung function when oxidants are present

to

Many constituents especially poly-organic matter


are toxic and carcinogenic, contribute to silicosis,
brown lung

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Module 1: An Overview of Engine Emissions and Air Pollution


Lecture 2: Engine Emissions and Air Pollution
Historical Overview: Engine and Vehicle Emission Control
Beginning with the identification during early 1950s that mainly the unburned hydrocarbons and
nitrogen oxides emitted by vehicles are responsible for formation of photochemical smog in Los-Angeles
region in the US, the initiatives and milestones in pursuit of vehicle/ engine emission control are given
in Table 1.6

Table 1.6
Engine Emission Control A
Historical Perspective

Year
1952

1965

Event and Milestone


Prof A. J. Haagen- Smit of Univ. of California demonstrated that the
photochemical reactions between unburned hydrocarbons (HC) and nitrogen
oxides (NOx) are responsible for smog (brown haze) observed in LosAngeles basin
The first vehicle exhaust emissions standards were set in California, USA

1968

The exhaust emission standards set for the first time throughout the USA

1970

Vehicle emission standards set in European countries

1974

Exhaust catalytic converters for oxidation of carbon monoxide (CO) and HC


were needed in the US for meeting emission targets. Phasing-out of tetra
ethyl lead (TEL), the antiknock additive from gasoline begins to ensure
acceptable life of the catalytic converters

1981

Three-way catalytic converters and closed-loop feedback air-fuel ratio control


for simultaneous conversion of CO, HC and NOx introduced on production
cars

1992

Euro 1 emission standards needing catalytic emission control on gasoline


vehicles implemented in Europe

1994

Catalytic emission control for engines under lean mixture operation introduced

1994

US Tier -1 standards needing reduction in CO by nearly 96%, HC by 97.5%


and NOx by 90%

2000-2005

Widespread use of diesel particulate filters and lean de-NOx catalyst systems
on heavy duty vehicles

2004

US Tier -2 standards needing reduction in CO by nearly 98 %, HC by 99%


and NOx by 95%

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 3: Introduction to Pollutant Formation
POLLUTANT FORMATION
The Lecture Contains:
Engine Emissions
Typical Exhaust Emission Concentrations
Emission Formation in SI Engines
Emission Formation in CI Engines

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 3: Introduction to Pollutant Formation
Engine emissions
SI engine vehicles without emission control have three sources of emissions

Exhaust emissions

Almost all of 100% of NOx and CO, and 60% of HC are emitted
through the engine exhaust or vehicle tailpipe

Crankcase emissions

About 20% of HC are emitted via crankcase blow by gases

Evaporative Emissions

Fuel evaporation from tank, fuel system, carburettor and permeation


through fuel lines constitute another 20% of total HC

CI engines on the other hand


exhaust gases

release all of harmful emissions into atmosphere through its

Typical Exhaust Emission Concentrations


SI Engine (Gasoline fuelled)
Depending upon engine operating conditions without catalytic control engine out emissions range :
CO

0.2 to 5% by volume (v/v)

HC

300 to 6000 ppmc1*, v/v

NO x

50 to 2000 ppm, v/v

*ppmc1 = parts per million as methane measured by Flame Ionization Analyzer/Detector(FIA or FID)
CO emissions are high under engine idling and full load operation when engine is operating on fuel rich
mixtures. HC emissions are high under idling, during engine warm-up and light load operation, acceleration
and deceleration. NOx are maximum under full engine load conditions.

CI (Diesel) Engines
Diesel engines usually operate with more than 30% excess air band the emissions are accordingly
influenced.
CO

0.03 to 0.1 %, v/v

HC

20 to 500 ppmc1

NO x

100 -2000 ppm

PM

0.02 to 0.2 g/m3 (0.2 to 0.5% of fuel consumption by


mass)

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 3: Introduction to Pollutant Formation
Emission Formation in SI Engines
Origin of SI engine exhaust emissions is shown schematically in Fig 2.1.

Schematic of progress of combustion in SI engine

Figurer. 2.1 and pollutant formation

NO x and CO are formed in the burned gases in the cylinder. Unburned HC emissions originate when
fuel escapes combustion due to several processes such as flame quenching in narrow passages present
in the combustion chamber and incomplete oxidation of fuel that is trapped or absorbed in oil film or
deposits
NO x is formed by oxidation of molecular nitrogen. During combustion at high flame temperatures,
nitrogen and oxygen molecules in the inducted air breakdown into atomic species which react to
form NO. Some NO 2 is also formed and NO and NO 2 together are called as NO x .
CO results from incomplete oxidation of fuel carbon when insufficient oxygen is available to
completely oxidize the fuel. CO rises steeply as the air-fuel (A/F) ratio is decreased below the
stoichiometric A/F ratio.
HC originates from the fuel escaping combustion primarily due to flame quenching in crevices
and on cold chamber walls, fuel vapour absorption in the oil layer on the cylinder and in
combustion chamber deposits, and presence of liquid fuel in the cylinder during cold start
Air-fuel ratio is one of the most important parameter that affect the engine exhaust emissions. Typical
variation in emissions with air-fuel ratio for premixed charge SI engines is shown in Fig. 2.2. The SI
engine is operated close to stoichiometric air-fuel ratio as it provides a smooth engine operation. Nitric
oxide emissions are maximum at slightly (5-10 %) leaner than stoichiometric mixture due to
combination of availability of excess oxygen and high combustion temperatures at this point. Carbon
monoxide and HC emissions reduce with increase in the air-fuel ratio as more oxygen gets available for
combustion. Lean engine operation to a certain critical value of air-fuel ratio tend to reduce all the three
pollutants. Further leaning of mixture results in poor quality of combustion and eventually in engine
misfiring causing an erratic engine operation and sharp increase in HC emissions. Normally, one would
like to operate engine on lean mixtures that would give low CO and HC, and moderate NO x emissions.
But, presently most engines are operated very close to stoichiometric conditions for catalytic control of

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NO x emissions,

Figure 2.2

Variation in CO, HC and NO x emissions for a SI


engine

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 3: Introduction to Pollutant Formation
Emission Formation in CI Engines
Schematic of a diesel injection spray is shown in Fig 2.3 . A fully developed diesel spray may be
considered to consist of three distinct regions based on the variations in fuel-air equivalence ratio,
across the cross section of the spray as seen radially outwards from the centreline of spray.
A fuel rich core where fuel-air equivalence ratio is richer than the rich flammability limits i.e.,
Flammable region in which

lies within the rich and lean flammability limits, i.e.,

A lean flame-out region (LFOR) where

is lower than lean flammability limits and extends up to

the spray boundary i.e.,

Figure.
2.3

Schematic representation of diesel spray, combustion and


pollutant formation for a direct injection diesel engine

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 3: Introduction to Pollutant Formation
Pollutant formation is strongly dependent on the fuel-air ratio distribution in
the spray:
NO is formed in the high temperature burned gases in the flammable region. Maximum burned
gas temperatures result close to stoichiometric air-fuel ratio and these contribute maximum to NO
formation.
CO is formed in fuel rich mixtures in the flammable region.
Soot forms in fuel-rich spray core where fuel vapour is heated by the hot burned gases
.
Unburned HC and oxygenated hydrocarbons like aldehydes originate in the region where due to
excessive dilution with air the mixture is too lean at the spray boundaries. In excessive lean
mixtures combustion process either fails to begin or does not reach completion. Towards the end
of combustion, fuel in the nozzle sac and orifices gets vaporized, enters the combustion chamber
and contributes to HC emissions.

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
POLLUTANT FORMATION
The Lecture Contains:
Formation of Nitrogen Oxides
Thermal NO

Rate Constants for Zeldovich Mechanism


Rate of NO Formation
NO Formation is a Function of Temperature and [O2 ]

Prompt NO
Fuel NO

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
Formation of Nitrogen Oxides
Nitric oxide is the major component of NO x emissions from the internal combustion engines. During
combustion, three probable sources of NO formation are:

(i)

Thermal NO

By oxidation of atmospheric (molecular) nitrogen at high temperatures in


the post-flame burned gases.

(ii)

Prompt NO

Formed at the flame front within the flame reaction zone.

(iii)

Fuel NO

Oxidation of fuel-bound nitrogen at relatively low temperatures

Thermal NO is the dominant source of nitrogen oxides in IC engines.

Thermal NO
NO is formed in the high temperature burned gases behind the flame front. The rate of formation of NO
increases exponentially with the burned gas temperature although, it is slower compared to the overall rate of
combustion.

Kinetics and Modelling of Thermal NO Formation


The following three reactions commonly referred to as the extended Zeldovich mechanism govern the
formation of thermal NO

(2.1)

(2.2)

(2.3)

k 1 , k 2 and k 3 are the reaction rate constants for the forward reactions and k -1 , k -2 and k -3 are for the reverse
reactions
The original Zeldovich mechanism consisted of the first two reactions (2.1) and (2.2) and the third reaction
(2.3) was added by Lavoie. The forward part of the first reaction (2.1) is highly endothermic with high
activation energy of about 314 kJ /mol and is a rate determining reaction in NO formation.

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
Rate Constants for Zeldovich Mechanism
The rate constants for the above reactions in units of cm3/mol-s and temperature in K are given in
Table 2.1

Table 2.1
Reaction rates for NO formation mechanism, cm3/mol-s, T in K

Reaction

Forward

Reverse

O + N2 NO +N

k1 = 1.8 x 1014 x
exp (-38,370/T)

k -1 = 3.8 x 1013 x
exp(- 425/T)

N + O2 NO + O

k2 = 1.8 x 1010T x
exp (- 4680/T)

k -2 = 3.8 x 109 T x
exp(- 20,820/T)

N + OH NO + H

k3 = 7.1 x 1013 x
exp (- 450/T)

k -3 = 1.7 x 1014 x
exp(- 24,560/T)

Rate of NO Formation
The rate of formation of NO using the three reactions (2.1) to (2.2) can be expressed by the following
equation;

[NO] = k 1 [O][N 2 ] k -1 [NO][N] + k 2 [N][O 2 ] k -2 [NO][O] + k 3 [N][OH] k


(2.4)
-3 [NO][H]

[] denotes the concentration of species in moles/cm3 .


Steady state approximation of [N]: Rate of formation and destruction of N is small relative

(i)

(ii)

to its concentration. Concentration of atomic N is of the order of 10 -8 mole fraction only,


which is much smaller compared to the other reacting chemical species.
O, OH, O 2 and O concentrations are governed by chemical equilibrium considerations as the
reactions governing concentration of these species are very fast at the combustion
temperatures..
Steady state assumption of [N] leads to,

[N] = + k 1 [O][N 2 ] k -1 [NO][N] k 2 [N][O 2 ] + k -2 [NO][O] - k 3 [N][OH] + k -3

(2.5)

[NO][H] = 0
Use of Eqs. 2.4 and 2.5 yield the rate of NO formation,
[NO] = 2 {k1 [O][N 2 ] k -1 [NO][N]}

(2.6)

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
Contd...
and from Equation 2.5 steady state concentration of N,

(2.7)

From the assumption of equilibration of O, OH, H and O 2 ,

(2.9)

Eliminating [N] and [H] using equations 2.7 and 2.8, the equation 2.6 gives,

(2.10)

where K = (k1 /k 1 )(k 2 /k -2 ) is equilibrium constant for the reaction N 2 + O 2 2NO.


The NO formation rates may be calculated by Eq. 2.10 using equilibrium concentrations of O, O 2 , OH and
N 2 . Most of NO formation takes place in the burned gases behind the flame front after combustion is
completed locally. The rate of NO formation being much slower than the combustion rates, the NO
formation process may be decoupled from combustion process and rate of formation of NO can be
calculated assuming equilibrium concentrations of O, O 2 , OH and N 2 .
By introducing equilibrium assumption in the calculations, the Eq. 2.10 is further simplified by using the
following notations;
R 1 = k 1 [O] e [N2 ]e = k -1 [NO]e [N]e
where R 1 is the reaction rate using equilibrium concentrations for the reaction (2.1).
Similarly,
R 2 = k 2 [N]e [O2 ]e = k -2 [NO]e [O] e ,

and

R 3 = k 3 [N]e [OH]e = k -3 [NO]e [H]e


Using the above notations the Eq. 2.10 is simplified to give rate of formation of NO as below,

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(2.11)

where w = R 1 /( R 2 + R 3 )

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
NO Formation is a Function of Temperature and O2
From Eq. 2.11 the initial rate of NO formation when [NO]/[NO] e << 1;

(2.12)

The concentration of atomic oxygen at equilibrium, using reaction O 2 O is given by;

(2.13)

Equilibrium constant K p(O) is

(2.14)

Using value of k 1 from Table 2.2 and, the Eqs. 2.13 and 2.14 the initial rate of NO formation then reduces to

(2.15)

Temperature being in exponential term in Eq.2.15, it strongly influences NO formation rates. From Eq. 2.15 it
follows that the NO formation is maximized under the conditions of high temperature and high oxygen
concentrations. These conditions occur at fuel-air equivalence ratios 5-10% leaner than stoichiometric mixture.
Typical combustion duration is about 1 to 2 ms in SI engines operating close to stoichiometric conditions at
3000 -5000 rpm. NO formation at peak pressure and temperature conditions may reach close to equilibrium
[NO] concentrations as illustrated below;
The characteristic time (

) necessary to reach equilibrium concentration of NO may be approximated as,

(2.16)

The mole fraction [NO]e can be estimated from the reaction O 2 + N 2 2NO, as

,mole fraction

(2.17)

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
Contd...
KNO is given by

and mole fraction of N 2 at equilibrium,

x [N2]e 0.71

From the above,

(2.18)

Time

Fig. 2.4

is in seconds, pressure, P is in atmospheres and temperature, T is in K.

Dependence of initial rate of NO formation on temperature and fuel-air equivalence ratio ( ). The

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dashed line shows adiabatic flame temperature line for different values of

. The maximum NO formation

rate occurs at slightly leaner than stoichiometric mixture.


Fig. 2.4 shows the initial NO formation rate as a function of temperature for different fuel-air equivalence
NO formation increases with temperature. And as is reduced more oxygen is
ratios. For a given value of
available resulting in higher NO formation for a fixed reactant temperature. In the real combustion systems,
the burned gas temperature also depends on the value of . On this figure, the adiabatic flame temperature
for a hydrocarbon fuel-air mixture initially at 700 K and combustion at constant pressure at 15 atm for different
fuel-air ratios is also shown. The adiabatic constant pressure combustion of a charge element as an
acceptable model for an internal combustion engine. The initial NO formation rate is seen to be highest for a
mixture slightly leaner than stoichiometric.

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
Example 2.1:
Using the Eq. 2.18 based on initial rate of NO formation estimate whether during typical SI engine combustion
the kinetically formed NO could reach the level of equilibrium concentrations

Solution
For the charge that burns early in the cycle the peak burned gas temperatures of 2700 K or higher could be
obtained. At full load
maximum cylinder pressure is of the order of 30 40 atm. Under real engine
conditions, the rate of NO formation changes with time as the temperature and pressure change with time
during the cycle and also the NO concentration (Eq. 2.11). However, for an approximate analysis let us
assume that the average temperature and pressure of the charge elements burnt early are 2700 K and 35 atm
At T= 2700 K and P = 35 atm for an early burn charge element

For an engine operating at 4500 rpm, it would take 10.3 CA to reach equal to equilibrium NO concentrations.
This time period is well within the typical combustion duration being in the range 30- 40 CA
For the charge elements burning later in the cycle the temperatures reached may be around 2300 K and
pressure may be down to 20 atm. At these conditions,
For a late burn element :

For a late burn element on the other hand it needs about 4.07 ms i.e., 110 CA which is too long a period in
the engine cycle. Due to expansion, the burned gas temperatures would have fallen by then to further low
levels of around 1300-1400 K and in the late burn elements the kinetically formed NO would never reach
equilibrium concentrations. The NO formation in the late burn elements is frozen at a value higher than that
predictted by the equilibirium considerations .This is demonstrated later in this module in Fig. 2.7.

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 4: Mechanisms of Nitrogen Oxides Formation
Prompt NO
In the flame reaction zone NO may be formed rapidly. The prompt NO is formed in the flame by
reaction of intermediate chemical species of CN group with O and OH radicals. The hydrocarbon
radicals CH, CH2 , C, C 2 etc. formed in the flame front react with molecular nitrogen to give intermediate
species such as HCN and CN by the reactions (2.19) to (2.21). Large concentrations of HCN near the
reaction zone in fuel rich flames have been observed and rapid formation of NO has been seen to be
associated with rapid decay of HCN.

(2.19)

(2.20)

(2.21)

The contribution of prompt NO in the stoichiometric laminar flames is estimated to be about 5 to 10


percent only. In the engines as the combustion occurs at high pressures, the thickness of flame front is
very small (~ 0.1 mm) and the residence time of chemical species in this zone is very short. Moreover,
the burned gases produced by the charge elements that burn early during the combustion process are
compressed to a much higher temperature than the temperatures attained immediately after
combustion. The formation of thermal NO in the burned gases behind the flame front therefore, is much
higher compared to any NO formation in the flame front. However, contribution of prompt NO may be
significant under lean engine operation or engine operation with high dilution such as use of exhaust
gas recirculation.

Fuel NO
Fuel NO is formed by combustion of fuels with chemically bound nitrogen. The fuel nitrogen produces at
first intermediate nitrogen containing compounds and reactive radicals such as HCN, NH3 , CN, NH etc.
These species are subsequently oxidized to NO. Although petroleum crude may contain about 0.6 %
nitrogen but gasoline has negligible nitrogen. Diesel fuels have higher nitrogen content than gasoline,
but this too is usually less than 0.1% by mass. The fuel nitrogen therefore, does not make significant
contribution to NO formation in automotive engines operating on gasoline, diesel, natural gas and
alcohols etc.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 5:Formation of NOx in SI Engines
The Lecture Contains:

NO Formation in SI Engines
Effect of Addition of Diluents on NO Formation

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 5:Formation of NOx in SI Engines
NO Formation in SI Engines
For computation of rate of formation of NO using Eq. 2.11 data are required on;

(i) Thermodynamic state of the combustion gases


(ii) Equilibrium concentration of O. OH, O 2 , N, N 2 and NO in the burned gases.
Thermodynamic Combustion Models
Temperature of the burned gases and subsequently the equilibrium composition for a given engine and
air-fuel ratio may be computed using a thermodynamic model from

(a)
(b)
(c)

measured cylinder pressure crank angle history


Use of empirical burn rates, or
Use of fundamental combustion models that are based on flame propagation models or
multi-dimensional combustion models.

Thermodynamic combustion models for SI engines are zero-dimensional and are only time dependent.
Space coordinates of the combustion chamber are not taken into account. Two types of thermodynamic
combustion models are used:
One Zone Combustion Model: It is the simplest form of thermodynamic combustion models
where the burned gas after combustion is assumed to mix instantaneously with gases burned
earlier and the unburned gases so that all the cylinder gases at a given instant is uniform in
composition and temperature. This model is too simplistic and unreal. It is unable to predict
Excepting gross engine performance parameters such models are unable to predict engine
performance and emissions with an acceptable degree of accuracy.
Two Zone Combustion Models: Two zone models consist of an unburned mixture zone and
a second zone consisting of the burned gases. The unburned and burned zones are separated
by a thin reaction zone (flame front) of negligible thickness and hence the mass of charge in the
flame front can be neglected.
Two zone fully mixed model: This model assumes that the burned gases
produced on combustion of the charge element during the given time period
instaneously mixes with the burned gases produced earlier. Thus, all the burned
gases at a given instant are uniform in temperature and composition. The unburned
gases are in a separate zone and obviously at a different and much lower
temperature. The pressure in the entire cylinder is however uniform.
Two zone unmixed model: At the extreme is an unmixed multi-zone model where
no mixing occurs between the burned gases produced by the mixture elements that
burn at different instants in the cycle. The unmixed model predicts that a
temperature gradient exists in the burned gases. The difference in temperatures of
an early burnt element (near spark plug) with a late burn element at the far end of

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the combustion chamber of around 400 K have been experimentally measured


supporting that the burned gases are not uniform in temperature and composition
supporting the unmixed combustion model. Although, the actual situation in the
combustion chamber may be somewhere between the fully mixed and unmixed
models, but the unmixed model is more realistic.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 5:Formation of NOx in SI Engines
contd..
Using unmixed model and an empirical relation giving mass fraction burned as a function of crank
angle, the computed engine cylinder pressure - crank angle (P-) history is shown on Fig. 2.5 .

Figure
2.5

Computed cylinder pressure- crank angle (P-) history using


unmixed combustion model and an empirical combustion rate
function.

Fig 2.6 shows the variation in temperature with respect to crank angle for (i) the unburned mixture
( T u) (ii) the charge element that burned at the beginning of the combustion process ( T bat x =0 ) and
(iii) the charge element that burned last at the end of combustion( Tb at x = 1.0 ). As seen the charge
element close to the spark plug that burns in the beginning itself reaches a much higher temperature
compared to the element that burns last. The difference in the calculated temperatures of two elements
at a given crank angle is seen close to 400 K

Unburned gas temperature (T u ), burned gas temperature for the


Figure.2.6 first burned element ( T b for x=0) and the last burned element
(T b for x =1.0).

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 5:Formation of NOx in SI Engines
Contd...
NO concentrations were computed by numerically integrating the Eq. 2.11. NO concentration in the
above two elements as a function of crank angle are shown in Fig 2.7 . The equilibrium concentrations
of NO for the two elements are also shown in this figure. In the early burned element as the peak
temperature reaches significantly high values due to compression to peak cylinder pressure ( the first
burned element attains the highest temperature of all), the kinetically controlled NO reaches to near
equilibrium levels. Later, as the temperature starts falling as a result of expansion, NO starts
decomposing. The rate of decomposition is controlled by the backward reactions of NO kinetics
(Reactions 2.1 to 2.3) until the NO chemistry freezes due to falling temperatures.

Kinetically formed NO in an early burned and a late burned

Figure 2.7 charge element. Equilibrium NO concentration in each of these


elements is also shown.

The net mass fraction of NO emissions in the exhaust is computed as the weighted average of the
frozen mass NO fraction over all the burned gas elements.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 5:Formation of NOx in SI Engines
Effect of Addition of Diluents on NO Formation
Burned residual gases left from the previous cycle act as charge diluents. A part of exhaust gas is also
recirculated back to the engine for diluting the intake charge to reduce NO formation. This process is
known as exhaust gas recirculation (EGR). Dilution by the burnt residual gases is also called as internal
EGR. The combustion temperatures decrease as a result of charge dilution and the lower combustion
temperatures result in lower NO levels. The effect of different diluents on NO emissions is shown on
Fig. 2.8(a) The equal volume of different diluents gives different NO reductions. CO 2 and H 2 O being
tri-atomic gases have higher specific heat and give larger NO reductions than the same volume of N 2 ,
He or Ar. The NO emission data with different diluents correlates very well with heat capacity (mass
flow rate of the dilutent x specific heat) irrespective of the chemical nature of the diluents as shown in
Fig. 2.8(b) . It shows that the effect of charge dilution on NO is almost entirely due to the heat
capacity of the diluting gases. The specific heat of the exhaust gas is higher than for air due to
presence of substantial fractions of CO 2 and H 2 O. Hence, EGR results in lower combustion
temperatures compared to those from dilution by nitrogen alone or by leaning of mixture.

Figure
2.8(a)

Effect of content of various diluents in intake air on NO


reduction in a SI engine

A negative effect of charge dilution is reduction in oxygen concentration in the charge and slowing down
of flame propagation speed and the rate of combustion. It causes further reduction in the burned gas
temperature and beyond a limit causes misfired combustion resulting in lower fuel efficiency and higher
unburned hydrocarbon emissions

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Figure
2.8(b)

NO reduction correlates well with diluents heat capacity in a


SI engine.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 6:Formation of NOx in CI Engines and NO2 Emissions
The Lecture Contains:

NO Formation in CI Engines
NO 2 Formation

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 6:Formation of NOx in CI Engines and NO2 Emissions
NO Formation in CI Engines
In the compression ignition engines, rapid combustion of fuel and air that are mixed during delay period
occurs 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
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.
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. 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 NO x 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.
The hypothesis that most of NO x in diesel engines is formed in the burned gases produced by
combustion at near stoichiometric conditions has been demonstrated by the following results. NO
formation index (EINO x ) in diesel engines has been correlated with the stoichiometric adiabatic flame
temperature,

using the following Arrhenius type expression

(2.23)

= Adiabatic flame temperature for stoichiometric mixture, K


E = overall activation energy, J/gmol
R = universal gas constant J/gmol.K
was evaluated at tdc motoring conditions using polytropic compression process. with polytropic
index, n = 1.33. The use of diluents like nitrogen, exhaust gas, oxygen and water varies the intake air
composition and hence the stoichiometric adiabatic flame

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 6:Formation of NOx in CI Engines and NO2 Emissions
Contd...
temperature. The measured NO x emissions with varying amounts of diluents at different engine loads
and speeds correlated well with

according to the relationship given in Eq. 2.23 . On a log plot,

the (EINO x ) data normalized with emissions obtained for standard air (without diluents) for several
engines had linear correlation with the reciprocal of

as shown on Fig 2.9. The activation energy

for DI engine was determined to be - 285.0 kJ/gmol, and for IDI engines equal to - 304.9 kJ/gmol. A
single value of E correlated the emission data varying by a factor of nearly 40 times. The good
correlation obtained between EINOx and

demonstrates the dominant importance of NO formation

in close-to-stoichiometric burned gas regions.

Figure 2.9

Correlation of NO x emission index with adiabatic flame


temperature of stoichiometric mixture (
) varied by
addition of nitrogen and oxygen as diluents and determined
for mixture conditions at top dead centre for motored
engines [14].

The engine design and operating conditions too affect the NO x formation process. The above model is
a very simple model and it showed good correlation for the engines of 1980s. For advanced engines
with very different injection parameters and fuel-air mixing processes, single overall activation energy
was found to have a poorer correlation than shown on Fig. 2.9.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 6:Formation of NOx in CI Engines and NO2 Emissions
Contd...
Depending upon the burned gas temperature, the contribution of different reactions to kinetics of NO
formation also changes and hence the deviations may be observed from the simple stoichiometric
adiabatic flame temperature model. However, the dominant contribution to NO formation still results
from the spray regions that burn in near stoichiometric conditions.
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
vapour, 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 may result due to mixing with cooler air and consequently resulting
in freezing of NO kinetics and the NO decomposition reactions. Thus, cooling of burned gases by mixing
with cooler air and fuel-air mixture in diesel engines causes more rapid freezing of NO kinetics, which
results in NO concentration frozen at higher levels compared to those in the SI engines.
Kinetic models based on the extended Zeldovich mechanism discussed earlier are widely used for
calculations of engine-out NO emissions from the DI diesel engines. At high pressures typical of diesel
combustion with high residual gas dilution (EGR), the Zeldovich mechanism alone may not predict
adequately NO formation. Additional reactions involving N 2 O in formation of NO as given in
reactions 2.24 2.25 have been proposed.

(2.24)

(2.25)

The significance of N2O mechanism for NO formation in the real engines however, is yet to be
established.
Summary of NO Formation in CI Engines
In the CI engines, most NO is formed in the burned gases resulting from near stoichiometric
combustion
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

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 6:Formation of NOx in CI Engines and NO2 Emissions
NO 2 Formation
Nitrogen dioxide emissions from the spark-ignition engines are negligibly small and constitute less than
2% of the total NO x emissions. NO emissions range from a few hundred ppm to several thousands of
ppm while, the maximum NO 2 emissions are around 60 to 70 ppm only compared to 3000- 4000 ppm of
NO at full load conditions. In diesel engines however, the NO 2 emissions account generally for 10 to 30
percent of the total NO x emissions. In diesel engines, NO 2 concentration may be in the range of 200 to
400 ppm compared to NO concentrations typically in the range of 1500 to 3000 rpm. NO 2 is rapidly
formed in the combustion zone by reaction of NO with HOO- radical.

(2.26)

Later in the post combustion gases NO 2 on reaction with atomic O - is converted back to NO and O 2 .

(2.27)

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 NO 2 back to NO and oxygen are frozen and
relatively higher concentrations of NO 2 result. The relative concentration of NO 2 with engine power
typically observed in diesel engines is shown in Fig.2.10. An increase in relative concentration of NO 2
with decrease in engine load as seen in Fig 2.10 supports this mechanism. As the engine load
decreases the air to 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 NO 2 decomposition reactions in diesel engines at lighter loads.

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Figure 2.10

Exhaust NO 2 concentration as percent of total NO x for a DI


diesel engine

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 7:Mechanisms of CO and HC Formation in SI Engines
Mechanisms of CO and HC Formation in SI Engines
The Lecture Contains:
FORMATION OF CARBON MONOXIDE
FORMATION OF UNBURNED HYDROCARBONS
HC EMISSIONS FROM SI ENGINES

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 7:Mechanisms of CO and HC Formation in SI Engines
FORMATION OF CARBON MONOXIDE
Carbon monoxide is formed during combustion of fuel-rich mixtures due to deficiency of oxygen. Combustion
of hydrocarbon fuels may be considered as a two-step process leading to complete combustion when carbon
dioxide is the final product.

Step 1
Conversion of hydrocarbons to CO: oxidation reactions involving intermediate species like smaller
hydrocarbon molecules, aldehydes, ketones etc lead to formation of CO as schematically shown below are.

(2.28)

RH represents a hydrocarbon where R stands for the hydrocarbon radical

Step 2
Conversion of CO to CO 2 : when sufficient oxygen is available. Hydroxyl radical OH is one the
principal oxidizing species and converts CO to CO 2 ,

(2.29)

The reaction (2.29) is quite fast and is under equilibrium at high temperatures. In fact, the reactions involving
C-O-H system may be taken in chemical equilibrium during combustion and large part of expansion stroke
when temperatures are above 1800 K.
CO emitted is higher than the equilibrium concentrations corresponding to the temperature and pressure
conditions at the end of expansion. The calculations show that until about 60 degrees after top dead centre,
the burned gases are close to equilibrium. However, late in the expansion stroke and during exhaust blow
down on opening of the exhaust valve as the gases cool down, the CO concentrations differ from the
equilibrium value. The predicted CO levels at the end of expansion computed by equilibrium considerations
during early part of expansion and CO oxidation kinetics ( Reaction 2.29) in the later part of expansion
correlated well with the experimental data as shown on Fig. 2.11 These CO values may be considered as
partial equilibrium vales. Detailed investigations have shown:
For rich mixtures (f>1), the average exhaust CO concentrations are close to equilibrium concentrations
during expansion.
For near stoichiometric mixtures (f 1) exhaust CO is close to computed partial equilibrium values.
For lean mixtures the measured CO is higher than the computed values using kinetic models. This
discrepancy may occur due to partial oxidation of unburned hydrocarbons released from crevices and
lubricating oil film and deposits on the combustion chamber walls during expansion.
For estimation of CO concentration a good approximation is to assume chemical equilibrium frozen at 1750 K.

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Fig 2.11

Comparison of calculated CO using partial equilibrium (kinetics in later


part of expansion stroke) and experimental data

CO emissions in real engines:


Mixture mal-distribution in multicylinder engines causes cylinder-to-cylinder variation in air-fuel ratio. It
results in significant increase in the average CO emissions. This is especially prominent in the
carburetted or single point throttle body-injected (TBI) engines.
Another contributing factor to higher CO emissions is non-uniform mixture distribution within the
cylinder.
During cold start of engine and acceleration rich mixtures are used resulting in higher CO emissions
Overall, the air-fuel ratio is the most important engine parameter affecting CO emissions. Other factors
influence CO mostly indirectly through changes in mixture composition and/or promotion of slow oxidation
reactions resulting in incomplete combustion.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 7:Mechanisms of CO and HC Formation in SI Engines
FORMATION OF UNBURNED HYDROCARBONS
The unburned hydrocarbons are also called volatile organic compounds (VOCs).
Unburned hydrocarbon emissions result as part of the fuel inducted into the engine escapes
combustion. Most of hydrocarbons in exhaust HC are the same compounds as in the fuel. A
typical petroleum fuel contains 100 to 200 different hydrocarbons (10 to 20 are the major
constituents) and other organic compounds. Thus, if the fuels are rich in aromatics and olefins
the exhaust hydrocarbons also consist of a high fraction of aromatics and olefins, which are
photo-chemically more reactive.
Almost 400 hundred different organic compounds are present in the engine exhaust. A number of
these compounds are formed during combustion process in the engine cylinder.
Nearly 50% mass of organic compounds emitted in the exhaust is similar to fuel in composition.
The balance 50% is composed of the chemical species which are produced by thermal cracking,
pyrolysis, chemical synthesis and partial oxidation of the fuel molecules during combustion.
Methane is also present in significant amounts in the exhaust of gasoline and diesel engines. As
methane is not photo-chemically reactive, hydrocarbon emissions now, are also measured
neglecting methane emissions and these are termed as non-methane hydrocarbons or nonmethane organic gases (NMHC/NMOG).
Hydrocarbon concentration in the exhaust is measured by flame ionization analyzer (FIA), which
is basically a carbon atom counter. The total hydrocarbon concentration measured by this method
is specified in parts per million as methane or C1 (ppmC 1 or simply ppmC). It means that if the
FIA is calibrated with propane (C3 H 8 ), the HC measurement reading is to be multiplied by a
factor of 3 to obtain HC concentration in ppmC.
Several engine processes contribute to the unburned fuel emissions. The sources of unburned
hydrocarbon emissions also vary with the engine design; whether it is a homogeneous SI or a
heterogeneous CI ignition engine, whether 4-stroke or crankcase scavenged 2-stroke engine. In the
crankcase scavenged, small two stroke SI engines, fuel-air mixture bypasses combustion and is directly
short-circuited to the exhaust port during scavenging period and the mixture short-circuiting is the main
source of hydrocarbon emissions in these engines.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 7:Mechanisms of CO and HC Formation in SI Engines
HC EMISSIONS FROM SI ENGINES
Main sources of hydrocarbon emissions in the four-stroke, homogeneous charge spark ignition engines are:

(i)

Flame quenching on the cylinder walls

(ii)

Flame quenching in crevices

(iii)

Absorption and desorption in oil film on cylinder walls

(iv)

Absorption and desorption in carbon deposits in the chamber

(v)

Misfired combustion or bulk gas quenching

(vi)

Liquid fuel in the cylinder

(vii)

Exhaust valveleakage,and

(viii)

Crankcase blow by gases

In the vehicles, fuel evaporation from fuel tank and fuel system is another source of unburned HC emissions.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 8:Mechanisms of HC Formation in SI Engines
Mechanisms of HC Formation in SI Engines
The Lecture Contains:
Flame Quenching in SI Engines
Quench Layer Thickness
HC Emissions from Wall Quenching
Crevice HC

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 8:Mechanisms of HC Formation in SI Engines
Flame Quenching in SI Engines
Photographic studies of flame region in a spark ignition engine immediately after arrival of flame close
to the combustion chamber walls have shown existence of a thin non-radiating layer adhering to the
combustion chamber. Flame propagates through unburned charge when the energy released on
combustion is able to maintain the reaction zone temperatures at a high enough level to sustain the
rapid combustion reactions. However, as the flame approaches combustion chamber walls, more and
more heat is lost from the flame to the walls.
Due to heat transfer from the flame to the walls,
temperature of the reaction zone gets lowered that slows down combustion reactions reducing heat
release rate. Finally, as the flame reaches in close proximity of the walls, the gas temperature ahead of
flame falls below ignition point and the flame gets extinguished. This phenomenon is known as flame
quenching.
The flame propagating normal to the single wall will quench at some distance away. When the flame is
propagating through a tube it may not propagate if the tube diameter is smaller than a critical value.
Similarly, flame may not propagate between the two parallel plates if the distance between the plates
is below a critical limit. The normal distance from the wall where flame gets quenched, or the gap
between two parallel plates, or diameter of the tube in which flame is just unable to propagate under
the given charge conditions, is called quench distance or quench layer thickness. The wall-quenching
effects are primarily due to heat transfer and not due to diffusion of species.

Quench Layer Thickness


Let us consider that flame is propagating normal to a single wall.

At the Instant of Flame Quenching

For a laminar flame and also as the flame is very close to the walls, heat from the reaction zone is
mainly transferred by conduction and, the convection effects may be neglected. Thus,

(2.30)

where
k

Thermal conductivity of the unburned mixture,

Characteristic temperature difference for heat transfer,

Quench distance,

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Unburned mixture density,

Laminar flame speed,

Heat release per unit mass of the mixture burned,

Average specific heat of burned gases, and

Temperature rise on combustion in the flame.

Introducing thermal diffusivity, a in the equation 6.39, we get

(2.31)

A similar relationship for the flame quenching between two parallel plates is also obtained. The
dimensionless quantity

is Peclet number.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 8:Mechanisms of HC Formation in SI Engines
Contd...
From the above:
Quench distance is inversely proportional to the laminar flame speed.
For a given fuel- air mixture composition, pressure and temperature,

is proportional to the

Peclet number at the flame quenching conditions.


Quench distance or quench layer thickness depends on several parameters viz., wall geometry, fuel
composition, mixture stoichiometry, flame speed, temperature and pressure of the reactants, thermal
conductivity and turbulence. Typical quench layer thickness for stoichiometric mixtures of different fuels
for laminar flame combustion are given in Table 2.2.
Table 2.2

Quench layer thickness,

(mm) for different fuel-air

mixtures,
=1, P = 1atm and T = 20 C

Fuel

, mm

Hydrogen

0.6

Methane

1.9

Propane

2.1

Isooctane

2.0

Methanol

1.8

In engine like conditions, typical two wall quench distance ranges from 0.2 to 1 mm. Peclet number for
flame quenching between two parallel plates is nearly 5 times of the single wall quench distance. Thus,
the single wall quench layer thickness would be in the range 0.04 to 0.2 mm. For example, in a SI
engine operating on normal gasoline, at an average cylinder pressure = 10 bar, = 0.2 m/s and a =
10-5 m2/s, single wall quench distance is estimated to be about 0.05 to 0.1 mm assuming

and

to be about equal in Eq. (6.40).

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 8:Mechanisms of HC Formation in SI Engines
HC Emissions from Wall Quenching
Single wall quench layer thickness typically varies from 0.05 to 0.1 mm. It decreases with increase of
engine load as higher wall temperature results at higher engine loads, which reduces heat loss to the
walls from the reaction zone, and consequently a smaller quench layer thickness is obtained. However,
at top dead centre the surface to volume ratio of the combustion chamber is at its maximum and at this
point the wall quench layer may comprise of 0.1 to 0.2 percent of the total charge inducted into the
cylinder.
Studies on combustion of pre-mixed fuel air mixtures in combustion bombs show that when all the
crevices in the bomb are eliminated by filling with solid material, unburned HC concentrations were just
about 10 ppmC only. Such low concentrations result as after flame quenching the hydrocarbons in the
quench layer thickness on the single walls diffuse in the hot burned gas quite early and get oxidized.
Typically, most hydrocarbons would get oxidized on diffusion in the high temperature burned gases
within 2-3 milliseconds of the flame quench. These studies showed that the contribution of single wall
quench layers to the total unburned HC emission is quite small.

Crevice HC
Crevices in the combustion chamber are narrow regions into which fuel-air mixture can flow but
flame cannot propagate due to their high surface to volume ratio causing high heat transfer rates
to walls.
The largest crevice in the combustion chamber is between cylinder wall and piston top land, and
second land.
Other crevices present are along the gasket between cylinder head and block, around intake and
exhaust valve seats, threads around spark plug and space around the central electrode of the
spark plug.
Piston ring - cylinder crevice is shown schematically in Fig. 2.12. Table 2.3 gives typical volumes
contained in different the crevice regions in the cylinder of a production engine. Total crevice volume is
about 3 to 5 percent of the clearance volume and the piston and cylinder crevice constitutes around 70
to 80 percent of the total crevice volume.

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Figure 2.12

Typical dimensions of piston top land


crevices.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 8:Mechanisms of HC Formation in SI Engines
contd...
Table 2.3

Typical Volume Contained in Engine Crevices, cm 3


(Engine Displacement Volume/ Cylinder = 352 cm 3 , CR = 9:1)
Volume,
cm3
Clearance volume per cylinder

Percent

44

100

Volume above first ring (top land)

0.51

1.32

Volume behind first ring

0.32

0.86

Volume between Ist and 2nd rings


(Second land)

0.40

0.88

Volume behind second ring

0.32

0.86

Total ring crevice volume

1.55

3.5

Spark plug thread crevice

0.20

0.45

Head gasket crevice

0.20

0..45

Total crevice volume

1.95

4.4

During compression and combustion, unburned charge is pushed into these crevices and at peak
pressure, maximum gas would be stored in the crevices. The gas composition into the crevices depends
on the location of spark plug. In the piston-cylinder crevices mostly unburned charge would be filled in
unless the flame has reached piston top in some location nearest to the spark plug before the peak
pressure occurs, which would result also in small amounts of burned gas being pushed into the crevice
in this location. The other crevices close to spark plug would be filled with a larger fraction of the burned
gas. During expansion, the stored gases in the crevices begin to flow back into the cylinder. Part of the
unburned charge from crevices that expands back into the combustion chamber is oxidized on mixing
with the hot burned gases.
Amount of HC Stored in Crevices include:
Contribution of crevice volume to HC emissions may be understood as follows. The crevice gas
temperatures are nearly equal to the temperature of walls which are cooled. Hence, the density of the
charge stored in the crevices is higher than in the cylinder. The maximum fraction of the unburned
charge stored in crevices, Es occurs at peak pressure and is given by;

(2.32)

where m, V, T and P are mass volume, pressure and temperature. The subscripts cr and o refer to the
conditions in the crevices and at the end of intake stroke in the cylinder, respectively. Pmax is the peak

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pressure in the cylinder.


Typically Pmax /Po = 40, To = 300 K and Tcr = 400 K. Taking piston top land crevice volume equal to
0.9 cm 3 and the engine cylinder volume of 300 cm 3 for a compact car, 9% of the charge is stored in
the piston ring crevice. The crevice charge would consist of 10 to 15 percent residual gases and some
burned gases forced into it when flame propagates across the crevice opening.
In a production engines ring crevice region may contribute 25 % to 50% to exhaust HC emissions
depending upon the operating conditions.
Increase in radial clearance between the piston and cylinder beyond two-plate quench distance would
allow flame penetration in the crevice. It would result in reduction of HC as the flame would be able to
penetrate in the crevice volume. However, increase in radial clearance would lead to increase in blow
by gases and loss in engine power output.
Under conditions of high residual gas dilution or use of very lean mixtures, the flame may quench much
before it reaches the crevice region. Thus, increase in crevice volume by increasing radial clearance
can result in an increase in HC emissions under engine operation on lean mixtures or with high EGR.
Example 2.2 A SI engine has bore x stroke = 76 x 76 mm and compression ratio equal to 9.0:1. Top
piston land height is 7 mm and clearance between piston and cylinder liner is 0.35 mm. At the end of
intake stroke the stoichiometric mixture of gasoline (C8H18) is at 0.09 MPa and 330 K. Peak cylinder
pressure during combustion reaches 3.0 MPa. The temperature of gas in the piston crevice region due
to heat transfer to the cylinder walls is 400 K. Calculate the amount of charge stored in the top land
crevice at the instant of maximum cylinder pressure. What fraction of the charge inducted is stored in
this crevice?

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 8:Mechanisms of HC Formation in SI Engines
Solution
Cylinder bore, B = Stroke, S =76 mm
Clearance between cylinder and piston, dc = 0.035 mm
Piston top land height, h = 7 mm Swept volume of the engine cylinder,

Volume of the cylinder at the end of intake stroke,

Volume of the top land crevice can be approximated,

Mass of charge stored in the crevice


Molecular weight of the stoichiometric charge of C8H18 and air (O2 +3.76 N2)

Mass of charge stored in the crevice at peak pressure,

Fraction of inducted charge stored in the crevice from Eq.2.32

Ans.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 9:Mechanisms of HC Formation in SI Engines.... contd.
Mechanisms of HC Formation in SI Engines.... contd.
The Lecture Contains:
HC from Lubricating Oil Film
Combustion Chamber Deposits HC
Mixture Quality and In-Cylinder Liquid Fuel

HC from Misfired Combustion

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 9:Mechanisms of HC Formation in SI Engines.... contd.
HC from Lubricating Oil Film
Fuel hydrocarbons are absorbed in the oil film present on the cylinder walls during intake and
compression strokes, which get desorbed back into the burned gases during combustion and expansion.
On combustion, the partial pressure of fuel in the burned gases becomes nearly zero and the
concentration gradient makes the fuel to be desorbed from oil and diffuse back into the burned gases.
The desorbed fuel vapours from oil film are oxidized depending upon the temperature, pressure and
composition of the burned gases.
The maximum amount of fuel that can be dissolved per unit volume of oil is given by:

(2.33)

where, n fo isthe number of moles of fuel absorbed in oil, n o is number of moles of oil per unit volume,
Xfc mole fraction of fuel in the combustion chamber gases close to the oil film, P is instantaneous
cylinder pressure, H is theHenrys constant. Mole fraction of fuel vapours in oil,

(2.34)

As n fo << n fo , x f can be approximated as n fo / n o .


Henrys constant is a measure of fugacity of the fuel components (solute) in liquid phase or inverse of
its solubility. Henrys constant increases with temperature and decreases exponentially with increase in
molecular weight of the solute (in present case the fuel). At 400 K, Henrys constant for n-hexane, isooctane and ethyl-benzene is 200, 120 and 45 kPa, respectively. A larger fraction of the heavier fuel
components would be absorbed in the oil as they have a smaller value of H. Taking average cylinder
pressure under compression stroke as 0.5 MPa and typical oil film temperature equal to 400 K, the
mole fraction of fuel vapour absorbed in oil film at equilibrium for the stoichiometric mixture of isooctane
and air would be about 0.07
.The lubricant oil film thickness is a strong function of oil viscosity and hence the oil temperature. It also
varies with engine speed. The oil film thickness on the cylinder wall varies between 1 and 10 m. At
temperature of 400 K, the diffusion time to reach equilibrium for fuel vapour absorption in oil film of 1
m thick ness is about 10 -3 seconds and for a 10 m thick film it would equal to 10 -1 seconds. For an
engine speed of 3000 rpm, intake and compression strokes together would take 2x10 -2 seconds. Thus,
for oil films of 1 to 2 m thickness state of equilibrium in fuel vapour absorption would be achieved
under engine conditions.
The absorption and desorption of fuel in the oil film and its contribution to the HC emissions involves
several processes. Some of the absorbed hydrocarbon vapours in oil are carried to the crankcase
where these are desorbed.

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It has been seen that when lubricating oil was added to fuel or to the engine cylinder or deposited on
the piston crown, the exhaust hydrocarbons increased in proportion to the oil added. The increased
exhaust HC from the engine were identified as unburned fuel and partially oxidized fuel species and not
the unburned oil or oil oxidation species.
Potential HC contribution of the engine oil film depends on the solubility of fuel in the engine oil and the
amount of engine oil present in the combustion chamber.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 9:Mechanisms of HC Formation in SI Engines.... contd.
Combustion Chamber Deposits HC
Deposits are formed in the intake system, on the valves, combustion chamber and piston crown after
engine operation for several thousand kilometres. The combustion chamber deposits are carbonaceous
in composition and porous in nature. Olefins, aromatics and heavier fuels result in higher deposit build
up. Engine operation for 50 to 100 hours under cyclic and variable load and speed conditions can result
in deposit thickness of around 100 mm in the combustion chamber.
The fuel-air-residual gas charge is compressed into pores of deposits. As the pore size is smaller than
the quench distance, the flame cannot penetrate into deposit pores. The unburned mixture comes out of
pores during expansion and diffuses back into burned gases. Some of these hydrocarbons will burn up
on mixing with the hot burned gases. But, as the temperatures drop on expansion a large fraction of
these may fail to get oxidized and are emitted from the engine.
On the other hand, the deposits formed on the combustion chamber surface reduce heat transfer and it
may decrease quench layer thickness. Prevention of heat transfer by the combustion chamber deposits
increases charge temperatures and hence lower HC emissions. However, the overall effect of deposits
is to increase HC emissions.
In the engine and vehicle tests, combustion chamber deposits are seen to increase HC emissions by 10
to 25 percent

Mixture Quality and In-Cylinder Liquid Fuel


Very rich fuel-air mixture has to be supplied during cold starting as fuel evaporation is poor at low
engine temperatures. During acceleration, delayed dynamic response of the fuel system to meet the
engine requirements again requires supply of overly rich-mixtures. The carburetted engines are to be
supplied a richer fuel mixture than the modern PFI engines as there is a delay for the metered fuel in
reaching the cylinder. Also, the carburettor is unable to precisely control the fuel quantity. The port fuel
injection systems (PFI) i.e., separate fuel injectors for each cylinder provide more precise fuel metering
and more uniform fuel distribution among cylinders. PFI also gives a better control of air-fuel ratio during
cold starting and response to transient operation compared to the carburettor.
Fuel injection process in a PFI engine is shown schematically in (Fig 2.13). Mixture preparation is
governed by factors such as:
Fuel atomization and droplet size
Fuel vaporization on the back of the intake valve depending upon its temperature, and
Mixing with intake air and hot residual gases. The hot residual gases flow back into the intake
manifold as the intake valve opens and its amount depends on the operating conditions. The
injected fuel comes into contact with these hot residual gases that help fuel vaporization.

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Figure 2.13

Schematic of Port Fuel Injection and fuel vaporization


process

Some features of fuel induction into the cylinder of PFI engines are:
The conventional PFI system produces the droplets of Sauter mean diameter (SMD) ranging from
130 m to 300 m. The droplets larger than 10 m are unable to follow the air stream and they
impinge on the combustion chamber walls producing a non-uniform fuel distribution in the
cylinder.
As the injection is made at the back of intake valve, liquid fuel film is formed at the port and on
the back of the valve. The intake air strips this liquid fuel film and carries along into the cylinder.
In the process, substantial amount of liquid fuel droplets enter the engine cylinder and is
deposited on cylinder walls.
Shearing of the liquid film from the back of intake valve and port by intake air produces larger
droplets than by the injectors which impinge on the cylinder walls depositing liquid fuel film.
Injection at a higher pressure although would produce finer droplets but the fuel jet velocity and
droplet momentum are also higher, which increases the probability of the impingement of the fuel
droplets on walls.
During cold start as 8 to 15 times of the stoichiometric fuel requirement is injected for the first
few cycles, more liquid fuel is deposited inside the cylinder.
The liquid fuel deposition inside the cylinder decreases as the engine is warmed up. During cold starting
and warm up, much of the injected fuel remains in the cylinder for several cycles. It vaporizes during
and after combustion and thus, contributes to higher HC emissions. During cold start, with PFI up to
60% higher HC emissions could result compared to fully vaporized and premixed air and fuel mixture. At
90 C coolant temperature, the contribution of the liquid fuel deposited inside the cylinder to HC
emissions is almost zero compared to 20 to 60 percent at 20 C.
In the modern catalyst equipped vehicles, more than 90 percent of HC emissions under standard test
driving cycle conditions result during the first minute of operation. due to use of over-rich mixtures

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during engine start-up and secondly the catalytic converter has not yet warmed up and is not functional.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 9:Mechanisms of HC Formation in SI Engines.... contd.
HC from Misfired Combustion
Engine may misfire under engine idling and low load operation as the residual gas dilution is high.
Presence of high residual gas content retards combustion and more fuel burns during expansion stroke.
However, during expansion as the cylinder pressure falls the temperature of the unburned mixture
ahead of the flame also decreases which may result in extinction of flame and consequently in partially
misfired combustion. Such bulk flame quenching in spark-ignition engines leads to very high HC
emissions. Use of excessively lean mixtures also decreases burning rates and increases incidence of
bulk gas flame quenching. The propensity to partial misfiring increases under transient engine operation.
Use of large amounts of exhaust gas recirculation (EGR) or high residual gas dilution though reduces
NO formation but results in high HC emissions.

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 10:Post-flame Oxidation of HC and Transport to Exhaust
Post-flame Oxidation of HC and Transport to Exhaust
The Lecture Contains:
Post-flame HC Oxidation
HC Transport to Exhaust
Summary of HC Emission Processes in SI Engines

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 10:Post-flame Oxidation of HC and Transport to Exhaust
Post-flame HC Oxidation
During expansion stroke, the hydrocarbons from the quench layer, oil film and crevices diffuse back into
the bulk combustion gases. These hydrocarbons that diffuse back into the burned gases oxidize inside
the cylinder and in the exhaust depending upon the burned gas temperature and the availability of
oxygen. HC levels in the cylinder prior to opening of exhaust valve are 1.5 to 2 times higher than the
concentrations in the exhaust. Empirical correlations have been obtained from the experimental data to
estimate HC oxidation in the cylinder and exhaust as given below:

(2.35)

where [ ] denotes concentration of reactants in moles per cm3, XHC and XO2 are the mole fractions of
HC and O2, respectively, t is time in seconds, temperature T in K and the density (p/RT) is in moles
per cm 3 .

From the oxidation rate given by the above expression, oxidation time, tox for a given
concentration [HC] can be estimated as below:

(2.36)

As the quench layers on the cylinder walls are thin, HC from these diffuse rapidly into burned gases and
get oxidized. When the bulk gas temperatures are higher than 1300-1400 K, the HC oxidize rapidly. The
unburned hydrocarbons from the crevices between piston and cylinder expand back into the bulk gases
later in the expansion and exhaust strokes when temperatures have fallen below 1300 K. Just before
exhaust valve opens, the gas temperatures are generally around 1250 K, but decrease below 1000K
after exhaust blows down. Thus, a significantly large fraction of HC emerging from crevices and oil
layers may not be oxidized.
It is estimated that about two third of the hydrocarbons stored in the crevices and absorbed in oil film
get oxidized inside the cylinder of the conventional gasoline engines under steady state, mid-load and
mid-speed engine operation. At lower loads, extent of postflame HC oxidation would be lower.
During postflame oxidation, partial combustion products and intermediate hydrocarbons due to
decomposition of fuel molecules are also produced. These compounds are not present in the original
fuel and constitute about 50% percent of the exhaust HC.
Oxidation to an extent of up to 45% of HC which leave the cylinder is possible if high enough
temperatures are maintained and the oxidation reactions are not quenched by sudden cooling. In the
exhaust port and manifold if residence time is of the order of 50 ms or longer and temperatures greater
than 1000 K are maintained, significant oxidation of HC is possible. The engine could be run at
stoichiometric or richer mixtures and with retarded spark timing to obtain a high exhaust gas
temperature, and calibrated amount of secondary air is injected at the exhaust port to oxidize and
reduce HC emissions. This technique was employed on production engines prior to catalytic emission
control.

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 10:Post-flame Oxidation of HC and Transport to Exhaust
HC Transport to Exhaust
Four quench zones basically exist in the engine cylinder. These zones are
cylinder head quench layer wall including spark plug crevice
cylinder wall quench layer and head gasket crevice
the quench layer on piston head, and
the quench zone around the piston above the top land crevice.
Depending upon the gas-dynamic flow during exhaust, the flow from these regions is expected to be
different. At the end of combustion, hydrocarbons are present in high concentrations along the
combustion chamber walls trapped in the deposits, oil films and crevices. During expansion stroke,
hydrocarbons flow out of crevices. Some of the hydrocarbons flowing out of crevices and desorbed from
oil film and deposits diffuse into the bulk gas, but most of these remain close to the walls. When the
exhaust valve opens, gases blow out of the cylinder at a high velocity. During the exhaust blow down
process, in the beginning the exhaust gas takes along HC from the quench zones (1) and (2), spark
plug and head gasket crevices which are closer to the exhaust valve and part of the hydrocarbons
released from crevices, oil films and deposits. Thus, the initial exhaust blow down gas is rich in
unburned hydrocarbons and about half of the total unburned HC are emitted.
During expansion, hydrocarbon -rich boundary layer is present along the cylinder walls as the fuel
vapours expand out of piston-cylinder crevice and desorbed from the oil film. Upward motion of the
piston during exhaust stroke scraps this hydrocarbon rich
boundary layer and gases from
quench zone (3) rolling these into a vortex along the periphery of piston crown.. The piston motion
pushes it towards cylinder head and this vortex may be detached from the piston crown and is partly
exhausted. This vortex mechanism leads to high HC concentration in the exhaust gases towards the
end of the exhaust stroke.
Typical variation in exhaust HC concentration and mass flow rate exiting the cylinder is shown in Fig.
2.15. Hydrocarbon concentration peaks during blow down and towards the end of the exhaust stroke.
The peak in HC concentration at the end of exhaust stroke is very high as it contains HC mostly
originating from the piston ring crevice, but the exhaust flow rate is small. Mass HC emission rates peak
during the exhaust blow down process as the exhaust flow rates are high. About half of the mass of HC
is exhausted during blow down itself and the remaining half later in the exhaust stroke. Another peak in
the HC mass flow rate occurs towards the end of exhaust stroke when the HC from the piston-cylinder
crevice region are flowing out as HC concentration is very high, although the exhaust flow rates are
small.
it has been estimated that under wide open throttle operation, about 2/3rd of the total unburned HC in
the cylinder are exhausted, the balance remaining in the residual gases. Under part load conditions,
about half of the unburned HC exit the cylinder.

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Figure
2.14

Schematic of hydrocarbons exiting from engine


cylinder

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Figure 2.15

Trends in variation of HC concentration and HC mass flow rate


at the exhaust valve during the exhaust process of an SI
engine.

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Module 2: Genesis and Mechanism of Formation of Engine Emissions


Lecture 10:Post-flame Oxidation of HC and Transport to Exhaust
Summary of HC Emission Processes in SI Engines
In a port fuel injection SI engine, typically:
About 9 percent of the total fuel supplied escapes normal combustion. Of the this Approximately
3 percent escapes as fuel itself through absorption in oil and deposits routes, and as liquid fuel
films deposited in the cylinder.
About 5 percent as fuel-air mixture due to flame quenching on walls and crevices, and leakage
through exhaust valves.
Around 1% of fuel air mixture escapes as crankcase blow by.
Of the fuel contained in crevices and quench layers about 2/3rd is oxidized inside the cylinder.
Of the fuel in oil layers, deposits and liquid fuel film only about 1/3rd is oxidized inside the
cylinder.
About 2.7 % of fuel exits the exhaust port and nearly 1 % is retained in the residual burned
gases.
Of the hydrocarbons exiting the exhaust port about 1/3rd is further oxidized in the exhaust
system.
Under warmed up operation, engine out HC emissions from a PFI are approximately 1.8 percent
of the fuel supplied. The balance 7.2 percent fuel that does not leave the cylinder is either
oxidized in the cylinder or at exhaust port and manifold or recycled in the residual gases and
crankcase blow by gases.
Approximate contribution of different sources to HC emissions for a port fuel injected SI engine is shown
in Fig. 2.16

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Figure 2.16

Different sources of hydrocarbon emissions in homogeneous


charge SI engine.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 11:Formation of HC Emissions in CI Engines
Formation of HC Emissions in CI Engines
The Lecture Contains:

HC Emissions from CI Engines


Overmixing of Fuel
Under-mixing of Fuel

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 11:Formation of HC Emissions in CI Engines
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. 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, and
Bulk quenching of combustion reactions due to cold engine conditions, mixing with cooler air or
during expansion.

Overmixing of Fuel
Overmixed region in a diesel spray injected in swirling air is explained schematically in Fig. 2.17. The
outer boundary of spray will have smaller droplets. Also, swirling air carries smaller droplets towards
downstream of the leading edge of the spray. The smaller droplets vaporize more rapidly and due to air
entrainment at the spray boundary the mixture is leaner. The central core of the spray consists of larger
droplets that evaporate relatively at a slower rate and air entrainment in the spray core is also low.
The local fuel-air ratio distribution varies with the radial distance from the spray axis. The fuel-air ratio
distribution expected in diesel spray is qualitatively noted on Fig.2.17. The outermost boundary of the
spray is characterized by the fuel-air ratio being zero at the boundary. A large lean mixture region
containing fuel vapours exists inside the outer boundary where equivalence ratio is less than the lean
limit ( 0.3). This region is termed as lean flame blow out region (LFOR).
The overmixing of fuel in the LFOR region near the spray boundary may result due to high air swirl
and/or longer time available before combustion starts (longer ignition delay). Overmixing results in overleaning of the mixture beyond the lean flammability limit and it will not auto-ignite or support
combustion. In the overmixed region, only slow oxidation reactions are likely to occur resulting in
partially oxidized products and unburned fuel. Most of the unburned hydrocarbons especially under idling
and light loads are expected to originate from the overmixed region.

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Figure
2.17

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.

Figure 2.18

Effect of ignition delay on HC emissions in a DI diesel


engine

The width of the LFOR region primarily depends on ignition delay, pressure and temperature in the
chamber, fuel type and air swirl. Increase in temperature and pressure would reduce width of LFOR as
the lean limit of combustion is extended. The magnitude of contribution of LFOR to unburned HC would
depend on the length of ignition delay, amount of fuel injected and rate of fuel air mixing during the
delay period. A longer ignition delay allows more time for the fuel vapours to diffuse farther into air and
a higher percentage of fuel would be contained in the LFOR. An increase in HC emissions with
increase in the ignition delay is observed for DI diesel engines as shown in Fig 2.18.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 11:Formation of HC Emissions in CI Engines
Under-mixing of Fuel
HC emissions also result from under-mixing of fuel with air. This can happen for the fuel injected later in
the cycle or because of over-fuelling of the engine. The fuel left in the injector sac volume and nozzle
holes at the end of injection on heating during combustion gets fully or partially vaporized. The
vaporized fuel from the nozzle sac and holes enter the engine cylinder at low velocity later in the cycle
during expansion stroke and has little time to mix with air when the gas temperatures are still high. This
portion of fuel therefore remains mostly unburned and is emitted in the exhaust. Nozzle sac volume has
been observed to be the main contributor to HC emissions in a DI engines
through the process of under-mixing of fuel. Effect of nozzle sac volume on HC is shown on Fig.
2.19. Two types of nozzle designs one with low sac volume and another valve covered orifice (VCO)
design are also shown. In VCO nozzles the nozzle sac is eliminated. The VCO nozzles however, are
not preferred as their durability is low due to overheating of the nozzle tip as in the other nozzles fuel in
the sac absorbs latent heat of vaporization and the nozzle temperatures are lower.

Figure 2.19

Effect of nozzle sac volume and type of nozzle hole on HC


emissions from DI diesel engine.

Fuel contained in the nozzle holes also contributes to the HC emissions as seen when the curve is
extrapolated to zero sac volume.
For the DI engines, at full load a minimum of about 40 percent excess air (f< 0.7) is usually supplied to
limit smoke emissions. Over-fuelling may occur during acceleration especially in turbocharged engines,
as the response of turbocharger to increase airflow rate is slower than the increase in fuel injection rate.
With increase in engine load (increase in fuel-air equivalence ratio), engine and cylinder gas
temperatures increase and therefore, HC emissions generally decrease until a critical fuel-air ratio is
reached. When excess air is reduced to around 10 percent (f = 0.9) or below HC emissions increase
sharply.
At low ambient temperatures during engine warm up or with retarded injection timing, some engine
cycles may misfire resulting in bulk quenching and high HC
emissions. Under these conditions, liquid fuel droplets may appear in the exhaust giving the exhaust a
white coloured appearance, known as white smoke

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 12:Mechanisms of Formation of Soot and PM
Mechanisms of Formation of Soot and PM
The Lecture Contains:

SOOT AND PARTICULATE EMISSIONS

Composition and Structure of Diesel Particulates


Typical Composition of Diesel Particulate Matter

Soot Structure
Diesel Smoke
Soot Formation Stoichiometry
Conceptual Models of Soot Formation

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 12:Mechanisms of Formation of Soot and PM
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.
Here, we will discuss particulate emissions only from the diesel engines as these are of major health concern and
are more difficult to control. Soot emissions have been associated with respiratory problems and are thought to be
carcinogenic in nature. The particle size is important as the particles smaller than 2.5 can reach lungs along with
the inhaled air and cause health problems. The particles smaller than 2.5 constitute more than 90 percent mass
of the total particulate matter in the diesel exhaust.
The fuel composition also is an important factor in soot production and emissions. For diffusion combustion sootforming tendency is generally in the following order;

Composition and Structure of Diesel Particulates


US Environmental Protection Agency (USEPA) defines the particulate matter as any substance other than water
that is collected by filtration of the diluted exhaust gases at or below 325 K (125 F).
Composition of particulate matter collected on a filter is schematically shown on Fig. 2.20. Various components
adsorbed on the surface of spherical soot particles are shown.

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Schematic representation of diesel particulate matter collected

Figure 2.20 from diluted exhaust on filter.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 12:Mechanisms of Formation of Soot and PM
contd...
Diesel particulate matter has two main components;
Dry soot or solid carbon material

Dry soot is mainly the carbonaceous fraction of the particulate and its typical
chemical formulae are C 8H, C 9H and C 10 H. About 5 to 10 % by mass oxygen and
0.5% nitrogen are also present. Typical empirical formula of dry soot would be
CH 0.11 O0.065 N 0.005 . Dry soot results from several processes like pyrolysis,
dehydrogenation and condensation of fuel molecules.
Soluble organic fraction (SOF) that can be extracted by a solvent like
dichloromethane.
The soluble organic fraction originates from the fuel and oil hydrocarbons, and hence has
H/C ratio 2, although depending upon engine operating conditions it may vary from 1.25
to 2.0. The hydrocarbons C 17 to C 40 are present in particulate SOF phase, the C 23 C 24
being close to the mean. Typically, SOF has an empirical formula CH1.65 O 0.1 N 0.007 . The
soluble organic fraction is adsorbed on the solid soot core. The SOF also consists of
partial oxidation products and poly aromatic
hydrocarbons besides hydrocarbons originating from fuel and the lubricating oil. The mass
content of SOF varies significantly depending upon engine design and operating
conditions, but mostly it is in the range from 20 to 45 percent.
In addition to SOF, sulphates originating from fuel sulphur, nitrogen dioxide and water are also absorbed
on the particle core formed by soot. Other inorganic compounds of iron, silicon (fuel contamination),
phosphorous, calcium, zinc (source is oil) etc. are also present in traces in the particulates.

Typical Composition of Diesel Particulate Matter


The content of different constituents of diesel particulate matter can be significantly different for different
engine designs. These also vary with the emission control technology employed and the fuel quality
particularly the sulphur content. Fuel sulphur content has been drastically reduced as the emission
standards are becoming more stringent. The typical particulate composition for a Euro 3 turbocharged,
after-cooled diesel engines is shown on Fig 2.21. Considerable reduction in carbon (dry soot) content,
fuel and oil derived SOF and sulphates have taken place since early 1990s when PM emission
standards were enforced for the first time and made further stringent during the following years. SOF
content depends on engine design, operating conditions, lubricating oil consumption and fuel quality. As
regards sulphates, with the current low sulphur fuels (sulphur content down to 50 to 350 ppm by mass
compared to 0.5 % prior to 1990), sulphate content would be less than 2 percent of total PM mass.

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Figure 2.21

Typical diesels PM composition for a Euro 3


engine.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 12:Mechanisms of Formation of Soot and PM
Soot Structure
Electron micrographs of soot have been obtained in diffusion flames and in the engine combustion
chamber. Soot is seen to be aggregates of primary spherical particles. The primary soot particles are
mostly in the 15 to 30 nm size range. Typical electron micrograph of soot obtained from acetylene-air
diffusion flame is shown in Fig. 2.22. Primary soot particles are seen as spheroids on the micrograph.
Primary particles of about 30 nm size and branched chainlike soot aggregates are clearly observed in
this micrograph at 80000 magnifications.
A single spherical soot particle contains 10 5 to 10 6 carbon atoms. Initially, the combustion-generated
soot particles have one hydrogen atom to about 8 carbon atoms, (C8 H)n with a density of approx. 1800
kg/m 3 .. The primary soot particles form aggregates in the combustion chamber of 100-200 nm in size
containing generally 20 to over 100 primary particles. These aggregates may further agglomerate to
particles as large as 1 . The aggregates usually resemble a cluster of spheres in branched or chain
like structure.

Figure 2.22

Transmission electron microscope (TEM) images of soot in


acetylene-air
diffusion flames. Micrograph at 80K magnification shows
branched chainlike soot
aggregates

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 12:Mechanisms of Formation of Soot and PM
Diesel Smoke
Visible black smoke emissions from diesel engine result on account of high concentration of soot in the
exhaust gas. All the diesel engine design and operating variables that affect soot formation and
oxidation also influence black smoke intensity. Initially, smoke emission standards for production diesel
vehicles were in force to control black smoke.
Smoke emissions increase with increase in engine load due to overall richer fuel-air ratios and
hence, the rated engine power was specified based on the maximum permitted smoke density to
curb black smoke emissions during engine operation. 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.
Smoke is measured by measurement of light absorbed (opacity) in a defined specific length of column
of exhaust gas. The smokemeters employing this principle are known as light extinction type of
smokemeter such as Hartridge or AVL smokemeters. Smoke has also been measured by filtering a fixed
volume of exhaust gases through a filter paper and the smoke stain thus formed is evaluated on a
grayness scale by a light reflectance meter (Bosch smokemeter).
As the diesel particulate matter (PM) mainly consists of soot and the adsorbed unburned hydrocarbons
(SOF) on soot core, the PM content has been related to exhaust soot content and HC concentration as
below;
(2.37)
Soot content and HC concentration are in mg/m 3 . Soot content can be roughly estimated from smoke
measurement from correlations developed by SAE (SAE Handbook), where soot content has been
correlated with Bosch and Hartridge smoke units and opacity measured by full flow type smoke meters.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 12:Mechanisms of Formation of Soot and PM
Soot Formation Stoichiometry
From equilibrium considerations soot will appear when oxygen is not sufficient to oxidize carbon even
to carbon monoxide, i.e., C/O atomic ratio in the mixture is greater than unity. Using the following
stoichiometric reaction for a hydrocarbon, C x H y ;

(2.38)

when x is greater than 2a i.e. C/O is greater than unity, solid carbon, C s or soot is produced during
combustion.
The fuel air equivalence ratio for the above reaction is;
(2.39)

For practical diesel fuels H/C ratio (y/x) 2. Hence, for the critical C/O = 1, the fuel-air equivalence
ratio, = 3. However, in practical systems the soot has been observed to form at C/O ratio of 0.5 to 0.8
indicating that soot formation is a kinetically controlled process. It may be noted that for methane (CH4),
theoretical critical is equal to 4. The critical C/O ratio for soot formation increases with increase in
temperature. Pressure has a strong influence, higher pressures yielding higher soot formation at the
same value off . In other words, increase in pressure results in lowering of critical value of f at which
soot is formed.

Conceptual Models of Soot Formation


Two conceptual models of soot formation in spray combustion have been suggested;
One model suggests that the soot is formed in a narrow zone of rich mixture at the spray
boundaries close to the diffusion combustion region.
Another conceptual model based on laser imaging studies of diesel spray combustion in a
supercharged engine at Sandia Laboratories has been proposed. Fig 2.23 shows schematically a
diesel spray jet. It is seen in these studies that the liquid jet is relatively short and the fuel ahead
of liquid jet is in vapour phase. It was seen that the soot appeard for the first time just
downstream of liquid jet in the rich premixed combustion region. The concentration of soot
increases and particle size grows as soot flows downstream towards the spray boundary. The
highest soot concentration and largest particle size are in the region forming head or leading
edge of the jet. The model suggests that the formation of soot precursors and consequently
generation of soot particles takes place in the rich premixed flame where fuel-air equivalence
ratio is in the range, =2 to 4. The soot particles grow in size as they pass through the spray
towards the spray leading edge. The soot finally gets oxidized in the diffusion flame at the spray
boundaries by OH radical rather than the molecular oxygen, O 2 .

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Figure2.23

Conceptual model of soot formation in diesel spray


combustion

The Sandia model varies from the earlier models as it suggests that the formation of soot is the result of
rich premixed combustion rather than the diffusion combustion phenomena. Further studies however,
are required to confirm validity of this hypothesis for all diesel engine combustion conditions.

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
Soot Formation Processes
The Lecture Contains:
Soot Formation Stages
Summary of Soot Formation Process
NOX -Particulate Emissions Trade Off

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Module 2:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
Soot Formation Stages
Soot formation consists of four main stages viz,
Inception and nucleation,
Surface growth,
Coagulation and Agglomeration, and
Oxidation.
Soot Inception and Nucleation
Soot nucleation is a non-equilibrium process and is not yet fully understood. The nucleation process
appears to consists of several processes viz.,
Thermal cracking or pyrolysis of long chain fuel molecules in an environment of oxygen
deficiency. During this process the large fuel molecules are broken into smaller molecules forming
soot precursors.
Condensation reactions and polymerization that result in larger molecules.
The third process is dehydrogenation process that increases C/H ratio of fuel molecules enroute
to soot formation.
The path to soot nucleation and formation also depends on temperature as below;
At T < 1800 K, condensation reactions of aromatics and pyrolysis of other highly unsaturated
hydrocarbons are likely to form soot.
At intermediate temperatures, 2800 > T > 1800 K, the thermal cracking leading to fragmentation
of fuel molecules to smaller unsaturated hydrocarbon molecules followed by polymerization
dominates soot nucleation.
Acetylene, poly acetylenes and poly unsaturated hydrocarbon
radicals are formed due to fragmentation reactions that lead to formation of soot.
At still higher temperatures T > 3000K the vapour phase condensation of molecules occurs to
form soot nuclei.
The aromatic condensation route for soot nucleation is a more direct and faster route. The
fragmentation to smaller molecules and polymerization to soot nuclei is a slower route.
Of all the products of fragmentation reactions and pyrolysis the acetylenes and poly aromatic
hydrocarbons are considered the most likely precursors leading to soot formation. These gas-phase
species on condensation reactions produce soot nuclei. Considering acetylene as an important soot
precursor the formation of large ring structures, i.e., PAHs leading finally to soot formation has been
proposed that involves the following three types of reactions known as Hydrogen-abstraction-C 2 H 2 addition (HACA) mechanism:

Reaction 1:
Hydrogen atom is removed from an aromatic molecule (AR) by a free hydrogen atom to form H2 and
aromatic radical (AR*);

(2.40)

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Reaction 2:
Addition of an acetylene to AR*;

(2.41)

Reaction 3:
Cyclization to form aromatic ring

(2.42)

Large PAH molecules are formed as this process repeats many times. The various PAHs formed
polymerize to form a solid phase soot nuclei of 1 to 2 nm diameter. These soot nuclei on further surface
growth produce soot particles.

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Module 3:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
Surface Growth
A large number of soot nuclei are generated during soot inception stage. The soot nuclei grow in size
as the gaseous products of fuel molecule fragmentation deposit on the surface of nuclei. The typical
fuel has atomic H/C = 2 while soot has H/C in the range 0.1 to 0.2. Soot growth is caused more likely
by the condensation of species with right H/C ratio on the nuclei surface with subsequent
dehydrogenation. Gas-phase deposition of acetylene proposed in the HACA reactions is one of the
mechanisms of surface growth. Here, in the Reactions 1 to 3 as above, the aromatic radical (AR*) is
substituted by a carbon atom (Cs ) on the edge of the soot surface and the process repeats itself.
Deposition of radicals of PAHs and small aliphatic hydrocarbons, which are present in high
concentrations in sooting flames, may also result in surface growth of the soot particles.
Coagulation and Agglomeration
Collision of two spherical soot particles may form a larger spherical particle. This process occurs in the
beginning when the particles are still small (<10nm) and are formed of a tarry liquid produced from
pyrolysis of hydrocarbons. Once the particles have become larger and solidified, the particles resulting
from collision resemble a cluster, like a bunch of grapes. Once the surface growth ceases, particles
coalesce in the shape of chainlike structure and this process is termed as aggregation.
The rate of decrease of particle number density, N during coagulation is given by

(2.43)

k is a rate constant that depends on pressure, temperature, gas density, particle size etc.
On integration the Eq. 2.43 yields,

(2.44)

where N0
is the initial number of particles. N/ N0 is inversely proportional to time and the initial
number of particles. Thus, the soot coagulation as a result of particle collision decreases as the number
of particles reduces due to coagulation and agglomeration.
The number of soot particles due to coagulation and agglomeration decrease rapidly during early part of
expansion process and agglomeration is almost complete at the end of expansion stroke in the engine.
The soot concentration is expressed by a term soot volume fraction, Fv . The soot volume fraction in
units of soot volume per unit volume of gas, is given by

(2.45)

where d is diameter of the spherical soot particles or diameter of a sphere of volume equivalent to an
aggregated particle and N is the number of particles in unit volume. Due to agglomeration, number of

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soot particles decrease but the Fv . remains unchanged.


oxidation.

It changes with surface growth or soot

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Module 3:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
Soot Oxidation
Oxidation of soot takes place during each stage of soot formation i.e., during formation of precursors,
nuclei, primary soot particles and aggregates. A large fraction of soot that forms early in the combustion
process is oxidized within the cylinder. Reactions with O, O 2 , OH, CO 2 and H 2 O oxidize soot. But, O,
O 2 and OH are the main oxidants. OH radical plays an important role in soot oxidation in fuel rich
conditions that exist in diffusion combustion systems. The OH radical is present in significant
concentrations in the reaction zone of diffusion flames and oxidizes soot in the flame region. In the post
combustion gases, O 2 is present in abundance and is the main oxidant. Rate of oxidation is also
influenced by the shape and size of the soot particles. As the particles grow in size they tend to
agglomerate instead of coagulation, and form clusters or chains. The oxidation of chain structure by O 2
is much slower than by OH.
Most widely used soot oxidation model in engines is that by Nagle and Strickland-Constable (NS-C).
The NS-C soot oxidation mechanism was obtained from studies on oxidation of graphite by oxygen at
1000 to 2000 C. The NS-C mechanism assumes presence of two types of oxidation sites on soot
particle surface. Site A is a nascent surface not covered by surface oxides and is more reactive. The
site B is covered with oxides and is less reactive. The sites A change to sites B depending upon
temperature and reaction time. The surface area fraction, x occupied by the sites A is calculated based
on a rate constant, k D. The NS-C mechanism for soot oxidation is given by

(2.46)

where;

From the soot oxidation rate, w the rate at which radius of a spherical particle is reduced may be
calculated as below,

(2.47)

, the density of soot may be taken equal to 1.8 g/cm 3 .


From this relation the time required to completely burn a spherical particle can be calculated. Using the
NS-C mechanism as above, at 1500 K it would take about 30 ms to completely burn a particle of 30 nm

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diameter.

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Module 3:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
Trends in Soot Oxidation Rates
Typical variation in soot oxidation rates in a diesel engine using NS-C model are shown in Fig. 2.24.
The oxidation rate depends on temperature, pressure and mixing rate. The soot oxidation rate initially
increases to a peak as the concentration of O 2 rises due to mixing with air. The oxidation rate
subsequently decreases as the gas temperature falls and more than offsets the effect of increasing O 2
concentration in the soot pocket. The mass of soot burned in the late mixing pocket is much lower (only
about 40%) than for the early mixing pocket. The high mass of soot burned in the early formed soot
pocket is due to high oxidation rate resulting from high temperatures rather than the higher residence
time.

Trends in soot oxidation rate in a diesel engine computed by


Figure 2.24. NS-C model for an early (at tdc) and a late formed (40 CA
atdc) soot pocket, mixing rate with air was kept constant.
The net soot emissions depend upon the rates at which soot is produced and oxidized. Temperature
plays an important role in net soot emissions. Temperature on one hand increases soot oxidation while
on the other hand it increases fragmentation of fuel molecules that may lead to higher soot formation.
The effects of several interacting factors thus govern the net soot emissions.

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Module 3:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
Example 2.3
A diesel engine is operating at overall f =0.6. Taking diesel fuel as (CH 2 )n and the combustion gas
temperature and pressure as 2200 K and 60 atm calculate the initial oxidation rate of soot particle using
Eq. 2.46 and the reaction constants as given for the NS-C mechanism. Estimate the period during
which a soot particle of 50 nm dia would get completely oxidized.
Solution
Combustion gas conditions are given as, P = 60 atm, T = 2200 K Eq. 2.46 gives the soot oxidation rate
as

In the beginning of oxidation we may assume x =1. Hence, the soot oxidation rate is,

For

, combustion stoichiometry for this engine may be written as

Total number of moles of products =1+1+1+9.4 = 12.4


Partial pressure of oxygen,
Reaction rate constants:
k A = 20 exp(-15,100/T) = 20 exp(-15100/2200) = 0.021 g/(cm2.s.atm)
k C= 21.3 exp(2060/T) = 21.3 exp (2060/2200) = 54.3 atmThe soot oxidation rate

Rate of particle burning in terms of rate of change of its radius,

Taking soot density = 1.8 g/cm3

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For a particle of dp = 50 nm diameter time duration required to burn completely,


t = dp /2 (dr/dt) = 50 x 10-9 x 100/ [2 x (2.56 x 10-3)] = 0.98 x 10-3 s or 0.98 ms
= 4.84 bar, at 2000 rpm engine speed it would take about 12 CA to burn a 50 nm
At 2200 K and
soot particle. Ans.

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Module 3:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
Summary of Soot Formation Process
Sequence of the different events taking place during soot formation process is summarized in Fig. 2.25.
Pyrolysis of fuel molecules produces soot precursors.
The precursors condense, polymerize and form soot nuclei which coagulate and also grow as a
result of continuing condensation of precursor molecules. Thus, the nuclei grow to primary soot
particles.
Soot primary particles then, form chainlike structures.
The soot particle surface growth finally ceases as the precursors are depleted or expansion in
the cylinder cools the gases terminating formation of the precursors.
In the diesel engines, the flame temperature being high around 2800 K, entire soot formation and
oxidation processes take place over a few milliseconds during engine combustion.
During expansion and exhaust strokes and in the exhaust system heavy hydrocarbons from unburned
fuel and oil condense and are adsorbed on soot particles. Water, sulphates and other trace inorganic
compounds such as ash formed by engine oil additives and fuel contaminants, wear particles etc. are
also adsorbed on the particulate matter.

Figure 2.25

Sequence of events leading to soot formation in diesel engine


combustion.

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Module 3:Genesis and Mechanism of Formation of Engine Emissions


Lecture 13:Soot Formation Processes
NO X -Particulate Emissions Trade Off
Nitrogen oxides and particulates are the main pollutants emitted by the diesel engines although
relatively small amounts of carbon monoxide and unburned hydrocarbons are also emitted. The
combustion temperature as discussed earlier has a strong influence on the formation of both the
nitrogen oxides as well as the soot. In the diesel engines, it is observed that when an engine design or
operational parameter is adjusted to decrease combustion temperature to obtain reduction in nitrogen
oxides emissions, soot and hence the particulate emissions increase. For example, when the injection
timing is advanced it increases combustion temperatures. A higher injection advance thus, results in
reduction of soot emissions but increase the NO x . Lower soot emissions at higher combustion
temperatures are attributed to higher soot oxidation rates. A typical effect of injection timing on soot
and NO x emissions is shown qualitatively in Fig.2.26. The selection of engine design parameters
therefore, has to be optimized to obtain reduction in NO x or PM without causing an excessive increase
in the other. This process of adjustment of engine parameters is known as NO x -PM trade off.

Figure 2.26

NO x - PM emission trade off as demonstrated by the effect of


injection timing on NO x and PM emissions .

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Module 3:Genesis and Mechanism of Formation of Engine Emissions

Questions
2.1 Show the effect of overall fuel-air equivalence ratio,

on CO, HC and NOx emissions for

DI diesel engines on the same lines as the Fig 2.2.


2.2

Plot NO concentration versus

for a CI and a SI engine on the same graph. Explain the

differences between the trends for the two engines, if any.

2.3 Calculate average molar specific heat of combustion products of octane and air at

= 1.0.

Compare it with that of air. Discuss why EGR is more effective than simply leaning of
charge in reduction of NO formation. The average molar specific heats in 300- 2500K
temperature range are; N 2 = 33.75, O2 = 35.59, CO2 = 55.37, H 2O = 44.94 kJ/kmol.K
2.4 Characteristic time, tNO in seconds for NO to reach equilibrium value during combustion is
given by

where T is in K, P in atm.
Calculate tNO for the charge elements that burn early and achieve average temperature equal
to 2800K and pressure 30 atm. What would be tNO for another charge element burning late
in the cycle when combustion temperature and pressure are 2000 K and 18 atm? If the engine
speed is 4000 rpm how many degrees crank angles are required to reach equilibrium value for
NO in each case.

2.5 A single cylinder SI engine has 75 x75 mm bore x stroke and 8.5:1 CR, piston top land
has 9 mm height and its diameter is 74.4 mm. Mixture conditions are 340 K and 100 kPa
at the beginning of compression. Engine volumetric efficiency is 0.8 and mixture before
entering the cylinder is at 300 K. The gas in the crevice can be assumed at wall
temperature equal 400 K. If peak cylinder pressure is 40 bar. Calculate;
(i)

the mass fraction of fresh mixture contained in piston-cylinder crevice at the point of
peak pressure.

(ii)

If one third of the crevice gas remains unburned what would be specific HC mass
emissions (g of HC/kWh), the brake specific fuel consumption of the engine is 300

g/kWh.
2.6 In a diesel engine, HC emissions with nozzle sac volume of 0.2 mm3 and 1.4 mm3 were
seen to be 125 ppm and 500 ppm HC emissions, respectively. Assuming variation in HC
emissions with nozzle sac volume is linear, what is the contribution of fuel contained in
nozzle orifice to HC emissions? If injector has five nozzle holes of length/diameter ratio
(ln/dn) = 4, calculate the dia of nozzle holes.
2.7 Calculate critical fuel-air equivalence ratio above formation of soot may be expected
theoretically when methane, benzene and typical diesel fuel (CH2)n are burned.

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Module 3: Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
Effect of SI Engine Design and Operating Variables on Emissions
The Lecture Contains:
SI Engine Variables and Emissions

Compression Ratio
Ignition Timing
Air Fuel Ratio
Residual Gas and EGR
Engine Speed
Cold Start and Warm-up Phase
Coolant Temperature
Summary

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
SI Engine Variables and Emissions
Any engine variable that affects oxygen availability during combustion would influence CO emissions.
The factors which influence flame quenching, quench layer thickness and post flame oxidation control
engine out HC emissions. The burned gas temperature-time history and oxygen concentration control
NO formation and emission. Hence the engine variables that influence burned gas temperature and
oxygen concentration would affect the NO emissions.
Principal design and operating variables affecting engine emissions are:
Design Variables :
Compression Ratio
Combustion chamber surface to volume ratio
Ignition timing
Valve timings and valve overlap
Air motion, swirl tumble etc
Charge stratification
Operating Variables :
Air-fuel Ratio
Charge dilution and exhaust gas recirculation (EGR)
Speed
Load
Coolant temperature
Transient engine operation: acceleration, deceleration etc.
The effect of some variables discussed below is typical in nature and variations in the trends with
specific engine design change are observed.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
Compression Ratio
The effect of compression ratio on engine emissions is shown on Fig. 3.1. The typical effect observed
when the engine CR was reduced from 10:1 (CR used on high performance engines during preemission control period) to 8.5 and 7.0:1 are given on this figure.
Use of high CR results in
(i) Higher burned gas temperature
(ii) Lower residual gas content
These lead to higher NO emissions on volume basis. However, as engine efficiency increases with
increase in compression ratio, brake specific NO emissions decrease. High CR combustion chambers
result in
(i) High surface to volume ratio and
(ii) A proportionately higher crevice volume.
(iii) Lower exhaust gas temperatures
Thus the volume of flame quenching regions increases resulting in higher HC emissions. The problem
is further enhanced as due to lower exhaust gas temperatures oxidation of the unburned HC is
reduced during exhaust process. These factors result in an increase in HC emissions with increase in
engine CR. At lower CR% fuel efficiency is also reduced thus increasing specific CO emissions.

Figure
3.1

Effect of reduction in compression ratio from 10:1 to 8.5:1 and


7.0:1 on SI engine emissions

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
Ignition Timing
The effect of ignition timing on NO and HC emissions is shown on Fig 3.2 When ignition occurs earlier
in the cycle more heat is released before and around the top dead center. Thus, with advanced ignition
timings higher peak cylinder pressures and temperatures result. As has been discussed lecture 5 with
increase in combution temperatures NO formation increases. Hence , higher NO emissions are obtained
as the ignition timing is advanced.
As the ignition timing is retarded more burning takes place during expansion stroke resulting in lower
peak combustion pressures and a lower of mass of charge is pushed into crevice volume. Also, at the
retarded ignition timings exhaust gas temperature increases as the engine thermal efficiency is
reduced. In the hotter exhaust gas with the retarded ignition timing higher oxidation rates of the HC
and CO in the exhaust system are obtained.. Due to these reasons, lower HC emissions are obtained
with retarded ignition timings. The disadvantage of the retarded ignition timing is lower engine
efficiency, lower power and a poorer fuel economy.
When the emission control legislation was introduced for the first time around 1970 in the USA and
Europe, ignition timing versus speed and manifold vacuum curves were among the first engine
parameters that were modified for control of NO x emissions due to ease of their adjustment.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
Contd...

Fig
3.2(a)

Fig

Effect of spark timing on NOx emissions.

Effect of ignition timing on HC

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3.2(b)

emissions.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
Air Fuel Ratio
The effect of air-fuel ratio on engine emissions has already been discussed in Lectures 3 , 5 and 7.
Carbon monoxide results due to deficiency of oxygen during combustion and is reduced as the
mixture is leaned. CO emissions are reduced to very low values as the mixture is leaned to =
0.90 0.95 i.e. air-fuel ratio is increased above the stoichiometric value by 5 to 10%. Further
leaning of mixture shows very little additional reduction in the CO emissions.
With increase in air fuel ratio, the initial concentration of hydrocarbons in the mixture is reduced
and more oxygen is available for oxidation. Hydrocarbon emissions therefore, decrease with
increase in air-fuel ratio until mixture becomes too lean when partial or complete engine misfire
< 0.8 engine may misfire more
results which cause a sharp increase in HC emissions For
frequently thereby increasing HC emissions sharply.
The highest burned gas temperatures are obtained for mixtures that are slightly (5 to 10 percent)
richer than stoichiometric. On the other hand, there is little excess oxygen available under rich
mixture conditions. As the mixture becomes lean, concentration of free oxygen increases but
combustion temperature start decreasing. The interaction between these two parameters results
in peak NO being obtained at about = 0.9 0.95.

Residual Gas and EGR


Burned residual gases left from the previous cycle or part of the exhaust gas recirculated back to engine
act as charge diluents. The charge dilution by recirculation of part of the exhaust gas back to the engine
is called exhaust gas recirculation (EGR). The combustion temperatures decrease due to charge
dilution caused by the residual burned gases or EGR , the decrease in combution temperatures is
nearly proportional to the heat capacity of the diluents as discusses earlier. The lower combustion
temperatures resulting from the residual gas dilution/EGR reduces NO formation and emissions as
shown on Fig 3.3.

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Figure
3.3

Effect of EGR on NO and HC emissions in normal burn and fast


burn SI engines.

As the EGR is increased the combustion rates become more and more slow, and combustion becomes
unstable. With increase in EGR cycle-to-cycle combustion variations increase and, more and more
engine cycles having only partial combustion are observed . The frequency of partial burn cycles
increases and these turn into misfired cycles at EGR rates of about more than 20%. . In the partial burn
and misfire cycles, combustion remains incomplete and results in high HC emissions. Moreover with
EGR the burned gas temperatures are reduced and post-flame oxidation also reduces. Increase in HC
becomes sharp as EGR increases beyond about 20 percent for a normal combustion engine. With EGR
rates of 20 percent or higher Fast burn engines due to higher flame speeds have higher burned gas
temperatures and tolerate higher EGR rates before the combustion
becomes very unstable and loss in fuel efficiency becomes unacceptably high. Fast burn rates are
usually obtained by use of high air swirl and increasing turbulence in the charge through use of suitable
designs of intake valve port and the combustion chamber.
The amount of charge dilution or EGR is usually limited to below 15% due to its adverse impact on
engine performance causing power loss, high specific fuel consumption and high unburned fuel
emissions.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
Engine Speed
Volumetric efficiency of the engine changes with speed, it being highest in the mid-speed range. At high
engine speeds the volumetric efficiency generally decreases resulting in high residual gas dilution.
Although heat transfer rates increase with increase in engine speed as a result of higher turbulence, but
total amount of heat transfer is lower due to shorter cycle time. This gives higher gas temperatures at
higher speeds. However, at high speeds a shorter time is available for NO formation kinetics. The net
result is a moderate effect of speed on NO although this is specific to the engine design and operating
conditions. Increase in exhaust gas temperatures at higher speeds enhances post flame oxidation of
unburned hydrocarbons. A reduction of 20 to 50 percent in HC emissions has been observed with
increase in speed from 1000 to 2000 rpm.

Cold Start and Warm-up Phase


Engine cold start and warm-up phase contribute significantly to unburned hydrocarbons. One of the
main sources of HC emissions during cold start and engine warm-up period is very rich fuel-air ratio
needed for ignition and combustion for several seconds after engine start. During cold start, the engine
has to be over-fuelled 5 to10 times the stoichiometric amount of gasoline. To obtain robust ignition on
the first cycle on cold start, a fuel vapour- air equivalence ratio above lean threshold limit (f = 0.7-0.9) is
required. This threshold is independent of the engine coolant temperature. The fuel-air equivalence ratio
supplied to the engine during cold start is in the range, f = 4 to 7.
For the first few engine cycles, a large fraction of inducted fuel is stored as liquid film in the intake port
and cylinder as only the most volatile fractions evaporate when the engine is cold. The liquid fuel films
do not participate in combustion and is emitted as unburned fuel emissions.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 14:Effect of SI Engine Design and Operating Variables on Emissions
Coolant Temperature
As the coolant temperature is increased, the contribution of piston ring zone crevice becomes lower due
to decrease in gas density within this crevice. Secondly, the top piston-land side clearance is also
reduced due to higher thermal expansion of the piston. A thinner oil film and reduced fuel vapour
solubility would result in reduced absorption of fuel vapours in engine oil. Increased postflame oxidation
at high temperatures also contributes to reduction in HC emissions. Increase in coolant temperatures
has been observed to reduce HC emissions by about 0.4 to 1.0 % per K increase in temperature. An
increase in the coolant temperature from 20 to 90 C, roughly results in 25% lower HC emissions and
hence, the need of a rapid engine warm up is obvious.
For reduction of the cold start and warm up HC emissions, an important area of development is to
improve the fuel injection and delivery to the cylinder with minimum wall wetting. Over-fuelling during
cold start and warm-up is to be kept at a minimum, while still forming the combustible charge.

Summary
The effects of some of the important engine design and operating variables on emissions from SI
engines are summarized below Table 3.1.

Table 3.1
Effect of SI Engine Design and Operating Variables on Exhaust
Emissions
(Source: IC Engines - Combustion and Emissions by Pundir, 2010)

Variable Increased

HC

CO

NO X

Compression ratio

Surface/volume ratio

Bore/stroke ratio

Ignition timing advance

Port fuel injection

Engine speed

Engine load

Coolant temperatures

Combustion chamber deposits

EGR

Intake swirl and turbulence

Fuel-air equivalence ratio

= increase; = decrease; = uncertain; - = no effect

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Module 3: Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
Effect of CI Engine Design and Operating Variables on Emissions
The Lecture Contains:
Engine Design Variables

Operating Variables
Compression Ratio
Direct Injection (DI) versus Indirect Injection (IDI) Engines

Combustion Chamber Design


Fuel Injection Timing and Injection Pressure

Engine load and Speed


Exhaust Gas Recirculation
Fuel Quality

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Module 3: Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
CI Engine Design and Operating Variables and Emissions
Important diesel engine variables that influence emissions are:

Engine Design Variables


Compression ratio
Combustion chamber type
Combustion chamber design
Injection system: injection pressure and timing, nozzle holes, nozzle sac volume

Operating Variables:
EGR
Engine speed
Engine load
Fuel quality

Compression Ratio
In the diesel engines the minimum compression ratio that can be used is governed by the ease
of engine cold starting ability. For the high speed direct injection engines CR of around 16 to
17.5:1 is used. The turbocharged heavy duty engines employ CR in the range of 13 to 14:1. Cold
starting requirements prevents further reduction in the compression ratio.
Use of higher compression ratio results in a shorter ignition delay period. A shorter delay would
result in less overmixing' of fuel and air and hence, lower HC emissions. Further, the higher
combustion temperatures obtained at a higher compression ratios tend to increase oxidation of
the unburned HC.
At a low compression ratio, a longer delay increases the fraction of fuel burned during the
premixed phase resulting in higher peak pressures and temperatures which cause an increase in
NO x formation. On the other hand, increase in compression ratio due to higher combustion
temperatures would tend to increase formation of NOx. If the ignition delay is too long the
combustion may begin in the expansion stroke reducing combustion pressure and temperature.
Too long an ignition delay leads to lower NOx emissions along with poor fuel efficiency.
Use of a low compression ratio results in too long a delay during engine warm up under cold
conditions, and it causes high emissions of unburned fuel which due to its appearance is called
white smoke'.
A high compression ratio leading to high combustion temperatures would increase soot formation
while on the other hand it increases soot oxidation.
For obtaining low particulate and NOx emissions simultaneously, an optimum compression ratio
is to be used.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
Direct Injection (DI) versus Indirect Injection (IDI) Engines
The DI and IDI engines have been in use for many years. The IDI engines were mostly employed in
high speed small engine applications. Now, after the development of high speed direct injection (HSDI)
engines the IDI engines due to their poor fuel economy are being phased out of production. The
combustion in IDI engines takes place in two stages; a rich mixture burns in the pre-chamber where all
the fuel is injected and the partially burned rich fuel- air mixture from the pre-chamber is transported to
the main chamber where due to presence of excess air combustion is completed. The jet of high
pressurepartially burned gases from the pre-chamber enters the main chamber generating high
turbulence that causes rapid mixing and most of the fuel burns as lean mixture.

Figure
3.4

Comparison of NO x concentrations in DI andDI diesel engines

A comparison of NO x emissions with DI and IDI engines is shown on Fig. 3.4. At light loads, most of NO
may form in the pre-chamber. But, at higher loads additional NO formation would occur in the main
chamber. Although temperatures are higher in the pre-chamber than the main chamber, but except at
light loads mixture is overall rich and hence, the lower formation of NO. In the DI engines, at the end of
premixed combustion higher peak pressures and temperatures are obtained compared to the IDI
engines and NO is formed in near stoichiometric mixtures during mixing controlled phase and post
combustion gases. Due to these factors overall, the indirect injection engines emit lower NOx. In the DI
engines due to low turbulence levels some of CO formed in the rich spray regions may not find the
required oxygen for complete combustion while thetemperatures are still high. It results in .higher CO
emissions than the IDI engines even though more excess air is present in the DI engines.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
Combustion Chamber Design
a. Dead Volumes
Air in the combustion chamber is contained in several different volumes like piston bowl, top land
crevice, piston cylinder head clearance, valve recess and head gasket clearance. Typical distribution
of clearance volume at tdc among different components for a DI diesel engine is shown in Table 3.2.
The piston bowl in DI diesel engines contains slightly more than 50% of total clearance volume at tdc.
The air contained in top land crevice, head gasket clearance and valve recess is nearly 15 % and is
poorly utilized during combustion. Even the air contained in the volume between piston crown and
cylinder head at tdc is poorly utilized. Piston-cylinder crevice volumes store morethan proportionate air
due to lower temperature in the crevice region compared to the temperature of air in the cylinder. A
reduction in crevice volume therefore, increases air utilization. Similarly, a lower clearance between
piston and cylinder head increases air utilization and reduces the possibility of fuel entering the crevices.
Reduction in poor air utilization' volumes results in lower particulate emission and fuel consumption..

Table 3.2
Volume Distribution of Combustion Chamber at
TDC
Piston bowl

55%

Piston Cylinder head 30%


Clearance Valve recess

6%

Top land crevice

7%

Head gasket

2%

b. Multi-Valves and Air Motion


Use of multiple valves (3 or 4) per cylinder increases flow area and hence, the volumetric efficiency of
the engine. Four valves per cylinder are now common in gasoline engines. In the direct injection diesel
engines use of four valves enables a centralized location of injector and combustion bowl in the piston.
The injector can be placed more centrally and vertically. Typical PM-NO x characteristics for 4- and 2valve per cylinder passenger car diesel engines are compared on Fig. 3.5.With two valves designs, the
injector is always offset and inclined. Injector inclination of 20 and 10 degrees from vertical has been
observed to give an increase of about 25 and 5 %, respectively in PM emissions due to poor fuel
distribution in the cylinder compared to a vertically located injector. Reduction of up to 4 to 7 % in
specific fuel consumption is also obtained at the same NO x emission level in a multi-valve engine with
centrally placed combustion bowl and injector.

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PM NO x trade-off for two valve and four-valve


Figure 3.5 passenger car DI diesel engines.

A centrally placed combustion bowl has lower swirl requirements and results in more equal fuel
distribution and availability of equal air to each spray for mixing. In four-valve engines, symmetrical air
motion in the piston bowl and equal fuel distribution between different sprays lead to optimum mixture
formation and combustion with very low smoke levels.
Use of lower air swirl in 4-valve engines compared to 2-valve engines for the same PM and NOx
emission levels, results in reduction of fuel -air overmixing' during premixed phase of combustion. As
overmixing' of fuel is an important source of HC emissions, lower HC emissions in 4-valve engines are
obtained.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
Fuel Injection Timing and Injection Pressure
Effect of fuel injection timing on NO x emissions from CI engines is quite similar to that of spark timing in
SI engines. Typical effect of injection timing on NO x , HC, smoke emissions and fuel consumption is
shown on Fig 3.6. With retarded injection timing, as expected the NO x emissions decrease sharply. On
the other hand an increase in smoke results with retarded injection timing If the injection timing is
retarded too much, HC emissions in naturally aspirated engines also may increase sharply. An increase
in injection pressure results in higher NO x and HC, but yields lower smoke and PM emissions. Effect of
injection pressure on PM emissions is shown on Fig. 3.7.
With high injection pressures of 1500 bars and higher, small nozzle orifices of about 0.15 mm dia. are
used. The high injection pressure and small nozzle holes give very good fuel atomization with very small
fuel droplets which vaporize rapidly resulting in low soot emissions

Figure
3.6

Effect of injection timing on emissions and fuel economy for a


heavy-duty diesel engine.

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Figure 3.7

Effect of Injection pressure on PM emissions for a


heavy duty diesel engine.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
Engine load and Speed
For developing higher power more fuel is injected in the diesel engine thereby reducing excess air,
which results in higher combustion and exhaust temperatures. A typical dependence of NO on air-fuel
ratio i.e., engine load has been shown in Fig. 3.4. Dependence of smoke on overall fuel-air ratio for a
direct injection diesel engine is shown on Fig. 3.8.

Figure
3.8

Effect of air-fuel ratio and engine load on soot


emissions for a DI diesel engine

With increase in engine load (increase in fuel-air ratio);


NO X and soot emissions increase.
With increase in engine load as the combustion temperatures increase and oxidation
environment for CO is more favourable, CO emissions decrease until excess air reduces to about
30 percent . With further increase in load and fuel-air ratio, CO emissions start increasing again
and rise sharply as still more fuel is injected to increase engine power output.
At maximum load, NO x , CO and soot are also at their maximum level. HC however, reduce
with increase in engine load as higher gas temperature lead to an increase in the oxidation
rates.
Engine brake thermal efficiency increases with engine load because the ratio of friction to brake
power goes down. Interaction among these factors results in lowest value of brake specific fuel
consumption (BSFC), and optimum value of brake specific nitrogen oxides (BSNOx ) and
particulate emissions at an intermediate load.
The variable speed engines are designed to give lowest fuel consumption at about 2/3rd of maximum

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speed at which heavy duty engines are normally operated. In turbocharged engines, the boost pressure
is reduced at low engine speeds resulting in higher fuel-air ratio. At high speeds pumping losses
increase and cooling decreases. The coolant and residual gases are hotter as the speed increases.
Both these factors increase NO x at high engine speeds. The HC and PM have an optimum at an
intermediate speed because time available for oxidation decreases at the higher engine speeds.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
Exhaust Gas Recirculation
The role of EGR is to act as inert diluents and heat sink that reduces the oxygen concentration during
combustion and lowers the combustion temperatures. The flame temperatures are reduced as a result of
EGR. The NO x formation being an exponential function of temperature, even a small reduction in flame
temperature has a large effect on NO x formation. Increase in heat capacity of charge caused by EGR
has generally been thought to result in reduction of NOx emissions from SI engines. However, in the
diesel engines, EGR can affect NO x reduction in three possible ways. These effects are:
Dilution effect: It is the reduction in inlet charge oxygen concentration
Thermal effect: It is the increase in inlet charge heat capacity, and
Chemical effect: Modification in combustion process as a result of dissociation of CO 2 and water
vapour
The dilution effect (reduction in inlet oxygen) is the dominant effect in case of diesel engines. The
chemical and thermal effects are relatively small.

Figure 3.9

Typical effect of effect of EGR on NOx, HC and fuel


economy for a turbocharged, intercooled passenger car DI
diesel engine

Typical effect of EGR on NO x , HC and CO emissions for a turbocharged passenger car DI diesel
engine is shown on Fig 3.9 . At around 10% EGR, 50% reduction in NO x is obtained with little change
in CO and HC. As the EGR rate is increased beyond 15 %, NO x decreases further, but CO, smoke and
HC are increased. The excess air declines with increase in EGR causing sharp increase in smoke and
loss in fuel economy.

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The effect of EGR at the same rate (% of intake air) on diesel NO x is lower compared to SI engine as
the exhaust gas in diesel engine contains smaller amounts of tri-atomic gas CO 2 .. Exhaust gas
recirculation has been used on diesel passenger cars since mid-1990s to reduce NO x emissions. This
is being applied now on more and more diesel engines as the emission standards are being tightened.

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Module 3:Influence of Engine Design and Operating Parameters on Emissions


Lecture 15:Effect of CI Engine Design and Operating Variables on Emissions
Fuel Quality
For petroleum fuels many of the properties such as hydrocarbon composition, natural cetane number,
volatility, viscosity and density are interdependent. As the fuel density decreases the fuel contains more
of paraffinic hydrocarbons, which results generally in higher cetane number and fuel volatility and lower
viscosity. So, the effect of change in one fuel quality parameter on emissions may be some times the
result of several interactions. A high fuel cetane number improves cold starting and results in faster
warm-up thus reducing cold engine HC emissions. As an increase in the cetane number reduces
ignition delay it results in lowering of HC and NO x emissions. On the other hand, with higher fuel
volatility a larger lean flame out overmixing' region may result and due to faster fuel evaporation the
fraction of fuel burned during premixed combustion is also higher. Therefore, an increase in NO x as
well as HC may be observed with more volatile diesel fuels. The fuel sulphur increases sulphates in PM
emissions increasing the particulate mass

Summary
The effect of various design and operating variables on DI diesel engine performance and emissions are
summarized in Table 3.3.

Table 3.3
Emission Trends with Engine Design and Operating
Variables for Diesel Engines
Parameter

BSFC

BSNOx

BSHC

PM

Engine design variables


Compression ratio

Stroke/Bore ratio
Crevice volume
Swirl
Valve number
Fuel injection variables
Injection pressure
Retarded injection timing
Sac volume
Number of holes (size smaller)
Pilot injection
Eccentricity of Injector

Operating parameters

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Engine speed
Engine load

Coolant temperature
Fuel cetane number
Fuel sulphur content
Fuel volatility

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Module 3:Influence of Engine Design and Operating Parameters on Emissions

Questions
(3.1) Calculate average molar specific heat of products of complete combustion of C 8H 18 with
fuel air equivalence ratio, =1.0 (typical of SI engine) and

= 0.7 (typical of CI engine

atfull load). EGR is used to control NO formation in IC engines. Using this information
explain why EGR is more effective in SI than in the CI engines? Show qualitatively on
the same graph the trends in percent reduction in NO with EGR rate for typical SI and CI
engine operation. Molar specific heat for the gases; N 2 = 33.75, O2 = 35.59, CO2 =
55.37, H 2O = 44.94 kJ/kmol.K.
(3.2) For a SI engine having the same swept volume its design is changed from square (bore=
stroke) to over square ( bore> stroke) configuration. Discus how will it affect the engine
emissions of HC, CO and NOx. An over square engine can be made to operate at a
higher engine speed. Howl an increase in speed would influence emissions? In all the
cases imep is kept nearly the same.
(3.3) Explain the trends in NO formation observed for DI and IDI engines shown on Fig. 3.4.
(3.4) Discuss why advancement of injection timing in a CI engine results in an increase in NOx
and HC emissions but in lower soot emissions.
(3.5) Following Table 3.3 show the trends on the effect of inlet air humidity, boost pressure,
valve flow area, mean piston speed, EGR and oxygen enrichment of air in the cylinder

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Module 4: Vehicle Emission Standards and Measurement


Lecture16:Emission Test Procedures
Vehicle Emission Standards and Measurement
The Lecture Contains:
EMISSION TEST PROCEDURES
Units of Emission Limits
EMISSION TEST CYCLES
Driving Cycles for Light Duty Vehicles
Heavy Duty Vehicle Engines
Motorcycles

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Module 4: Vehicle Emission Standards and Measurement


Lecture16:Emission Test Procedures
EMISSION TEST PROCEDURES
The vehicle emission limits are specified based on a standard test procedure, which includes;
A specified vehicle driving or engine operation schedule of varying speeds and loads which
represents real life driving/usage pattern of the vehicles and engines. The test schedule of
vehicle or engine operation is known as driving cycle.
Use of emission sampling systems and analyzers that operate on the working principles specified
in the emission regulations.
The new production vehicles and engines are tested for compliance with the emission standards in a
government approved laboratory.
The USA and particularly the state of California have led the world in developing vehicle emission test
methods and in
setting the vehicle emission limits. The test cycles used in the USA, Europe and
Japan for emission measurement and certification of vehicles/engines for compliance with the standards
differ and so also the numerical values of the emission limits. Therefore, direct comparison between
standards in different countries is generally not possible.

Units of Emission Limits


Two types of emission limits are specified in the standards
For the light and medium duty vehicles, passenger cars and, two and three wheelers are in terms
of mass of pollutant emitted per unit distance travelled i.e., g/km ( g/mile in the USA , 1 g/km =
1.61 g/mile).
For heavy duty vehicles and engines test is carried on the engine itself and the limits are
specified in terms of mass of pollutant per unit of work done, i.e., g/kW-h or g/bhp-h (1 g/kW-h =
1.34 g/bhp-h) .
The test cycle and measurement procedures have been accordingly developed whether test is to be
done on a vehicle or on the engine.

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Module 4: Vehicle Emission Standards and Measurement


Lecture16:Emission Test Procedures
EMISSION TEST CYCLES
The US and European driving cycles used for emission measurement are presented below. Most of the
other countries follow either the European or the US test methods except Japan which has its own
driving cycles. In India European test methods are used except for the motorcycles and three wheelers.

Driving Cycles for Light Duty Vehicles


The emission test driving cycles are composed of a cold start period, idling, moderate acceleration and
deceleration, and cruise modes. The test cycle is given in terms of vehicle speed versus time. The light
and medium duty vehicles are driven through the prescribed driving cycle on a chassis roller
dynamometer. During operation the engine is required to develop road horse power that depends on
the vehicle speed fopr a given vehicle. The road horsepower requirement versus speed data as
provided by the vehicle manufacturer or determined by vehicle coast down test is stored into chassis
dynamometer controller to simulate the real life road operation of the vehicle. The vehicle weight i.e.
inertia needed during transient modes of the driving cycle is simulated by mechanically changing the
rotating masses or electronically changing the inertia on the roller dynamometer. A typical emission test
facility with a vehicle operating on chassis dynamometer is shown in Fig 4.1

Figure 4.1

View of a vehicle emission test and


facility

chassis dynamometer

European Test Driving Cycle


The driving cycles followed in Europe for light and medium duty vehicles is shown in Fig. 4.2. The
European test cycle is composed of steady operation modes derived from the actual vehicle operation
data on road. Although it consists of acceleration and deceleration modes but as all the modes
represent averaged operating conditions, the cycle is often referred to as steady mode cycle. The
European test cycle as given in Fig. 4.2 was implemented from Euro 1 emission standards in 1992. It

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has two parts;


(i) an urban driving cycle (ECE 15) and
(ii) an extra-urban driving cycle (EUDC)
The break-up of different operating modes in the two parts of the cycle is also given in Figure 4.2.

ECE-15 cycle

EUDC Cycle

Distance, km

4.052

6.955

Time, s

780

400

Average speed, km/h

19

62.5

Maximum speed, km/h

50

120

Acceleration, %time

21.16

Maximum Acceleration, m/s2

0.833

Deceleration, % time

13.8

Maximum Deceleration, m/s2

-1.389

Idle, % time

35.4

Steady speed, % time

29.3

Figure
4.2

European driving cycle for light and medium duty vehicles: ECE
15 cycle followed by extra urban driving cycle (EUDC).

Prior to Euro 1 regulations, only the ECE 15 cycle was used. The low speed urban test cycle consists of
repetition of 15 mode cycle four times without interruption for a total duration of 780 seconds. The total
distance covered is 4.052 km at an average speed of 19 km/h. The high-speed test cycle called as
Extra Urban Driving Cycle (EUDC) is carried out after the ECE-15 cycle. This high-speed cycle has
maximum speed of 120 km/h. The EUDC part gives a higher contribution to NOx while the ECE-15
cycle has more contribution to CO and HC emissions.
Emission measurement commences with the engine cold start at the beginning of the first ECE-15
mode cycle itself. The emissions are measured using CVS technique as explained later.

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Module 4: Vehicle Emission Standards and Measurement


Lecture16:Emission Test Procedures
contd...
US FTP-75 Cycle
The US test procedure known as Federal Test Procedure -75 (FTP-75) is a transient cycle consisting of
a typical actual driving trace for the light duty vehicles. It consists of four phases as shown on Fig 4.3.:
Cold transition phase of 505 seconds with a weighting factor of 0.43
Stabilized phase of 867 seconds with a weighting factor of 1.0
Hot soak phase of 10 minutes
Hot transition phase; repeat of first phase of 505 seconds with a weighting factor of 0.57

Cycle Details:
56.7 mph
(91.2
km/h)

Length

11.09 miles (17.85 km)

Max. Speed :

Time

1372 s + (600 s stop) + 505 s


The first 505 s are
repeated
after a 10 minute stop (hot
soak)

Idle

Av. Speed

21.3 mph (34.3 km/h)

Steady speed :

20.5%

Deceleration :

26.5%

Figure
4.3

17.3 %

US FTP-75 emission test cycle for light duty vehicles; the driving
cycle for motor cycles is shown by dotted line.

The total vehicle driving schedule is of 31 minutes. In addition, after operation for 1372 seconds engine
is switched off in hot condition to allow hot soaking period of 10
minutes. The total distance covered is 11.09 miles. The vehicle is preconditioned before test by soaking
it for 12 hours at a temperature between 20 to 30 C. The test begins with cold start. FTP-75 procedure
was the first to use CVS (Constant Volume Sampling) method for measurement of the mass of the
pollutants emitted per km or mile travelled.. The sample of diluted exhaust gas with air from CVS system

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is collected in three separate bags, one each for the three phases of vehicle operation. The
concentration of pollutant in each bag and total volume of diluted exhaust gases for each test phase is
determined to calculate the mass of pollutants emitted.. Weighting factors corresponding to each phase
are used to give mass emission values for the total cycle.

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Module 4: Vehicle Emission Standards and Measurement


Lecture16:Emission Test Procedures
Heavy Duty Vehicle Engines
European Test Procedure
The first European test procedure for heavy duty vehicles, R-49 used 13-mode test having five
different load points each at the rated and peak torque speeds and three idling speed points one in the
beginning one in the middle and the third at the end. Each mode had a different weighing factor. A
new test procedure has been adopted from the year 2000 along with implementation of Euro 3
standards. It consists of two separate tests each of about 30 minutes duration as below;
(i)

13-mode steady state cycle (ESC) with a dynamic load response (ELR) smoke test

(ii) A transient test cycle (ETC)

The steady state cycle (ESC) is used to prevent abnormally high emissions if an engine is made to
operate at extreme conditions where emission controls may not be very effective. On the other hand,
the transient cycle (ETC) represents the actual operating conditions and is better suited for the engines
operating on alternative fuels or employing aftertreatment devices. For certification to Euro 3 standards,
the conventional diesel engines are tested by the ESC only. However, the diesel engines with advanced
emission control systems such as after-treatment devices and the SI engines such as natural gas
engines are tested by both the procedures. From the Euro 4 standards implemented in year 2005, all
heavy-duty engines are tested by both the ESC and ETC test procedures.
ESC and ELR Tests
The ESC and ELR test procedures are shown in Figs 4.4 and 4.5. Weighting factors for the ESC test
for each mode are also shown on Fig. 4.4.
The test is carried out at three engine speeds and idle. The test speeds are determined as shown on
Fig 4.4. At each of the three speeds, emissions are measured at 25%, 50%, 75% and 100 % loads. To
ensure that there are no abnormal operating conditions which could result in abnormally high emissions,
testing agency is authorized to select three more modes as indicated. The dynamic load response
(ELR) test is carried out for smoke emissions. The engine is accelerated from 10% load to full load at
maximum possible acceleration. In this way engine runs through the entire fuel/air ratios defined by the
engine fuel management system. Thus, smoke emission from the diesel engines is measured for the
entire range of fuel delivery i.e. fuel-air ratios. Peak smokes emissions are compared with the
permissible limits as specified in the standards.

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Figure 4.4

European ESC heavy-duty exhaust emission procedure 13


mode cycle.

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Module 4: Vehicle Emission Standards and Measurement


Lecture16:Emission Test Procedures
contd...

Figure 4.5 European ELR dynamic response test for smoke emissions.

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Figure 4.6

European heavy-duty exhaust emissions transient test cycle


(ETC).

The vehicle speed time and normalized torque -time curves for the ETC are shown in Fig. 4.6. The
cycle was derived from the data collected on different road types i.e., highway, urban and rural roads,
under varying traffic density, road gradients and distance between stopping points. The data were
collected for different types of vehicles such as trucks, buses and city buses. The normalized figures are
integrated in three sub-cycles of
10 minutes each. For establishing limits, emissions from the three sub- parts of the cycle may be
measured separately and later combined using weighting factors.
US Heavy Duty Test Procedure
In the USA until 1984, a steady state test cycle consisting of 13 different engine speed and load
combinations was used for measurement of gaseous exhaust emissions from the heavy-duty vehicle
engines. Emissions were measured under engine idling, and at rated and maximum torque engine
speeds as in European R-49 cycle but at different engine loads and the engine operating modes had
different weighting factors than the European test procedure. From 1985, a transient mode test replaced
the 13-mode test. This test cycle was developed from the driving pattern data measured in New York
and Los Angeles. The cycle represents driving pattern only for the city operation. It contains the traffic
characteristics of congested urban, uncongested urban and city expressway driving. The US transient
cycle test is run over a full range of load and speed conditions with equal weighing factor to each
operation point of the cycle. The total test consists of three phases, cold start cycle, hot soak and hot
start cycle; each phase of 20 minutes duration. Data on engine speed, load and gaseous emissions are
monitored once per second. Computer controlled engine test bed and data acquisition are used. The
emission results are integrated over the test cycle. The weighting factors for the cold start and hot start
cycles are 1/7 and 6/7, respectively.

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Module 4: Vehicle Emission Standards and Measurement


Lecture16:Emission Test Procedures

Figure 4.6

US Heavy Duty Emission Test Transient


cycle

Motor cycles
US test cycle for motorcycles has already been shown on Fig. 4.3. In Europe and India, different test
cycles have been and are being followed. However, there is an attempt to harmonize the test cycle all
over the world and a world motorcycle emission test cycle (WMTC) as shown in Fig 4.7 has been
developed. European Union countries have now defined emission test limits as an alternative to the
European test cycle, ECE-40. More and more countries are expected to adopt WMTC.

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Figure 4.7

World motorcycle emission test cycle


(WMTC).

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
The Lecture Contains:

EMISSION STANDARDS
Light Duty Vehicles
Heavy Duty Engines
Motorcycle Emission Standards

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
EMISSION STANDARDS
The vehicle emission standards were implemented for the first time in 1965 when control of crankcase
hydrocarbon emissions from gasoline passenger cars was required as per the law. Use of positive
crankcase ventilation (PCV) system on the gasoline passenger cars became necessary to prevent
emission of hydrocarbon rich crankcase blow by gases into atmosphere. At the same time, the exhaust
gas emission standards for new cars were also established in the state of California and in 1968, US
enacted legislation to implement nationwide vehicle emission regulations. In Europe , vehicle emission
standards were implemented beginning from the year 1970. Over the years, the emission standards
have become more and more stringent and have driven the development of advanced engine designs
and emission control technology. Now, nearly all the countries all over the world have enforced vehicle
emission regulations of varying severity following largely either the US or the European regulations.The
emission limits that are in force in the US and Europe and the trends thereof over the years are
discussed below.

Light Duty Vehicles


US Standards
The US emission standards for passenger cars are given in Table 4.1 since the limits were set for the
first time under the Clean Air Act of 1968. The standards set for 1975 were rather stringent such that
the oxidation catalytic converters were required on most cars. Amendments to Clean Air Act in 1977
resulted in the standards that required in 1980/1981 reduction of 90% in HC and CO, and 75% in NO x .
The 1980-81 standards resulted in widespread use of 3-way catalyst technology.
During 1990s, the 1977 amendments were found inadequate as 9 US cities had higher ozone levels
and 41 cities higher CO levels than the air quality standards. The 1990 Clean Air Act Amendments
(CAAA) followed resulting in further tightening of the emission standards besides other measures like
introduction of better quality fuels such as the reformulated gasoline. The new emission regulations
known as Tier 1 were implemented from 1994 and Tier 2 standards from 2004 through to 2009. It is
seen that the current production vehicles emit less than 1% of emissions of pre-control era vehicles.
In the mean time California introduced a new set of emission regulations (Table 4.2) and called the
vehicles meeting these regulations by the name of different grades of low emission vehicles (LEV) such
as TLEV ( Transitional), LEV, ULEV (Ultra), SULEV (Super Ultra) and PZEV ( Partial zero emission
vehicles).

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
Table 4.1
US Federal Emission Standards for
Passenger Cars, g/mile
Evap.
g/test

NMOG/
NMHC

CO

NO x

Pre-control (1966)

15 (3)

90

6.2

6.0

1975

1.5 (3)

15

3.1

2.0 (4)

1981

0.41 (3)

3.4

1.0

2.0 (5)

Year

PM (1)

HCHO(2)

US Federal

Tier1(6) , 1994

(7)

Gasoline

0.25(0.31)

3.4
(4.2)

0.4 (0.6)

Diesel

0.25(0.31)

3.4
(4.2)

1.0 (1.25)

0.08
(0.10)

1.7

0.2

0.02

Tier2 (8) , 2004 0.125


2009

0.018

(7)

NMHC/NMOG = Non-methane hydrocarbons or organic gases

(1) For diesel vehicles only (2) for alcohol fueled vehicles only (3) Total hydrocarbons (4) Carbon canister trap
method (5) SHED (Sealed Housing Evaporative Determination) technique, the 6.0 g/test limit represents about
70 % less than 2.0 g/test by carbon trap method (6) values in parentheses for full useful life equal to 100,000
miles, (7) new limits (8) To be phased in between 2004-2009,limits for all types of light duty vehicles
GVW<8500 lbs at the end of full useful life 120,000 miles. Eight different emission categories called bins' in the
given range to which vehicles can be certified and average NO x of the total fleet of a manufacturer not more
than 0.07 g/mile.

Table 4.2
California Emission Standards for Passenger
Cars, g/mile (1)
Year

NMOG/
NMHC

CO

NOx

PM (1)

HCHO (2)

Evap.
g/test

TLEV, 1996

0.125 (0.156)

3.4 (4.2)

0.4 (0.6)

(0.08)

0.015 (0.018) 2.0

LEV, 2000

0.075 (0.090)

3.4 (4.2)

0.2 (0.3)

(0.08)

0.015 (0.018) 2.0

ULEV, 2001

0.04 (0.055)

1.7 (2.1)

0.2(0.3)

(0.04)

0.015 (0.018) 2.0

LEV 2, 2004

0.075(0.090

3.4 (4.2)

0.05 (0.07)

(0.01)

0.015 (0.018) 2.0

ULEV2,2004

0.040(0.055)

1.7(2.1)

0.05(0.07)

(0.01)

0.008 (0.011) 2.0

SULEV2, 2004

(0.010)

(1.0)

(0.02)

(0.01)

(0.004)

PZEV (2)

0.010

1.0

0.02

0.01

0.004

2.0

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(1) Limits in parentheses at the end of durability run for 100,000 miles and from the year 2004 at
120,000 miles. (2) Partial zero emission vehicles (PZEV) limits are for 150,000 miles durability.

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
European Standards
European emission standards for the light duty vehicles are given in the Table 4.3. Before1992 i.e. prior
to Euro 1 standards, emission limits were based on ECE-15 cycle and varied with vehicle reference
weight, the higher emissions were permitted for the heavier passenger cars. From 1992 however, the
same limits for all the passenger cars irrespective of vehicle weight as in the US were introduced. EU
standards up to Euro 3 stage require durability demonstration for 80,000 km or 5 years, whichever
occurs first. In lieu of actual durability test, the manufacturers may use the following deterioration
factors:
Gasoline cars: 1.2 for CO, HC and NO x
Diesel cars: 1.1 for CO, NO x and HC+ NO x , 1.2 for PM
Euro 5 stage requires durability of 160,000 km or 5 years, whichever occurs first. The emission
standards for the light duty trucks and medium duty vehicles also, have been laid down and can be
found in the European regulations.

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
contd....
Table 4.3
European Emission Standards for
Passenger Cars, g/km
Vehicle
Type

Description
1992 Euro 1

All

CO
2.72

HC
-

NO x
-

(3.16)
1996 Euro 2

2000 - Euro 3 (3)

2005 Euro 4

2009 - Euro 5

2014 Euro 6

HC+NO x

PM

0.97

0.14 (1)

(1.13)

(0.18) (2)

Gasoline

2.2

0.50

Diesel IDI

1.0

0.70

0.08

Diesel DI

1.0

0.90

0.10

Gasoline

2.3

0.20

0.15

Diesel

0.64

0.50

0.56

0.05

Gasoline

1.00

0.10

0.08

Gasoline

1.00

0.10

0.08

Diesel

0.50

0.25

0.30

0.025

Gasoline

1.0

0.10 (4)

0.06

0.005 (5,6)

Diesel

0.50

0. 18

0.23

0.005 (6)

Gasoline

1.0

0.10 (4)

0.06

0.005 (5,6)

0.50

0. 08

0.17

0.17

0.005 (6)

(1)

PM limits apply only to diesel cars.

(2)

Values in parentheses are conformity of production (COP) limits. From Euro 2 standards
type approval and COP limits are the same

(3)
(4)
(5)
(6)

40s idle phase preceding test eliminated


0.068 g/km NMHC (non-methane hydrocarbons)
applicable only to lean burn gasoline direct injection engines
Likely to be reduced to 0.003 with new measurement method .

Since 1991/1992 when the European vehicles needed catalytic exhaust aftertreatment to meet the
regulations drastic reductions in emission limits have been enforced. Relative emissions limits since
1990 (pre-Euro1) to Euro 4 limits are shown on Fig 4.8. The Euro 4 limits were only about 5 to 15 % of
the pre 1990 limits. Beyond Euro 4 standards, drastic reductions in diesel NO x and PM emissions are
required. The diesel passenger car NO x would be reduced to just 1/3 rd and PM to 1/5 th of Euro 4
limits.

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
contd....

Figure 4.8

Evolution of EU emission standards (light duty)

Heavy Duty Engines


Most heavy-duty vehicles are powered by the diesel engines. Hence, the heavy duty engine emission
regulations have been directed more towards reduction in NO x and PM emissions.
US Standards
The US emission standards for the engines of heavy-duty vehicles (GVW >3855 kg) are given in Table
4.4. The emission limits applicable from the model year 2007 specify a drastic reduction over the year
2004 standards. The PM standards will be fully effective from the year 2007. The NO x and NMHC
standards are to be phased-in for the diesel engines between 2007 and 2010.
Emission durability is to be demonstrated over the useful life of the vehicles that varies from 8 years or
176,000 km for light heavy-duty engine vehicles (>8,860 kg <15000 GVW) to 8 years or 465,300 km for
heavy heavy-duty vehicles (> 15000 kg GVW).To make the year 2007 standards effective, diesel fuel
sulphur is to be reduced to 15 ppm maximum down from the earlier limit of 500 ppm.

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
contd...
Table 4.4
US Federal Heavy Duty Engine Emission
Standards, g/bhp-h, (US HD-Transient cycle)
NMHC +
NO x
NO x

PM

Year

CO

HC

1988

15.5

1.3

10.7

0.60

1990

15.5

1.3

6.0

0.60

1991

15.5

1.3

5.0

0.25 (0.25)

1994

15.5

1.3

5.0

0.10 (0.07)

1996

15.5

1.3

5.0

0.10 (0.05) (1)

1998

15.5

1.3

4.0

0.10 (0.05)(1)

2.4

0.10 (0.05)

2.5

0.10 (0.05)

0.2

0.01

2004(2)
Option 1 15.5

Option 2 15.5 0.5 (3)


2007

15.5

0.14
(3)

Note: values in parentheses apply to urban buses

(1)

PM standard in use is 0.07 g/hp.h

(2)

Engine manufacturers may use either of the two options.

(3)

NMHC limits apply.

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
European Standards
The European regulations for new production heavy-duty diesel engines since Euro 1 stage are given in
Tables 4.5 and 4.6. These standards apply to both heavy-duty highway vehicles as well as to urban
buses. The test cycle was changed with the implementation of Euro 3 standards in the year 2000. To
meet the Euro 4 standards and beyond, diesel engines need some form of aftertreatment devices such
as oxidation catalysts, particulate filters, de-NO x catalysts etc. From Euro 3 regulations, heavy-duty
engines operating on gaseous fuels are tested also on ETC in addition to ESC cycle. However, for
compliance with Euro 4 or later standards, all heavy-duty engines are to meet ESC, ELR and ETC test
limits. Evolution of European emission regulations for heavy duty vehicles is shown on Fig. 4.9.

Table 4.5
European Heavy Duty Diesel (CI) Engine Emission Standards
g/kWh (smoke in m -1 ) [2-4]

Euro1

Euro 2

Euro 3

Date &
Category

Test cycle

CO

HC

NO x

PM

1992 <85 kW

ECE R-49

4.5

1.1

8.0

0.61

1992 >85 kW

4.5

1.1

8.0

0.36

Oct. 1996

4.0

1.1

7.0

0.25

Oct. 1998

4.0

1.1

7.0

0.15

2.1

0.66

5.0

0.10

Oct. 2000

ESC & ELR

Smoke

0.8

0.13*
Euro 4

Oct 2005

Euro 5

Oct. 2008

Euro 6

Jan. 2013

ESC& ELR

ESC

1.5

0.46

3.5

0.02

0.5

1.5

0.46

2.0

0.02

0.5

1.5

0.13

0.4

0.01

*For engines of less than 0.75 litre /cylinder swept volume and rated speed of more than 3000 rpm.

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
Table 4.6
Emission Standards for CI and SI
Engines, ETC Test, g/kWh
Date &
Category

Test
cycle

CO

NMHC CH 4 (1)

NO x

PM (2)
0.16

Euro3

Oct. 2000

ETC

5.45

0.78

1.6

5.0
0.21 (3)

Euro 4

Oct. 2005

4.0

0.55

1.1

1.1

0.03

Euro 5

Oct. 2008

4.0

0.55

1.1

2.0

0.03

Euro 6

Jan. 2013

4.0

0.16 (4)

0.5

0.4

0.01 (5)

(1) for natural gas engines only; (2) not applicable for gas fuelled engines for approval to Euro 3 and
Euro 4 standards; (3) for engines of less than 0.75 litre/cylinder swept volume and rated speed above
3000 rpm; .(4) THC (total hydrocarbons) limits apply for diesel; (5) particle number limit may apply to
prevent ultra fine particles from flow through ( or partial flow) filters.

Figure 4.9

Evolution of European Heavy duty


Emission Standards

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
Emission Standards in India
India has adopted the European emission limits on a slightly modified driving cycle for the light duty
vehicles. The overall emission limits and test procedures for the heavy duty vehicles however are the
same as those in Europe . In India , the emission limits are being enforced by a time lag of around 5
years as shown in Table 4.7.

Table 4.7
Indian Emission Regulations
(light duty emission standards with a modified EUDC maximum speed limited to 90 km/h)
Year of
Level of European Emission
Implementation Standards
2000

E uro 2: four metro-cities (1)


Euro 1: rest of the country

2003

Euro 2: seven more cities (2)

2005

Euro 3: thirteen cities


Euro 2: rest of the country

2010

Euro 4: thirteen cities


Euro 3: rest of the country

(1) Delhi , Mumbai, Kolkatta, Chennai


(2) Banglore, Hyderabad , Ahmedabad, Pune, Surat , Kanpur , Agra ; added from the year 2005Sholapur and Lucknow

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Module 4: Vehicle Emission Standards and Measurement


Lecture17:Emission Standards
Motorcycle Emission Standards
Asian countries have a very large population of motorcycles and mopeds and these vehicles are
estimated to contribute very heavily to urban air pollution. Taiwan and India have lead enforcement of
stringent emission limits for two wheelers. Although the USA and Europe have implementd emission
regulations for the two wheelers many decades back, but the number of these vehicles not being very
large the standards were not tightened for a long time. However, now in these countries too very
stringent limits are being enforced. Motorcycle emission standards in some countries are given in Table
4.8. Presently, most countries follow different test procedures. However, as discussed earlier, a world
motorcycle test cycle has been developed and in future most countries are expected to use WMTC.

Table 4.8
Worldwide Motorcycle Emission
Standards
Country/Year/
Type of
Motorcycle

Test
Cycle

Emission
Limits, g/km

Durability,Kms
NO x HC+NO
x

CO

HC

12.0

5.0

2006 < 279 CC

12.0

1.0

12,000-30,000

> 280 CC

12.0

1.4

6,000 -18,000

2010 < 279 CC

12.0

1.0

> 280 CC

12.0

0.8

ECE 47

1.0

1.2

ECE 40

5.5

1.2

0.3

5.5

1.0

0.3

USA
1980

FTP-75

Europe
2003 < 50CC
> 50<
150CC
> 150 CC
2006 > 50<
150CC

ECE 40
(1)

2.0

0.8

0.15

> 150 CC

ECE15
+EUDC

2.0

0.3

0.15

2007< 130 km/h

WMTC

2.62

0.75

0.15

30,000

>130
(optional) 2.62
km/h max. Speed

0.33

0.22

30,000

2.0

2.0

1.5

1.5

30,000

India , 2000
2005 (2)

IDC
(cold)
IDC

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(cold)
2010 (2)

IDC
(cold)

1.0

1.0

30,000

(1) Warm-up period before emission measurement of ECE 15 cycle eliminated.


(2) For catalyst equipped motorcycles an emission deterioration factor of 1.2 applies.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
The Lecture Contains:
EMISSION MEASUREMENT
CO and CO2 NDIR Analyzers
Flame Ionization Detector (FID)
Chemiluminescence Analyzer (CLA)
Smokemeters
Constant Volume Sampler (CVS)
Particulate Emission Measurement
Partial Flow Dilution Tunnel
Full Flow Dilution Tunnel

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
EMISSION MEASUREMENT
The emission regulations specify the type, principle of operation used and generic construction of the
exhaust gas analyzers which can be employed for emission certification of vehicles and engines. Table
4.9 gives the type of analyzers used for measurement of different exhaust gas constituents.

Table 4.9
Measurement Principles of Exhaust
Gas Analyzers
Gas component

Measurement Principle

CO

NDIR (Non-dispersive infrared)

HC

FID (Flame Ionization detector)

NO x

CLD (Chemiluminescence detector)

CO and CO 2 NDIR Analyzers


Beer-Lambert's Law is used for operation of NDIR analyzers by measuring the degree of absorption of
infrared (IR) radiations when they pass through a column of gas. The fraction of incident radiations
absorbed is given by,

(4.1)
where
I = Radiation energy absorbed
I0 = Incident radiation energy
k = characteristic absorption constant for the gas, m2 /gmol
c = concentration of the gas, gmol/m 3
d = length of the gas column, m

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
contd...
NDIR analyzer is shown schematically in Fig. 4.10.
As the absorption of IR radiations is measured only in a narrow range of wavelengths (not the
entire range of wavelength of IR radiations) which has specifically a high absorbance for the
particular gas, the technique is called as Non-dispersive infra-red'. For example carbon
monoxide has a strong absorbance in the wavelength band of 4.5-5 m.
The analyzer measures differential in absorption of energy from two columns of gas; (i) the gas
to be analyzed in the sample cell' and (ii) a gas of fixed composition like N 2 contained in the
reference cell which is free of the gas of interest and relatively non-absorbing in the infrared
region.
The infrared beam from a single source is usually split into two beams of the same intensity,
one each for the sample and reference cells.
The detector is divided in two compartments separated by a flexible diaphragm; one section
receives transmitted IR energy from the sample cell and the other from the reference cell.
The detector is filled with the gas of interest, so that the energy transmitted to the detector is
fully absorbed.
The flexible diaphragm of the detector senses the differential pressure between the two sections
of the detector caused by the difference in the amount of transmitted IR energy absorbed. The
deflection in the diaphragm is used to generate an electrical signal that determines the
concentration of the gaseous species of interest.
A rotating interrupter in the path of IR beam is put to generate AC signal output that can be
amplified.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
contd....
NDIR analyzers enable accurate measurements of CO and CO 2 in the exhaust gases.

Schematic of an NDIR analyzer for measurement of


Figure 4.10 CO and CO concentration.
2
NDIR instruments are seldom used for measurement of hydrocarbons except in the garage type
analyzers as the IR absorbance to different hydrocarbons varies substantially. The unsaturated
hydrocarbons are primarily responsible for photochemical smog but they do not have an adequate
absorption in the IR wavelength range that is specific to the saturated hydrocarbons and vice versa.
Sensitivity and response of NDIR to the exhaust HC is typically only half of the probable true value. NO
absorbs only weekly in the infrared region. Moreover, CO, CO 2 and water vapours interfere seriously;
hence NDIR analyzers are also not used for NO measurement.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
Flame Ionization Detector (FID)
Pure hydrogen-air flames are practically ion-free but on introduction of even little amount of
hydrocarbons the flame causes considerable ionization and becomes electrically conducting. The
ionization current is proportional to the number of carbon atoms present in the hydrocarbon molecules.
Thus, FID is effectively a carbon atom counter e.g., one molecule of propane generates three times the
response generated by one molecule of methane. The measurement of HC by FID is expressed as parts
per million of methane i.e. as ppmC 1 i.e., ppm of hydrocarbon containing equivalent of one carbon
atom. The HC concentration is commonly written as ppmC. HC concentration measured as ppm
propane (C3 ) is to be multiplied by a factor of 3 to convert it to ppmC. All classes of hydrocarbons i.e.,
paraffin, olefins, aromatics, etc. show practically the same response to FID. Oxygenates, e.g. aldehydes
and alcohols however, have a somewhat lower response.
FID essentially consists of a hydrogen-air burner and an ion collector assembly as shown in Fig. 4.11.
Sample gas is introduced with hydrogen in the burner assembly and the mixture is burned in a diffusion
flame. An electric potential is applied between the collector plates that makes the ionization current to
flow and generate signal proportional to HC concentration in the sample gas. This current is amplified
and the output signal is measured.
A well-designed burner will generate ionization current that is linearly proportion to hydrocarbon content
over a dynamic range of almost 1 to 10 6 . The commercial FID analyzers have the most sensitive
range set at about 0-50 ppmC and the maximum range reaching 0-100,000 ppmC.
Hydrogen is mixed with helium in ratio of 40:60 to decrease flame temperature that increases flame
stability. The FID analyzer is calibrated with propane or methane mixtures in nitrogen. For the
measurement of hydrocarbons in diesel exhaust, sampling line and FID are heated to a temperature of
191 11C to minimize condensation of heavy hydrocarbons present in the diesel exhaust in the
sampling system.

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Figure
4.11

FID for HC measurement.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
contd...
Measurement OF Non-Methane Hydrocarbons (NMHC)
Presently, the emission standards are specified in terms of non-methane hydrocarbons. Methane
content of HC emissions is determined by one of the following methods:
Gas chromatographic (GC) method or
Non-methane cutter (NMC) method
In the GC method, sample is injected into GC column which separates the sample into two parts:

(i) CH 4 -air-CO, and


(ii) NMHCCO 2 H 2 O.
A molecular sieve column separates methane from air and CO before passing it to FID. Thus methane
content is measured that is deducted from the total hydrocarbon content.
In the NMC method, all hydrocarbons except CH4 are oxidized to CO 2 and water on a catalyst, so that
when the gas sample is passed through NMC only CH4 is detected by HFID. The NMC cutter is
calibrated for catalytic effect on CH4 and higher hydrocarbon (ethane) mixtures in presence of water
vapours with values typical of exhaust gas at or above 600 K. The sample can be alternatively passed
through NMC or bypasses the NMC. In this manner, the total HC and methane alone present in the
exhaust gas sample are determined.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
Chemiluminescence Analyzer (CLA)
When NO and ozone (O 3 ) react a small fraction (about 10% at 26.7 C) of excited NO 2 * molecules is
produced as per the following reactions:

(4.2)
(4.3)
As the excited molecules of NO 2 * decay to ground state, light in the wavelength region 0.6-3.0 m is
emitted. The quantity of excited NO 2 produced is fixed at a given reaction temperature and the intensity
of light produced during decay of excited NO 2 is proportional to the concentration of NO in the sample.

Figure
4.12

Schematic and flow diagram of a c hemiluminescence NO x


analyzer.

A schematic diagram of the chemiluminescence NO x analyzer is shown in Fig. 4.12.


The sample containing NO flows to a reactor where it reacts with ozone produced from oxygen in
ozonator' .In the reactor NO is converted to NO 2 .
A photomultiplier tube detects the light emitted by the excited NO 2 . The signal is then amplified
and fed to recorder or indicating equipment.
For the measurement of nitrogen oxides (NOx ), NO 2 in the sample is first converted to NO by
heating in a NO 2 - to-NO converter prior to its introduction into the reactor. At 315 C, about 90
percent of NO 2 is converted to NO 2 . The total concentration of NO x in the sample is thus,
measured as NO. When the sample is introduced in the reactor bypassing the NO 2 - to- NO
converter, concentration of NO alone is determined. The difference between the two
measurements provides the concentration of NO 2 in the sample.
The response of the instrument is linear with NO concentration. The technique is very sensitive
and can detect up to 10 -3 ppm of NO x .
The output signal is proportional to the product of sample flow rate and NO concentration. As the

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method is flow sensitive an accurate flow control is necessary. The calibration and operation are
done at the same flow rate and reactor temperature.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement

Smokemeters
In the filtration type smokemeters like Bosch smokemeter a fixed volume of the exhaust gas is drawn
through a white filter paper of specified quality. The density of smoke stain obtained on the filter paper
is evaluated using a reflectance meter which gives the measure of smoke density of diesel exhaust gas.
Now, mostly light extinction/absorption smokemeters based on Beer-Lambert Law are used. The light
extinction type smokemeters are more commonly called as opacimeters' as these provide a more
realistic measurement of the visible smoke emissions from diesel engines.
. Both the sampling type and full flow type opacimeters are in use. The construction requirements,
installation and operational details of opacimeters are described in the relevant international standards.
A sampling type smokemeter is shown schematically in Fig. 4.13.

Figure 4.13

Schematic of a sampling type light


extinction smokemeter.

An incandescent lamp with a colour temperature in the range of 2 800 K to 3 250 K or a green light
emitting diode (LED) with a spectral peak between 550 nm and 570 nm is used as light source. The
transmitted light is received on a photocell or a photo diode (with filter if necessary). When the light
source is an incandescent lamp, the receiver should have maximum response in the range 550 nm to
570 nm wavelength as is for the human eye.
When light from a source is transmitted through a certain path length of the exhaust gas, smoke opacity
is the fraction of light that is absorbed in the exhaust gas column and does not reach the light detector
of smoke meter. The absolute smoke density is given by the absorption coefficient, k s which has units
of m -1 and is given by:

(4.4)

where L is length of smoke column in meter through which light from the source is made to pass, I0 is
the intensity of incident light, I is the transmitted light falling on the smokemeter receiver.

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In the full flow type smokemetersm, the light source and detector are placed directly across the exhaust
gas stream usually at the end of exhaust pipe. In this case, path length of smoke measurement varies
with the cross sectional size of the exhaust gas stream or tail pipe. Hence, conversion charts of the
measured value to the absolute smoke density, k s for different exhaust pipe diameter or path lengths
are made available for the full flow smoke meters.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement
Constant Volume Sampler (CVS)
When emissions are to be measured from a vehicle being run on a driving cycle sampling of the
representative gas is very critical. Constant Volume Sampling (CVS) is used in European, US and other
tests to make it possible that a representative sample of the exhaust gas is withdrawn for measurement
of the gaseous emissions.

Figure 4.14

C onstant volume sampling (CVS) unit using critical flow


venturi (CFV-CVS ) for measurement of mass of the exhaust
emission.

A Constant Volume Sampling (CVS) system is shown schematically in Fig. 4.14 . In the CVS system;
The entire exhaust gas from the vehicle is diluted with the filtered room air. An air to exhaust
gas dilution ratio of about 10:1 is used. The dilution with air lowers partial pressure of unburned
hydrocarbons and water, and prevents their condensation in the sampling line.
The diluted exhaust gas is drawn by a constant volume pump system employing either a
positive displacement pump (PDP) or a critical flow venturi (CFV) and a blower. A PDP capacity
of about 10 to 12 m3 /min of air flow provides sufficient dilution for most passenger cars
The volume flow rate of the diluted exhaust (exhaust gas + air) is maintained constant
throughout the test .
Before the diluted exhaust gas enters the CFV or PDP, its temperature is controlled within the
5 C of the average gas temperature during the test by a heat exchanger.
From the diluted gas a small sample is continuously withdrawn and collected in evacuated
Teflon bags. This process integrates the concentration of the pollutants over the entire driving
schedule. A small part of the dilution air is sampled simultaneously and collected in a separate

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bag to correct for any background concentration of pollutant present in the dilution air.
The sample bags are analyzed after the test is completed.
The mass of individual pollutants is determined from its measured concentration in the sample
bag, its density and the total volume flow rate of the diluted exhaust during the test through CVS.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement

Particulate Emission Measurement


For measurement of particulate emissions, the gas is diluted with air in a dilution tunnel and, a sample
is continuously collected from the diluted gas and filtered to collect particulate matter. The mass of the
collected PM is measured to determine specific PM emissions in terms of g/km or g/kWh.
The dilution tunnels are of two types
Partial flow, and
Full flow dilution tunnel

Partial Flow Dilution Tunnel


In the partial-flow system, only a small part of the exhaust stream is diluted. To withdraw a true
representative of the exhaust gas the following systems have been developed;
Isokinetic sampling systems
Flow controlled systems with concentration measurement, and
Flow controlled systems with flow measurement
In an isokinetic system, the gas velocity in the sampling tube which leads the sampled exhaust gas to
dilution tunnel is kept same in magnitude as the velocity of the bulk exhaust gas stream. In this way, an
undisturbed and uniform exhaust gas sample flow at the inlet of sampling probe is obtained.
An isokinetic system is shown schematically in Fig. 4.15. Raw exhaust gas is transferred from the
exhaust pipe to the dilution tunnel (DT) through isokinetic sampling probe (ISP) and the transfer tube.
The differential pressure of the exhaust gas between exhaust pipe and inlet to the probe is measured
with a pressure transducer. The signal is fed to a flow controller that controls the suction blower and, a
differential pressure of zero at the tip of probe is maintained. Under these conditions, exhaust gas
velocities in the exhaust pipe and probe are identical and the flow through isokinetic probe is a constant
fraction of the exhaust flow. The sampling rate can be obtained by the ratio of cross sectional areas of
probe and the exhaust pipe. The dilution airflow rate is measured with the flow meter. The dilution ratio
is calculated from the dilution air flow rate and exhaust sample to total exhaust flow ratio.

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Module 4: Vehicle Emission Standards and Measurement


Lecture18:Emission Measurement

Figure 4.15

Partial flow dilution systems with


isokinetic sampling probe.

Full Flow Dilution Tunnel


In the full flow system, entire exhaust of the engine/vehicle is diluted with the filtered room air. The full
flow system is quite large in size and expensive. A full-flow double dilution tunnel is shown
schematically in Fig. 4.16 . For small engines/vehicles only the primary dilution tunnel is used. For the
large engines to provide the desired dilution ratio, the gas is diluted again in the secondary dilution
tunnel. The sample is withdrawn for measurements from the secondary dilution tunnel in the large
engines. The dilution ratio is maintained around 10:1. The temperature of the diluted exhaust gases at
the primary filter is maintained at 325 K or less by a heat exchanger. The flow rate of diluted gas is
kept constant during the test by a CVS system.
After thorough mixing of exhaust and air in the dilution tunnel, a constant flow rate sample is extracted
that is filtered through a Teflon coated glass fibre filter. The mass of particulate is determined by
weighing the particulate mass collected on the filter. A reference filter is used to determine the
particulate mass in the dilution air for correction of PM measurement for the background PM. The filter
papers are conditioned before and after filtration to prevent condensation of any moisture or deposition
of foreign particulate matter from atmosphere. With the full flow dilution tunnel and CVS system,
gaseous pollutants are also measured simultaneously with particulates

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Figure
4.16

Full flow dilution tunnels for measurement of


particulate emissions

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Module 4: Vehicle Emission Standards and Measurement

Questions

(4.1) Average engine-out emissions before catalytic treatment from a SI engine car operating on
stoichiometric gasoline-air mixture are CO = 12 g/km, HC = 1.5 g/km and NOx (as NO) = 1.0
g/km. The fuel consumption of car is 80 g/km. Estimate the average concentration of
pollutants CO (as % volume), NO (ppm), HC (ppmc1). Take gasoline as isooctane,
universal gas constant = 8314.3 kJ/kmol.K.
(4.2) The above car meets the Euro 3 standards CO = 2.3 g/km, HC = 0.2 g/km and NOX = 0.15
g/km. What would be the concentration of each pollutant in the exhaust gas at exit of the tail
pipe.
(4.3) In the US FTP cycle (Fig 4.3) the first 505 seconds of driving schedule is repeated after 10
minutes of hot engine soak. How would the average emissions of CO, HC and NOX differ
during the initial and the last 505 seconds of the driving cycle?
(4.4) Discuss why NDIR does not measure the unburned hydrocarbons correctly even though it is
calibrated with standard mixtures of n-hexane in nitrogen gas.
(4.5) A light extinction type smoke meter has smoke column length, L= 430 mm and it shows
smoke density of 60% (60% light is absorbed in the smoke column). Determine absolute
smoke density of the exhaust gas in terms of m-1. The full flow type of smoke meters are
used by fitting them at the end the exhaust pipe. The smoke column length for the full flow
smoke meter may be taken equal to the exit diameter of the exhaust pipe. Make a table for
the absolute smoke density varying from 0.25 m-1 to 2.5 m-1 in steps of 0.25 m-1 correlating
the smoke opacity readings observed with the sampling smoke meter having L = 430 mm
and full flow smoke meter fitted to the exhaust pipe of 100 mm dia.
(4.6) Discuss the advantages and disadvantages of the full and partial flow dilution tunnels for
measurement of PM emissions.
(4.7) To measure emissions under fluctuating and transient operating conditions of a vehicle
during the driving cycle operation, the emission analyzers having very fast response are
required so that instantaneous concentration measurement for the pollutants can be done
and the concentrations are then integrated over the driving cycle to determine emissions in
terms of g/km. Such emission analyzers are not yet available and there is also delay in the
sampling line from the exhaust to analyzer. Discuss how a constant volume sampling (CVS)
system functions and this problem is taken care of. In case, the entire exhaust gas during
the driving cycle is collected in a big balloon and then the average pollutant concentration is
determined, what may be the disadvantages compared to the CVS system.

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Module 5:Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
EMISSION CONTROL FOR SI ENGINES/VEHICLES
The Lecture Contains:
AN OVERVIEW AND CONTROL OF ENGINE-OUT EMISSIONS
Categorization of Emission Control Techniques
ENGINE DESIGN PARAMETERS
Engine Compression Ratio
High Turbulence Combustion Chambers
Fuel System
Valve Gear Design
Variable Swept Volume and Downsizing

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Module 5:Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
AN OVERVIEW AND CONTROL OF ENGINE-OUT EMISSIONS
During 1950s the road vehicles were found to be the principal source of air pollution in the US cities.
Carbon monoxide, unburned fuel (hydrocarbons), nitrogen oxides and smoke particulates were identified
as the main air pollutants. Now, carbon dioxide has been added to the list of harmful gaseous emissions
due to its global warming effect. Initially, to solve the local air pollution problem during 1960s efforts
were mainly focused on reduction of CO from gasoline vehicles and black smoke emissions from diesel
vehicles. Another area of priority attention was the prevention of blue smoke emissions caused by
excessive consumption of engine lubricating oil which resulted from worn out piston rings, cylinder bore
etc.
The first emission control for the spark ignition engines involved adjustments of air-fuel ratio. It was
followed by control and adjustment of other engine parameters such as mixture control under idling,
acceleration and deceleration, spark timing, precision manufacturing of key engine components such as
piston, rings, cylinder head gasket to minimize crevice volume, cams, valves etc. Positive crankcase
ventilation (PCV) system was introduced on gasoline vehicles during mid 1960s to prevent release into
atmosphere of hydrocarbon-rich crankcase blow by gases
As the emission standards were tightened, exhaust aftertreatment devices such as catalytic converters
were introduced for the first time in 1974-75 and more advanced modifications in engine design and fuel
system were employed. Electronic fuel and engine management become necessary during 1980s to
meet the then emission regulations. Further advancements in engine, fuel system and emission control
technology have emerged in the meantime. Multi-valve cylinder engines became common and variable
valve actuation was applied in production vehicles during late 1980s. In mid 1990s, gasoline direct
injection stratified charge (DISC) engines were put into production by Japanese auto-manufacturers.
Besides all-round advancements in engine technology and aftertreatment systems happening all the
time, in the past few years alternative power trains also for vehicles have been developed which provide
a higher fuel efficiency in addition to low emissions. Hybrid electric vehicles (HEV) are already in market
place. The HEV has IC engine as a primary source of power but employ electric propulsion powered by
storage batteries as the main propulsion unit. Fuel cell vehicles using hydrogen as energy source are in
an advanced stage of development and they completely eliminate the use of IC engines as a propulsion
system

Categorization of Emission Control Techniques


The emission control techniques may be grouped into the following broad categories:
Engine design and fuel system parameters
Engine add-ons to enable reduction of engine-out emissions and
Exhaust aftertreatment

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Module 5: Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
ENGINE DESIGN PARAMETERS
The following engine parameters have large influence on emissions and hence have undergone
substantial modifications since the pre-emission control era.
Engine compression ratio,
Combustion chamber design low crevice volume, high turbulence
Spark timing
Air-fuel ratio
Fuel system design: carburetor giving way to fuel injection
Multivalves and variable valve actuation
Engine temperature control

Engine Compression Ratio


Engine compression ratio affects
Surface to volume ratio of the combustion chamber
Engine combustion temperature
Thermodynamic efficiency
Fuel octane number for knock free engine operation
The premium high performance car engines during 1960s employed CR of 10 to 11:1. The engine CR
was lowered to 8.5 to 9.0:1 when stringent emission standards were legislated for the first time in 1975.
The combustion chamber with a lower CR has lower surface/volume ratio resulting in a reduction in
volume of quench layer on the combustion chamber surface. Typical effect of surface/volume ratio of
combustion chamber is shown on Fig, 5.1. Moreover, for a low CR engine the crevice volume would
also be proportionately lower. These factors in turn would reduce HC emissions. Higher exhaust
temperatures resulting with low CR would promote oxidation of HC and CO in exhaust system.
At low CR the peak combustion temperatures are lower and hence low NOx formation.
Introduction of catalytic converters made the use of unleaded gas necessary. As the petroleum refinery
economics dictated the use of unleaded gasoline of a low octane number, engine CR had to be
lowered.
The principal disadvantage of low CR engine is that it has a poorer fuel efficiency that also results in
higher CO2 emissions.
The premium high performance car engines during 1960s employed CR of 10 to 11:1. The engine CR
was lowered to 8.5 to 9.0:1 when stringent emission standards were legislated for the first time in 1975.
However, due to development of high turbulence engine combustion chambers and use of port fuel
injection system it has been possible to use a somewhat higher engine CR. The modern gasoline
engines have CR mostly in the range of 9.0 to 9.5:1.

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Fig 5.1

Effect of surface/volume ratio of combustion chamber on HC


emissions

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Module 5: Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
High Turbulence Combustion Chambers
Small cylinders with hemispherical and pentroof type combustion chambers are now more commonly
used in SI engines.
Small cylinder engines can be operated at higher speeds whicht increases turbulence and tends
to reduce HC emissions..
Smaller cylinders have smaller amount of burned gases that form the high temperature adiabatic
core. More heat transfer takes place from the burned gases as the walls are nearer to the bulk
gases. It results in lower NO x .
The compact hemispherical combustion chambers shape (Fig 5.2a) provides the lowest surface
to volume ratio and minimum tendency to engine knock.
The hemispherical combustion chamber although may employ multiple valves,
the two valve
configuration is more common as it is difficult to accommodate 4-valves at the necessary valve
positioning angles. The valve heads along with the surface of combustion chamber form a profile that
looks like a hemisphere. Both the intake and exhaust valves are inclined increasing valve port area that
results in higher volumetric efficiency. The chamber has a low surface to volume ratio. The intake ports
are provided with a suitably curved geometry to generate high rate of air swirl.

Fig 5.2 (a)

Hemispherical combustion chamber (generally with two


valves)

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Module 5: Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
contd...
A shallow angle pent-roof type combustion chamber (Fig. 5.2b) is a good compromise as it
allows use of 4 valves of optimum size and positioning. A higher volumetric efficiency and tumble
air motion are obtained in these combustion chambers resulting in higher burning rates. These
compact combustion chambers have lower heat transfer losses. Thus, quench layer thickness is
minimized lowering HC emissions.
Pentroof combustion chamber being shallow compared to hemispherical combustion chamber it has
somewhat higher surface to volume ratio. However the pentroof combustion chamber is a good
compromise between compactness of the combustion chamber and use of multiple valves. A shallow
angle pentroof type combustion chamber allows optimum valve size and their positioning in multiplevalve engine configuration. Pentroof combustion chambers having 2 and 3 intake valves and total of 3
to 6 valves per cylinder are in use. The 4-valve combustion chambers are the most common The
inclination of the intake and exhaust valves to each other tilts the pair of valve heads such that they
resemble to an arch and take the shape of a pentroof, hence the name. The spark plug is located close
to centre. Mixture from the intake port flows across the cylinder to the walls from where it is deflected
downwards direction and rolls perpendicular to the axis of the cylinder in a tumbling motion. This motion
is called air tumble.

Fig
5.2(b)

Pentroof combustion chamber with 4-valves for modern SI


engines

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Module 5: Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
Fuel System
Trends in development of gasoline engine fuel introduction system are shown in Fig 5.3. Until 1980
practically all gasoline SI engines employed carburettors. Only a few premium model gasoline cars
employed electronic fuel injection (EFI) system. Initially, a single point EFI injecting fuel at the throttle
body was used. It was also known as throttle body injection (TBI) system and it provided more precise
fuel metering than the carburettor. However, from 1990 onwards electronically controlled multi-point port
fuel injection (MPFI or PFI) system replaced the carburettor on all the production cars in the USA. Port
fuel injection systems require one injector per cylinder that injects fuel into intake port of each cylinder.
Some engines use an additional injector to supply extra fuel required during starting and warm-up.

Figure 5.3

Trends in development of fuel system technology for SI


(gasoline) engines

The PFI has the following advantages over the carburettor and TBI system;
Increased power and torque due to improved volumetric efficiency: the venturi
system needed for carburettor is eliminated and less fuel vaporizes in the intake manifold, which
increase the volumetric efficiency
Faster fuel evaporation: Improved fuel atomization leads to smaller droplets and a faster
fuel evaporation.
More uniform fuel distribution: for each cylinder the fuel is metered separately by the
corresponding port fuel injector
More rapid dynamic response to changes in throttle position and hence
transient operation: Faster fuel evaporation leads to rapid mixture formation and faster
dynamic response. Hence, less fuel enrichment is required during acceleration.
More precise control of air-fuel ratio: use of closed loop feedback control system that
employs exhaust oxygen sensor very precise control of air-fuel ratio is obtained so the
unnecessary fuel enrichment of the engine can be prevented
More precise control of air-fuel ratio cold-start and warm up: less extra fuel
compared to carburettor is necessary during cold start and warm up.

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Module 5: Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
contd...

Figure
5.4

Comparison of engine-out emissions from carburettor and open


loop PFI engine passenger cars.

In the EFI systems, for control of fuel injection rate and in turn the air-fuel ratio, airflow to the engine is
measured by a hot-wire or hot-film anemometer. Air-fuel ratio is more precise. Use of measured air flow
rate data by the engine fuel management system results in an automatic compensation for changes in
air flow resulting from variations in engine speed, load, exhaust back pressure or change in volumetric
efficiency due to valve adjustments, engine wear, deposit build-up etc.
The typical emissions from a car equipped with carburettor and open loop PFI systems are compared in
Fig. 5.4. Use of port fuel injection alone provided 20- 30 % reduction in HC and 50 to 60% reduction in
CO compared to carburettor when tested over the urban driving cycle. The NO x however, increased by
about 45% as for smooth engine operation overall a leaner mixture was used with PFI. In the closed
loop controlled stoichiometric operation of the engine, the effect of PFI on NO x would not be very
significant, while lower CO and HC are obtained due to more uniform fuel distribution among the
different engine cylinders.
Gasoline direct injection (GDI) system has been employed for the direct injection stratified charge
(DISC) engines. During mid 1990s, Mitsubishi and Toyota introduced DISC engines on the production
cars. The DISC engine operates as lean as 40: 1 air-fuel ratio and provides large reductions in engineout emissions. Now however, stoichiometric GDI engines are also being considered for production.
These engines are discussed in detail later in the section on advanced engines.

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Module 5: Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
Valve Gear Design
Multiple Valves:
Four valves (2 intake and two exhaust valves) per cylinder are now common on the SI engines. The
use of multiple valves:
Increases valve flow area compared to two valves
Spark plug can be placed centrally reducing the maximum flame travel distance hence faster and
less knocking tendency combustion,
Only one intake valve may be used at low speeds and low loads to obtain high intake mixture
velocity giving high turbulence and swirl that improves combustion at light loads. At high speeds
and high loads both valves are open.
The two intake valves may be provided with different valve timings and different valve lifts to
obtain higher volumetric efficiency.
The two valves may use different port designs to obtain the desired fluid motion in the cyliunder
Variable Valve Timings and Lift
A large valve overlap is required to obtain high volumetric efficiency at high engine speeds to
make use of the ram effect
At low engine speeds due to backflow of residual gases in the intake system a low valve overlap
is desired.
With increase in valve overlap, residual gas fraction at low speeds increases giving lower NO x
emissions, but HC emissions increase.
Ideally the valve timings should vary with the engine speed.
The intake gas flow velocity through the valves governs the air motion and turbulence in the
engine cylinder and hence the rate of combustion and performance For fixed intake valve lift,
intake airflow and turbulence would be reduced at low engine loads and speeds, which may not
be adequate for good combustion. Hence a variable valve lift is required that would depend on
engine load and speed for good combustion and engine performance.
Variable valve timing control allows for continuously variable camshaft phasing over the entire power
range of the engine. Honda has developed electronically controlled variable valve timing and lift (VTEC)
system. Toyotas system is known as VVTi (intelligently controlled variable valve timing). Other
manufacturers have developed their own designs of varable valve actuation. The NO x emissions with
fixed and typically with variable valve timings are compared on Fig. 5.5. Reductions of 30 to 70 % in
NOx with variable valve timing are observed. Change in HC emissions between the fixed and variable
valve timings is however, small. The CO emissions however, are a function of air-fuel ratio.

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Fig 5.5

Typical emissions with fixed and variable valve


timings.

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Module 5: Emission Control for SI Engines


Lecture19:Emission Control by Engine Design Variables
Variable Swept Volume and Downsizing
The passenger cars during city driving operate at light loads when high pumping losses, poor fuel
efficiency and high HC and CO emissions are obtained. Operation of the engine with lower swept
volume would be at a higher mean effective pressure which would result in better fuel economy and
lower CO and HC emissions. For the 6- and 8-cylinder engines, the effective engine swept volume
has been varied by deactivating the valve operation of half of the cylinders during city operation. This
technology although has been applied to 4-cylinder engines as well but is better suited for the large
engine having 6- and 8-cylinders. On high driving all the cylinders come into operation. The cylinders
are electronically switched on and off without the sudden acceleration and deceleration of vehicle being
felt. When operating only on half the number of cylinders, friction losses are also reduced as overhead
camshafts of the two cylinders are not in operation.
Using a lower displacement engine and develop the required full throttle torque and power by
supercharging is another approach to improve fuel economy and reduce emissions particularly the HC.
A lower swept volume engine would operate at higher mean effective pressures and would have lower
fluid and mechanical friction losses. At part loads, the supercharged and downsized engine can result
in fuel economy improvements of upto 25% and accompanied benefits related to lower CO, HC and
CO 2 emissions.

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Module 5: Emission Control for SI Engines


Lecture20:ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
The Lecture Contains:
Crankcase Emission Control (PCV System)
Evaporative Emission Control
Exhaust Gas Recirculation
Water Injection

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Module 5: Emission Control for SI Engines


Lecture20:ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
Crankcase Emission Control (PCV System)
A small amount of charge in the cylinder leaks past piston rings into crankcase of the reciprocating
engines. Near top dead centre (TDC) when the rings change their position in the grooves at the end
of compression stroke, combustion has already begun and the cylinder pressures are high. A significant
part of charge stored in the piston- ring-cylinder crevice leaks into the crankcase. These gases are
known as crankcase blow by and their flow rate increases as the engine is worn out and the piston cylinder clearances and ring gaps increase. In the homogeneous charge engines, the crankcase blow by
gas is high in HC concentration. Only a small fraction of the gas stored in the ring crevices and hence
blow by gases may consist of partially burnt mixture. This source contributes about 20 percent of total
hydrocarbons emitted by an uncontrolled car.

Figure
5.6

Schematic of a PCV
system.

The crankcase blowby gases in the uncontrolled engines were ventilated to atmosphere under the effect
of pressure difference occurring naturally between the crankcase and atmosphere. For control of
crankcase emissions, the blowby gases are recycled back to the engine assisted by a positive pressure
drop between the crankcase and intake manifold. When engine is running and intake charge is throttled
the intake manifold is at a lower pressure than the crankcase. The blow-by gases mix with the intake
charge to be burned inside the engine cylinder to CO 2 and H 2 O. A typical PCV system is shown in Fig.
5.6. A tube connects crankcase or cylinder head cover to the intake manifold below throttle valve, which
leads the blowby gases back to the engine. Due to suction effect of intake manifold as the pressure in
the crankcase falls, ventilation air
from the air cleaner is drawn into the crankcase that continuously purges it. A one-way valve (PCV

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valve) is used to control the flow of blowby gases PCV valve restricts flow of blowby gases during idling
and very light loads which otherwise would cause excessive leaning of the charge by ventilation
air.Under normal engine operation, PCV valve is fully open providing free flow of the gases while under
high intake manifold vacuum the flow is restricted.

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Module 5: Emission Control for SI Engines


Lecture20:ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
Evaporative Emission Control
In the uncontrolled vehicles, fuel vapours from the fuel tank and carburettor were vented into the
atmosphere that constituted about 20% of all hydrocarbon emissions from a gasoline passenger car.
From 1970, evaporative emission control was required to be employed on production gasoline vehicles
in the USA.
The evaporative emission control system consists of a device to store fuel vapours produced in
the fuel system due to evaporation.
A canister containing activated charcoal is used to store the fuel vapours.
The vapours produced in the fuel tank normally collect in the fuel tank itself and are vented to
the charcoal canister when fuel vapour pressure becomes excessive. The fuel vapours from the
tank and carburettor led to and adsorbed into the charcoal. In the PFI engines only the fuel tank
is connected to the canister.
When engine is running, the vacuum created in the intake manifold is used to draw fuel
vapours from the canister into the engine. Purging air is sucked through the canister which leads
the fuel vapours from canister to the engine. An electronically controlled purge valve is used.
During engine acceleration additional mixture enrichment can be tolerated and under these
operating conditions the stored fuel vapours are usually purged into the intake manifold.
This system is a fully closed system. A sealed fuel tank filler cap is used and a stable fuel tank
pressure is maintained by the purging process of the canister.
A typical schematic layout of evaporative control system is shown in Fig. 5.7. Given below are some of
the measures adopted to achieve near zero evaporative emissions as required in California;
Sealed fuel tank is kept under vacuum to prevent permeation of fuel through walls of a polymer
fuel tank and leakage of fuel vapours through filler cap.
Fuel tubing made of high density polymer or steel to reduce/prevent fuel permeation.
Better canister technology and more effective activated charcoal.
Employment of refuelling vapour recovery (ORVR) system as during vehicle refuelling maximum
share of fuel evaporative emissions escape..
A carbon trap to arrest the escape of fuel vapours from intake manifold. When the vehicle is
standing and is under hot soak fuel vapours can escape past the throttle body into atmosphere.

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Figure
5.7

Schematic of an evaporative emission control system for a PFI


engine.

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Module 5: Emission Control for SI Engines


Lecture20:ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
Exhaust Gas Recirculation
Effect of addition of diluents to the intake charge for lowering of combustion temperatures and
consequently reducing the formation of NO x has been discussed in Module 2 .The heat capacity of the
exhaust gas is higher than the air as it contains significant amount of tri-atomic gases CO 2 and water
vapours. Therefore, addition of exhaust gas to fresh intake charge has a higher effect in lowering the
combustion temperatures compared to simple leaning of the charge..
EGR is defined as a mass percent of total intake flow:
(5.1)
where

i is the total mass flow into the engine.

Typically, only about 5 to 10 % EGR rates are employed. At higher EGR rates, frequency of partial and
complete misfire cycles increases resulting in unacceptably higher HC emissions and loss in fuel
economy and power. EGR systems are made to operate mostly in the part-load range. These are
deactivated at engine idle, because large amount of residual gas is already present in the cylinder.
Many times the system is deactivated at full throttle conditions as the vehicle rarely operates under
these conditions during city operation.
A schematic layout of EGR system is shown in Fig 5.8. An EGR control valve is used to regulate flow
of EGR depending upon engine operating conditions. The intake manifold pressure or exhaust back
pressure may be used to control EGR rate as these parameters vary with engine load. In the modern
engines, EGR rate is controlled by the engine electronic control unit. A pressure sensor in the exhaust
or intake provides signal to the electronic control module of the engine, which in its turn regulates the
operation of the EGR valve.
Electronically controlled EGR valves actuated by high-response stepper motor are being used on
modern engines. Their fast response during transient operation makes it possible to reduce NO x more
than what is obtained by use of a mechanically controlled EGR valves. Effectively a lower rate of EGR
can be employed to obtain the same reduction in NO x that results in a lower penalty on HC emissions

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Figure 5.8

EGR system mechanically controlled by intake manifold


pressure

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Module 5: Emission Control for SI Engines


Lecture20:ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
Water Injection
Water has been added to the high performance, reciprocating aero SI engines during Second World
War to suppress engine knock. Water addition to intake charge has been investigated by many
researchers to reduce NOx formation. Water addition to intake charge is another form of charge dilution
to reduce combustion temperatures.
Water has been directly injected into intake manifold or used as water-fuel emulsion. Emulsifying
chemicals in about 2 percent by volume are added to form water-gasoline emulsions. The stability of
emulsion may be around a few days. The addition of emulsifiers usually reduces the fuel octane
number. With water addition ranging from 10 to 30% by volume of gasoline, large reductions in NO x are
possible However, high increase in HC is observed although only a slight increase in CO occurs.
Some times a small improvement in BSFC with small addition of water is observed but the BSFC
increases with higher amounts of water addition. This approach has not been found practical due to
harmful effects of water addition as HC and BSFC increase, and corrosion of engine components is also
encountered.

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
The Lecture Contains:
INTRODUCTION TO EXHAUST AFTERTREATMENT
THERMAL REACTORS
Catalytic Reactors
Catalyst
Catalyst Substrate
Palletized Catalysts
Metal Monoliths
Washcoat
Converter Housing
Space Velocity and Converter Size

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
INTRODUCTION TO EXHAUST AFTERTREATMENT
Improvements in engine design and adjustment of engine parameters carried to control engine
emissions were inadequate to meet the first set of stringent emission regulations introduced in the USA
from 1975. Devices were developed to treat exhaust gas for conversion of engine emissions to harmless
gases. Conversion of pollutants present in the exhaust gas is termed as exhaust aftertreatment. Two
basic types of exhaust treatment systems were considered;
Thermal reactors
Catalytic reactors or converters
Initially, thermal reactors for oxidation of HC and CO to CO 2 and H 2 O were developed. However, as
high conversion rates of pollutants could not be obtained in the thermal reactors these did not find
widespread application and very soon
the catalytic converters became
a standard exhaust
aftertreatment device for the spark ignited engine vehicles.

THERMAL REACTORS
If high exhaust gas temperatures are maintained and sufficient free oxygen is present in the exhaust
gases, CO and HC can be oxidized in the engine exhaust system. Oxidation rate of HC can be
estimated by an expression given in Module 2. Thermal conversion efficiency for HC and CO as a
function of temperature is presented in Fig 5.9.

Figure 5.9

Conversion efficiency versus temperature for thermal oxidation


of HC and CO

For 50% oxidation of CO and HC temperatures in excess of 500 and 600 C, respectively are
required.
For conversion of 80 percent, temperatures required are about 600 and 750 C for HC and CO,
respectively.
Residence time in reactor is another is another important variable. At 750 C, conversion of HC
up to 90 percent may be obtained in 100 ms while at 850 C only 50 ms are required. Similarly,
for 90 percent oxidation of CO 250 ms and 70 ms would be necessary at 750 C and 850 C,
respectively.

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The thermal reactors are to be located in the exhaust manifold.


In the conventional spark ignition engines, the gas temperature near the exhaust port may vary from
about 300 C at idle to 900 C at full load. Exhaust gas temperature are higher for rich mixtures and
increase with retard of spark timing. When the exhaust gas flows down the exhaust pipe, it cools at a
rate of about 50 C to 100 C/meter. The design of the thermal reactors has the following features to
ensure adequately high gas temperatures;

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
contd...
The thermal reactor has to be located as close to the exhaust port as possible. In fact, the
exhaust manifold is modified to act as thermal reactor.
Exhaust manifold is made as a two wall design with an air gap in between to reduce cooling of
the exhaust gases. Volume of the manifold is increased to increase residence time for the gases
to undergo oxidation reactions.
Engine is operated rich to obtain high exhaust gas temperature and secondary air amounting to
10 to 20% of air flow to the engine is injected at the port by an engine driven or electrical air
pump. The rate of secondary air injection is controlled so that excessive cooling of the exhaust
gas does not result which otherwise may chill out the oxidation reactions.
Oxidation of 1.0 percent CO in the gases increases gas temperature by about 145 C. Hence, with rich
engine operation and secondary air injection sustained oxidation reactions of HC and CO occur giving
higher conversion compared to lean engine operation when the starting temperatures are lower by
about 100 C. Rich mixture operation and use of retarded ignition timing result in deterioration of fuel
economy. Overall, the thermal reactors provide rather low conversion rates as during city driving
conditions engine operates at part load and exhaust gas temperature are quite low. The thermal
reactors have no effect on NO x emissions.

Catalytic Reactors
Catalytic converters are now a standard fitment to SI engine powered vehicles. The exhaust gas flows
over a bed of catalyst where pollutants are converted to harmless gases. The catalyst lowers the
reaction temperature and hence high conversion rates are obtained compared to thermal reactors. A
catalytic converter consists of the following main elements besides housing;

(i) Catalyst
(ii) Catalyst substrate or support, and
(iii) Intermediate coat or washcoat
Catalyst
The active catalyst material is required to posses the following main characteristics
High specific reaction activity for pollutants
High resistance to thermal degradation
Good cold start performance, and
Low deactivation caused by fuel contaminants and sulphur Other desirable requirements are low
cost.

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
contd....
The oxides of base metals such as copper, chromium, nickel, cobalt etc. have been studied. The base
metal oxides are effective only at higher temperatures. In addition, they sinter and deactivate when
subjected to high exhaust gas temperatures experienced at high engine loads. Their conversion
efficiency is severely reduced by sulphur dioxide produced by sulphur in fuel. The noble metals
platinum (Pt), palladium (Pd) and rhodium (Rh) were found to meet the above mentioned performance
requirements. In practice, only the noble metals are used although these are expensive.
Mixtures of noble metals are used to provide higher reactivity and selectivity of conversion. Following
are typical formulations;
Pt : Pd in 2:1 ratio for oxidation catalysts
(Pt + Pd): Rh in ratio of 5 :1 to 10: 1 for simultaneous oxidation and reduction such as in 3-way
catalysts
Palladium has higher specific activity than Pt for oxidation of CO, olefins and methane. For the
oxidation of paraffin hydrocarbons Pt is more active than Pd. Platinum has a higher thermal resistance
to deactivation. Rhodium is used as a NOx reduction catalyst when simultaneous conversion of CO, HC
and NO x is desired as in the 3-way catalytic converters.
The amount of noble metal used typically varies from about 0.8 to 1.8 g/l (25 to 50 g/ft3) of catalytic
converter volume. For a passenger car the total amount of noble metal in the converter is typically in
the range 0.8 g to 2 g.
The active metal is in a highly dispersed state when impregnated on the surface of the catalyst support.
The size of the noble metal particles on the fresh converter is about 50 nm. However, when used the
noble metal particles sinter and may grow to a size of around 100 nm.

Catalyst Substrate
The active catalyst material is impregnated on the surface of catalyst substrate or support. The function
of catalyst substrate is to provide maximum possible contact of catalyst with reactants. Following are
the main requirements of catalyst substrate:
High surface area per unit volume to keep a small size of the converter
Support should be compatible with coating of a suitable material (washcoat) to provide high
surface area and right size of pores on its surface for good dispersion and high activity of the
catalyst.
Low thermal capacity and efficient heat transfer properties for quick heat-up to working
temperatures.
Ability to withstand high operating temperatures up to around to 1000 C.
High resistance to thermal shocks that could be caused by sudden heat release when HC from
engine misfire get oxidized in the converter.
Low pressure drop
Ability to withstand mechanical shocks and vibrations at the operating temperatures under road
conditions for long life and durability of 160,000 km and longer
The following types of catalysts supports are used;
Pellets
Monolithic supports

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Ceramic monoliths
Metal monoliths

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
Palletized Catalysts
The first catalytic converters introduced in 1970s and used until early 1980s employed spherical ceramic
pellets, which were packed in a catalyst bed. The pellets of 3 to 6 mm dia were made of - alumina
(Al2 O 3 ) The porous surface of alumina pellets provides a large surface area on which the noble metal
salts are impregnated to a depth of about 250 m. The pellet catalysts are loaded with approximately
0.05% by weight of noble metals. A typical pellet type catalytic converter is shown in Fig 5.10.
The gas flow through the packed bed pellet reactors is a mix of axial and radial flow so as to provide
large flow area and reduce flow resistance. The gas flow through pellet bed is turbulent resulting in high
mass-transfer rates. The packed bed catalysts suffer from the following disadvantages:
High pressure drop
Are heavy, have high thermal inertia and hence slow to warm-up.
Loss of catalyst from abrasion due to rubbing of pellets against each other.
Therefore during 1980s the ceramic honeycomb or metallic matrix monolith converters replaced the
pellet type converters.

Pellet type catalytic

Figure 5.10 converter.


Ceramic Monoliths

A ceramic monolith is shown schematically in Fig 5.11. It has parallel flow channels or cells of square or
triangular cross section. The flow through these channels is laminar. The ceramic material commonly

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used is porous cordierite (2MgO. 2Al2 O 3 .5SiO 2 ). The monoliths are characterized by cell density (cells
/in2 or cells/cm2 of monolith cross section area) and wall thickness of the cells. A typical substrates
used during 1980s and 1990s had 400 cpsi (cells /in2 ) and a wall thickness of 6x10 -3 inch (0.15 mm),
and it is designated as 400/6.The unit cpsi used is cells /in2 of cross section area of monolith ( 1 cpsi =
6.45 cells /cm2 ) . In the current vehicles, the ceramic substrates of 600/4 configurations are quite
common. The 900/2.5 and 1200/2 substrates are also being used for special catalytic converters such
as closed-coupled catalysts for cold start and warm-up emission control. With increase in cell density,
geometric surface area (GSA) increases providing more catalyst activity for the same volume of
substrate. However, at higher cell density the cell dimensions get smaller and flow resistance (Rf )
increases. Open front area of the substrate is expressed as percent of cross sectional area
perpendicular to the flow direction and represents actual flow area for gases. Some important
characteristics of ceramic monoliths of different structures are given in Table 5.1. Due to high surface
area, the high cell density substrates provide overall higher emission .reductions.

Figure
5.11

Ceramic monolith catalyst substrate having square


cells.

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
contd...
Table 5.1
Key characteristics of Ceramic Monoliths, Square
Cells

Parameter

Ceramic Cell Density , cells per in2 / wall


thickness,10 -3 in
(cells per cm 2 / wall thickness , mm)
400/6.5
(62/0.17)

600/4
(93/0.10)

900/2.5
(140/0.064)

Substrate diameter, mm

105.7

105.7

105.7

Substrate length, mm

98

76

76

Substrate volume, l

0.86

0.67

0.67

GSA, m2/ l

2.74

3.48

4.37

OFA, %

75.7

81.4

85.6

Rf , litres/cm 2

3074

3990

5412

Substrate mass, g

339

202

156

Metal Monoliths
Metallic monoliths as an alternative to ceramic were introduced to provide high mechanical strength.. In
metallic monoliths, alternate flat and corrugated thin foils of made of high temperature and corrosion
resistant steel containing aluminium, are wound in a spiral shape to form the honeycomb structure. The
foils are about 0.05 mm thick and even thinner foils down to 0.02 mm thickness are now used. The
honeycomb structure is fixed in an outer metal shell called as mantle.. Front view of a metallic monolith
substrate is compared with ceramic monolith in Fig 5.11.
The size of corrugations in the corrugated foil is designed to obtain the required cell geometry and cell
density. Various geometries of corrugations and hence the varying
designs of cell structure are used to enhance turbulence. The coiled foils are coated with a special
brazing material and brazing joins the coil with housing so that it functions as a single unit. The
washcoat is applied to these monoliths mostly after their fabrication into final shape.

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Frontal View of Metallic


Monolith

Ceramic Monolith
Cells
Figure
5.11

Metallic Monolith Cells

Frontal view of a metal monolith and comparison of cell


formation in ceramic and metallic monoliths

The foil thickness of a metallic monolith of 400-cpsi is typically 0. 0.04 to 0.05 mm compared to 0.15 to
0.20 mm for an early 400-cpsi ceramic monolith. A comparison of flow and physical characteristics of
ceramic and metal monoliths is given in Table 5.2. The metallic monoliths in general, have 20 to 30%
higher GSA and 10 to 20 % higher OFA. The mass of metallic monolith is however, about 2 times
higher than the ceramic monolith of the same volume and cell density. The thermal capacity of metallic
monoliths is 15 to 80% higher than the comparable ceramic monoliths. The metallic monoliths however,
have 10 to 15% lower backpressure. A disadvantage with metal monoliths is that these cool down faster
at lower loads and have to be fitted as close to the engine as possible taking into account the peak
temperatures that might occur. The metallic support is non-porous and special techniques to obtain
adherence of wash coat and hence catalyst on the surface have to be employed.

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment

Table 5.2
Comparison of Characteristics of Metallic and Ceramic Monolith Catalyst
Substrates
Metallic
Monolith

Ceramic
Monolith

Wall thickness, mm

0.02 - 0.04

0.06 -0.20

Range of cell density , cells / cm2

16 - 186

16 - 186

OFA (uncoated) for 62 cells / cm2, % cross section

89- 91

67 -75.0

area

3.2

2.4-2.8

Thermal conductivity, W/m.K

14-22

0.1-0.8

Specific Heat capacity, kJ/kg.K

0.4- 0.5

0.75-1.05

Density, g/cm 3

7.4

2.2-2.7

Coefficient of thermal expansion, 1/K

15

Maximum short duration operating temperature, C

1275-1375

1400

Maximum continuous operating temperature, C

900-1150

1200

Mass (105.7 mm dia. x 98 mm length) 62 cells / cm2, g

680

340

Characteristics
Geometric Data

GSA (uncoated) for 62 cells / cm2, m2/l


Physical Data

Metallic monoliths have the following advantages compared to the ceramic monoliths:
Higher mechanical strength
High thermal conductivity and faster warm-up
Higher flow area and lower pressure drop
Higher tolerance to high temperature spikes
Higher conversion efficiency
Smaller size
No special housing is required.

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
Washcoat
Monolithic substrates have a geometrical surface area of 2.0 - 4.0 m2 /l of its volume. This is too low to
provide high contact area between the catalyst and reacting gases for high conversion rates. A thin
layer of -Al 2 O 3 seeded with other oxides as washcoat is
applied to the monolith cells to increase effective surface area for dispersion of catalyst material. About
20 percent of other oxides consisting of cerium oxide (CeO 2 ) and stabilizers such as zirconium oxide
and barium oxide are added to alumina. The washcoat has pores of varying sizes ranging from 0.2 to 1
m. The ceramic monolith walls are porous and surface is rough so that good adhesion of washcoat is
obtained.
High surface area created by Al 2 O 3 washcoat and dispersion of active catalyst deposited by solution
impregnation is shown schematically in Fig. 5.12. Adhesion of washcoat to metallic monoliths requires at
first pre-treatment of surface to make it rough and improve its bonding characteristics with ceramic
washcoat materials. For the prefabricated metallic monoliths then, a procedure similar that for the
ceramic monoliths may be followed.

Conceptual model of catalytic sites dispersed on a high


Figure 5.12 surface-area Al O washcoat.
2 3
The washcoat constitutes 5 to 15 percent of the mass of ceramic monoliths. Its thickness typically
varies in the range 10-30 m on the walls. The washcoat increases actual surface area of the catalyst
substrate to 10000-40000 m2 /l of monolith volume. are added.

Converter Housing
The ceramic monolith is mounted in a metal casing made of high quality corrosion resistant steel. A mat
made of ceramic material around the ceramic monolith holds it tightly inside the casing. The mat
protects the ceramic monolith against mechanical impact and vibrations, and also acts as heat
insulation. The ceramic mat is made of aluminium silicate that expands as it is heated.
As the temperature of mat rises, gas bubbles are formed inside the mat and it ensures proper tightening
of the ceramic monolith in the housing and sealing to prevent any bypass of the exhaust gases. The
metallic monolith converters are easier to mount as the metal mantle that holds the metallic honeycomb
structure is welded or brazed in the exhaust system of the engine.

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Module 5:Emission Control for SI Engines


Lecture21:Engine Exhaust Aftertreatment
Space Velocity and Converter Size
The catalytic converter monolith volume is typically 0.5 to 1 times of the engine swept volume. Space
velocity characterizes the residence time available to gases to undergo chemical reactions in the reactor
bed. The space velocity is inversely proportional to the residence time and is defied as,

(5.2)
In the catalytic converters for SI engines, the space velocity typically reaches up to 50 s-1. Higher the
space velocity that can be used to achieve required conversion rates, smaller is the volume of the
converter required. Higher usable space velocities have been achieved through improvements in the
design of substrate, wash coat and catalyst dispersion technologies.

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Module 5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
The Lecture Contains:
OXIDATION AND 3-WAY CATALYTIC CONVERTERS
Oxidation Catalytic Converters
Reduction and 3-Way Catalytic Converters
3 -Way Catalytic Converters
Oxygen Sensor

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Module 5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
OXIDATION AND 3-WAY CATALYTIC CONVERTERS
Since 1975, in the production gasoline vehicles two main types of catalytic converters have been used:

Oxidation catalytic converters


3-Way catalytic converters.
The catalytic converters for the first time were used to reduce only HC and CO emissions from the US
gasoline passenger cars in 1975. As these converters reduced HC and CO by oxidation, they were
called as oxidation' catalytic converters. NO x emission standards were met by use of EGR at that time.
The engines were operated on rich mixtures and with application of EGR engine out NO x emissions
were reduced. Secondary air was injected in the exhaust system upstream of the converter to provide
sufficient oxygen for oxidation of CO and HC on the catalyst. Later, when the NO x standards were
made stringent from 1981, reduction catalysts were also developed. An exhaust gas oxygen sensor
developed in the early 1980s facilitated engine operation at near stoichiometric mixtures that made it
possible to simultaneously oxidize CO and HC to CO 2 and H 2 O and reduce NO x to N 2 . As all the
three pollutants were converted simultaneously in the same reactor these were termed as 3-way
catalytic converters. T he three-way catalytic converter is presently a standard fitment on most gasoline
passenger cars.
During mid-1990s, gasoline direct injection (GDI) engines with charge stratification were introduced in
the market by two Japanese car manufacturers. During part load city operation, these GDI engines work
as stratified-charge engines with overall very lean air/fuel mixtures. For NO x control in these engines,
lean de-NO x catalytic converters have been developed. The de-NO x x catalysts and other advanced
catalyst systems such as for cold start HC control are discussed later.

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Module 5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
contd...
Oxidation Catalytic Converters
The oxidation catalyst converts CO and HC to CO 2 and H 2 O at substantially low temperatures and at
higher conversion efficiency tan the thermal reactors. The required oxygen for oxidation reactions is
made available either by operating engine lean or by injecting secondary air ahead of the catalytic
converter when engine is operated rich. Vehicles employing the oxidation catalysts were generally
tuned rich for better NO x control and secondary air injection was employed
The conversion efficiency of a catalytic converter is defined as:

Light-Off Tempersature
The catalytic conversion efficiency depends upon the exhaust temperature and its relationship with
temperature is shown on Fig 5. 13. The temperature at which 50% CO or HC conversion is obtained is
defined as the light off temperature. The catalyst light off temperature is desired to be as low as
possible for good emission reduction during actual vehicle operation. . The light off temperature for a
new catalyst varies from about 220 C for CO to 260 - 270 C for HC. With ageing, the catalyst light off
temperature increases. For the first generation catalytic converters, t he temperature of operation was in
the range of 250 600 C and the typical gas space velocity during vehicle operation varied from 3 to
30 s -1 .

Figure
5.13

Conversion efficiency dependence on temperature for an


oxidation catalyst

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Module 5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
Reduction and 3-Way Catalytic Converters
For reduction of NO x , the CO, HC and H 2 which are present in the exhaust during rich engine operation
are made to react with NO x over a catalyst when NO x is converted to N 2 . Possible reactions under
reducing conditions are given in Table 5.3.

Table 5.3
Possible Reactions for Reduction of
NO x

1.

NO + CO

2.
3.

NO + 5CO + 3H2 O 2NH 3 + 5CO 2


2NO + CO N2 O + CO 2

4.

NO + H2

5.

2NO + 5H2 2NH 3 + 2H2 O


2NO + H2 N2 O + H2 O

6.

+ CO 2

+ H2O

A number of catalysts like CuO, NiO, monel etc., were studied for NO x reduction However, their NOx
conversion efficiency being just 25 to 35 % only, they did not find acceptance. Rhodium (Rh) from the
noble metal group has been found to be the most successful reduction catalyst so far and is being used
in actual systems. .
The concentration of NO x being relatively small, only small fractions of CO, HC present in exhaust is
utilized in the reduction reactions. Most of HC and CO is required to oxidized simultaneously or in a
separate reactor.. Initially, separate reduction and oxidation catalyst systems were considered but their
operation was complex, the engine had to be operated rich. Also, some ammonia is generated during
reduction reactions, which is oxidized again to NO in the downstream oxidation reactor. Due to these
reasons, the dual-bed catalysts did not find much acceptance and the 3-Way catalyst was developed
and used on cars around 1980.

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Module 5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
contd...
3 -Way Catalytic Converters
The essential condition to simultaneously oxidize CO and HC and reduce NO x on the same catalyst bed
is to operate engine at very close to stoichiometric air-fuel ratio. Under stoichiometric engine operation,
enough reducing gases CO and HC are present in the exhaust to reduce NO x to N 2 and at the same
time enough oxygen to oxidize CO and HC. Thus, all the three pollutants are removed simultaneously in
a 3-way catalyst. . Dependence of conversion efficiency for the three pollutants on fuel-air equivalence
ratio in a 3-way catalyst is shown in Fig. 5.14 . High conversion rates of over 80% of all the three
pollutants are obtained in a small window of about 0.12 A/F unit width (0.997 < f < 1.005) around the
stoichiometric air-fuel ratio.

Figure
5.14

Conversion efficiency of a 3-way catalytic converter as


a function of air-fuel ratio.

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Module5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
contd...
A closed loop feedback controlled fuel management system is used for precise control of air-fuel
ratio. A simple closed-loop feed back engine fuel management system is shown schematically in
Fig. 5.15.
An oxygen sensor installed in the exhaust system detects presence of free oxygen in the exhaust
gas which determines whether the fuel-air mixture is leaner or richer than stoichiometric.
The signal from the oxygen sensor is fed to a microprocessor controlled fuel management system
to adjust fuel injection rate so that the engine operates in a narrow window around the
stoichiometric set point.
Fuel-air ratio oscillates around the set point at a frequency of 0.5 to 1 Hz as the fuel flow is
varied.
Signals of air mass flow rate, engine load, speed, spark timing temperatures and several other
parameters are also fed to the engine electronic control unit for management of engine operation.
Carburetors were found to be incompatible with such control systems although initially electronically
controlled carburetors were developed and used. Now, multipoint port fuel injection system is a standard
feature of engines using 3-way catalytic converters.

Figure 5.15

A simple closed-loop feedback control system for


air/fuel ratio control

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Module 5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
contd....
Modulation of F/A Window
Oscillations in fuel flow rate around the set point widen considerably the F/A window, thereby adversely
affecting the conversion efficiency. To maintain high conversion efficiency for all the three pollutants, the
adverse effect of these oscillations in F/A ratio is countered by use of an oxygen storage/release system
in the catalyst wash coat. Components like cerium oxide (CeO 2 ) and zirconium oxide (ZrO2 ) are
added to the washcoat. CeO2 acts as oxygen storage system and widens the air-fuel ratio window
when high conversion rates of all the three pollutants are possible. CeO2 undergoes the following
chemical changes as the mixture transits from rich to lean and back due to variations in fuel-flow rate.
Rich Operation:

(5.4)
Lean operation:

(5.5)
During fuel rich operation, CeO2 releases oxygen for oxidation of CO and HC and in the process gets
itself reduced to Ce2 O 3 When the engine operation becomes lean as a result of control of fuel flow by
engine fuel management system, Ce2 O 3 gets oxidized back to CeO2 by reacting with excess O 2 or NO.
These reduction-oxidation (Redox) reactions in cerium oxide continue and effectively even in a wider
F/A (nearly 0.06 F/A ratio) widow high conversion efficiency of all the three pollutants is obtained.

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Module 5:Emission Control for SI Engines


Lecture 22:Oxidation and Three Way Catalytic Converters
Oxygen Sensor
The exhaust gas oxygen sensor (EGO) also called, as -sensor' or lambda sensor' is used to control
air-fuel ratio within about 1% of stoichiometric value for operation of 3-way catalysts. The sensor is
fitted in the exhaust pipe just upstream of the catalytic converter. EGO operates on the principle of
electro-chemical cell. Lambda-sensor is used to detect the presence or absence of free oxygen in the
exhaust gas. Typical construction of an EGO is shown in Fig 5.16. Solid zirconium oxide (ZrO2 )
stabilized with yttrium oxide (Y2 O 3 ) is used as electrolyte. The outer and inner surfaces of the hollow
cylindrical are coated with porous platinum to form inner and outer electrodes. The outer electrode is
exposed to the exhaust gas while the inner electrode to air having a fixed oxygen concentration. Due to
catalytic effect of platinum electrode the exhaust gas reaches equilibrium composition very rapidly.. The
electrochemical reactions at the electrodes produce oxygen ions that carry current through solid
electrolyte producing a voltage signal. The e.m.f. voltage, e 0 produced is a function of the ratio of
partial pressures of oxygen at the two electrodes and is given by Nernst equation (Eq 5.6) :

where R is the universal gas constant, T is sensor temperature in K, F is Faraday constant equal to
9.649 x 10 7 C/kmol,

and

are partial pressures of oxygen in the reference gas and the

sample, respectively.
The partial pressure of oxygen in the exhaust gas increases by many orders of magnitude (from about
10 -20 to 10 3 P a at 500 C) as the fuel equivalence ratio varies from 1.01 to 0.99 . The effect of fuel
air equivalence ratio on sensor output signal is shown on Fig. 5.17. The sensor output voltage increases
rapidly during transition from lean to rich mixture. For rich conditions a voltage of about 800 mV is
produced and for lean mixtures about 50 mV is generated. The stoichiometric point is set at about 0.5
V. Voltage signal lower than the set point is taken by the engine control unit as lean mixture and higher
voltage signal as the rich operation.

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Module 5:Emission Control for SI Engines


Lecture23:Advanced Catalysts for HC Control

(a)

Figure 5.16

(b)

(a) an unheated oxygen sensor (b) heated oxygen sensor


(HEGO)

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Figure 5.17

Oxygen sensor output voltage as a function of fuelair equivalence ratio

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Module 5:Emission Control for SI Engines


Lecture23:Advanced Catalysts for HC Control
contd...
The temperature of sensor electrolyte affects its conductivity and hence the output voltage. The
optimum operation temperature for the oxygen sensor is between 300 and 600 C. During engine warmup the unheated EGO sensor is not operative. Electrically heated exhaust gas oxygen (HEGO) sensors
are therefore used.
For meeting ULEV emission requirements, the performance of 3-way catalyst is to be further
improved and oscillations in air-fuel ratio are to be minimized. For this, a new sensor which measures
actual oxygen content in the exhaust and the engine control unit responds gradually to the changes in
air-fuel ratio is used. This sensor is known as universal exhaust gas oxygen (UGEO). With the use
UEGO, a better control of air-fuel ratio is obtained and 3-Way catalyst operates in a very narrow
window of high conversion efficiency (Fig 5.18).

Figure
5.18

Comparison of fuel- air ratio window of operation


for UEGO and HEGO

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Module 5:Emission Control for SI Engines


Lecture23:Advanced Catalysts for HC Control
The Lecture Contains:

Catalytic Converters for Cold Start HC Emission Control

Electrically Heated Catalysts


Close-Coupled Catalysts
Hydrocarbon Adsorber /Trap Systems

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Module 5:Emission Control for SI Engines


Lecture23:Advanced Catalysts for HC Control
ADVANCED CATALYTIC EXHAUST AFTERTREATMERNT
Catalytic Converters for Cold Start HC Emission Control
Figure 5.19 shows HC emissions on US EPA cycle beginning from the instant when the engine is
started from cold. Also, the LEV and ULEV HC limits are shown on this figure.

Figure
5.19

HC emissions during cold start in US FTP cycle. LEV and


ULEV emission limits are alsoshown.

From this figure it is observed that;


About 60 to 80% of total US FTP cycle HC emissions are produced during the first 2 minutes of
vehicle operation after cold start.
To meet LEV standards catalyst should become functional within 80 seconds
For ULEV limts the catalyst should become functional within 50 seconds
Electrically heated catalysts (EHC)
Close-coupled catalysts
Hydrocarbon traps

Electrically Heated Catalysts


The converters can be electrically heated before the engine started. In the metallic monoliths, metal
honeycomb itself has been used as a heating element. Use of thin steel foils reduces thermal capacity
of the catalyst. However, electrical heating still requires considerable energy to be drawn from the
battery particularly in cold climates. Under cold ambient conditions the batteries are subjected to very
high power drain. This becomes more difficult proposition as at the low ambient temperatures the
battery activity is low and a high amount of energy is also required to crank and start the engine.

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Module 5:Emission Control for SI Engines


Lecture23:Advanced Catalysts for HC Control
contd....
Close-Coupled Catalysts
A rapid catalyst light off is achieved by installing the converter very close to the engine to minimize heat
losses from the exhaust gases as shown on Fig. 5.20. The catalysts installed so close are called closecoupled' catalysts. These catalysts have the following features;
The close-coupled catalysts are designed mainly for oxidation of HC.
In the close-coupled catalysts, CeO2 is removed from the substrate washcoat as. CeO2 has
excellent properties for oxidation of CO.
The closed coupled catalysts have a small volume to improve light-off characteristics.
These are designed to oxidize only part of HC and little CO so that generation of very high
temperatures in the catalyst bed is prevented.
HC oxidation in thee close-coupled catalyst raises the exhaust gas temperature so that the main
under floor catalyst becomes operational rapidly within a short time. The under-floor catalyst
mounted downstream converts the remaining HC and, also the CO and NO x .

Figure
5.20

Schematic of exhaust system fitted with closed coupled


catalyst

The main 3-way catalyst is installed sufficiently down stream of the exhaust manifold under the floor of
the vehicles. These are also termed as underfloor catalytic converters'. The converters should not be
exposed to excessively high temperatures during full engine load conditions and steep accelerations
when the initial exhaust gas temperature at the inlet of the converter itself are quite high. During
accelerations the unburned HC and CO concentrations are higher than the cruising conditions and their
oxidation in the converter to achieve typically more than 90% conversion releases high amounts of
energy that raises the gas temperatures substantially. However during engine cold start and warm-up
conditions, the underfloor catalyst does not function as the gas temperatures are low and it also cools
down as it flows from the exhaust port to the converter. With implementation of ULEV and US Tier 2
standards, HC emission control under engine cold start and warm-up operation are also required.
To reduce HC and CO emissions under cold engine conditions mew types of converters have been
developed. For the direct injection stratified charge (DISC) engines, NOxemissions under over all lean
engine operation are to be controlled. As the 3-way catalysts do not control NOxunder lean engine
operation, new types of catalysts to reduce NOX for lean mixture operation have been developed.

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Module 5:Emission Control for SI Engines


Lecture23:Advanced Catalysts for HC Control
contd...
Hydrocarbon Adsorber /Trap Systems
A closed coupled catalyst needs up to 40 seconds to become operational after cold start and hence,
considerable portion of the engine out emissions escapes the closed coupled catalyst. A more
advanced system has been developed that adsorbs and stores HC on an adsorbent which are released
once the catalyst downstream reaches the light off temperature. A typical HC adsorption-release cycle is
shown on Fig 5.21.

Figure
5.21

HC adsorption and release


cycle for a HC trap

Typical layouts of the hydrocarbon adsorber/trap and main catalysts are shown in Fig 5.22 .

Figure
5.22

A schematic layout of exhaust system with


hydrocarbon trap and main catalyst.

In another design, the hydrocarbon adsorber and the oxidation catalyst are integrated in one unit. This

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is followed downstream by the main catalytic converter for reduction of emissions under normal engine
operation. In another advanced configuration of the integrated adsorber-catalyst system, double layered
catalyst structure is coated on a cordierite substrate. The catalyst structure is shown schematically in
Fig 5.23. The HC adsorbent is coated as the bottom layer close to the substrate and the normal 3-way
catalyst as the upper layer. Under low temperatures the HC are adsorbed and released and get
oxidized as the catalyst gets heated. However, under normal operation the adsorber being at higher
temperature it does not absorb HC and all the emissions are converted in the main 3-way catalyst
system.

Figure 5.23

A two layer configuration of HC adsorbent and 3-way


catalyst loaded on the same ceramic substrate.

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Module 5:Emission Control for SI Engines


Lecture 24:Lean de-NOx Catalysts and Catalyst Poisoning
The Lecture Contains:
Lean de-NO x Catalysts
NO x storage-reduction (NSR) catalyst
SCR Catalysts
CATALYST DEACTIVATION
Catalyst Poisoning

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Module 5:Emission Control for SI Engines


Lecture 24:Lean de-NOx Catalysts and Catalyst Poisoning
Lean de-NO x Catalysts
The gasoline direct injection (GDI) engine operating in stratified charge mode is a a lean-burn sparkignited engine that gives 20 30% higher fuel efficiency compared to the conventional stoichiometric
engine The diesel engines also operate with 40% or more excess air. The 3-way catalytic converter
cannot provide NO x reduction in the lean burn SI and the diesel engines. Lean de-NO x catalyst
technology has been developed to meet the needs of these engines. Two main types of lean de-NO x
catalyst technology are;
NOx storage-reduction (NSR) catalyst or NO x trap
Selective catalytic reduction (SCR)

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Module 5:Emission Control for SI Engines


Lecture 24:Lean de-NOx Catalysts and Catalyst Poisoning
contd...
NOx storage-reduction (NSR) catalyst
In the NSR catalysts NO x is trapped under oxygen-rich conditions in an alkaline earth material like BaO
which is incorporated in the noble-metal containing washcoat of 3-way catalyst. The NO x trap concept
is shown schematically in Fig. 5.24 .

Figure
5.24

Schematic of a NSR
Catalyst (NO x trap).

NO is first converted to NO 2 over Pt catalyst from the oxygen rich exhaust

(5.7)
The NO 2 is temporarily stored on alkaline metal oxide BaO forming its nitrate,

(5.8)
The trap is saturated with NO x in about 60 seconds. A precisely controlled spike of rich mixture is then
supplied to the engine so that HC and CO in significant amounts are present in the gases. The required
rich mixture for SI engine may be obtained by the
synchronized control of fuel injection pulse width. The stored NOx is reduced by the HC and CO) during
a short period of about a second.. The NO x reduction takes place on a noble metal catalyst.

(5.9)
Lean NO x traps have high conversion efficiency in a relatively narrow temperature range of 350 450
C. However, different vehicle operating modes produce widely differing exhaust gas temperatures and
the overall conversion efficiency of NSR catalysts is 30 to 35% only. Another problem is poisoning of
the trap by fuel sulphur. Fuel sulphur of less than 5 ppm is necessary for operation of NSR catalysts.

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Module 5:Emission Control for SI Engines


Lecture 24:Lean de-NOx Catalysts and Catalyst Poisoning
SCR Catalysts
Selective reduction catalysts applied in SI engines work on the principle of direct reduction of NO x by
hydrocarbons injected into exhaust stream. In the diesel engines the SCR system uses ammonia
produced from urea is used as the reducing agent or reductant'. The urea SCR systems would be
discussed in detail in Module 6. In the lean-mixture environment, NO x may be reduced by HC as per
the following reaction:

(5.10)
The exhaust gas stream should have right type of HC in right concentrations to complete the above
reaction and reduce nitrogen oxides. Propane is effective at around 500 C and ethylene at 160-200 C.
Zeolites like Cu/ZSM-5 have been studied as SCR catalysts. However, these catalysts are sensitive to
water vapour and sulphur dioxide, and hence so far, have had only a limited success.

CATALYST DEACTIVATION
The automotive catalysts in the USA are required to meet the emission standards for 192,000/240,000
km. of life, The fresh catalysts while meet the standards but during vehicle operation their conversion
efficiency deteriorates due to ageing and poisoning effects by the contaminants that may come from fuel
or engine lubricating oil that burns in the cylinder. The catalyst is subjected to high temperatures
exceeding 900 C, thermal shocks and mechanical vibrations. Contaminants originating from fuel that
cause serious catalyst poisoning, are sulphur and lead (now the gasoline is free of lead), and from
lubricating oil are zinc and phosphorous compounds.

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Module 5:Emission Control for SI Engines


Lecture 24:Lean de-NOx Catalysts and Catalyst Poisoning
contd..
The catalyst deactivation causes ;
Increase in light off temperature, and
Decrease in maximum conversion efficiency
Two types of catalyst of deactivation are encountered in practice:
Catalyst poisoning
Thermal deactivation

Catalyst Poisoning
The contaminants can poison the catalyst in the following manner:
Deposition on the active catalyst sites chemically reacting with catalyst
Accumulation of the contaminants on the outer surface of the catalyst physically restricting
contact of the exhaust gases with the catalyst. This is termed as blanketing effect'.

Figure 5.25

Effect of lead poisoning on a 3-way


catalytic converter.

Lead as tetra ethyl lead was used for many years as antiknock additive in gasoline. Lead oxides and
other lead compounds formed during combustion cause very rapid degradation of the catalyst
performance. About 10 to 30 percent of the lead in the fuel gets deposited on the catalyst sites and
catalyst washcoat. A typical effect of lead on the conversion efficiency of a Platinum/Rhodium 3- way
catalyst is shown on Fig. 5.25. A lead deposition of about 0.5 % of catalyst weight causes 50% drop in
the conversion efficiency. Now, the gasoline almost all over the world is lead free.
Sulphur naturally occurs and is present in small amounts in petroleum fuels It causes catalyst
poisoning, Pd being more sensitive than Pt and Rh.. In a test, after 160,000 km vehicle operation fuel
with sulphur of 575 ppm increased the catalyst light off temperature to 299 C from 277 C with 40 ppm
sulphur fuel.
Zinc and phosphorous additives used in lubricating oil get converted to oxides during combustion and
form zinc pyrophosphate glaze over large areas of the catalyst surface,

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which seals the passage of exhaust gas to the catalyst sites. Silicon coming from contamination of fuel
clogs the protective sheath of the sensor restricting the diffusion of gases to the surface of the sensor
element. It affects the response of oxygen sensor which adversely affects conversion efficiency of the
closed loop controlled three-way catalysts.

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Module 5:Emission Control for SI Engines


Lecture 25:Thermal Catalytic Deactivation, Summary of SI Emission Control
The Lecture Contains:

Thermal Deactivation

Summary of SI Engine Emission Control

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Module 5:Emission Control for SI Engines


Lecture 25:Thermal Catalytic Deactivation, Summary of SI Emission Control
Thermal Deactivation
During normal city driving, exhaust temperatures are normally below 600 C. However, overheating of
catalyst may occur due to engine malfunction such as ignition failure, misfire or excessively rich
operation. The very high concentration of unburned hydrocarbons in exhaust when oxidized in converter
leads to excessively high catalyst bed temperatures. When the catalyst is exposed to temperatures
above 900-1000 C, loss in catalyst surface area and loss in dispersion of catalyst particles due to
sintering are obtained. Ignition failure for about 20 seconds may completely destroy the catalyst.
Sintering caused by high temperatures results in;
Under high temperatures, the catalyst particles migrate, coalesce or atoms in vapour phase get
transported from smaller particles to larger particles. These process form large particles by
combination of several small catalyst particles. Thermal sintering of the catalyst particles reduces
catalyst activity.
As the temperature increases to 1200 C,

-alumina changes to

-alumina resulting in

washcoat shrinkage, loss of micro-pores and reduction in catalyst surface area by a factor of 10.
The catalyst particles are also trapped inside the collapsed pores which then are unable to come
into contact with the gases.
Thermal deactivation increases light off temperature. After ageing at 730 C, the catalyst had a
surface area of 21.5 m2 /g of washcoat that reduced to 11.4m 2 /g after ageing at 1000 C. The
corresponding light off temperatures were about 250 and 320 C, respectively.

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Module 5:Emission Control for SI Engines


Lecture 25:Thermal Catalytic Deactivation, Summary of SI Emission Control
contd..
The sintering of precious metal and wash coat are shown schematically on Fig. 5.26

Figure
5.26

..

Conceptual representation of sintering of noble metal and


washcoat material and masking of catalyst sites by
contaminants

For the ceramic monolith catalytic converters, the temperature limit during 1990's was about 900 C.
Improvements in the washcoat technology and use of metallic monoliths has raised this limit to around
1050C . The correlation of different deactivation mechanisms of 3-way catalysts with operating
temperature is summarized in Fig. 5.27 . The preferred operating range of the catalysts has gone up
from 400 700 C in 1980s to a maximum temperature of 1000 C in 1990s through development of
better washcoat and catalyst formulations. The catalytic converters now are being mounted very close to
the engine for cold engine emission control and hence higher catalyst temperatures Development of
new substrate materials like SiC has contributed to catalyst operation at much higher temperatures than
before.

Temperature,
C

Effect on Catalyst

1700

High Temperature Ceramic melts

1500

Standard Cordierite Monolith Melts

1400
Cordierite phase changes to Mullite
1300

Washcoat deterioration ? Alumina


changes to a Alumina

1100

900

Pt-Pd alloy forms in oxidizing A/F


Diffusion of Rh2O3 in Al 2O3 ,

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Alumina begins

sintering

800
Pt-Pd and Pt-Rh alloy forms in
Reducing A/F
700

Platinum sinters
Reaction of Zn and P with
washcoat

500

300

Catalyst Light-off

100

Figure
5.27

Summarized view of effect of operating temperature on


functioning and deactivation of 3-way catalysts

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Module 5:Emission Control for SI Engines


Lecture 25:Thermal Catalytic Deactivation, Summary of SI Emission Control
Summary of SI Engine Emission Control
The emission control technologies adopted since the emission standards were implemented for the
first time in the USA are summarized in Table 5.4.

Table 5.4
Summary of Developments in Emission Control Technology for Gasoline
Passenger Cars

Year

Model

Technology

1963

Positive crankcase ventilation (PCV) system

1968

Evaporative emission control

1973

EGR, Secondary air injection, Thermal reactor, Spark advance ontrol

1975

Oxidation catalytic converter for CO and HC, Lead-free gasoline

1977

4-Valve combustion chambers

1981

3-Way catalysts for control of CO, HC and NO x , -sensor, and electronic


control

1988

Variable valve timing and lift, VVT, Honda VTEC

1990

Port fuel injection (PFI) universally adopted, death of carburetor

1994

Onboard Diagnostics (OBD) systems

1996

First DISC engines by Mitsubishi and Toyota, de-NO x catalysts

1999

Phasing in of LEV standards, closed-coupled catalysts

2004

HC- adsorber/traps catalysts, thin wall substrates

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Module 5:Emission Control for SI Engines


Questions
(5.1) What is the significance of space velocity of a catalytic converter? A gasoline car powered by
a 1.2 litre swept volume engine is fitted with a catalytic converter of 1.2 litre. The maximum
speed of the engine is 5,500 rpm and when operating at maximum load it has volumetric
efficiency of 0.8. Taking inlet conditions as 100 kPa, 300K and stoichiometric mixture,
calculate the maximum space velocity encountered in the converter if the exhaust gas enters
the catalyst at 500 K. Take gasoline as octane.
(5.2) In the above converter, exhaust gas with 1.2% CO and 1000 ppmC1 HC enters. If
conversion efficiency of the converter is 90 % for CO and HC, estimate increase in the gas
temperature under steady state operation of the engine and converter. The LHV of gasoline
is 44 MJ/kg and of CO is 10.1 MJ/kg. The specific heats of gases are: N 2 = 33.75, O2 =
35.59, CO2 = 55.37, H 2O = 44.94 kJ/kmol.K
(5.3) In a gasoline car exhaust gas with 9.0, 0.8 and 0.6 g/km of CO, HC and NOx enters the 3way catalytic converter. During city trip of 15 km for the first 1.5 km the exhaust gas
temperatures being low the catalyst has overall only 20% conversion efficiency. For the
remaining trip, efficiency of conversion is 85%. Find the average vehicle emissions for the
trip in g/km.
(5.4) An inventor claims that he has developed a non-catalyst thermal reactor when fitted in the
exhaust muffler converts HC and CO by 50%. Under the full engine load peak combustion
pressure are about 40 bar and temperature is 2500 K. Under the other conditions the peak
combustion temperatures and pressures would be lower than these. The exhaust blows
down to 1.1 bar pressure. The polytropic index of expansion process is about 1.28. As the
gas flows through the exhaust pipe its temperature falls by 50% when it reaches the exhaust
muffler. The residence time for the exhaust gas in the muffler is 100 ms. In view of the
above information verify the acceptability of these claims.
(5.5) An engine misfires and HC concentration in the exhaust gas suddenly rises to 50,000
ppmC1. Estimate the extent of sudden increase in the gas and catalyst temperatures for a
ceramic monolith converter. The converter volume is 0.85 litre, mass 340 g, specific heat is
0.9 kJ/kg. K.
(5.6) If the engine in Problem 5.5 is fitted with metal monolith converter of the same size having
mass of 680 g and specific heat of 0.5 kJ/kg.K what would be the maximum temperatures
reached. Assume the unburned HC are like gasoline in composition and have the same LHV
as given in Problem 5.2.
(5.7) For cold start emission control discuss the advantages and disadvantages of the closed
coupled catalysts, electric heated catalysts and HC traps.

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Module 6:Emission Control for CI Engines


Lecture 26:An Overview of CI Engine Emission Control
The Lecture Contains:

EMISSION CONTROL IN CI ENGINES


AN OVERVIEW OF CONTROL OF CI ENGINE EMISSIONS

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Module 6:Emission Control for CI Engines


Lecture 26:An Overview of CI Engine Emission Control
AN OVERVIEW OF CONTROL OF CI ENGINE EMISSIONS
For emission control in the CI engines, usually called as the diesel engines the following are important;
CI engines emits pollutants in solid (soot), liquid (poly aromatic hydrocarbons, fuel and oil
components, sulphur acids) as well as those in gaseous (CO, HC, NO x ) state.
Emissions of nitrogen oxides and particulate matter from diesel engines are of main concern.
Emission regulations do have limits for CO and HC as well from the CI engines, but
concentration of their emissions is rather small and these have been relatively easy to control
through improved engine and fuel system design.
NO x - PM trade off (discussed in Module 2) governs selection and optimization of many engine
design variables e.g, injection timing, injection pressure, boost pressure etc as change in some
engine variables may although causes reduction in NO x but increases PM and vice versa.
Engine design changes to reduce NO x emissions many a times result also in higher brake
specific fuel consumption (BSFC). This is important as the emissions of the greenhouse gas,
CO 2 are also to be reduced.
The development efforts like for the SI engines have been focused on reduction of engine-out
emissions and treatment of the exhaust gases. Improvements in fuel quality also have been made to
meet the needs of advanced emission control technology.
In CI engines, mixture formation and combustion is heterogeneous and complex in nature. It is
governed by;

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Module 6:Emission Control for CI Engines


Lecture 26:An Overview of CI Engine Emission Control
contd...
Mixture formation which depends on interactions between the injection spray, air motion and
combustion chamber geometry.
Air motion swirl, squish etc,
Injection spray formation -precise control of fuel injection process is necessary for formation of
the desired spray and fuel atomization.
Combustion chamber type- Indirect Injection or Direct Injection. The indirect injection engines are
being phased out of production due to their poor fuel efficiency.
Intake boost pressure
Turbocharging especially with variable boost pressure coupled with EGR results in substantial
reductions in both the NO x and PM.
Exhaust aftertreatment such as diesel particulate filter (DPF), diesel oxidation catalysts (DOC),
selective catalytic reduction (SCR) of NO x etc., are already in use.
An overview of various technologies and direction of research and development which have been
pursued to control NO x and PM emissions from the CI engines are presented in Figs. 6.1 and 6.2
respectively.

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Module 6:Emission Control for CI Engines


Lecture 26:An Overview of CI Engine Emission Control
contd....

Figure 6.1

An overview of NO x reduction
techniques in CI engines

The technologies used for control of PM emissions are presented on Fig. 6.2.

Figure 6.2

An overview of PM reduction
techniques in CI engines

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR
EMISSION CONTROL BY ENGINE VARIABLES AND EGR
The Lecture Contains:

FUEL INJECTION VARIABLES


ELECTRONIC FUEL INJECTION (EFI) SYSTEMS

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR

EMISSION CONTROL BY ENGINE VARIABLES AND EGR


FUEL INJECTION VARIABLES
Demands Made on Injection System
To achieve low soot formation, rates of fuel-air mixing are to be enhanced. Fuel injection and air motion
in the cylinder are key parameters to achieve rapid fuel-air mixing. The following strategy is adopted to
improve fuel air mixing and the diesel engine combustion, which leads to reduction both in the soot and
NO x formation:
Use of high fuel injection pressures and smaller nozzle hole size to produce very fine fuel
atomization for rapid fuel evaporation and mixing with air.
Fuel spray not to impinge on walls but fuel to be distributed mainly within the air inside the
combustion chamber.
Matching of injection spray configuration and development with in-cylinder air motion for rapid
fuel-air mixing throughout the injection duration period
Use of variable injection timing, multiple injection and injection rate shaping technology
High Injection Pressures
The mass flow rate of fuel injected, mf is given by:

, kg / cycle

(6.1)

where C d is coefficient of discharge, An is nozzle flow area in m2 , f is fuel density in kg / m3 , (Pinj Pcyl ) is the pressure drop across nozzle orifice in Pascals, is the injection duration in degrees crank
angle and N is the engine speed in RPM.
Generally, Pinj >> Pcyl .,
Thus, for a given injection rate

and injection duration in crank angles, the injection pressure

should vary with speed as,

(6.2)
The speed of engines for road vehicles from lowest working speed to rated speed may vary by a
factor of; N max/Nmin = 4 to 5..To achieve similar injection duration and spray penetration from the lowest
to rated engine speed, the injection pressure therefore, is required to vary by a factor of 16 to 25. This
of course is not possible in practice but it has led to use of as high an injection pressure as possible. In
the pre-1990 engines,

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR
contd...
maximum injection pressures were limited to about 700 bars. Since then, the injection pressures have
increased to a value exceeding 2000 bars. Modern electronic fuel injection systems employing unit
injectors, common rail systems etc. provide use of very high injection pressures.
The beneficial effects of high injection pressure are;
Improved fuel atomization producing finer fuel droplets.
The smaller fuel droplets evaporate at a faster rate resulting in rapid fuel-air mixing.
A shorter injection duration
With shorter injection duration injection timing may be retarded. Fuel may now be injected closer
to TDC in hotter air giving shorter ignition delay, resulting in emission benefits
Higher spray penetration and better air utilization.
The effect of peak injection pressure on PM-NO x trade off is shown on Fig. 6.3. The width of band on
this figure relates to the contribution of lubricating oil to the particulate emissions. With increase in peak
injection pressure, the PM-NO x trade-off curve moves closer to origin indicating reduction both in the
PM and NO x , although the reductions in PM at a given NO x level are more obvious as seen in Fig 6.3
.

Effect of peak injection pressure on PM-NOx trade-off for a

Figure 6.3 turbocharged, inter-cooled, DI diesel engine.


Injection Rate Shaping and Multiple Injection
NO x formation is influenced by
(i)
(ii)
(iii)

duration of ignition delay,


amount of fuel injected during delay period, and
the rate of mixture preparation within the combustion chamber.

The shape of ideal rate of injection curve during ignition delay and the main injection period depends on

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engine load and speed. General principles of fuel injection scheduling are;
rate of fuel injection within the delay period must be kept small to reduce the amount of fuel
burned during pre-mixed combustion phase, and
during the main injection period, rate of injection should be increased steeply to inject fuel within
a short period when the temperature and pressure in the combustion chamber are high for rapid
combustion of the injected fuel.

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR
contd....
The pilot injection is a form of multiple-injection with two injection pulses. In the pilot injection, a small
quantity of fuel (about 10% of fuel per cycle) is injected 3 to 10 crank angle degrees before the main
injection event. The pilot-injected fuel has more time to undergo precombustion reactions .When the
main fuel injection is made, the combustion begins soon after, resulting in a short delay period. As the
pilot fuel quantity injected during delay period is rather small, the peak rate of combustion pressure rise
and peak pressures are reduced. Typical pilot injection strategy and cylinder pressure are shown on
Fig. 6.4.

Pilot injection, injector needle lift and combustion pressure

Figure 6.4 traces in a naturally aspirated diesel engine at low loads.

With pilot injection, the injection timing of main fuel can be retarded to give low NO x emissions without
adversely affecting the engine power and fuel efficiency. Also, with pilot injection less fuel burns as
pre-mixed and a larger fraction of fuel burns in diffusion combustion mode. In the normal engine, NO x
reduction is obtained by retarding the injection timing which results in higher smoke and PM emissions,
and higher BSFC. Results with pilot injection and conventional engine with retarded injection are
compared in Table 6.2. At the same NO x emission levels of 5.5 g/kWh, with pilot injection typically 23 %
lower PM, 50% lower HC and 4 % lower BSFC were obtained.

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR
contd...

Table 6.2
Comparison of Performance and Emissions of Pilot Injection and
Conventional
Injection with Retarded
Timing

Conventional Retarded Injection Timing

Pilot Injection

NO x , g/ kW-h

5.5

5.5

PM, g/kW-h

0.58

0.45

HC, g/kW-h

2.57

1.25

249

238

BSFC, g/kW-h

ELECTRONIC FUEL INJECTION (EFI) SYSTEMS


Electronically controlled fuel injection systems have the capability to fulfill the ideal injection rate
requirements,. The EFI also are capable of providing multiple injections. Electronically controlled diesel
fuel injection systems have the following advantages over the mechanically controlled injection systems
as they provide:
Very high injection pressures exceeding 2000 bar
Precise control of injection timing.
Precise fuel metering to control power output and limit smoke.
Extremely low cylinder to cylinder variation in the quantity of fuel injected.
Injection rate shaping with controlled initial rate of injection to reduce noise and emissions
Sharp end-of-injection to eliminate nozzle dribble, prevent nozzle fouling and, reduce smoke and
hydrocarbon emissions.
Injection rate shaping for controlling heat release rates during pre-mixed and diffusion
combustion phases for controlling smoke and NO x formation.
Electronically controlled unit injectors, distributor pumps and common rail injection systems are in use.
Electronic Unit Injectors
In the electronic unit injectors (EUI) the injection pumping element that raises the fuel to injection
pressure and the injector nozzle are integrated into one unit. One each of the EUI is directly mounted on
every engine cylinder. The injection pump plunger of every EUI is driven directly by the engine camshaft
via a rocker arm. The electronic unit injectors were introduced on heavy-duty diesel truck engines in the
USA around 1990 as these could develop much higher pressures than the in-line mechanical injection
systems. A EUI design is shown in Fig. 6.5. In this design, metering of the fuel delivery is done by the
plunger and the injection timing is controlled by opening and closing events of the solenoid valve of the
EUI. Normally, the fuel from the plunger bypasses the solenoid valve and the fuel goes back to the
return fuel line. As soon as the solenoid valve closes the fuel bypass passage, a high pressure is
generated in the fuel passage above the

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR
contd...
injector nozzle and the fuel is injected. Opening of the solenoid valve releases the fuel pressure and the
injection ends. Another design of EUI developed by Cummins Engine Company, Inc. consists of two
plungers in the same unit injector, one controls injection timing and the other controls the injection
quantity. As the dead volume between the pumping plunger and injector nozzle is very small, very high
injection pressures can be used with a high reliability and injection efficiency. Operation of the EUI at
more than 2500 bars has been demonstrated.

Figure
6.5

A typical electronic unit injector for


high pressure.

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The EUI can be used to provide pilot injection. A constant fuel temperature at each injector must be
kept so that each injector delivers the same mass of fuel to each engine cylinder. A number of sensors
provide input data on the engine speed, load, camshaft position, inlet manifold air temperature and
pressure, coolant temperature etc., to the electronic control unit (ECU) for control of fuel injection
quantity and injection timing. For small high-speed diesel engines, EUI is not employed due to its large
size and high cost. Instead, electronic distributor pumps are used. Now, the common rail injection
systems are finding wider application in the small size, high speed multicylinder diesel engines.

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR
contd...
Common Rail Diesel Injection (CRDI) Systems
In the common rail systems, the high fuel pressure is generated by a common pump that is separate
from the injectors. The fuel pressure is independent of engine speed and load. A typical layout of the
common rail systems is shown in Fig. 6.6.The CRDI has four main components;
(i)

high-pressure pump

(ii)

high-pressure distribution rail (common rail) and pipes

(iii)

injectors, and

(iv)

Electronic engine control unit (ECU).

A mechanical pump raises the fuel pressure and feeds the common rail with fuel at high pressure. The
common rail is connected to the injectors by short pipes. A solenoid valve in each injector controls the
injection timing and quantity.

Figure 6.6

Schematic layout of a common rail


diesel injection system

In one design of the common rail systems, the rail pressure is same as the injection pressure. In
another design known as intensified CRDI system, the fuel pressure in rail is lower and it is multiplied
by a factor of 3:1 to 10:1 in the injector body by a stepped piston to raise it to the injection pressure.
The CRDI systems mostly operate at pressures of around 1600 bars.
The injection pressure characteristics of the CRDI, EUI and inline pump- nozzle systems are compared
in Fig 6.7. The main advantage of the common rail system over the conventional in-line jerk pumps is
that injection pressure is constant and independent of engine speed and load. For inline pump- nozzle
systems, the injection pressure is quite

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Module 6:Emission Control for CI Engines


Lecture 27:EMISSION CONTROL BY ENGINE VARIABLES AND EGR
contd..
low at low engine speeds which increase due to inertia effects at high speeds. It is therefore, difficult to
obtain the required engine performance with low emissions throughout the engine speed range with
inline fuel injection systems. Electronic unit injectors are better than the inline systems but the CRDI
provides more flexibility as a constant injection pressure is maintained at all engine speeds. In the
common rail systems, the injection timing and rate can be varied precisely depending upon the engine
requirements.
As very high injection pressures are possible with electronically controlled CRDI, its benefits are
available through out the engine speed range. Because of reduction in particulate emissions due to high
injection pressures, higher EGR rates can be used at part loads to reduce NO x emissions, which lead to
a better NO x -particulate trade off. With the common rail systems, injection rate shaping and pilot
injection are also easier to implement.

Figure 6.7

Peak injection pressure as a function of engine speed for


different fuel injection systems.

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Module 6:Emission Control for CI Engines


Lecture 28:Emission Control by Design Variables and EGR ( Contd.)
The Lecture Contains:
TURBOCHARGING
Control of Boost Ratio and Variable Geometry Turbocharging
CONTROL OF ENGINE OIL CONSUMPTION
EXHAUST GAS RECIRCULATION
Cooled v/s Un-cooled EGR
EGR Systems for Turbocharged Engines

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Module 6:Emission Control for CI Engines


Lecture 28:Emission Control by Design Variables and EGR ( Contd.)
TURBOCHARGING
Presently, almost all the modern light, medium and heavy-duty diesel engines are turbocharged. A
turbocharger consists of a turbine driven by the engine exhaust gas which is directly coupled to a
compressor. The fresh air from the atmosphere is drawn into the compressor of turbocharger where its
pressure and hence density are raised before it enters the engine cylinder The higher mass flow of air
in the turbocharged engines compared to the naturally aspirated engines of the same swept volume,
results in an increase in engine power, lower fuel consumption, better transient operation response and
lower specific exhaust emissions (in g/kW-h). Advantages of turbocharging are;
With turbocharging, excess air of more than 50% can be easily used in DI engines while still
developing enough engine power.
Due to higher air density and higher temperatures at the end of compression stroke shorter
ignition delay period is obtained.
As a result of shorter ignition delay period , the fraction of fuel burned during premixed
combustion phase decreases resulting in lower NO x emissions.
A shorter delay period gives lower HC emissions.
With turbocharging, the injection timing can be retarded to further lower NO x emissions without
compromising fuel efficiency and power.
High excess air results in lower soot emissions.
Inter-cooling of the boosted air charge further increases charge density and lower intake
temperatures helps in reducing NO x emissions.
The effect of turbocharging (TC), aftercooling (TCA) and injection retard typically observed on the NO x
particulate trade off compared to naturally aspirated diesel engines is shown in Fig. 6. 8.

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Figure 6.8

Effect of turbocharging on NO x -Particulate


trade off.

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Module 6:Emission Control for CI Engines


Lecture 28:Emission Control by Design Variables and EGR ( Contd.)
Control of Boost Ratio and Variable Geometry Turbocharging
For the conventional turbocharger, boost pressure ratio characteristics vary nonlinearly with the airflow
rate. At the low airflow rates, the boost pressure ratio is small. The pressure ratio increases as a power
law of air flow rate. As the flow rate increases the boost pressure ratio increases disproportionately.
Secondly, at low engine speeds the available exhaust gas energy is low and hence, boost pressure is
also low which further compounds the problem. The turbine power therefore, is matched to provide
adequate airflow to the engine at low engine speeds. At high speeds, a waste gate valve is used that
makes the exhaust gas to bypass the turbine. As the engine speed increases, an increasing fraction of
total exhaust gas is made to bypass the turbine directly to the atmosphere to reduce power of the
turbine. These are fixed geometry turbochargers and their use results in a compromise between lowspeed and high-speed performance of the engine.
Variable geometry turbochargers (VGT) have been developed to overcome the limitations of the fixed
geometry turbochargers. The VGT are better matched with the engine operational needs. The turbine of
VGT has movable vanes that can change turbine flow area or the angle at which the exhaust gas enters
or leaves the turbine rotor. VGT are also designed where both the flow area as well as angle at which
gas enters or leaves the rotor can be changed simultaneously. A reduction in turbine flow area
increases upstream exhaust gas pressure and it results in an increase in speed of the turbocharger and
higher boost pressure. With the variable geometry turbochargers, the closed loop control of engine
boost pressure by ECU is possible.
The VGT have been introduced on the automotive engines during the late 1990s in Europe and their
use is increasing. Although, the variable geometry turbochargers were primarily developed to improve
low speed torque and transient response, but their use also provides emission reduction under low
load operating regime and a better optimization throughout engine operating range is possible.

CONTROL OF ENGINE OIL CONSUMPTION


Engine lubricating oil enters combustion chamber through;
Valve guides,
Piston ring/liner interface and
Turbocharger seal.
Part of the engine oil gets burnt but 10 to 40% of oil entering combustion chamber may not burn at all.
The unburned oil gets adsorbed on soot particles during exhaust process and forms soluble organic
fraction of the particulates. The ash produced on combustion of organometallic lubricating oil additives
containing Ca, Ba, Zn, P etc., may also become important as the emission limits are lowered.
Depending on engine load and speed, oil consumption may vary from 0.1 to 0.4 % of fuel consumption.
The oil thus could contribute 5 to 50% of mass of PM emissions depending upon the engine operating
conditions.
Due to importance of contribution of engine oil to particulates, the oil consumption in the modern
engines is being reduced through improved designs of piston, piston rings, valve guides and control of
surface geometry and roughness of the cylinder liners. The engine oil consumption levels are being
lowered to 0.1% of fuel consumption at rated engine power.

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Module 6:Emission Control for CI Engines


Lecture 28:Emission Control by Design Variables and EGR ( Contd.)
EXHAUST GAS RECIRCULATION
Exhaust gas recirculation has been widely used since 1970s to reduce NO x emissions in the SI
engines. During 1990s, when emission standards for diesel passenger cars in Europe were tightened,
EGR found application for the first time in small high speed engines and later in the heavy duty diesel
engines as well.
With the use of EGR, reduction in NO x is accompanied with an increase of smoke, particulate and HC
emissions. Fuel consumption also increases with the use of EGR.
As the EGR is applied, excess air decreases. With 25% EGR in a turbocharged engine at full load
operation, the excess air ratio decreased from around 1.7 to 1.3. Simultaneously with 25% EGR, the
NO x reduced by 85%, smoke increased manifold from around 0.5 Bosch smoke units to 3.5 Bosch units
and BSFC increased by 8%. Smoke and BSFC increased sharply beyond about 12% EGR rate.
At part loads when air-fuel ratios are high, EGR rates even up to 50% can be applied. In practice, on
the production engines, EGR is applied at part loads and at high loads NO x control is obtained by
retarding injection timing. A typical EGR map for a passenger car diesel engine is shown on Fig 6.9.
EGR rates are varied with engine load and speed and an electronic control of EGR is usually employed.
In addition to the input data on engine speed and load, EGR is controlled based on air mass flow rate.
Air mass flow rate is measured by a flow meter. From air flow signal the engine control unit determines
EGR rate from a look-up table to control EGR rates. Measurement of airflow rate compensates for any
changes in volumetric efficiency that may result due to deposit build-up in combustion chamber, valve
timing adjustment etc.

Figure
6.9

Typical EGR rate map for a passenger car DI diesel


engine.

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Module 6:Emission Control for CI Engines


Lecture 28:Emission Control by Design Variables and EGR ( Contd.)
Cooled v/s Un-cooled EGR
Cooling of EGR before mixing with air has the following possible effects;
Lower intake charge temperature would further reduce NO x formation.
Higher intake charge density, higher volumetric efficiency and higher oxygen content in charge
would give higher flame temperatures resulting in higher oxidation of soot.
A higher volumetric efficiency provides lower BSFC.
Lower charge temperatures would result in longer ignition delay period, more premixed
combustion and higher unburned HC emissions.
For the same reduction in NO x , loss in fuel economy is lower with cooled EGR compared to uncooled EGR.
Due to a better NO x - BSFC trade-off, the cooled EGR is more commonly employed in practice.

EGR Systems for Turbocharged Engines


Two methods are used for application of EGR in the turbocharged engines. The layouts of the two
systems given below are shown on Fig. 6.10.

Low- Pressure Route: Exhaust gas from downstream of turbine is tapped and inducted to the intake
side of the compressor. In this method, the required pressure difference across the EGR valve is easily
obtained and EGR is possible over a wide range of engine operation. The main disadvantage is that
the exhaust gas along with air also passes through the compressor and intercooler resulting in
durability problems of compressor due to presence of soot particles.
High-Pressure Route: Exhaust gas from the upstream side of the turbine is tapped and led to the
exit side of the compressor. The EGR gas does not pass through the intercooler or compressor. EGR is
additional to the intake charge of compressor and amount of oxygen in the charge remains constant.
With this method, higher reductions in NO x can be achieved with lesser increase in smoke and
particulate emissions.
In the high-pressure route of EGR sufficient pressure difference between pressure upstream of turbine
and downstream of compressor is not available under all the engine speed-load conditions. At high
loads the pressure at the exit of compressor may be higher than the pressure upstream of turbine. To
introduce EGR at high engine loads:
(i)
and

Turbine back pressure is increased, by use of a variable geometry turbocharger,

(ii)
A venturi is fitted between the compressor and intake manifold. The EGR is
introduced at the throat of
venturi.

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Figure
6.10

Schematic layouts of (a) Low Pressure Route and (b) High


Pressure Route EGR system for turbocharged, inter-cooled
diesel engines.

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment

The Lecture Contains:


DIESEL EXHAUST GAS AFTERTREATMENT
DIESEL OXIDATION CATALYSTS
Design Features of DOC
NO x Storage-Reduction (NSR) Catalysts
Selective Catalytic Reduction (SCR)

NH 3/NOx Ratio and Ammonia Slip


SCR Catalyst System
Comparison of NSR and SCR Catalyst Systems

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
DIESEL EXHAUST GAS AFTERTREATMENT
The combustion process and hence the exhaust gas composition and its thermodynamic state in diesel
engines differ from SI engines. The main differences are;
The overall air-fuel ratio in the diesel engines varies from about 19:1 to 75:1 resulting in large
variations in the exhaust gas composition with excess oxygen always present in the exhaust
gases.
Due to heterogeneous combustion in diesel engines, a large concentration of particulate matter is
present in the exhaust gases.
The exhaust gas temperature varies usually from 150 to 350 C. The gas temperatures at the exit
turbocharger are further lower compared to temperatures at the exhaust port due to expansion in
the turbine
In the European heavy duty engine cycle the exhaust temperatures vary from 200 - 400 C although
in the US transient cycle the gas temperatures may reach up to 600 C. On the other hand in the driving
cycle for light duty vehicles the gas temperatures vary in the range of 150 350 C only. Until the year
2000, the diesel vehicle emission standards in the US and Europe were largely met by use of improved
injection system, engine combustion improvements, EGR and turbocharging. The three-way catalytic
converters are unable to function in diesel engines as a high amount of excess oxygen is always
present in the exhaust gases. Hence, the nature of exhaust treatment in diesel engines is considerably
different than for the stoichiometric SI engines. In the light duty diesel vehicle segment, diesel oxidation
catalysts have found application for the Euro 2 and 3 vehicles. For the later standards such as Euro 4
and 5, advanced forms of exhaust aftertreatment like diesel particulate filters and lean de-NOx catalysts
are being employed.
Exhaust aftertreatment in diesel engines may be grouped in two broad categories;
Diesel catalytic exhaust aftertreatment and
Diesel particulate filters (DPF)

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
DIESEL OXIDATION CATALYSTS
The diesel oxidation catalyst is also termed as DOC. The DOC works in a similar fashion as the
oxidation catalytic converter in the gasoline engines. However, the performance of DOC differs from
oxidation catalysts in gasoline engines due to;
Low exhaust gas temperatures
Presence of particulate matter in the diesel exhaust and
High fuel sulphur content compared to gasoline
Typically use of DOC depending on engine design and operating conditions results into;
30 80% conversion of the gaseous HC
40 to 90 % reduction of CO
Dry soot does not get oxidized. But, oxidation of 50 to 80% of soluble organic fraction and some
PAH occurs that gives 30 to 50 % reduction in total PM emissions.
Conversion of fuel sulphur to SO3 and emission of sulphuric acid aerosol.
The fuel sulphur on combustion gets converted to sulphur dioxide in the combustion chamber. The
SO2 however, gets further oxidized to SO3 on the catalyst which combines with water vapours to form
sulphuric acid aerosols which is also termed as sulphate emissions. Part of SO3 produced is stored on
the catalyst. The reactions involving fuel sulphur proceed on the catalyst as below:
Oxidation of SO2 :

SO 2 + O2 SO 3

(6.3)

Sulphate storage:
SO3 +MO (washcoat metal oxide) MSO4

(6.4)

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd....

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd...
The particulate emission reduction by DOC is influenced by the exhaust gas temperature as shown on
Fig. 6. 11. The optimum temperature range for the DOC operation is observed to be from about 200 to
350 C. At lower temperatures poor oxidation of SOF and PAH is obtained and at temperatures higher
than 350 C a high conversion of SO2 to sulphates results in an increase of mass of PM emissions.

Effect of exhaust gas temperature on conversion of

Figure 6.11 particulate mass by DOC.

The diesel fuels during early 1990s contained 0.2 to 0.3 % sulphur by mass Due to high fuel sulphur
content the DOC design has to address to the following requirements;
Minimize conversion of SO2 to SO3 at high exhaust gas temperatures
Minimize formation and storage of the sulphate on the catalyst.
Good conversion of SOF so that DOC reduces the mass of PM emissions in addition to
conversion of HC and CO.
As sulphur in the diesel fuels has been reduced to around 0.03% the sulphate formation on DOC is not
of serious concern. .

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd...
Design Features of DOC
The catalyst volume is typically equal to the engine swept volume. A DOC although, may appear
similar to the oxidation catalysts used for gasoline vehicles but the following differences in the design
features are incorporated;
Ceramic monoliths of a lower cell density having 200 to 400 cpsi are normally used to keep it
free of clogging by soot.
As alumina is more readily gets converted to Al 2 (SO 4 ) 3 , different washcoat materials like
titanium oxide, silicon dioxide, or mixtures of 50 % CeO2 and 50% -Al 2 O 3 are used.
Mainly platinum is used in DOCs with metal loading varying from 0.5 to 2.0 g/l.
The diesel oxidation catalyst is placed downstream of the turbocharger and experiences much
lower temperatures (100-550 C) compared to the gasoline engine catalyst (300-1100 C). The
thermal deactivation of DOC is not a major problem.
Diesel engines burn more lubricating oil in the cylinder and the engine oils have a higher metal
additive content than the gasoline engines. The pore structure of washcoat must be formed to
tolerate larger amounts of these inorganic oxides

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
DIESEL DE-NOX CATALYSTS
The diesel engine exhaust always has high amount of excess oxygen.

Conversion of NO x to N 2
requires a reducing atmosphere. In the diesel engines due to oxidizing atmosphere in the exhaust, a
NO x reduction catalyst different than the conventional 3-Way catalyst is required. For reducing NO x in
the oxygen rich atmosphere, the reducing agents also termed as reductants are necessary. The
reductants can be supplied either from the engine itself or added by external sources in the exhaust.
Hydrocarbons or ammonia are the two most frequently used reductants. As discussed earlier, the main
strategies employed for NO x reduction in oxygen rich atmosphere are:
NO x Storage Reduction (NSR) Catalysts
Selective Catalytic Reduction (SCR)
Low temperature plasma/catalyst systems are also being developed for application to diesel engines.

NO x Storage-Reduction (NSR) Catalysts


The NO x storage-reduction catalyst system or NO x Trap was first developed for application to gasoline
direct injection, lean-burn DISC spark ignited engines. It has been discussed in Module 5. In the diesel
engines, diesel derived hydrocarbons are used as reductants. The principle of operation and basic
features of Diesel NSR catalysts are the same as for the lean burn SI engines. The first step is to
absorb NO x (NO converted to NO 2 on the catalyst itself) on rare earth metal oxides and the second
step is release of NO x in presence of hydrocarbons for reduction to N 2 .
For significant reduction in NO x , typically 2 to 5:1 HC/NOx molar ratios are required. Normally, engine
out hydrocarbon emissions are quite low in the diesel engines. In the diesel NSR system, hydrocarbons
are added to the exhaust gas by;
post injection of fuel in the cylinder after the main fuel injection event
adding secondary fuel into the exhaust system.

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd...
About 2% of the main injection quantity is injected 90 to 200 CA after the main injection in the
cylinder. The common rail injection system is well suited for providing post injection.
The best NO x storage and conversion efficiency of NSR catalysts are obtained in a narrow
temperature range of 200-350 C. Peak conversion efficiency may reach around 55 to 60% but overall
conversion efficiency under driving cycle conditions is only around 35%. A number of catalyst modules
to reduce space velocity and improve over all conversion have been employed in prototypes.

Sulphur Poisoning of NSR Catalysts


Sulphur on combustion forms sulphur dioxide, which gets oxidized to SO3 over the catalyst and reacts
with the rare earth oxides to form their sulphates such as barium oxide present in washcoat gets
converted to barium sulphate. The mechanism of sulphur poisoning is similar to the mechanism of NO x
trapping by the catalyst. Hence, presence of sulphur in fuel reduces NO x trapping efficiency. Even with
5 ppm sulphur in fuel the conversion efficiency has been seen to drop by half after about 25000 kms of
operation.
To improve the catalyst resistance to sulphur poisoning new formulation of the adsorber material are
being developed. The NSR catalysts so far are not being applied in diesel engines.

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd...
Selective Catalytic Reduction (SCR)
The selective catalytic reduction of NO x by ammonia has been applied now for several decades in the
stationary systems like gas turbines, utility boilers, diesel engine power plants, and incinerators. Now,
SCR is being used in heavy duty diesel vehicles quite widely in Europe to meet Euro 4 and later
emission standards. On the road vehicles, urea is used as the carrier of ammonia. Hydrolysis of urea is
carried out at first on a catalyst on board of the vehicle to produce ammonia and carbon dioxide.
Ammonia then, reacts on the SCR catalyst with the NO x and converts it to nitrogen. Vanadium and
titanium oxide mixture (V2 O 5 + TiO2 + WO 3 ) coated on a ceramic honeycomb substrate of 200- 400
cpsi is used as SCR catalyst. The basic chemical reactions in the urea-SCR process are as follows:
Hydrolysis of Urea:

(NH 2 ) 2 CO + H2 O CO 2 + 2 NH 3

(6.5)

NOx Reduction:

4NO + 4 NH 3 +O2 4 N2 + 6 H2 O

(6.6)

6NO 2 + 8 NH 3 7N2 + 12 H2 O

(6.7)

Urea concentrations of 30 to 40 % in water solution are stored on board as the temperature of


crystallization is the lowest (-11 C) for 33% solution.

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd...
NH 3 /NO x Ratio and Ammonia Slip
Based on the stoichiometric considerations, 90% conversion of NO x requires the NH3 /NO x molar ratio
of about 0.9, assuming NO 2 constitutes 10% of NO x . Concentration of NO x in the exhaust gases varies
depending upon engine operating conditions. Hence, for a vehicle continuously variable injection rate of
urea is required.
If more urea than stoichiometric requirements is injected, unreacted ammonia is
emitted in the exhaust which is called ammonia slip. To minimize ammonia slip, a dynamic urea
dosage system governed by engine operating conditions is to be employed. Even with the dynamic
dosage system, ammonia slip occurs during transient operation.
Typical conversion efficiency at different NH3 /NO molar ratio and ammonia slip are shown on Fig 6.12.
With increase in NH3 /NO molar ratio NO x conversion efficiency increases and but the ammonia slip
also increases. An oxidation catalyst is therefore, added to SCR system to prevent emissions of
ammonia.

Figure
6.12

NO x conversion and ammonia slip for a SCR catalyst as


a function of NH 3 /NO x ratio.

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd...
SCR Catalyst System
The basic SCR system using urea consists of three catalysts viz.,
Hydrolysis catalyst
SCR catalyst, and
An oxidation catalyst to oxidize ammonia slip
NO x conversion efficiency can however, be improved at low catalyst temperatures (< 300 C) when all
the NO x is converted to NO 2 before entering the SCR catalyst. An additional oxidation catalyst
therefore, ahead of SCR catalyst is used in the modern SCR systems. A typical SCR system for
heavy-duty vehicles is shown schematically in Fig. 6.13. NO x conversions of more than 70 % have been
obtained with SCR over the HD driving cycle. On road, over all reductions of close to 68 % have been
obtained for heavy duty trucks. Urea consumption is about 5.5% of the fuel consumption. Urea
requirements for several thousand kms of operation can be stored on board.

Figure
6.13

Schematic layout of SCR catalyst system using preoxidation catalyst.

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Module 6:Emission Control for CI Engines


Lecture 29:Diesel Exhaust Gas Aftertreatment
contd...
Comparison of NSR and SCR Catalyst Systems

Table 6.3
Comparison of SCR and NSR de-NO x
Technologies

Selective Catalytic Reduction


(SCR)
Advantages:
High conversion rate up to
90%
Technology
already
developed and used in
stationary applications

Disadvantages:
Costly and large space
requirements
Injections
of
another
substance i.e., urea/ammonia
as reductant
Dynamic dosage control of
reducing agent needed
Extra oxidation catalyst for
excess ammonia and SOF
necessary
Additional urea distribution
network required

NOx Storage Reduction (NSR)


Catalyst
Advantages:
Using HC and CO exhaust
emissions as reducing agents
Oxidation of SOF, HC, CO
emissions possible due to the
use of specially coated zeolite
catalysts
Disadvantages:
Lower conversion rates (up to
about 35% only)
Engine/Fuel
system
development
for
providing
higher HC emissions needed in
order to avoid additional HC
injection before catalyst

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Module 6:Emission Control for CI Engines


Lecture 30:Diesel Particulate Filters
The Lecture Contains:

Diesel Particulate Filters


Regeneration of DPF
Active DPF Regeneration

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Module6:Emission Control for CI Engines


Lecture 30:Diesel Particulate Filters
DIESEL PARTICULATE FILTERS
Diesel particulate filters (DPF) also called as particulate traps have been developed to filter out PM
from the diesel exhaust gases to meet very stringent emission limits. Alumina coated wire mesh,
ceramic fiber, porous ceramic monoliths etc., have been studied as filtration media. Presently, ceramic
monolith of honeycomb type structure is used to trap the particulate matter as the gas flows through
its porous walls. These filters are also termed as ceramic wall flow filters.
A ceramic honeycomb type particulate filter is shown in Fig. 6.14. In this cellular structure, alternate
cells are plugged at one end and open at the opposite end. The exhaust gas enters the cells that are
open at the upstream end and flows through the porous walls to the adjacent cells. The adjacent cells
are open at the downstream end from where the filtered gas exits .to the atmosphere. Flow path of
gas through walls of the filter is also shown on Fig 6.14.

Figure
6.14

Ceramic wall flow filter for diesel


particulate

Some advantages of wall flow filters over other filtration media are;
The wall flow filters have a large filtration surface area per unit volume
The pore size of walls can be controlled to provide gas flow without excessive pressure drop.
Very high filtration efficiencies close to 98% are possible with ascceptable pressure drop.

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Module6:Emission Control for CI Engines


Lecture 30:Diesel Particulate Filters

DPF Material, Cell Density


DPF material should be chemically inert and have low thermal expansion and high melting
temperature.
Porous cordierite ceramic
has been commonly used for diesel
particulate filters. Its melting temperature is
The soot burns without catalyst at a temperature of

. However, if the soot starts

to burn uncontrollably the DPF may experience temperature of 1300 C or higher resulting in
melting of the ceramic filter. Typical temperatures achieved in the ceramic filter when soot
gets burned are shown on Fig 6.15 for a 100 and a 200 cpsi DPF. Due to lower thermal
capacity of the 100cpsi DPF, higher ceramic temperatures result when soot deposited on the
DPF is burned. To overcome possible meltdown due to uncontrolled regeneration of DPF more
advanced materials withstanding even higher temperature are required.

Maximum temperature attained during uncontrolled


regeneration for two diesel particulate filters (144
Figure 6.15 mm dia X 150 mm length) having 100 and 200 cpsi
cordierite substrates, 200 cpsi substrate has
higher mass hence lower peak temperatures.

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Module6:Emission Control for CI Engines


Lecture 30:Diesel Particulate Filters
Contd...
High melting point materials of NZP family like Na

, and silicon carbide SiC have

also been developed for diesel particulate filters. Melting point of NZP material is
and of SiC of about 2400 C.
Diesel particulate filters commonly have a cell density of 100-cpsi or 200 cpsi with 0.30 to 0.45
mm wall thickness. The 200-cpsi substrates provide 41 % higher filtration area but have a
higher pressure drop.
Filters with circular cross section are mostly used due to their superior mechanical strength and
high thermal resistance as they experience less severe temperature gradients and have more
uniform temperature distribution. Cylindrical filters are easy to pack and install on vehicle.
Filter size is normally equal to the swept volume of the engine.

Pore Size and Soot Holding Capacity


For good mechanical strength, wall porosity is kept about 48-50%.
Pore size range from 12 to 35 m.
Pore size of about 35 m gives filtration efficiency of 60-75%
20 to 25 m pore size filters are used for 80-90 % efficiency and
12 to 14 m pore size for efficiency > 90%.
With higher pore size filtration efficiency as well as pressure drop is low. Hence, optimization of pore
size, cell density and wall thickness is essential.
Soot loading before regeneration ranges 5 to 10g/ l volume of substrate. When a 10-20 m
pore size DPF was loaded with soot in the range of 5 to 10 g/liter of substrate volume,
pressure drop was 7 kPa and 11 kPa with 5 and 10-g/liter soot loading, respectively.

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Module6:Emission Control for CI Engines


Lecture 30:Diesel Particulate Filters
Regeneration of DPF
It is relatively easy to filter and collect the particulate matter in the trap but the soot is to be burned
in-situ i.e., regenerate the trap so that pressure drop across the filter is kept always at an
acceptable level.
Soot and other particulate get collected on the filter that although improves the filtration
efficiency, but it results in an increased pressure drop across the filter. The pressure loss in
the new and clean filter is about 70 mm H 2 O for the 0.1 m/s gas velocity in filter channels.
Design considerations limit soot loading to about 10 g/l of filter volume before filter should be
cleaned or regenerated. As the soot is collected upto the limit of 10g/l, pressure drop increases
. An increase of engine backpressure by 350 mm
results in 1 %
to 300-350 mm of
loss in fuel economy at 65-km/h vehicle speed.
For engine out PM emissions of about 0.25 to 0.33 g/kW-h and engine power output of about
17 kW/ liter swept volume, 10g/l soot would get collected on DPF in about 2 hours. Hence, the
DPF regeneration should take place approximately every 2 hours. The soot in the filter is to be
burned in-situ.
Burning of soot particles begins at about 540 C. Such high exhaust gas temperatures do not
occur during engine operation for sufficiently long periods of .time. The diesel exhaust gas
temperatures in the exhaust pipe typically reach to about 300C only.
For regeneration of the DPF, therefore additional measures are to be adopted.

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Module6:Emission Control for CI Engines


Lecture 30:Diesel Particulate Filters

Types of Regeneration Systems


Regeneration of the DPF to its original clean state has been a challenging task. Two types of
regeneration systems have been investigated and a few developed for employment on production
vehicles
Active regeneration
Passive regeneration

Active DPF Regeneration


A positive source of heat is employed to raise temperature of DPF to about 540 C. When oxidation of
soot starts, the exothermic reactions sustain the combustion of soot particles and the DPF is
regenerated. In the active regeneration systems, sensors are used to monitor pressure drop across
the trap. On receiving the signal from the sensor, the exhaust gas temperature is increased above
500 C by any one of the following techniques:
Engine throttling
Use of electric heater upstream of filter
Use of burner upstream of filter
Throttling of air reduces airflow that results in decrease of overall air-fuel ratio, which increases the
combustion and exhaust temperatures. However, engine throttling increases the engine pumping
losses which results in loss of fuel efficiency. Throttling also decreases oxygen concentration in the
exhaust and for oxidation of soot 2-5% oxygen in the exhaust is necessary. Hence, the extent of
throttling is to be controlled. Under normal cruising conditions, throttling is unable to increase the
exhaust temperature to the levels needed for regeneration. Hence, throttling can work only at high
loads, which is deliberately applied to raise the gas temperatures. It also increases HC, CO and
smoke emissions. Engine throttling as a means of trap regeneration therefore, has had only a limited
success.
For electric filter regeneration, power to the electric heater is supplied by the engine alternator. A
typical truck DPF regeneration system may require a 3 kW heater. The electric regeneration hence,
needs a high battery back-up or is to be done while the vehicle is in garage, which may not be
accepted by the operators as regeneration is required quite frequently.

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Lecture 30:Diesel Particulate Filters
Burner Regeneration
A diesel fuel burner is placed in the exhaust in front of the filter to regenerate the diesel particulate
filter. This system can perform at all engine speeds and loads. Two types of system have been used;
1. burner full flow system and
2. burner bypass system
In the full flow system the total exhaust gas is to be heated to about 540 C. A large air pump for the
burner and high burner fuel consumption are needed. Complex electronic controls to regulate burner
fuel flow to maintain safe levels of gas temperature at inlet of filter are necessary. In the bypass
system, only a small part of exhaust is allowed to flow through the filter when regeneration is carried
out. A smaller air pump is required. A bypass burner regeneration system is shown on Fig 6.16.
Regeneration process is independent of engine operating conditions, as the filter during regeneration
is isolated from the engine exhaust. The fuel consumption by the burner to heat the inlet face of the
filter to 540 C is an order of magnitude lower compared to the full flow system. The relative
magnitudes of energy required to raise the exhaust temperature to 540 C in the full flow and bypass
type burner regeneration system (10 % of total flow) are presented in Fig 6.17 for a 5.7 liter diesel
engine.

Figure
6.16

Schematic of diesel-fuelled Burner Bypass


Regeneration system for Diesel Particulate Traps

The inlet face when heated to 540 C, soot oxidation begins. Increase in temperature of the gas
accelerates combustion of soot further. The burning process progresses from the front and oxidizes
soot in the remainder of the filter.

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Module6:Emission Control for CI Engines


Lecture 30:Diesel Particulate Filters
Control of Active Regeneration
The active regeneration is carried out once the filter is plugged and when the pressure drop across
the filter increases to the threshold level. The entire filter is plugged with soot. The regeneration
process starts at the front end and progresses towards downstream. Once the regeneration starts,
heat released further heats-up the filter and soot burns at a progressively increasing rate. This may
lead to uncontrolled rate of soot burning and high rates of heat release. Eventually, it may melt the
filter substrate. Therefore, the filter temperatures are to be monitored continuously. To control
temperatures during regeneration, the burner may be shut off midway through the regeneration cycle
to prevent melting of the filter substrate. The DOF regeneration is thus, a carefully controlled process.

Figure
6.17

Energy required to heat exhaust gas to 540 C for


full flow and by-pass diesel particulate filter
regeneration systems, 5.7 liter diesel engine.

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Module 6:Emission Control for CI Engines


Lecture 31:Diesel Particulate Filters (contd.)
The Lecture Contains:
Passive/Catalytic Regeneration
Regeneration by Fuel Additives
Continuously Regenerating Trap (CRT) Syatem
Partial Diesel Particulate Filters
Summary of Diesel Engine Emission Control

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Lecture 31:Diesel Particulate Filters (contd.)
Continuously Regenerating Trap (CRT) System
The principle of CRT is based on the fact that
the molecular oxygen.

is a much superior oxidizing agent for soot than

oxidizes the dry carbon soot trapped in the filter below 300 C by the

following reactions:

2NO 2 + C CO 2 + 2NO

(6.11)

(6.12)
Although the trap substrate can be coated with a catalyst material to reduce soot oxidation
temperatures to as low as 200 C, but installation of an oxidation catalyst upstream of particulate
which then oxidizes the soot has been found more
filter where NO is preferentially converted to
effective. The catalysts used are noble metals. The oxidation catalyst is a flow through ceramic
monolith using Pt-Pd catalyst impregnated on Al 2 O 3 washcoat.
The schematic of a CRT is shown in Fig. 6.18.
is produced by oxidation of NO upstream of
DPF. The soot trapped in the downstream DPF is continuously oxidized on the filter substrate by
thus keeping the particulate filter essentially clean and the exhaust backpressure remains nearly
unchanged.

Figure
6.18

Schematic of a continuously
regenerating trap (CRT).

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Module6:Emission Control for CI Engines


Lecture 31:Diesel Particulate Filters (contd.)
Passive/Catalytic Regeneration
The active regeneration systems need complex control systems and are expensive. The passive
regeneration systems employ catalysts to reduce soot oxidation temperatures to the levels that lie
within the normal exhaust gas temperature range. The catalyst is either added to diesel fuel in the
form of additives or is impregnated on the surface of the filter substrate. Another approach for
passive regeneration uses a special oxidation catalyst in front of the ceramic wall flow particulate filter
to promote soot oxidation. This system is known as the continuously regenerating trap (CRT).

Regeneration by Fuel Additives


Several fuel additives based on Fe, Ce, Mn, Zn, Cu and Pb lower the soot oxidation temperature.
Cerium and copper based additives in 60 to 100 ppm concentration have been found very effective in
lowering soot ignition temperature to about 300 C and soot regeneration has been achieved at
temperatures below 400 C. The additives on oxidation produce metal oxides which promote
oxidation of soot. For example, cerium fuel additive is converted to cerium oxide on combustion and
on reaching the DPF it catalyses soot oxidation. The oxidation mechanism is as below;
1.

Oxidation of soot:

(6.8)
2.

Oxidation of CO

(6.9)
3.

Ce2 O 3

being an unstable compound gets converted back to CeO2 in the exhaust gas as
excess oxygen is available
(6.10)
These reactions are quite fast and are completed within 2 to 6 seconds once the temperature is
sufficiently high. The fuel additive based approach for particulate trap regeneration is considered quite
promising. The additive can be dosed into the fuel line when required by automatic dosing equipment
on board of the vehicle.

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Module6:Emission Control for CI Engines


Lecture 31:Diesel Particulate Filters (contd.)

Fuel sulphur is an important factor that affects conversion of NO to NO 2 on the oxidation catalyst and
hence the efficiency of CRT. Fuel sulphur lower than 30-ppm has been found necessary to maintain
the functioning of CRT at an acceptable level. In Europe, where low sulphur fuel is available several
thousand vehicles with CRT are in operation. To achieve the best performance of CRT, the following
conditions should be met:
Sulphur-free fuel (sulphur <30ppm) is necessary to prevent catalyst poisoning
For best performance temperature should be in the range 250 450 C.
The
/ soot ratio should be adequately high otherwise
available will be too low to
oxidize soot.

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Lecture 31:Diesel Particulate Filters (contd.)
Partial Diesel Particulate Filters
Although wall flow diesel particulate filters have very high particulate trapping efficiency, but their
regeneration over the entire life span extending up to 496,000 kms for heavy duty vehicles is a
challenging problem. In Europe, many diesel vehicles meeting Euro 4 standards are fitted with wall
flow particulate filters as original equipment. Metal supported flow- through diesel filters employing
CRT operational principle have also been developed recently These filters have been developed to
provide 50 to 70 percent reduction in PM emissions and therefore, are called as Partial Particulate
Filters. Like CRT, upstream in the first section an oxidation catalyst is installed where NO is
oxidized to NO 2 . In the second section, which consists of flow-through type filter element collection of
soot and its combustion processes occur.
.A schematic cut-away section and working principle of the filter is shown on Fig. 6.19. The metal PM
filter consists of flat and corrugated foils in a flow-through monolithic configuration. The corrugated
foils are stamped to produce blades like structure to direct the flow towards the flat foil. The flat foil is
made of porous sintered metal fleece (wool) packed in the form of a sheet and compressed between
metal foils. Part of the exhaust gas is directed by the blades in the corrugated foil towards the porous
metal wool that traps the particulate matter. The soot trapped by the metal wool is oxidized by NO 2
generated on the catalyst in the upstream first section. The design of this diesel particulate filter has
open channels and it does not get clogged due to excessive accumulation of soot as happens in the
wall flow filters on failure of regeneration. All the exhaust is able to flow through the open channels if
the metal fleece is choked. However, in such a situation removal of PM from exhaust does not take
place. Typical cell density of these filters is 200 cpsi. With use of these particulate filters reduction in
PM emissions ranging from 30 to over 70 % have been obtained.

Working principle of metal supported partial

Figure 6.19 PM filter-Catalyst

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Lecture 31:Diesel Particulate Filters (contd.)
Summary of Diesel Engine Emission Control
Developments in diesel engine emission control technology that have taken place over several
decades are summarized in Fig. 6.20. The developments have been directed towards advancements
in technology to control;
Engine out emissions and
Exhaust after treatment

Summary of advancements in diesel emission

Figure 6.20 control technology.

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Lecture 31:Diesel Particulate Filters (contd.)
Summary of advancements in diesel emission control technology.
As seen from the Fig 6.20, the engine technologies have been able to reduce emissions to Euro IV
emission levels. The technologies employed progressively included;
Turbocharging with inter-cooling
Variable geometry turbocharging
Improved fuels esp. low sulphur in addition to low final boiling point and closer control on
density, viscosity etc.
High injection pressures
Optimization of combustion bowl geometry and air motion
EGR
Aftertreatment Technology for Euro V and beyond:
The second stage is the exhaust after treatment. In some engine models even to meet Euro IV
standards diesel oxidation catalysts and SCR de-NOx catalysts were employed. However, for Euro V
and later standards some form of exhaust treatment is almost essential. Most engines would employ:
Diesel particulate filters: DPF or CRT
de -NOx catalysts: SCR or other types

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Module6:Emission Control for CI Engines

Questions
(6.1) A diesel engine is fitted with mechanical injection pump with 60MPa peak injection pressure.
Another engine of the same size developing the same power is employing common rail
injection system with 160 MPa injection pressure. Both the engines operate at the same rated
speed. Discus the likely differences between the two engines with respect to (i) injection
duration (ii) nozzle hole size (iii) atomization and droplet size (iv) injection timing (v) fuel
evaporation , mixing (vi) ignition delay and premixed combustion (vii) over all combustion
rates (vi) PM and NOx emissions.
(6.2) Calculate stoichiometric NH3 / NO x ratio for reduction of NO x in SCR catalysts if the entire
NO x is only NO, and consists of 5 and 10% NO 2 by volume. If 20 % more NH3 than
stoichiometric requirements is supplied calculate ammonia slip in ppm if the NO x
concentration in the exhaust gas before conversion was 2000 ppm.
(6.3) A diesel particulate filter (DPF) fitted to a 12 litre DI diesel engine is to be regenerated. The
engine has volumetric efficiency of 88%, is operating at 67 % excess air and 2000 rpm. The
ambient air conditions are 101 kPa and 300 K. For burning the soot collected on the DPF, the
exhaust gas temperature is to be raised to 540 C. The exhaust gas temperature entering the
DPF is 350 C. Determine the power of an electric heater to raise the exhaust gas temperature
to the required level if the entire exhaust gas is to be heated. The specific heat of the gases in
the relevant temperature range is N 2 = 30.27, CO 2 = 46.56, O 2 = 31.96, 36.44 kJ/kmol. K.
(6.4) Given the LHV of soot = 33.8 MJ/kg , if in a DPF of 1 litre volume 10 g of soot is burned
estimate the temperature reached in the DPF. The combustion of soot begins at 540 C. The
mass of the DPF is 400 g and its specific heat is 0.9 kJ/kg.K.
(6.5) Refer Fig 6.20. Discuss how various technologies have helped in reduction of engine out
emissions from the diesel engines.
(6.6) A diesel engine has BSFC = 240 g/kWh. In the engine cylinder, lubricating oil enters through
piston rings and valve guides which amounts to 0.2 % by mass of the fuel consumption. Of the
engine oil in the cylinder, 80% is burned and rest is exhausted as SOF of particulate
emissions. Estimate the specific PM emissions solely contributed by the engine oil. How do
these compare with the Euro IV PM emission limits for heavy duty engines?

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 32:Stratified Charge Engines
ADVANCED COMBUSTION SYSTEMS AND ALTERNATIVE POWERPLANTS
The Lecture Contains:
DIRECT INJECTION STRATIFIED CHARGE (DISC) ENGINES
Historical Overview
Potential Advantages of DISC Engines
DISC Engine Combustion Requirements
Methods of Charge Stratification and Combustion
Modes of DISC Engine Operation
DISC Engine Performance and Emissions

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 32:Stratified Charge Engines

ADVANCED COMBUSTION SYSTEMS AND ALTERNATIVE


POWERPLANTS
DIRECT INJECTION STRATIFIED CHARGE (DISC) ENGINES
Historical Overview
For many decades the researchers have pursued development of direct injection stratified charge SI
engines to have overall very lean engine operation for higher fuel efficiency. Charge stratification is a
means of ensuring repeatable ignition without misfire and stable combustion while using overall very
lean fuel-air ratios that is otherwise not possible with homogeneous mixtures. In the stratified charge
engines, the mixture composition is varied within the combustion chamber such that stoichiometric or
slightly richer mixture exits near spark plug to provide good ignition characteristics and the mixture
gets progressively leaner away from the spark plug. Overall air-fuel ratio in the cylinder is significantly
leaner than the stoichiometric.
A typical configuration of DISC engine is shown on Fig 7.1. Liquid fuel is injected in the cylinder. The
fuel spray is directed by air motion or by the geometry of piston crown or by combination of the both
towards spark plug. By the time fuel spray reaches the spark plug electrodes some fuel gets
vaporized and forms combustible mixture with air. The vaporized fuel in spray is then ignited by
spark, combustion begins and the flame spreads in the combustion chamber.

Figure 7.1

Schematic of a direct injection stratified


charge (DISC) engine combustion system

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Lecture 32:Stratified Charge Engines
contd...
Development of
direct injection stratified charge engines started in 1950s when Mercedes Benz
developed an engine employing mechanical injection system. It was followed by development of two
very widely known DISC engine prototypes during 1960s: Ford Programmed Combustion (PROCO)
engine and Texacos Stratified Charge (TCCS) engine. Both of these engines employed mechanical
jerk type fuel injection systems.
These engines could not be put into production as maintaining
proper charge stratification under all engine loads and speeds was not possible. Moreover, the spray
was directed very close to spark plug, which resulted in frequent spark plug fouling and also emission
of black smoke at high engine loads.
During early 1970s, Honda developed a divided chamber stratified charge engine using two
carburettor. A small carburettor provided rich mixture to the auxiliary small chamber where spark plug
ignited the mixture. The lean carburettor supplied mixture to the main chamber and the overall
mixture in the engine was significantly leaner than stoichiometric. The burning mixture from the small
chamber flowed via a small throat into the main chamber like in the divided chamber diesel engines.
This engine was called Honda CVCC (compound vortex combustion chamber) engine. The Honda
CVCC engine had high fluid dynamic and heat transfer losses, and it also required catalytic
aftertreatment for the medium size and bigger cars to comply with the then US emission standards.
The production of this engine did not continue much longer.
During 1990s, fuel economy improvement to reduce emissions of CO 2 , a greenhouse gas became a
major thrust of research. As the DISC engine has the potential to give high fuel efficiency at part
loads, it resulted into a renewed interest in DISC engine development. Mitsubishi and Toyota Motors
introduced DISC engine powered cars during mid 1990s. These engines operate in stratified mode at
part loads and in stoichiometric mode at high loads.

Potential Advantages of DISC Engines


The direct injection stratified charge SI engines have the potential to provide following advantages
over the premixed homogeneous charge engines;
The mixture being rich near spark plug good ignition characteristics without misfire are
obtained.
High combustion temperatures obtained as a result of initial burning of rich mixtures near spark
plug produce high flame speeds that burn the lean mixtures in the cylinder away from spark
plug.
The overall air-fuel ratio can be very lean reaching 40:1 to 50:1giving high fuel efficiency.
An unthrottled engine operation is possible such that the engine power may be controlled by
varying only the fuel flow. It would reduce pumping losses.
The end gases being very fuel lean, precombustion reactions would be very slow leading to
reduced knocking tendency. Hence, a higher compression ratio can be used further improving
the fuel efficiency.
Presence of rich mixture near spark plug keeps the formation of NO x at low levels. The mixture
that burns early is deficient in oxygen although it attains high combustion temperatures.

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Lecture 32:Stratified Charge Engines
contd...
Overall mixture being lean very low CO is produced as the CO produced early in combustion
can be oxidized within the cylinder itself by the excess oxygen available.
The mixture in piston ring crevice region being very lean the contribution of crevices to HC
emissions would also be very low.
The direct injection of fuel in the cylinder can decrease HC emissions during warm-up after
cold start as liquid fuel film is not formed in the intake manifold and port. Also, a smaller fuel
quantity needs to be injected during cold start compared to PFI engines.
With direct injection of gasoline a faster dynamic response is possible hence a flatter air-fuel
ratio curve during acceleration can be used that provides lower HC emissions.
The DISC engines can tolerate higher EGR rates than the homogeneous charge SI engines
and hence larger reductions in NO x

DISC Engine Combustion Requirements


For stratified charge engine operation the following main requirements are to be met to obtain good
combustion:
Combustible mixture must form quickly.
The liquid fuel and fuel over-rich zones should be minimum at the time of ignition
Suitable air motion is to be provided during compression stroke and at the time of fuel injection
to accomplish charge stratification and transport mixture to the spark plug in a reproducible
manner cycle after cycle. Air motion may be aided by a suitably designed cavity on the piston
crown.
Wetting of piston crown and spark plug by excessive liquid fuel deposition is to be prevented.
Over mixed zones having excessively lean mixtures beyond flammability limits as well as under
mixed over-rich zones are to be avoided.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 32:Stratified Charge Engines
Methods of Charge Stratification and Combustion
The methods of charge stratification and combustion that have been studied and some of these
employed in production engines may be grouped in the following three types. These are also shown
on Fig. 7.2.

Spray, flow and wall controlled DISC

Figure 7.2 engine combustion.

Spray Controlled: The fuel spray characteristics primarily controls the charge stratification in this
strategy. Ignitable mixture is formed at the boundaries of the fuel spray. The spark plug is placed
close to the spray as it is there that the ignitable mixture is present at the time of ignition. Formation
of good quality mixture becomes difficult at high engine loads. The combustion being highly sensitive
to spray characteristics smoke formation is often observed at high loads. Wetting of the spark plug by
liquid fuel causes frequent spark plug fouling.
Wall Controlled: In the wall-controlled concept, fuel injection is directed towards a specially
designed piston cavity. The piston cavity is off centre. The spark plug is located away from the fuel
injector on the side of combustion chamber. Fuel impinges on the piston cavity walls where it
evaporates and mixes with air. An intense reverse tumble charge motion transports the mixture to
spark plug electrodes.
Flow Controlled: Mixture is formed by interaction between fuel spray and suitably directed air
motion like swirl or tumble. The spark plug and injector are generally widely spaced in these
configurations. The air motion transports mixture to the spark plug such that the ignitable mixture is
present at spark plug electrodes at the time of spark. When air motion is well organized, the
combustion chamber walls do not get wetted by liquid fuel and a stable stratified charge operation is
obtained over a wide range of engine operation.
The characteristics of combustion process obtained with the three charge stratification and
combustion methods are compared in Table 7.1

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 32:Stratified Charge Engines

Table 7.1
Comparison of DISC engine combustion process parameters with Spray,
Wall and Flow controlled approaches, 2000 rpm, imep =2.8 bar

Combustion parameter

Spray
controlled

Wall
controlled

Flow
controlled

Injection timing, btdc (approx.)

60

50 -55

40

Ignition timing
ends, CA

3 to 5

35 -40

10 -15

20 25
45
75-80
10

10

10
25
50-55
5

after

injection

Combustion duration, CA
0 -5% heat release
0- 50%
0- 85%
85-90 %

30
50-55
30

In the spray controlled method formation of mixture takes longer hence initial heat release rates are
small and the combustion duration corresponding to 0 -5% heat release is much longer compared to
the other two methods. . On the other hand in the wall controlled approach, although the fuel initially
evaporates quite rapidly due to hot walls, but it takes longer to evaporate all the injected fuel Thus,
the end of combustion is significantly delayed with the wall controlled method compared to other
methods. The flow controlled method has the shortest combustion duration due to better mixture
preparation and high intensity of fluid motion and turbulence. In practice, the production DISC engines
use a combination of both the wall and air flow controlled strategies to obtain good ignition and
combustion characteristics. Mitsubishi engine uses a specially designed piston cavity and tumble air
motion while Toyota engine employs a specially designed piston cavity and air swirl.

Modes of DISC Engine Operation


The early DISC engines such as Ford PROCO and TCCS attempted to operate in stratified charge
mode throughout the engine operation range but it proved to be unsuccessful and acceptable engine
performance and emissions over the entire speed-load range could not be obtained. With mechanical
injection system precise control of injection timing also could not be maintained. The current direct
injection gasoline engines operate in the stratified charge mode at part loads and up to medium
speeds while at high engine loads the engine are made to operate as stoichiometric homogeneous
charge engines. This is controlled by fuel injection timing.
Stratified Charge Operation: Fuel is injected late in the compression stroke There is not enough
time for fuel to fully mix with air and a stable charge stratification at part loads at the time of ignition is
obtained. Engine operates unthrottled and very lean overall air-fuel ratios reaching up to 50:1 are
used.
Homogeneous Stoichiometric Operation: Fuel is injected early in the intake stroke to allow
adequate time before ignition for fuel evaporation, mixing and formation of homogeneous mixture At
high loads, early fuel injection timing is used to operate the engine in stoichiometric homogeneous
mode.

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Homogeneous Lean Operation: Engine operates homogeneous lean in the mid-load range. This
is the transition zone from stratified mode at low loads to stoichiometric operation at full engine load.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 32:Stratified Charge Engines
Injection strategy and typical operation regimes for a DISC engine are shown in Fig. 7.3 and their
features are summarized in Table 7.2. The different features of DISC engine operation are
summarized in Table 5.2

Figure 7.3 Fuel injection and operation strategy for DISC engines
Table 7.2
Features of DISC Engine
Operation

Stratified

Homogeneous
stoichiometric

Homogeneous lean

Injection timing

Compression stroke

Intake stroke

Intake stroke

Air-fuel ratio

24 -50

14.7

24 to 14.7

Intake Throttling

Low

High

Medium

Mitsubishi and Toyota introduced 4-cylinder, DISC engine powered cars for the first time during 1996.
Other manufacturers have also developed DISC engines. The DISC engines use 10 to 12:1
compression ratio and fuel is injected at 50 to 120 bar injection pressure. The leanest air-fuel ratio
used is more than 40:1 reaching as lean as 55:1.

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DISC Engine Performance and Emissions


The performance of a swirl dominated DISC engine is compared to that of a lean burn PFI engine on
Fig. 7.4. Main differences observed are;
The lean limit of homogeneous charge PFI engine was about 25: 1 A/F ratio, while the DISC
engine could be operated well beyond A/F ratio of 40:1.
The specific fuel consumption of DISC engine was lower by up to 20% compared to
stoichiometric PFI engine. Other studies also showed 30 percent improvement in BSFC of
DISC engines over the conventional PFI engine. Lower SFC results due to less throttling or
unthrottled engine operation, and lean air-fuel ratio and higher compression ratio.
PFI engines exhibit a continuous decrease in NO x emissions as the mixture is leaned from
near stoichiometric mixture. Very low NO x emissions without EGR are obtained at air-fuel
ratios higher than 20:1. DISC engine is seen to give significantly high NO x levels even at
overall air-fuel ratio of 45:1. In the DISC engine considerable amount of charge is contained in
the combustion zones with stoichiometric or near stoichiometric mixture. The local burnt gas
temperature in these zones is at higher level leading to higher NO x formation than when the
engine is operating in lean homogeneous mode at the same overall air-fuel ratio.
The DISC engines have a higher tolerance of EGR before the combustion stability and fuel
consumption becomes unacceptably poor as the mixture in the vicinity of spark plug in DISC
engines is stoichiometric or richer and a stable combustion even with 40% or higher EGR rates
is possible.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 32:Stratified Charge Engines
contd...

Figure 7.4

Comparison of performance and NO x emissions of DISC and lean


burn PFI engines.

The DISC engine gives much lower HC emissions than the PFI engine during engine cold start,
engine warm-up phase and transient conditions. In the PFI engines during cold start and transient
conditions, the amount of fuel entering the engine cylinder is not the same as being injected at the
port as some fuel gets deposited at the port forming liquid
fuel film. Hence, in the PFI engine very rich mixture is to be supplied to have quick cold start. In DISC
engines, as the fuel is directly injected in the cylinder there is no delay of fuel being inducted into the
cylinder. The DISC engines on the contrary can be started on stoichiometric or even slightly overall
lean mixtures. After engine is switched on, the DISC engine achieves stable combustion in the very
first or second cycle while the PFI engine requires about 10 cycles to attain stable combustion. The
cold start HC emissions from a DISC engine are nearly 1/4th of that of PFI engine. CO emissions of
DISC engines are very low due to overall very lean engine operation.
For the success of DISC engines, catalytic reduction of NO x under lean engine operation is required.
Although with EGR large reductions in engine out NO x emissions are obtained, but lean operating
limit is narrowed with high EGR and during lean homogeneous engine operation high EGR cannot be
used. Therefore, lean de-NO x catalyst technology is essential to meet stringent emission standards in
future while maintaining fuel economy benefits of the DISC engines. Mitsubishi and Toyota DISC
engines employ a lean de-NO x catalyst in addition to EGR to reduce nitrogen oxide emissions to the
level of Euro 4 and beyond emission standards.

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Module 7:Advanced Combustion Systems and Alternative Powerplants


Lecture 33:HCCI and CAI Engines
The Lecture Contains:
HCCI/CAI ENGINES
HCCI v/s CAI
Basics of HCCUI/CAI Process
CAI GASOLINE ENGINES
Methods to Obtain CAI
Regime of CAI Operation
Emissions with CAI and SI Engine Operation

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 33:HCCI and CAI Engines
HCCI/CAI ENGINES
Stringent emission standards and the need to reduce greenhouse gas, CO 2 emissions from vehicles
has led to intensive research on new combustion systems namely, the homogeneous charge
compression ignition (HCCI) or controlled autoignition (CAI) engines. These combustion concepts
have the following features;
HCCI/CAI involves autoignition of very lean homogeneous mixtures of fuel and air so that the
combustion temperatures are low.
Due to low combustion temperatures NO x formation is negligibly small. NO x formation is two
orders of magnitude lower than those from the current SI and CI engines
Very little soot is formed as the homogeneous charge is burnt.
High fuel efficiencies similar to DI diesel engines can be obtained as very lean mixtures are
burned.
The first attempts to utilize HCCI/CAI combustion were made to control irregular and misfiring
combustion in 2-stroke SI engines at light loads by Japanese researchers during late 1970s.
Autoignition of the homogeneous charge was obtained by retaining large amounts of hot residual gas
containing partially oxidized hydrocarbons and active chemical species in the cylinder. Honda motors
applied this form of combustion on a motorcycle engine prototype during mid-1990s, which was
termed as Active Radical Combustion (ARC). Fuel economy improvements of about 30% and HC
reduction of 50% were obtained compared to normal 2-stroke engine operation. The autoignition of
lean homogeneous charge has been called by a variety of names such as Active Thermo Atmosphere
Combustion (ATAC), Premixed Charge Compression Ignition (PCCI), Premixed Lean Diesel
Combustion (PREDIC), Active Radical Combustion (ARC), Controlled Autoignition (CAI),
Homogeneous Charge Compression Ignition (HCCI) etc.

HCCI v/s CAI


Application of autoignition of lean homogeneous charge has been studied in the conventional gasoline
as well as diesel engines. The processes adopted to auto-ignite homogeneous charge and the
objectives of its application to SI and CI engines are some what different
In the gasoline engines, external heating of intake charge or use of hot residual gas has been
employed to cause controlled autoignition of high octane gasoline or natural gas air mixtures.
Therefore, the auto-ignited combustion process when applied to gasoline engines has been termed as
controlled autoignition (CAI). The main objective of CAI application to the gasoline engines is
reduction in fuel consumption and NO x emissions.
In the conventional diesel engines, the fuel air mixture is heterogeneous and compression of air to
high temperature is used to auto-ignite diesel fuel. The diesel fuel has low self-ignition temperature. In
application of this concept to diesel engines, the main approach is to premix as much fuel as possible
before autoignition without encountering negative effects of auto ignition on combustion parameters
and emissions. Autoignition may be caused by other forms of heating of fuel-air mixture in addition to
compression heating. This process when applied to diesel engines is usually called as homogeneous
charge compression ignition (HCCI). The main objective of HCCI application in the diesel engines is
to reduce NO x and particulate emissions.
It may be noted that fundamentally the HCCI and CAI processes are the same.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 33:HCCI and CAI Engines
Basics of

HCCUI/CAI Process

Control of emissions of nitrogen oxides and soot from the IC engines has proven to be most difficult.
The origin of NO x and soot during combustion conditions are shown on a Fuel- Air Equivalence Ratio
Temperature ( T) plot on Fig 7.5. This plot is based on calculations done for n- hydrocarbon and
air combustion. In CI engine, the combustion conditions in terms of equivalence ratio and combustion
temperature vary across the combustion chamber and also vary with respect to time. Regions of SI
and CI engine combustion are identified on this plot and discussed as below:
around 1
Conventional SI engine combustion takes place in a premixed homogeneous charge with
and is shown in the right hand bottom corner. A point is shown for stoichiometric homogeneous SI
engine combustion. The combustion temperatures here are in the range of 2400 to 3000 K. NO
formation is a function of oxygen content and temperature of the burned gases. NO concentration is
shown qualitatively by the density of dotted points and is maximum at higher temperatures for slightly
leaner than stoichiometric mixtures. At a given temperature, NO reduces for the further lean mixtures
and for the rich mixtures with > 1.8 NO is negligible even at the high combustion temperatures.
The region of conventional diesel combustion is shown by a cluster of circular points on this plot.
These points refer to local mixture conditions and not the overall fuel-air ratio. The conditions show
formation of high concentrations of either soot or NO x locally in CI engine combustion. During
combustion of spray, in the core region

> 3 and combustion temperatures are in the range 1800 to

2400K. This is the region of soot formation. Concentration of soot increases as

increases at a

given temperature of combustion. Here any hardly NO formation is expected. At the spray boundary,
fuel burns as lean premixed charge or in near stoichiometric conditions as diffusion flame, which is
and T conditions
shown by the cluster of points on the left side of SI combustion region. These
belong to NO formation in CI engine. Here, no soot but high NO x is formed.
The region of desired HCCI/CAI operation is shown in the lower left corner on this plot which would
result in low NO x as well low soot formation. Here mixture is much leaner than =1and the
combustion temperatures are lower than 1900 C. This is the combustion region which is being
created in the combustion chamber for implementation of HCCI concept.

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Lecture 33:HCCI and CAI Engines

Figure 7.5

The Fuel air equivalence ratio Temperature diagram for hydrocarbon air mixture conditions for formation of soot and NO x . The conditions of
normal SI and CI engine operation and target region
for HCCI/CAI for low NO and soot formation are shown.

The HCCI/CAI combustion process has two main steps:


(i) Preparation of lean premixed, homogeneous fuel-air mixture, and
(ii) Autoignition leading to combustion of lean premixed charge.
Different approaches have been investigated to accomplish the above steps leading to HCCI/CAI
combustion

CAI GASOLINE ENGINES


The objective of CAI combustion in gasoline engines is to obtain high fuel efficiency and low NO x
emissions, the PM emissions already being insignificant. Fig. 7.6 compares P-V diagrams for a SI
and CAI engine operation. It may be noted that the combustion in CAI engine is much faster and it
approaches close to constant volume combustion.

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Figure 7.6

Comparison of P-V diagrams for SI and CAI


combustion.

Controlled autoignition (CAI) of homogeneous charge requires:


Charge is kept at a high temperature for sufficient duration
Composition of charge to ensure acceptable rate of combustion and low NO x formation
-

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Lecture 33:HCCI and CAI Engines
Methods to Obtain CAI
The following parameters have been used to obtain the required temperature, pressure and
composition of charge for CAI operation:
Residual gas content or EGR
Compression ratio
Intake mixture temperature
Intake mixture pressure
Fuel-air ratio
Coolant temperature
Injection timing in gasoline direct injection engines
The practical engines have to operate in CAI/SI dual mode. The SI engine mode at high loads is
required to have good specific power output. The autoignition of gasoline or natural gas requires CR >
20:1.Such high CR would be unacceptable at high loads when fuel-air ratio is to be increased as
severe engine knock would result. The engine CR is to be limited to around 10:1. Hence, increase of
CR to obtain CAI operation has not been a practical option. Intake mixture heating by using the waste
heat of the exhaust gas although helpful but gives a further loss in volumetric efficiency as already a
highly diluted charge is used to control the heat release rates subsequent to autoignition.
The most practical approach for CAI operation is use of large amounts of hot residual gases.
Trapping of the residual gases inside the cylinder also termed as internal EGR has been found a
more acceptable approach. A negative valve overlap period is used to retain high amount of residual
gases in the cylinder. The exhaust valve is closed before the piston reaches top dead centre in the
exhaust stroke and to prevent backflow of the burned gases in the intake system, the intake valves
open well after TDC. The relative valve timings for a standard SI engine and for CAI operation are
compared in Fig. 7.7.
To get maximum expansion work ideally the exhaust valves are to be opened at the usual time in the
cycle but are to be closed earlier. The intake valve is to open late while they should close as in the
normal SI engine operation. To obtain this flexibility in SAI-SI dual mode operation fully flexible,
variable valve actuation systems are necessary which are very complex in construction and presently
are not in production. In the practical engines, use of low valve lift cam profile provides substantial
reduction in valve opening period. This approach along with variable cam timing devices has been
used in prototype engines. By varying the exhaust valve closing time load can be varied.
As the
exhaust valve closes earlier to trap more residual gases, less fresh charge is admitted resulting in
lower engine output. The valve timings with lower valve lift are also shown on Fig. 7.7.
The trapping of residual gas in the cylinder results in high charge temperatures.. At high loads, the
auto ignition however, may occur too early and high rates of pressure rise would result.

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Lecture 33:HCCI and CAI Engines

Valve timings and lift using residual gas trapping method for CAI

Figure 7.7 operation.

Regime of CAI Operation


CAI operation was studied on a single cylinder engine using exhaust gas recirculation and heating the intake
charge to 320 1 C by an air heater. The fuel was injected at intake port . The CAI region is presented on a
plot in Fig 7.8 with fuel-air equivalence ratio, and EGR mass rate as variables. The CAI region is enveloped
by three engine operation regimes viz;
(i) Engine knock: It is experienced as

increases. The knock limited

increases as the rate of EGR

increases

(ii) Misfire: Engine misfire of the charge results as EGR is increased and the engine bmep is decreased.
(iii) Partial burn: For the fuel-air equivalence ratio less than about 0.2. As the fuel-air equivalence ratio
decreases, the heat released also decreases lowering the average combustion temperatures resulting in
partial burn and misfire.
Knock limited imep of 3.8 bar was observed. For an imep = 3.0 bar, depending upon

the EGR in the range

of 40 to 55% was required to obtain CAI operation.

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Figure 7.8

CAI operation regime enveloped by regions of partial burn, misfire and


knocking combustion; single cylinder SI engine, CR = 11.5, 1500 rpm.

The region of CAI operation forms only a small fraction of the total engine speed-load operation regime with
the present status of development. CAI operation of a SI engine is typically obtained for engine speeds from
1000 to 3500 rpm. At 1000 rpm, knock free CAI operation using EGR is possible up to about 5 bar bmep that
reduces to nearly 2 bar bmep at 3500 rpm. On the other hand the SI engine full load bmep is about 10 bar
and the rated engine speed typically is around 6000-7000 rpm. The practical engines could be operated in
mixed CAI-SI mode. At low and medium loads and at
vehicle cruising speeds engine operates in CAI mode but during cold starting, at idling and at high load and
speeds the engine operates in conventional SI mode.

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Lecture 33:HCCI and CAI Engines
Emissions with CAI and SI Engine Operation
The emissions from an SI engine that operated in CAI mode at part loads are compared with the
homogeneous stoichiometric SI engine on Fig. 7. 9. The engine used negative valve overlap ranging from
140-200 crank angle for CAI operation. Residual gas fraction varied from 40 to 70%. The intake air
temperature was increased to 50 C by external heating. The NO x emissions with CAI operation are extremely
low. HC emissions were higher as use of very lean mixtures results in partial misfired combustion increasing
HC emissions. CO emissions decreased by 80 % and the fuel consumption was lower by 15% at engine
speeds of above 2000 rpm.

Figure 7.9

Comparison of indicated specific emissions of CAI (


engine ( = 1.0), IMEP = 2.6 bar, 3000 rpm..

=0.77) and SI

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Module 7:Advanced Combustion Systems and Alternative Powerplants


Lecture 34:HCCI Diesel Engines
The Lecture Contains:

HCCI DIESEL ENGINES


Emissions with HCCI Operation
Regimes of HCCI and Conventional CI Engine Operation

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Lecture 34:HCCI Diesel Engines
HCCI DIESEL ENGINES
The objective of application of HCCI concept to the diesel engines is control of NO x and particulates
simultaneously which otherwise is difficult to achieve in the conventional CI engines. For HCCI combustion the
efforts are directed mainly towards:
Creation of premixed, lean homogeneous mixture, and
Compression ignition and control of rate of combustion to obtain low emissions and optimum engine
performance.
The basic objective is to increase the formation of premixed charge prior to ignition so that a large fraction of
the fuel per cycle burns as premixed. Subsequent to ignition the rate of combustion is to be controlled to keep
it within acceptable limits. The different methods which may be adopted to achieve the above two objectives
are:
Premixed Charge Formation:
Fuel introduction in Intake manifold or port
Early (much before the conventional injection timing) and multiple direct fuel injection in the cylinder
Late direct fuel injection (at TDC or later) in the cylinder
The different fuel injection timings that may be adopted in a diesel engine to obtain a long ignition delay and
consequently a high fraction of premixed charge before start of combustion are shown schematically in Fig
7.10. For HCCI mode of operation a high fraction of premixed charge is essentially required before start of
compression ignition .
Ignition and Combustion Control:
Multiple/split injection
High amount of EGR
Reduction in compression ratio

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Figure
7.10

Formation of lean premixed charge in HCCI engine concepts based on


fuel injection timing.

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Lecture 34:HCCI Diesel Engines
Intake Manifold or Port Injection:
With fuel injection in the intake manifold or at the port sufficient time is available for the fuel to
vaporize and mix with air and high degree of mixture homogeneity is achieved. As the boiling point
of diesel fuel is high the fuel vaporization may be enhanced by heating of intake manifold.
Autoignition occurs due to compression. In this approach, very low NO x down up to 1/100th of the
conventional diesel operation are possible. Smoke is very low, but higher HC and CO emissions are
obtained as considerable fraction of lean homogeneous mixture may not burn or burns only partially.
Intake charge heating although, improves fuel evaporation and charge homogenization, but results in
early ignition causing high rate of pressure rise and noisy combustion. If no intake heating is used,
some fuel may remain in liquid state until late in the compression stroke causing locally over rich
mixtures resulting in formation of soot. EGR has been employed along with intake mixture heating to
retard autoignition and control rate of combustion. Use of very lean mixtures also results in retard of
ignition but it limits imep to very low values that can be obtained without knocking combustion. Use of
a lower engine compression ratio to retard ignition results in loss of engine efficiency. Thus, intake
manifold fuel injection is not considered a practical approach for HCCI operation due to its negative
effects on fuel efficiency and hydrocarbon emissions and low knock limited value of imep
Early In-Cylinder Injection:
This approach has two advantages:
(i) Higher temperatures and density compared to intake air are available. Hence, External heating of
air is not necessary and,
(ii) One injection system can be used for early injection for HCCI operation and also for the
conventional diesel combustion operation at higher loads.
Sufficient time is available when the fuel is injected early in the compression stroke to fully vaporize
and form homogeneous mixture with air at the time of ignition.
One of the problems faced in practice is that the fuel is injected early during compression when the
density of air is low. It results in long length of spray penetration and the liquid fuel may impinge on
the combustion chamber and cylinder walls. To prevent fuel impingement redesigning of the injection
system may be necessary. Some of the approaches used are:
Injector in the centre of the cylinder with more number ( numbering up to 30) of smaller holes
Use of two side injectors opposite to each other so that spray travel distance is larger
compared to the central injector.
Multiple injection events with small quantities in each injection. A multiple injection strategy
using common rail injection system is shown in Fig 7.11. The first injection is made around 90
btdc followed by equally spaced several injection pulses. It allows each fuel pulse to mix well
with air. The main injection is made at tdc.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 34:HCCI Diesel Engines
contd...
The engine compression ratio is reduced to13.5 - 14:1 so that ignition delay is long to allow formation
of a homogeneous mixture. In split/multiple injection approach, the first injection is made at least 50
to 60 btdc. Cooled EGR is used to retard start of combustion of the premixed charge so that a
higher engine power is obtained before knock combustion results. The low temperature autoignition is
obtained near tdc just prior to main injection. The main fuel injection is made slightly after tdc. This
strategy shows improved combustion efficiency without excessive CO and HC emissions.

Figure
7.11

Schematic of multiple injection strategy for HCCI


operation of a diesel engine

Late In-Cylinder Injection:


If the injection is made very close to or after tdc the fuel encounters a gradual decrease in gas
temperature and pressure. It results in a long ignition delay and allows more time for mixture
formation and favourable conditions for HCCI combustion are obtained. As most of the fuel now burns
as premixed, a drastic reduction in soot formation is observed and high rates of EGR can be used to
obtain very low NO x .
The late injection strategy has the advantage in that the start of combustion is better related to the
injection timing and hence the combustion process can be controlled by injection timing. Also, very
little changes are necessary in the injection equipment.
Nissan Motor Corporation developed an HCCI diesel engine using late injection strategy with low
compression ratio. They called it MK (modulated Kinetics) combustion system. Late fuel injection and
low compression ratio were combined with 30 45 % EGR to prolong ignition delay beyond end of
injection. Injection timing was around 3-6 degrees btdc. Injection duration was reduced by use of high
injection pressures and larger nozzle orifices such that the injection duration was 4-10 CA shorter
than the delay period. The fraction of fuel that burns premixed increases substantially giving very low

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soot formation. Use of EGR and low compression ratio gave low NO x emissions. NO x obtained were
less than 1/10 th and PM emissions less than half at 6 bar bmep and 2000 rpm compared to
conventional diesel engine.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 34:HCCI Diesel Engines
Emissions with HCCI Operation
Emission potential of HCCI operation relative to conventional diesel engines is illustrated in Fig 7.12. The
HCCI engine employed multiple early injection strategy with compression ratio equal to 13.4:1 and high
rates of EGR. The NO x emissions were just 0.074 times (7.4%) and soot emissions were only 5.5% of the
conventional CI engine operation. NO x emissions with HCCI operation ranged from 0.01 to 0.06 g/kWh and
the soot emissions were below 0.02 g/kWh. Nearly 95% reduction in soot and NO x emissions are obtained
compared to the conventional diesel operation. However, due to quenching of combustion in excessively
lean mixture HC increased to 348%. CO increased to 487% of the conventional CI engine. As the mixture
is not entirely homogeneous and some over rich zones exist more CO is produced. Although excess air is
present in burnt gases but the combustion temperatures are low to promote oxidation reactions of HC and
CO in the post combustion gases.

Fig 7.12

Comparative emissions with HCCI and conventional


CI engine operation; multiple early injection strategy
of HCCI operation.

Regimes of HCCI and Conventional CI Engine Operation


Developments in application of HCCI combustion to conventional diesel engines may be summarized as
below:
Most of the strategies for HCCI operation essentially attempt to increase the fraction of fuel burned
as premixed charge.
The premixed charge obtained with early and more so with late in-cylinder injection actually may not

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be fully homogeneous.
The attempt is to keep local fuel-air ratio lean to reduce soot formation.
Most of the highly premixed charge undergoes precombustion reactions and burns simultaneously
such that no flame front is present and low temperatures are maintained.
The production diesel engines are unable to operate on homogeneous charge through out the entire
operational range. HCCI mode of operation is feasible only at part loads. At high loads, conventional
diesel combustion is to be employed.
Combustion concepts likely to be employed in the different speed-load operation regimes of a future diesel
engine are shown on Fig 7.13. As the HCCI operation in the entire range of engine loads and speeds is
not possible , it is envisaged that the future low emission engines would operate in combination of HCCI
operation at low BMEP and the conventional compression ignition mode in the high BMEP region . The
technologies already developed for control of emission in the conventional CI mode such as EGR ,
turbocharging , high pressure injection would be employed during high engine power operation.

Figure 7.13

Combustion concepts and operation map for a future clean diesel


engine

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Module 7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants
The Lecture Contains:
ALTERNATIVE PROPULSION SYSTEMS
HYBRID ELECTRIC VEHICLES (HEV)
Main Components of HEV
Types of HEVs
FUEL CELL
Fuel Cell Power Output
Factors Favouring Fuel Cell
Fuel Cell Types
Energy Sources for Fuel Cell
Prototype Fuel Cell Vehicles

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants
ALTERNATIVE PROPULSION SYSTEMS
Following factors provided motivation for the development of alternative propulsion systems for road
vehicles;
Global warming - Reduction desired in the emission of greenhouse gas, carbon dioxide
Control of urban air pollution
Higher energy efficiency - to prolong availability of petroleum fuels as the crude reserves
are diminishing
Energy security to be independent of import of energy from other countries
The design of power unit of vehicles is governed by several factors e.g., type of available fuel/energy,
economics of energy availability and environmental considerations. The following vehicle power plants
have been under detailed investigations and some of them are already introduced in the market.
Hybrid - electric propulsion
Fuel cells
Gas turbines
Stirling engine
Batteries for electric vehicle
The hybrid electric and fuel cell vehicles hold a greater promise of practical application. Hybrid
electric vehicles are built around the existing reciprocating IC engines and some vehicle models are
already in market. The fuel cell vehicle is a zero emission vehicle and all the major auto- companies
are pursuing its development as a future power plant. Hence, only these two are discussed here.

HYBRID ELECTRIC VEHICLES (HEV)


Motivating factors for HEV development are;
Power required by vehicle to operate within cities may be around 4 to 7 kW although the rated
engine power ranges from 25 to over 100kW. The engine thus, operates in the city under very
low load conditions giving high fuel consumption and emissions.
Small engine can be employed and operated at constant load and speed at the point of its
maximum efficiency, and another propulsion system can take care of the transient operation.
High vehicle fuel efficiencies are thus, obtained.
Engine can be tuned to its lowest emissions at the operating load and speed point
Emission control and exhaust after-treatment at steady engine load and speed operation is
more efficient.
Hybrid electric vehicle (HEV) allows achieving precisely this objective.
The hybrid electric vehicle employs two different energy storage and two different propulsion systems:
A conventional propulsion system like IC engine, and
An on-board rechargeable electric energy storage system coupled with electric motor(s)

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants
Main Components of HEV
The HEV is an intermediate step between conventional IC engine power train and full electric vehicle.
It has the following main components:
A prime mover: IC engines are most commonly used, gas turbine or Stirling engine can also
be used
Electric motor in parallel or series
Electric generator
Battery to store electricity and run motor
Regenerative braking system using devices like flywheel, ultra-capacitor etc.
Power transmission system
The high performance nickel-metal hydride (Ni-MH) batteries are more commonly used as the main
energy storage device. Recently, Lithium-ion (Li- ion) batteries, which have higher energy storage
capacity (2.5 kWh/kg) compared to the Ni-MH batteries (1.4 kWh/kg) are also being used on some
hybrid vehicles. To supplement the batteries, other energy storage systems such as flywheel and
ultra or super-capacitors are also used. The flywheel stores energy during vehicle
braking/deceleration and the super-capacitors store energy when the power drawn from the batteries
is low and the excess engine power is available. The super capacitors are capable of generating short
bursts of very high power

Types of HEVs
Two basic types of HEV are
(i) Series and
(ii) Parallel type.
Other variants of the two basic types have also been developed. The HEV configurations are shown
in Fig 7.14
Series Hybrid
In the series hybrid, electric motor is the only propulsion unit. It is connected with the drive wheels.
The engine is coupled with an alternator/ generator that runs the motor as well as charges batteries.
All the energy from the engine to the wheel passes through electric machine and hence, it is called
as series HEV. The electric power is always generated on board. The engine is not required to follow
the transient operation needs of the vehicle.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants
Parallel Hybrid
In the parallel hybrid, the engine and motor (run by battery) are mechanically connected to wheels
and traction can be provided simultaneously by both the power units. When the engine is unable to
meet the power requirement of the vehicle (such as under acceleration), energy from the battery
supplements the vehicle demand. Engine is thus, subjected to transient demands and consequently
fuel efficiency is poorer and emission penalties occur.
Mixed hybrid
In the mixed hybrid, an alternator run by the engine continues to charge batteries. The power to the
wheels flow directly from the engine as well as from the batteries charged by the alternator
simultaneously as in the parallel hybrids. Toyota Prius car, one of the most successful HEVs is a
mixed hybrid vehicle.
Plug-in hybrid
Most cars run less than 50 to 60 km/day in cities. Thus, a near zero emission vehicle can be
designed if a small size battery pack provides this range during city driving and when the vehicle
needs to run more distance the IC engine drives the vehicle. The batteries are charged every day by
the mains supply. Such hybrids are called as Plug-in- Hybrid Electric Vehicle (PHEV).

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Figure
7.14

Hybrid Electric Vehicle


Systems.

Already a few million HEVs are in use. The gasoline engines used on HEV run on Atkinson cycle to
improve thermal efficiency with large reduction in pumping losses. The Atkinson cycle is implemented
by late closing of intake valve (72 to 105 after bdc) while keeping the expansion ratio close to 13:1.
The power output of the engine is increased by supercharging.
The fuel efficiency improvements of nearly 50% in city driving and 30% on combined city and
highway driving have been obtained.
HEVs have met the SULEV emission standards (NMHC = 0.01, CO = 1.0, NO x = 0.02 g/mile).
HEV powered by diesel engine have obtained 25 % better fuel economy than the comparable
diesel vehicle. The NO x and PM emissions are lower by nearly 45 and 65 %, respectively.
The diesel hybrids produce up to 50% less CO 2 than the gasoline engines and 30 to 35% less
than the diesel engines making the diesel-hybrid more fuel efficient and environment friendly
than the gasoline engine hybrid.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants
FUEL CELL
Working Principle
Fuel cell was invented in 1839 by Sir William Groves. It is an electro-chemical device, which
continuously converts the chemical energy of fuel directly to electricity. The working principle of H 2 O 2 fuel cell is shown on Fig. 7.15.
The fuel-cell has two electrodes made of porous material coated with platinum as catalyst.
The electrodes are separated by a solid semi-permeable electrolyte.
Hydrogen flows into fuel cell on catalytic anode and gives up an electron.
Negatively charged oxygen at cathode attracts hydrogen protons through the solid electrolyte
membrane. On cathode, hydrogen and oxygen ions combine to produce water.
The electrons flow through external circuit producing current.

Figure 7.15

Schematic of
cell.

H2 O2 fuel

Fuel Cell Power Output


Open circuit standard EMF of fuel cell at reference condition is given by

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(7.1)
where:
= Gibbs free energy of formation for the reaction at reference condition of 298 K, and 1 atm
n = no. of electrons per molecule of fuel e.g. for H 2 -O 2 fuel cell n = 2
F = Faraday constant = 96,485 Coulombs/ electron mol.
At the other operating conditions, EMF of the fuel cell is,

(7.2)
where PH 2 , PO2 , PH 2 O are the partial pressures in atm.
Fuel cells can also use and operate directly on other fuels like methanol and methane Theoretical
EMF of some fuel cell systems is given in Table 7.3

Table 7.3
Theoretical EMF for Some Fuel Cells at reference
conditions

Fuel

Reaction

E0 , V

H2

H2 + 0.5 O2 H2 O

1.229

1.006

1.214

Methane CH 4 + 2O2 CO 2 +2H2 O(l)


CH 3 OH (l)+ 1.5O2 CO 2 +2H2 O
Methanol
(l)

Actual cell voltage is lower and is about 50 to 60% only of the theoretical EMF due to;
Slow rate of chemical reactions
Internal cell resistance
As the current drawn is increased beyond about 0.7 A/cm 2 , the concentration polarization
causes a further voltage drop.
Typical fuel cell characteristics are shown on Fig. 7.16. The change in current and voltage efficiencies
versus current drawn from the fuel cell are shown.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants

Fuel cell efficiency

Figure 7.16 characteristics.


Factors Favouring Fuel Cell

Varieties of sources for generating hydrogen are possible to reduce dependence on crude
petroleum
Vehicles with zero emissions of CO, HC, NO x and PM can be built.
On board reforming of methanol, ethanol or hydrocarbon fuels can be employed to generate
hydrogen. Thus, the existing fuel distribution network can be used.
Fuel cells are more efficient under part load operation than the IC engines. These are not
limited by the Carnot efficiency. At full power output, the internal resistance and concentration
polarization losses increase resulting in the loss of fuel-cell efficiency and it drops close to that
of the IC engines. Efficiency of fuel cell is compared with that of gasoline and diesel engines
on Fig. 7.17.

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Comparison of efficiency of fuel cell with conventional

Figure 7.17 internal combustion engines

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants
Fuel Cell Types
Fuel cells are classified by the electrolyte used. The different types of fuel cell developed for various
applications are given in Table 7.4. For vehicle application, the temperature of fuel cell operation and
start up time are important. The PEM (proton exchange membrane) fuel cell has been accepted
presently as best suited for vehicle application as it can be started in about 30 seconds and it
operates at acceptably low temperatures. The PEM fuel cell consists of an electrolyte membrane in
the form of a thin film of approximately 0.1 mm thickness made of sulfonated fluorocopolymer or an
aromatic polymer. A typical automotive fuel cell stack consisting of 640 PEMFC developed 129kW
peak power with continuous rating of 102 kW, weighed 100 kg and occupied 58 litres of space

Table 7.4
Fuel Cell Types and their
Characteristics

Temperature
Electrolyte
operation, C

Type

Alkaline (AFC) KOH (OH-)

of

60-120

Startup
%
time,
hours

Power
range
and
application

35-55

Very
short

<
5kW,
military, space

System
Efficiency
HHV

Proton
Exchange
Membrane
(PEMFC)

Polymer
Electrolyte
(H+)

20-120

32-45

5 250 kW,
<
High
power
0.01(30
density,
seconds)
automotive

PAFC

Phosphoric
Acid (H+)

160 -220

36-45

1 -4

200 kW, CHP

MCFC

Molten
carbonates
(CO-3)

550-650

43-55

5 -10

200 kW - MW,
CHP
and
stand alone

5 -10

2 kW - MW
CHP
and
stand
alone,
High efficiency

Solid doped
Solid
oxide
Zr-oxide (O- 850-1000
(SOFC)
)

43-55

Energy Sources for Fuel Cell


The following sources can supply energy to fuel cells
Hydrogen
Methanol
Ethanol
Hydrocarbon fuels, gasoline and diesel
Hydrogen-oxygen fuel cell provides the highest EMF and power density (W/cm 2 ). Hydrogen either can
be directly stored on-board of vehicle or generated by steam- reforming of fuels such as methanol,

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ethanol and hydrocarbons. The purity of hydrogen is very important for operation and longer life of
fuel cell as even small concentrations of carbon monoxide and sulphur are highly detrimental. The
products of fuel reforming are to be cleaned to supply hydrogen to the fuel cell. Although in principle,
methanol, ethanol, gasoline, diesel and other hydrocarbons can be reformed to supply hydrogen, but
so far only methanol reforming on board has been successfully used. Direct methanol fuel cell
(DMFC) where methanol is fed directly to the fuel cell for oxidation and generation of electricity, is
another option being developed for automotive use. . Electrolysis of water using nuclear energy and
the renewable solar, wind, hydro and wave energy is the other route to generate hydrogen. The
electrolysis route appears to be a long term solution once the low cost renewable or nuclear power is
available. On board storage of hydrogen is another important factor for commercial success of FCV.
Hydrogen can be stored in the form of gas, liquid, metal hydrides as hydrogen or in chemically
combined form such as methanol and NaBH4 (sodium borohydride). High pressure storage systems
of hydrogen at 700 bars have been developed. The different methods of hydrogen storage on board
are compared in Table 7.5. So far most FCV prototypes have however, used the high pressure (350
700 bar) hydrogen tanks.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Lecture 35:Alternative Powerplants

Table 7.5
Comparison of Hydrogen Storage Methods for Fuel Cell
Vehicles

Name

Storage
Temp, C

Storage
Hydrogen by
Pressure, MPa mass, %

Volume,litre/ kg
of H 2

High pressure
Ambient
cylinder

35 to 70

2 to 4.5

40 -70

Liquid H 2

Ambient

14

25

Fe-Ti hydride - 10

2.5

<2

36

Methanol

Ambient

Ambient

12.5

10

NaBH4

Ambient

Ambient

10.58

9.5

- 252

Prototype Fuel Cell Vehicles


From the early FCV prototypes such as Necar-1 by DaimlerChrysler, considerable progress has been
made in the fuel cell vehicle development. Necar-1 had a 50kW fuel-cell stack with 30 kW propulsion
system, hydrogen storage capacity of about 2 kg at 300 bar, maximum speed of 90 km/h and a range
of 130 km. Honda FCX vehicle built in 2004 is powered by a fuel cell stack of 86 kW, 4.3 kg of
hydrogen is stored at 350 bar. It is a normal size car having 150 km/h maximum speed and 395 km
range. The vehicle on US FTP cycle achieved fuel economy of 91.8 km/kg of H 2 . By the year 200607, through development of more efficient fuel cells and 700 bar cylinder pressure storage systems
the range of vehicles exceeding 500 km has been attained. Presently the cost of fuel cells is higher
by a factor of 2 to 3 compared to gasoline engines of the same power output. Honda Co. believes
that by the year 2018 the FCV could be produced at costs that are commercially viable.
The FCV has varying impact on the CO 2 emissions as it depends on the hydrogen generation
process.. Obviously, if the hydrogen or methanol is produced from natural gas the CO 2 advantage of
FCV over the conventional IC engines is not significant. If methanol is produced from natural gas to
provide fuel for the fuel cell, the effect on CO 2 reduction in fact, is negative. The comparative CO 2
emission scenario would again change when the IC engines are fuelled by the renewable fuels like
ethanol or biodiesel.

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Module7:Advanced Combustion Systems and Alternative Powerplants


Questions
(7.1) Three different approaches are used to obtain charge stratification viz., spray jet controlled,
wall controlled and flow controlled Discuss the differences in the duration of initial
heat release rate ( 0 to 10%) and heat release rates towards the end of combustion ( 80
to 90%) with the three methods. What factors are responsible for these differences?
(7.2) What type of emission control technologies may be employed to reduce HC and NO x
emissions in the DISC engines operating in the different air-fuel ratio regimes?
(7.3) What are significant differences between CAI and HCCI engine systems from the point of
mixture preparation and charge homogeneity?
(7.4) What are main methods being studied to HCCI combustion in the diesel type engines?
Discuss their merits and demerits.
(7.5) Why is it not possible to build a practical engine to operate in HCCI mode in the whole
speed and load range of a SI or CI engine?
(7.6) Discuss why a HEV is more energy efficient than the vehicles powered by the conventional
IC engine
(7.7) Discuss why a HEV is more energy efficient than the vehicles powered by the conventional
IC engine
(7.9) Discuss why the energy efficiency of fuel cells at part loads is much higher than for the IC
engines.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 36:Hydrocarbon Fuels and Quality Requirements
FUELS AND EFFECTS ON ENGINE EMISSIONS
The Lecture Contains:
Transport Fuels and Quality Requirements
Fuel Hydrocarbons and Other Components
Paraffins
Cycloparaffins
Olefins
Aromatics
Alcohols and Ethers
GENERAL FUEL QUALTY REQUIREMENTS

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 36:Hydrocarbon Fuels and Quality Requirements
TRANSPORT FUELS AND QUALITY REQUIREMENTS
Petroleum crude is presently the main source of automotive fuels although alternative fuels like
natural gas, LPG are also being used in large numbers of road vehicles in some countries. The
renewable fuels like ethyl alcohol and biodiesel too are being used in the form of blends with the
petroleum derived gasoline and diesel fuels. Petroleum crude
contains over 25000 compounds
mainly the hydrocarbons composed of hydrogen and carbon elements. A number of these compounds
also contain sulphur in varying amounts and, nitrogen and oxygen in small quantities. The
commercial liquid engine fuels are the mixtures of a few hundred different hydrocarbons.
Typically, the petroleum transport fuels contain about 85 - 86 percent carbon and 14 15 percent
hydrogen by mass. Sulphur containing compounds are also present in significant amounts.
In this module at first chemical composition and key characteristics of petroleum derived fuels and
how they influence engine combustion and emissions are covered. Later, the most promising
alternative fuels are also discussed.

Fuel Hydrocarbons and Other Components


Hydrocarbons are broadly grouped into paraffins, cycloparaffins (naphthenes), olefins and aromatics.
The olefins are not present in the crude petroleum but are generated during processing and refining
of crude when the practical transport fuels are being produced.

Paraffins
The paraffins are saturated hydrocarbons which are also known as alkanes. The carbon atoms have
single bond between them. The large alkane molecules are either straight chain or branched chain.
The empirical formula for the paraffin family is C n H 2n+2. Methane (CH 4 ) is the first member of this
family, the higher members being ethane (C2 H 6 ), propane (C3 H 8 ), n-heptane, n-octane,
isooctane (C8 H 18 ), n- hexadecane (n-cetane) and so on. The straight chain paraffins are called
normal- (n-) and branched chain are called iso- paraffins. Structures of some paraffins are given
below. There are several isomers of isooctane depending upon the position of the branches. The
isooctane that is most commonly referred to is 2-2-4 trimethyl pentane having five carbon atoms in
straight chain and three methyl groups in 2, 2 and 4 carbon atom positions.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 36:Hydrocarbon Fuels and Quality Requirements
Cycloparaffins
The carbon atoms are present in a ring structure and a single bond exists between carbon atoms.
Cycloparaffins or naphthenes have the formula, C n H 2n and cyclopropane (C3 H 6 ), cyclobutane
(C4 H 8 ), cyclohexane (C6 H 12 ) etc., are its examples. The cycloparaffins having more than 6 carbon
atoms are not common.

Olefins
Olefins or alkenes are open chain hydrocarbons having one or more carbon-carbon double bonds.
The compounds having one double bond are called mono-olefins and their empirical formula is
C n H 2n . The examples are ethylene, propylene, butene, octene etc. Those having two double bonds
are called as diolefins or dienes, the chemical formula being C n H 2n-2 . The position of the double
bond (s) is indicated by a prefix like 1-octene, 1, 3- butadiene etc. The diolefins are highly unstable
during storage and therefore, are undesirable compounds in the engine fuels. Another family of
unsaturated hydrocarbons has triple carbon-carbon bond. These compounds are known as acetylenes
or alkynes. The empirical chemical formula for alkynes is C n H 2n-2 and the first member of the series
is acetylene (C2 H 2 ). Higher alkynes are similar to higher alkenes with each double bond replaced by
triple bond

Aromatics
Aromatics are double bonded hydrocarbons arranged in a ring structure of carbon atoms. Each ring of
aromatics has 6 carbon atoms. Benzene (C6 H 6 ) is the first member of the family. Benzene structure
has three double bonds which alternate in position between carbon atoms. Other aromatics are
formed when hydrogen atom(s) attached to carbon in the aromatic ring is substituted by an alkyl

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radical such as methyl-, ethyl-, propyl- etc. Some examples of aromatics having side chains attached
to ring are toluene (methylbenzene), ethyl benzene, xylene (dimethyl benzene) etc. Many aromatic
hydrocarbons have two or more aromatic rings such as naphthalene, anthracene, benzo(a)pyrene.
These compounds are known as polycyclic aromatic hydrocarbons (PAH).

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 36:Hydrocarbon Fuels and Quality Requirements

Alcohols and Ethers


Alcohols as engine fuel have been of interest for a long time. In the hydrocarbons when a hydrogen
atom is substituted with hydroxyl radical (OH), alcohols are formed. Among the alcohols, methyl
alcohol (CH 3 OH) and ethyl alcohol (C2 H 5 OH) are considered as alternative fuels. Ethers, such as dimethyl ether (DME) has been investigated as diesel engine fuel and methyl teriary butyl ether (MTBE)
is being used as a high octane blending component in gasoline.

General Fuel Quality Requirements


Many properties of the fuels influence engine performance and emissions. The most important
properties of liquid fuels, gasoline and diesel most of which are specified in the fuel quality standards
are given in Table 8.1

Table 8.1
Important Characteristics of Liquid Petroleum
Fuels

Gasoline

Diesel

Distillation

Ignition quality
number)

(Cetane

index, Cetane

Reid vapour pressure

Distillation (volatility), 90% boiling point

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Heat of combustion*

Heat of combustion*

Density

Density

Antiknock
number)

quality

(Research

and

Motor octane

Viscosity

Oxidation stability

Aromatic content

Gum content, mg/100ml

Sulphur content

Lead content

Storage stability

Sulphur

Injection system cleanliness

Benzene
Sediments

Sediments

* Heat of combustion is not specified in the fuel quality standards

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 36:Hydrocarbon Fuels and Quality Requirements
cont....
Properties specific to gasoline and diesel are measured by a variety of test methods described in the
relevant ASTM, ISO and other standards. The properties of engine fuel have been changing since
the first engine was developed. A number of factors, most important being the vehicle emission
control, have been responsible for changes in the fuel properties over the last few decades. The
relationship of fuel properties with engine performance are qualitatively described in Table 8.2.

Table 8.2
Requirements of Automotive
Fuels

Fuel Quality

Relationship with Engine and Vehicle Performance

Combustion characteristics

Better ignition and combustion properties result in higher fuel


efficiency and lower emission of pollutants. High octane number
for SI engine and a high cetane number for CI engines is
necessary for good combustion

High heat of combustion

For the same mass of fuel on board a higher operation range of


vehicle is obtained.

High volumetric energy content

A smaller fuel tank improving vehicle space utilization and


packaging. Liquid fuels being sold on volume basis, it results in
better economics for the operators.

Low temperature performance

A significant fraction of fuel is required to evaporate at low engine


temperatures for better engine cold start and warm-up, good lowtemperature drivability and better fuel economy and emissions.

High temperature drivability

For ease of hot starting, good hot weather drivability and low
evaporative emissions, volatility of fuels is appropriately controlled
to meet the needs of seasonal and geographical variations in
ambient temperature.

Oxidation stability

Good low temperature oxidation stability reduces fuel deterioration


during storage and deposit formation in the fuel system and
engine combustion chamber.

Deposit formation control

Deposit control additives are now widely used for minimizing


deposit formation and maintenance to get better fuel economy and
low emissions during the vehicle service life.

Material Compatibility

It is essential to prevent corrosion of metallic and deterioration of


fuel system rubber and elastomeric components

Flow characteristics

Fuel has to be in fluid condition at low ambient temperatures. It is


particularly critical for diesel fuels. Also, appropriate diesel fuel
viscosity is essential for flow as well as for good injection
characteristics

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 36:Hydrocarbon Fuels and Quality Requirements
Fuel Quality Relationship with Emissions
Fuel properties can affect emissions directly as well as indirectly. Some fuel components by
themselves may pose health hazards or adversely influence the environment. Some other fuel
properties influence engine combustion and engine durability, while some other properties accelerate
deterioration in the performance of emission control devices and systems. These fuel qualityemission interactions are given in Table 8.3

Table 8.3
Fuel Quality Interactions with
Emissions

Type of
Interactions

Gasoline characteristics

Diesel characteristics

Direct emission Lead content, Front end volatility, Sulphur, Poly aromatic hydrocarbon content
of pollutants
vapour pressure, benzene content
Effect
combustion

on Octane number, volatility, oxygen Cetane number, Viscosity, Density, Volatility


content, final boiling point
(mid and tail-end boiling points), aromatic
content

Effect on engine Lead content, Final boiling point, Tail-end volatility and final boiling point,
cleanliness and Oxidation
stability,
Storage Carbon residue, Sulphur content, Oxidation
maintenance
stability, Corrosion resistance
and storage stability, Sediments
Durability
of Lead content, Sulphur, Sediments Sulphur
emission control
devices

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
The Lecture Contains:
Motor Gasoline
Antiknock Quality
Distillation
Reid Vapour Pressure
Oxidation and Storage Stability
Hydrocarbon Composition
Sulphur
Oxygenates
Contaminants
Summary of Gasoline Properties on Emissions
Reformulated Gasoline
Trends in Gasoline Specifications

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
MOTOR GASOLINE
Motor gasoline is a mixture of nearly 400 different hydrocarbons consisting of n-paraffins, isoparaffins, olefins, aromatics and some cycloparaffins. Typical gasoline has hydrogen to carbon atom
ratio in the range 1.8 to 1.95 and it may be assigned a molecular formula, C 8 H 15 . It is liquid at
room temperature and boils in the range from about 35 to 215 C. The principal characteristics of
gasoline that are important for engine performance and emissions have been given in Table 8.1. Key
fuel properties and their effects on engine performance and emissions are discussed below.

Antiknock Quality
In SI engines, use of a higher compression ratio results in higher thermal efficiency and higher engine
power. With increase in compression ratio however, knocking combustion occurs. Persistent and high
intensity combustion knock causes engine overheating, loss in efficiency and may lead to mechanical
damage to the engine components particularly under high load operation. To prevent or minimize
knocking combustion, gasoline of a high antiknock quality is needed.
Knock resistance of a fuel is measured by octane number (ON), which is determined by comparing
knocking combustion characteristics of the sample fuel to that of standard reference fuels in a
standardized
CFR (Cooperative Fuel Research, USA) test engine. The two reference fuels that
define the octane scale are:
A fuel with high knock resistance: Isooctane (C8 H 18 ) or 2-2-4 trimethyl pentane given octane
number equal to 100, and
A fuel with low knock resistance: n-heptane (n-C 7 H 16 ) given octane number equal to 0.
The blends of these two reference fuels define the intermediate octane number on a linear scale. For
example, a blend of 90 % isooctane and 10% n-heptane has 90 ON.
The ASTM CFR knock test engine used worldwide is a single cylinder, variable compression ratio
engine The engine compression ratio can be varied while the engine is running between 3 and 30 by
moving cylinder and cylinder head assembly up or down with respect to the crankshaft. Thus the
engine clearance volume is changed while the swept volume remains constant. A knock sensor is
mounted on the combustion chamber and knock signal is a function of rate of pressure rise during
combustion. Two test methods performed for automotive fuels on the standard CFR test engine are:
Research method (ASTM D-2699) that measures Research Octane Number (RON), and
Motor method (ASTM D-2700) measuring Motor Octane Number (MON).

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
contd.....
The engine
operating conditions for the research and motor methods are given in Table 8.4.
During the test, the air-fuel ratio of the engine with the sample fuel is adjusted for maximum knock
intensity. Then on these settings, the engine compression ratio is varied and the knock intensity
obtained with the test fuel is bracketed by two blends of the reference fuels that differ by not more
than 2 ON units. The octane number of the sample fuel is obtained by interpolation between the
knock intensity readings for the two blends of the reference fuels and their octane numbers. The
octane number above 100 ON is determined by using isooctane and varying amounts of TEL
(tetraethyl lead) in terms of ml TEL/ per litre. Tetraethyl lead is an antiknock additive. ASTM standards
have specified octane numbers to the blends of isooctane and TEL.

Table 8.4
Engine Test Conditions for ASTM Research and Motor
Methods
Operating Conditions

Research Method

Motor Method

Engine Speed, RPM

600

900

Inlet temperature, C

52

149

Inlet Pressure

Atmospheric

Atmospheric

Humidity, kg/kg of dry air

0.0036-0.0072

0.0036-0.0072

Coolant Temperature, C

100

100

Spark Advance, CA btdc

13 (constant)

19-26 (varies with CR)

Air-fuel ratio

Adjusted for maximum Adjusted for maximum


knock
knock

The test operating conditions used in Motor Method viz., higher intake mixture temperature and
higher spark advance are likely to produce more knock and thus, the method is more severe. For
the most fuels motor octane number is lower than the research octane number. The difference
between RON and MON is known as fuel sensitivity:
Fuel Sensitivity = RON MON

(8.1)

The fuel sensitivity for fuels is mostly in the range 0 to 12 octane units. The reference fuels being
paraffins, the paraffinic hydrocarbons have low octane

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
contd.....
sensitivity while the olefins and aromatics have high octane sensitivity. The commercial gasoline have
fuel sensitivity around 7 to 10 units. The test engine operates at low speeds and has an old design of
combustion chamber. In the production high speed engines, under actual operation at varying load,
speed and ambient conditions the antiknock performance of commercial motor gasoline may match
neither to research method nor to motor method under all operating conditions. In Europe therefore,
both the RON and MON for a gasoline are specified in the standards.. Many national gasoline
specifications like those in the USA and India use average of the research and motor octane numbers
to specify the antiknock quality of motor gasoline. The average of RON and MON is termed as
antiknock index (AKI):

AKI = (RON+MON)/2

(8.2)

Earlier, tetra-ethyl lead (TEL), an anti-knock additive was used to produce high octane number fuels
at a low cost. However, in 1975 when the gasoline vehicles for the first time employed catalytic
converters for emission control, lead was required to be phased out of gasoline. Lead by itself is
hazardous to human health. Now, gasoline is totally lead-free in most of the countries. The lead-free
gasoline is blended with high-octane fuel components like aromatics, isoparaffins, alcohols and methyl
tertiary butyl ether (MTBE) to improve its anti-knock quality.
Octane number has no direct effect on engine emissions. Severe knocking increases combustion
temperatures and may result in higher NO formation. The fuel octane number may affect emissions
through dependence of engine compression ratio on the octane number. For lead free gasoline,
hydrocarbon composition depends on its octane number. High ON lead free gasoline may contain
more of aromatics and olefins and hence unburned hydrocarbons also are likely to have higher
concentration of aromatics and olefins, which are more photo-chemical reactive.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
Distillation
The distillation characteristics of gasoline are presented by a curve relating percent volume of fuel
evaporated to temperature as shown in Fig 8.1. Temperatures for evaporation of 10 % (T10), 50%
(T50), 90% (T90) and final boiling point (FBP) of fuel are important features of the distillation curve
and their limits or equivalent are specified in the gasoline standard specifications.

Figure 8.1

Typical disillation curve of motor


gasoline

Distillation range influences engine exhaust emissions through its effect on fuel evaporation
characteristics, mixture formation and hydrocarbon composition. HC emissions during cold start and
warm-up may be influenced by the front-end volatility (T 10 ). An increase in T50 has been seen to
decrease HC emissions. A lower T90 has been seen to increase CO and NO x emissions in some
engines but it reduces other air pollutants; butadiene and formaldehyde which are known as air
toxics.

Reid Vapour Pressure


Reid vapour pressure (RVP) is measured at 37.8 C in a closed bomb having 4 times the volume of
liquid fuel.. At low ambient temperatures for good cold starting and faster engine warm-up a high
vapour pressure is required. But, in warm and hot ambient conditions, a high Reid vapour pressure
results in high evaporative emissions and may overload the carbon canisters of the evaporative
control system with the hydrocarbon vapours. RVP has good correlation with the fuel evaporation
losses during refuelling and from the fuel tank and carburettor. Evaporative hydrocarbon emissions as
a function of RVP and ambient temperature are shown on Fig. 8.2. The evaporative emissions
increase almost linearly with increase in RVP. For a given fuel RVP, the evaporative hydrocarbons

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increase as the ambient temperature increases.

Figure 8.2

Dependence of evaporative hydrocorbon


emissions on RVP and ambient temperature .

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
Oxidation and Storage Stability
The fuel may remain in the storage and transportation systems for several weeks. During storage
before it is consumed, fuel undergoes slow oxidation under the atmospheric conditions producing
gummy substances. Low temperature oxidation stability of gasoline is measured in terms of induction
period (ASTM D 525) and existent gum test (ASTM D381). Induction period measures oxidation
characteristics at a specified temperature and pressure in presence of oxygen denoting the time
period when sharp drop in oxygen pressure occurs, which indicates the beginning of oxidation. The
existent gum is a resin like substance that is formed due to slow oxidation of gasoline during
transportation, handling and storage which is present in the fuel sample. To improve oxidation
stability of gasoline chemical additives known as antioxidants are used.
The gum formed in gasoline during storage, leads to formation of deposits in carburettor, fuel
injectors, intake manifold, on intake ports and intake valves, and in the combustion chamber. The
gums clog fuel metering orifices, result in sticking of intake valves and form carbon deposits in the
combustion chamber. Deposit formation in fuel system and combustion chamber lead to loss in fuel
efficiency and
increase in carbon monoxide and unburned hydrocarbon emissions. Plugging of the fuel injector holes
reduces fuel flow rate that disturbs the calibration of feedback controlled engine fuel management
system. A 30 percent flow reduction in port fuel injectors has been seen to increase HC emissions by
10 to 30 %.
The formation of deposits in the combustion chamber increases the effective engine compression
ratio. These deposits being porous in nature act like small crevices adsorbing hydrocarbons during
compression. The hydrocarbons released from the combustion chamber deposits during expansion
stroke escape combustion resulting in higher HC emissions. The combustion chamber deposits can
increase HC and NO x emissions by up to 10 to 15%. To prevent deposit formation in the engine
intake, fuel system and combustion chamber, detergent/ dispersant type additives are added to
gasoline.

Hydrocarbon Composition
Olefins and aromatic hydrocarbons are high octane gasoline components but affect engine emissions
in several ways;
Olefins have poor oxidation and storage stability and their presence leads to formation of
higher existent gum.
Reduction in olefin content lowers emissions of the air toxic 1, 3-butadiene.
Lowering the content of smaller molecular weight olefins in gasoline, reduces ozone forming
potential of evaporative hydrocarbons.
Aromatics have higher adiabatic flame temperatures and hence, a tendency for higher NO
formation.
Combustion of aromatics leads to higher deposit formation in the combustion chamber.
Benzene is a natural constituent of gasoline and also is formed in the combustion chamber due
to dealkylation of alkylbenzenes. Lower benzene and aromatic content of fuel results in lower
exhaust and evaporative benzene emissions, Benzene being carcinogenic in nature its content
in gasoline is now controlled to less than 1% by volume in many countries.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
Sulphur
Sulphur has a significant deactivation effect on the catalytic converter reducing its efficiency. The
conversion efficiency of modern 3-Way catalysts may reduce by 40 % with 900 ppm sulphur
compared to 100 ppm sulphur in fuel. Most of the loss in 3-Way catalyst efficiency caused by sulphur
is recovered once the engine is operated on low sulphur fuel. More advanced catalysts systems like
de-NO x catalysts and the closed-coupled catalysts operating at high temperatures suffer more serious
and
poermanent loss of efficiency. NSR de-NO x catalysts require practically sulphur-free (< 5 ppm by
mass) fuel for their operation.
Sulphur also has an adverse effect on the working of heated exhaust oxygen sensor by deactivation
of platinum electrodes.

Oxygenates
Oxygen containing compounds like alcohols and ethers which may be blended in gasoline are
commonly termed as oxygenates. The alcohols and ethers that are permitted as blending components
in gasoline are given in Table 8.5. The amount of oxygenates or oxygen content of fuel for use in
engines designed to operate on the conventional petroleum fuels is limited mainly due to;
(i) Leaning effect of mixture caused by presence of oxygen in the fuel, which may increase NO x
emissions,
(ii) Effect on fuel Reid vapour pressure particularly when blending methanol
(iii) Adverse effect on the fuel system materials.
The oxygen in the fuel is limited to 2.7% mass of O 2 maximum in the USA and 2.5% O 2 maximum in
Europe. Now in the USA, use of methanol as a blending component of gasoline is not permitted due
to its toxic nature.

Table 8.5
Permissible Limits of Oxygenates in Gasoline in
Europe
Oxygenate Type

% vol.

Methanol, suitable stabilizing agents must


be added

Ethanol, stabilizing
necessary

agents

may

be

Isopropyl alcohol

Tertiary butyl alcohol

Iso-butyl alcohol
Ethers containing 5 or more carbon atoms
per molecule

10
7

Other organic oxygenates or their mixtures 2.5% m/m oxygen, not exceeding the individual limits

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defined in the regulations

fixed above for each component

Use of oxygenates in gasoline have the following features;


Addition of oxygenates results in lower CO and HC emissions primarily due to mixture leaning
effect more so in the carburettor vehicles.
When oxygenates are added, oxygen is attached with some of the fuel molecules and hence
an enhanced oxidation of fuel may be expected resulting in somewhat higher reduction in CO
and HC emissions than the leaning effect alone.
The magnitude of CO emission reduction for the closed loop feedback controlled vehicles using
3-Way catalysts is low as the mixture leaning effect occurs only during engine warm-up and
acceleration phases. Under normal operating conditions, the feedback system controls air-fuel
ratio close to stoichiometric.
Excessive leaning caused by oxygenates can result in poor vehicle drivability and higher
unburned hydrocarbons. Leaning effect may increase NO x .
Use of oxygenates particularly alcohols also increases emissions of formaldehyde, which is a
known carcinogen and has high photochemical reactivity.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
Contaminants
Contaminants like silicon may get into gasoline fuel at fuel distribution outlets due to poor housekeeping or due
to waste solvents being used as blending component at the market place. Silicon can cause failure of oxygen
sensors even in very small concentrations. Water can be present in dissolved as well as in free form in
gasoline. Water may lead to blockage of fuel lines, icing of intake system during severe winters in cold
countries and corrosion of fuel system components. Water content limits for gasoline are specified in the fuel
specifications.

Summary of Gasoline Properties on Emissions


Effects of gasoline quality on the engine emissions are summarized in Table 8.6. The effects of fuel quality on
emissions are also dependent on vehicle technology. In this table the results for catalyst equipped vehicles are
presented.

Table 8.6
Summary of Effects of Gasoline Properties on Emissions from
Catalyst Cars

Property

Change

Reduce Lead

0.013 0.005

g/l

HC- HC- NO Benzx


ene
Exh Evap

Butadiene

Aldehydes

-0

-0

-0

Lead CO

Add Oxygenate 02.7% O2

0-

+0

Reduce
Aromatics

50 20% v/v

+0

+0

Reduce
Benzene

3 2 % v/v

Reduce Olefins 10 5% v/v

+0

-0

-0

Reduce Sulphur 380 20 ppm 0

0 - *

Reduce RVP

70 60 kPa

-0

Increase E100

35 65%

0-

-0?

0 -

Increase E150

85 90%

0-

*Contradictory results obtained in different investigations.


Key: 0 = No effect;
0 = -2 to 2% effect; or = 2 to 10% effect; or = 10 to 20 % effect; or
= > 20% effect; ? = Insufficient data

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
Reformulated Gasoline
During late 1980s, in several large US cities the ambient air quality could not meet the prescribed
limits for CO and ozone even after enforcement of the then stringent vehicle emission standards. The
US Clean Air Act Amendments of 1990 therefore, legislated additional measures besides further
tightening of the emission standards. Five organic compounds called Air Toxics were identified for
control through fuel quality modifications. These toxic substances emitted through exhaust and fuel
evaporation are: benzene, formaldehyde, acetaldehyde, 1, 3 butadiene and polycyclic organic matter
(POM).
Gasoline quality was proposed to be modified for introduction in the big cities that did not meet the
ambient air carbon monoxide and ozone standards. This modified gasoline was called reformulated
gasoline (RFG). The RFG programme in the USA was implemented in two phases as given in Table
8.7.

Table 8.7
Performance Targets of US Reformulated Gasoline
Programme

RFG Programme

Performance Target

Phase 1(Started on Jan 1, 1995)

15 to 17% reduction in both the


exhaust and evaporative emissions of
volatile organic compounds (VOC) and
air toxics compared to 1990 industry
average gasoline. NO x however, must
not increase above the 1990 gasoline.

Phase 2(Started on Jan 1, 2000)

25-29% reduction in VOC, 17-20%


reduction in air toxic emissions and 5 to
7% reduction in NO x

The RFG is basically a gasoline containing oxygenates for reduction in CO and through control of
volatility and composition to reduce VOC and Air toxics. All the reformulated gasolines were required
to contain a minimum of 2 % by mass (m/m) oxygen and a maximum of 1% by volume (v/v) benzene.
The RFG must not contain heavy metals. Further, their average T90 , sulphur, and olefins contents
must not be higher than the 1990 average gasoline. Typical properties of Phase 1 and Phase 2 RFG
are shown in Table 8.8

Table 8.8
Characteristics of Typical US Reformulated
Gasoline

Properties
Aromatics, %v/v

Phase 1- RFG

Phase 2- RFG

23.4

25.4

Olefins, %v/v

8.2

4.1

Benzene, %v/v

1.3

0.93

RVP, kPa, Summer

50

46

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Winter

79

T50, C

94

94

T90, C

158

145

Sulphur, mass ppm

305

31

11

11.2

MTBE, %v/v
Ethanol, % v/v
Oxygen , % mass
Heavy metals
Detergent Additives

2.0 2.7
Not permitted
Compulsory

2.0 2.7
Not permitted
Compulsory

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 37:Motor Gasoline
contd....
Average effects of reformulated gasoline on emissions from catalyst equipped cars are compared with
those from a regular conventional unleaded gasoline on Fig. 8.3. These effects are primarily due to
leaning effect caused by presence of oxygenates. The CO and HC emissions are reduced significantly
while a small increase in NO x emissions is observed.

Comparison of effects of reformulated gasoline on emissions for

Figure 8.3 catalyst equipped cars with those with regular grade unleaded
gasoline

Trends in Gasoline Specifications


As the effect of gasoline properties on engine out emissions and on performance of catalytic
converters is quite significant, fuel specifications all over the world have been progressively revised.
Engine and vehicle manufacturers in Europe, America and Japan are making efforts to harmonize fuel
quality through out the world. They have come out on fuel quality recommendations based on the
level of emission control technology and customer satisfaction, which are referred as Worldwide Fuel
Charter. As an example of current day gasoline properties, Indian Specifications of Euro IV emission
compliant fuel are given in Table 8.9

Table 8.9
Indian Specifications for Euro IV/Bharat Stage IV Emmission Norms
Compliant Motor Gasoline
Characteristics

1 Density @ 15C, kg/m3

Limits
Gasoline 91 RON

Gasoline 95
RON

720-775

720-775

10-45

10-45

2 Distillation:
a) % evaporated at 70C (E-70), v/v

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b) % evaporated at 100C (E-100), v/v

40-70

40-70

c) % evaporated at 150C (E-1500), v/v ,


min

75

75

d) Final boiling point, C, max

210

210

e) Residue, percent by volume, max

3 Research Octane Number (RON), min

91

95

4 Motor Octane Number (MON), min

81

85

5 Existent gum, g/m3, max

40

40

6 Sulphur, total, mg/kg, max

50

50

0.005

0.005

8 Reid vapour pressure (RVP) at 38C, kPa,

60 (67)

60 (67)

9 Benzene content, percent by volume, max

10 Olefin content, percent by volume, Max

21

18

11 Oxidation stability, minutes, Min

360

360

12 Aromatic content, percent by volume, Max

35

35

13 Oxygen content, percent by mass, Max

2.7

2.7

Nil

Nil

c) Iso-Propyl alcohol

10

10

d) Iso-butyl alcohol

10

10

15

15

7 Lead content (as Pb), g/1, max

14 Oxygenates, percent by volume, Max


a) Methanol
b) Ethanol

e) Tertiary-butyl alcohol
f) Ethers containing 5 or more 'C' atoms
per molecule
g) Other Oxygenates

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 38:Diesel Fuels
The Lecture Contains:
DIESEL FUELS
Ignition Quality
Distillation Range
Viscosity
Chemical Composition
Sulphur Content
Lubricity
Summary of Effect of Diesel Fuel Quality on Emissions

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 38:Diesel Fuels
DIESEL FUELS
Diesel fuel is a mixture of a few hundred hydrocarbons derived from refining of crude petroleum.
When petroleum prices were low, the diesel fuels were produced mostly by blending various refinery
streams from the atmospheric distillation unit of petroleum refineries. To meet the increasing demand
of the diesel fuels, products of secondary refinery processes like thermal and catalytic cracking,
hydro-cracking, vis-breaking etc., also are used as blending components of the current diesel fuels.
The diesel fuel streams evaporate generally in the temperature range of 150- 390 C. The key
properties of the diesel fuel have already been given in Table 8.1. Besides these, other significant
properties include cold flow characteristics at low ambient temperatures, water and sediment content
etc. The important diesel fuel quality parameters are discussed below.

Ignition Quality
Ignition quality is a measure of ease of self-ignition of diesel fuel when the fuel is injected in hot
compressed air in the engine cylinder. Cetane number (CN) is the most widely accepted measure of
ignition quality as it is measured by a test on the engine. The cetane number scale is defined in
terms of blends of two pure hydrocarbons used as reference fuels;
A high ignition quality hydrocarbon: n- Hexadecane or Cetane ( n-C 16 H 34 ) given CN =100
Another hydrocarbon with poor ignition quality: Hepta-methyl nonane (HMN) assigned CN =15.
The cetane number scale is given by:
CN = % n-cetane + 0.15 x % HMN

(8.3)

Cetane number is measured in a standard single cylinder, variable compression ratio CFR engine
according to ASTM D613 method. The test engine is a prechamber diesel engine. The test conditions
are:
(i) Intake air temperature = 65.6 C,
(ii) Coolant temperature = 100 C,
(iii) Engine speed = 900 rpm,
(iv) Injection advance = 13 btdc.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 38:Diesel Fuels
contd....
Engine compression ratio is varied to obtain start of combustion at top dead centre i.e. ignition delay
is maintained equal to 13 CA for the test fuel and two blends of reference fuels that bracket the
compression ratio obtained with the test fuel. The reference fuel blends should not be more than 5
CN units apart. The cetane number of the test fuel is determined by interpolation from the
compression ratio values and the corresponding cetane numbers of the reference fuel blends.
Correlations of ignition quality with the physical properties of the diesel fuels have also been
developed for ease of quality control during refining. These correlations are applicable only to the
neat petroleum derived diesel fuels when no additives are used to improve ignition quality. The
Calculated Cetane Index (CCI) determined by ASTM D 976 or ASTM D 4737 methods are more
commonly used as an alternative to CN for the neat diesel fuels. The calculated cetane index is not a
substitute for ASTM cetane number. It is only a supplementary parameter for predicting cetane
number when used keeping in view its limitations. The CCI calculation methods are not suitable for
pure hydrocarbons, or non-petroleum based fuels derived from coal.
ASTM D 976 uses a two variable equation to determine CCI from the mid-boiling point and density of
the diesel fuel as below,
CCI976 = 454.74 - 1641.416 D + 774.74 D 2 - 0.554 B + 97.803 (log B)2

(8.5)

where:
D = density at 15C (g/ml) determined by Test Method ASTM D 1298.
B = 50% evaporation (mid-boiling) temperature (C) determined by Test Method ASTM D 86 and
corrected to standard barometric pressure.
ASTM D 4737 is a newer more exhaustive method in which CCI is correlated to four variables; the
density and temperatures for evaporation of 10% (T 10 ), 50% (T 50 ) and 90% (T 90 ). Details are
available in the relevant standards and other texts.
CCI values are quite close to the cetane number. Several national fuel standards also specify cetane
index values in addition to cetane number.
Cetane or ignition improvers are used to improve ignition quality of the diesel fuels. Nitrates like
isopropyl nitrate, cyclo-hexyl nitrates, ethyl-hexyl nitrate (EHN) and peroxides like di-tertiary-butyl
peroxide are used as cetane improvers. These compounds readily decompose at the engine
compression temperatures and produce free radicals that accelerate precombustion reactions and
thereby reduce ignition delay. The cetane improvers are used typically in dosages of around 500 to
2000 ppm by volume.
With high cetane fuels cold starting is easier and engine warm up is faster. Therefore, use of high CN
fuels results in lower HC emissions during engine warm-up phase and the reduction in HC is more
significant at low ambient temperatures. High cetane number fuels give shorter ignition delay and
thus, reduce the amount of fuel burned in premixed phase which results in lower peak combustion
pressures and temperatures. Therefore, high CN fuels are expected to give lower NOx emissions.
Typical effect of CN on NO x emissions is shown on Fig. 8.5. Ratio of NO x emissions obtained for 58
CN fuels relative to that obtained with 50 CN fuel are shown at different engine loads. Depending
upon the engine load, up to 6 - 8% lower NO x may result with increase of CN from 50 to 58. At full
engine load however, a slight increase in NO x with increase in CN was seen.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 38:Diesel Fuels
contd...

Effect of cetane number increase from 50 CN to 58 CN on NO x

Figure 8.5 emissions; natural and additive improved cetane number fuels
have slightly different effects..

Effect of CN on PM emissions depends on the engine design. For high speed, light duty engines a
small reduction in PM emissions with high CN has been observed while low speed, heavy duty
engines showed no significant change. With high cetane fuels the ignition delay is shorter and more
fuel burns in diffusion combustion phase, which may increase soot emissions depending upon the
engine operating conditions and design. Current fuel specifications are setting minimum limits of more
than 50 units for the CN and minimum cetane index is also being specified as the natural high
cetane fuels generally give overall better engine performance with respect to PM and HC emissions.

Distillation Range
A typical distillation curve for diesel fuel is shown in Fig. 8.6. The temperature for 50 percent
distillation temperature or mid-boiling point, 90 percent point and the final boiling point are the
important distillation parameters.
Lower the boiling point of the fuel, more readily it vaporizes and mixes with air giving more complete
combustion. The mid boiling volatility is also correlated to the other physico-chemical properties like,
density, viscosity and ignition quality. A higher mid boiling point fuel has higher density and viscosity,
and usually a lower CN. Low mid boiling point fuels give faster cold starting and hence lower HC
emissions. The fuel components boiling above 350 C may not burn completely, forming high soot
concentrations and combustion chamber deposits. Fuels with high T90 and final boiling point are seen
to result in an increased injector coking leading to poor combustion and higher smoke emission.

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Figure 8.6 Typical distillation characteristics of diesel fuel.


For the modern diesel fuels low maximum permissible limits for T90 or T95 around 350 to 360 C are
being stipulated due to their negative long-term effects on emissions

Density
The density of diesel fuel varies generally in the range 810 to 880 kg/m 3 . The density, volatility,
cetane number, viscosity and heat of combustion of petroleum fuels are interrelated. An increase of
10 percent in density increases the volumetric energy density (MJ/ m3 ) of the fuel approximately by 6
percent. The balance 4 percent is accounted for by the decrease in heat of combustion (MJ/kg) for
the 10% heavier (higher molecular weight) fuels is metered volumetrically by injection pumps. The fuel
density affects engine calibration and power as the fuel mass injected/stroke varies with fuel density.
High-density fuels also have a higher viscosity thus, influence injection characteristics. Increase in the
fuel density advances the dynamic injection timing by up to 1 CA. Thus, the fuel density affects
engine combustion and emissions.
PM emissions generally increase with increase in fuel density. As the fuel injection system is
calibrated for a particular fuel density, the current fuel specifications set narrow limits acceptable fuel
specific gravity e.g. from 0.82 to 0.85.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 38:Diesel Fuels
Viscosity
The viscosity of diesel has a strong influence on fuel atomization, a high viscosity fuel resulting
in larger fuel droplets.
An increase in viscosity reduces spray cone angle and increases spray penetration.
Low viscosity on the other hand, results in an increase in leakage of fuel past the pumping
elements and loss of fuel system calibration.
High viscosity of fuel is necessary for lubrication and protection of the injection equipment from
wear.
Most fuel specifications limit kinematic viscosity of diesel fuel in the range 2.0 to 5.0 centistokes.

Chemical Composition
Olefins adversely affect oxidation and storage stability of diesel fuels. Poor fuel oxidation
stability results in formation of gummy substances which cause plugging of fine fuel filters and
sticking of injector needles.
As the aromatic content of fuel increases, the particulate and PAH emissions increase.
Fuels with high aromatic content have a lower natural cetane number and its consequent effect
on combustion and emissions.
Aromatics have higher flame temperatures and hence increase in aromatic content of fuel is
expected to result in higher NO x emissions.
An increase in polycyclic aromatic content generally results in higher PM emissions. .
The diesel fuel specifications in the USA, Europe and several other countries now limit aromatic
content to 10 percent maximum. Also, limits on the poly-aromatic hydrocarbons are being specified.
One side effect of reduction in aromatic content is reduction in lubricity characteristics of the diesel
fuels causing durability problems of injection pump and injectors.

Sulphur Content
Sulphur on combustion produces sulphur dioxide (SO 2 ), of which about 1 to 3% is oxidized to
sulphur trioxide (SO 3 ) and forms sulphates found in particulate emissions. The balance of SO2
is exhausted as gas.
Typically, increase of 500 ppm in sulphur content contributes to about 0.01 g/kWh increase in
diesel PM emissions.
The sulphur trioxide on combining with water forms sulphuric acid that causes wear of engine
cylinder liner and piston rings.
Sulphur increases deposit formation in the combustion chamber and the deposits become
harder in presence of sulphur.
Fuel sulphur has deleterious effect on functioning of advanced after-treatment devices such as
NO x storage- reduction (NSR) catalysts, continuously regenerating diesel particulate traps
(CRT) and catalyzed diesel particulate filters (CDPF). The sulphur dioxide and trioxide poison
the catalyst. NSR catalysts require practically sulphur free (< 5 ppm) fuel.
In CRT, conversion of NO to NO 2 ahead of CRT is reduced by sulphur as it poisons the
catalyst. Sulphur lower than 30 ppm is necessary for functioning of CRT
In most countries during early 1990s, sulphur content of diesel fuel was in the range from 0.2 to 0.5%

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(2000 to 5000 ppm) by mass. After the year 2000, a number of European countries made available
the diesel fuels with less than 0.005% (50 ppm) sulphur. A large number of countries around the
world have diesel fuels with sulphur below 0.05% for road vehicle application. Trends in diesel fuel
sulphur content in some countries are given in Table 8.10.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 38:Diesel Fuels
contd....

Table 8.10
Trends in Diesel Fuel Sulphur in Some
Countries

Country/Region

Effective date/Fuel Grade

Maximum allowable sulphur


content, % m/m

European Union

1994
1996
2000

0.2
0.05
0.035

Sweden

1990
1993 EC1
EC2
EC3

0.20
0.001
0.005
As per the EN 590 standards

UK

1996
0.05
1998 (Ultra low sulphur grade, 0.005
ULSD)

Japan

1997

0.05

India

1995
2000
2005
2010

0.5
0.2
0.05
0.005

Lubricity
The injection pump and injectors are lubricated by the diesel fuel itself. The heavier, high viscosity
hydrocarbons and polar compounds provide natural lubricity to the diesel fuel. Hydro-treating of diesel
fuel to remove sulphur also converts and removes polar compounds. Consequently, as the sulphur
content of diesel fuel decreases, the lubricity of diesel fuel goes down resulting in excessive injection
pump wear. A high frequency reciprocating rig (HFRR) test in which wear scar size on a standard
test piece with the test fuel is measured, provides good correlation to the injection pump wear in real
life. The HFRR test limit of 460m wear scar diameter has been accepted in European diesel fuel
specifications to provide adequate protection against injection pump wear.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 38:Diesel Fuels
Summary of Effect of Diesel Fuel Quality on Emissions
Effect of changes in important diesel fuel properties on CO, HC, NO x and PM emissions has been
investigated in several programmes in Europe and the USA and also by other investigators. The
overall effects of fuel properties on emissions are qualitatively summarized in Table 8.11.

Table 8.11
Summary of Overall Effects of Diesel Fuel Property Changes on
Emissions

Vehicle
type

Fuel Property

Property Change CO

HC

NOx

PM

Light-duty
vehicles

Increase CN
Reduce density
Reduce T95
Reduce PAH
Reduce sulphur

50 55
850 820 kg/m3
370 330 C
6 3 % v/v
2000 500 ppm

-0
?
0

-0
?
0

0
0
-0
?
0

-0
?

Heavy-duty
vehicles

Increase CN
Reduce density
Reduce T95
Reduce PAH
Reduce sulphur

50 55
850 820 kg/m3
370 330 C
6 3 % v/v
2000 500 ppm

0
-0
?
0

0
-0
?
0

-0
?
0

-0
?

Key:

0 = No effect;
0 = -2 to 2 %; or = 2 to 10%;
or = >20%;
? = Insufficient data

or = 10 to 20%;

Diesel Fuel Specifications


Engine technology is being continuously modified and upgraded to meet the newer and more stringent
emission regulations. Accordingly, the diesel fuel quality also has undergone significant improvements
particularly related to CN, sulphur content, tail end volatility and wear protection of injection system. In
some countries, bio-diesel is also being blended with diesel fuel. To keep injection pump calibration at
acceptable level with diesel-fuel and biodiesel blends, a maximum oxygen content limit has been
specified in the Indian fuel specifications. The key diesel fuel properties in Europe and India are
given in Table 8.12.

Table 8.12
Diesel Fuel Specifications in Some
Countries

Property

Europe (EN590:
1999)

India (IS 1460) (BS IV 2010)

Cetane number, min.

51

51

Cetane index, min

46

46

Density @ 15 C, kg/m3

820-845

820-845

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Viscosity @40 C, mm2/s

2.0 -4.5

2.0-5.0

Sulphur, %m/m, max.

0.035

BS III: 0.035
BS IV: 0.005
-

Total aromatics, % m/m, max.


Polyaromatics, (di+tri++), max.

11

11

Distillation:
% recovered at 250 C, max.

65

T 85, C, max.

350

T90, C, max./range

T95, C, max.

360

360

FBP, C /range

Flash Point, C, min.

55

35

Carbon residue, % m/m, max.

0.30

0.30

Water content, mg/kg, max.

200

200

Oxidation stability g/m3, max.

25

25

Particulates, mg/l

24

Lubricity(HFRR scar dia. @ 60 C), m

460

460

Oxygen content, % by mass max.

0.6

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 39:Alternative Fuels
The Lecture Contains:
ALTERNATE FUELS
Properties of Alternative Fuels
Alcohols: Methanol and Ethanol
Natural Gas
Effect of Natural Gas on Emissions
Liquefied Petroleum Gas

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 39:Alternative Fuels
ALTERNATE FUELS
Most important alternative fuel candidates are: ethanol, methanol, natural gas, liquefied petroleum gas
(LPG), vegetable oil esters commonly called as biodiesel and hydrogen High petroleum prices during
1980s provided motivation for development programmes for use of ethyl alcohol produced from agricultural
products as motor fuel in countries like Brazil. During the same period, clean burning properties of
methanol and its easy production from natural gas led to technological development activities on methanol
in the USA. Methanol being liquid it is better suited than natural gas for storage on-board of vehicles.
However, due to its toxicity and its corrosive nature towards fuel system materials, interest in methanol as
automotive fuel has gone down although a number of demonstration fuel cell vehicles (FCV) using
methanol have been developed. Presently, natural gas and biodiesel have attracted maximum attention of
the governments, vehicle manufacturers and fuel suppliers. Hydrogen is considered as an alternative
transport fuel in the long term especially for the fuel cell powered vehicles. .

Properties of Alternative Fuels


Some of the key properties of the main alternative fuel candidates are compared in Table 8.13 with those
of conventional petroleum fuels. Key properties to be considered for :
Combustion and Performance: Heat of combustion, heat content of stoichiometric mixture, octane
number (SI engine) , cetane number (CI engine), boiling point ( esp., cold start), flammability limits
Emissions: Chemical composition and nature, adiabatic flame temperature
Storage and Handling: Boiling point, volumetric energy density, vapour pressure, flammability limits
Keeping the above in view the main alternative fuels are being discussed below

Table 8.13
Properties of Various Fuels for
Vehicles

Property

Gasoline Diesel Methanol Ethanol Natural Propane DME RME Hydrogen


gas

Mol.wt.

110

Specific
gravity
LHV, MJ/kg

195

32.04

46.07

18.7

44.10

46.1

300

0.72-0.78 0.820.88

0.796

0.794

0.72

0.51
liquefied

0.67
liquid

0.882 0.090

44.0

42.5

19.9

26.8

50.0

46.3

28.4

37.7

120

Heat
of 305
vaporization
,kJ/kg

250

1110

904

509

426

410
at 20
C

Boiling
C

point, 30-215

180370

65

78

-160

-43

-24.9

330340

-253

RON
(MON)

90-98
(80-90)

112
(91)

111
(92)

120-130 112
(120(97)
130)

106

Cetane
number

45-55 -

>55

51-52 -

2.015

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Stoichiometric 14.7
A/F
ratio,
mass

15.0

6.43

8.94

17.12

15.58

LHV of stoich. 3.50


mixture,
MJ/m3

3.14

3.28

3.10

3.38

2.88

2151

2197

2227

2268

2383

69.0

71.2

54.9

64.5

Adiabatic
flame
temperature
(K)

2266

Stoichiometric 71.9
CO2
emissions,
g/MJ fuel

75.4

9.0

69.0

11.2

75.5

34.13

LHV= Lower heating value

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 39:Alternative Fuels
contd...
Example 8.1:
Calculate energy content of 1 m3 of stoichiometric mixture of methane with air at 1 atmosphere
pressure (101 kPa) and 298 K. LHV of methane is 50 Mj/kg.
Solution:
Stoichiometric mixture composition of methane is given by

Total moles of fuel-air mixture = 1 + 2 x 4.76 = 10.52


Energy content of mixture consisting of 1 kmol of methane:
= mol wt x LHV
= 16 x 50 = 800 MJ
Volume of stoichiometric mixture consisting 1 kmol of methane

Energy content per unit volume of stoichiometric mixture = 800/258.07 = 3.10 MJ/m3
Ans.

Alcohols: Methanol and Ethanol


Methanol at present is produced mostly from natural gas although both methanol and ethanol can be
produced from renewable sources. Methanol may be produced near the natural gas field and it being
liquid can be more easily handled and transported over long distances compared to natural gas.
Ethanol is produced almost entirely from the renewable agriculture sources by fermentation of sugar,
grains, tapioca etc.
Alcohols in engines may be used as:
Low concentration ( 5 to 10% by volume) blends in gasoline
Neat alcohol or high level ( 85% by volume) blends
Neat ethanol (95% ethanol + 5% water) and anhydrous ethanol blended up to 20% in gasoline have
been widely used in Brazil during 1980s. In the USA, use of ethanol was promoted due to agricultural
surplus for blending in the reformulated gasoline as oxygenate. Use of 5 to 10% ethanol as a
blending component in gasoline is permitted in Europe and India.
Now, ethanol is the preferred
oxygenate replacing MTBE. As mentioned earlier, methanol due to its toxicity is not permitted any
more for blending into gasoline. The 10 percent ethanol-gasoline blends used in the USA are
commonly referred as Gasohol. Key features of alcohols as motor fuel are;

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Lecture 39:Alternative Fuels
contd...
Alcohols are a preferred alternative for SI engines only due to their high octane number. A higher
engine compression ratio could be used to obtain a higher engine thermal efficiency.
Cetane number of methanol and ethanol are close to 5 and 8, respectively.
Direct injection alcohol engine prototypes operating similar to diesel/CI engines have also been
developed using either a positive source of ignition or high dosage of ignition quality improvers (3 to
7% by volume).
Alcohols are not easily miscible in the diesel fuels. To prepare alcohol-diesel blends high amounts of
emulsifiers or solublizers are required.
Heating value of ethanol is approximately 60 percent and that of methanol is only 45 % of gasoline.
The stoichiometric air-fuel ratio due to presence of oxygen in the molecule is much lower than the
gasoline.
The volumetric energy content of stoichiometric mixture (gaseous state) of alcohols and gasoline
however, are not very different. Thus, engine specific power output that may be obtained with
alcohols and gasoline is nearly the same.
The latent heat of vaporization of methanol and ethanol is nearly 4 and 2.7 times, respectively
compared to gasoline. Cold starting performance with neat alcohol is therefore, poor compared to
gasoline.
Flames of neat alcohols in air are not easily visible to the naked eye. Hence, 15% gasoline is mixed
to alcohol for making the flame visible in case of an accidental fire.
A large number of investigations have been carried out with alcohols as engine fuel. Emissions with low
level alcohol blends as well as with neat alcohols have been studied. CO and NO x emissions show no clear
trend although lower flame temperatures with alcohol may result in lower NO x emissions. With neat alcohol
operation, as the emissions of most of the volatile organic compounds in the exhaust would consist of
alcohols or aldehydes only, the photo-chemical reactivity and the ozone forming potential is lower with
alcohol fuel operation.
The main advantages and disadvantages of alcohols with respect to conventional gasoline and diesel fuels
are summarized in Table 8.14.

Table 8.14
Advantages and Disadvantages of Alcohol Motor Fuels Compared to Gasoline
and Diesel

Performance
Parameter

Compared to gasoline and


diesel fuels

Advantages/Disadvantages

Flame temperature

Lower

Potentially lower NOx emissions and


lower heat losses

Vapour pressure

Lower

Poor cold starting and warm up


performance, higher
unburned
fuel
emissions
during
starting/warm up phase

PM emissions

Lower

Due to clean burning characteristics


PM emissions are
even lower than
the gasoline engines

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Air Toxic Emissions

Lower

Lower benzene
emissions

and

1,3 butadiene

CO and NOx Emissions

Similar

No definite trend is observed, So, no


advantage over
petroleum fuels have been noted

Aldehyde emissions

Higher

Formaldehyde
and
emissions are higher

Nature of sources

Renewable esp. of ethanol

Sources more widespread around the


world, hence
better energy security. Lower net CO 2

acetaldehyde

emissions.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 39:Alternative Fuels
Natural Gas
Natural gas has been used now for more than 50 years as fuel for stationary engines for power
generation, and agricultural machinery. Several million natural gas vehicles are in operation in
Argentina, Brazil, Australia, Italy, India and Pakistan, besides other countries. In the USA, stringent
particulate emission standards for the urban buses implemented from the year 1994 was the
motivation for development of natural gas operated urban buses.
The principal constituent of natural gas is methane (80 to 95% by volume). The balance is composed
of small amounts of other hydrocarbons such as ethane, propane and other gases like nitrogen,
carbon dioxide, water, hydrogen sulphide and some trace gases. Composition of natural gas varies
from source to source. Composition of natural gas from two different sources is given in Table 8.15.
Large variations in gas composition can have significant effects on engine performance and
emissions, especially if the engine performance and emissions are optimized on a fixed gas
composition. The natural gas before transportation or use is upgraded by removing water, hydrogen
sulphide and condensable higher hydrocarbons.
To minimize variations in engine emissions and performance, and to ensure a minimum heating value
to customers, specifications for natural gas sold commercially as fuel have been established.

Table 8.15
Typical Composition of Natural Gas from Two Different
Sources

Constituent, mole%

Natural gas 1

Natural gas 2

Methane
Ethane
Propane
C4 and higher
Carbon dioxide
Nitrogen

94.8
2.9
0.8
0.2
0.1
1.2

84.8
7.7
1.7
0.5
5.2
0.1

Natural gas liquefies at -161 C at atmospheric pressure. To use liquefied natural gas (LNG) as
automotive fuel, cryogenic systems are required. Therefore, natural gas is stored on board in highpressure cylinders at pressure of 200 to 300 bars as compressed natural gas (CNG). Storage of
natural gas at high pressure on board provides an acceptable range of vehicle operation.
High antiknock quality of natural gas makes it a fuel that is better suited for spark- ignition engines.
The following types of natural gas engines have been developed:

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 39:Alternative Fuels
Bi-fuel Operation: The conventional gasoline vehicles are converted to operate either on gasoline
or natural gas.
Dedicated NG Operation: Vehicle operating only on natural gas using spark ignition.
Dual-fuel CI engine Operation: Natural gas usually is carburetted/ inducted along with intake air
and gaseous fuel is ignited by diesel injection spray. The amount of diesel used may be as low as
10%.
As natural gas has very high octane number, dedicated natural gas engines can be built with a high
compression ratio of around 11:1, which results in significant improvements in fuel efficiency and
lower carbon dioxide emissions. Lean burn spark ignited, high compression ratio heavy duty engines
can be built to give very low particulate emissions compared to diesel engines and a high-energy
efficiency similar to IDI engines. The stoichiometric SI engines can utilize three-way catalysts and
therefore, it provides the greatest emission reduction potential.

Effect of Natural Gas on Emissions


Light-duty SI, natural gas engines run at stoichiometric conditions and use 3 Way catalysts. With
natural gas, mixture enrichment during cold starting which is needed with gasoline operation is not
required as the fuel is already in gas phase. Hence, with natural gas operation lower unburned fuel
emissions during cold starting and warm-up phase are obtained. Similarly, as very little mixture
enrichment is necessary during warm-up and transient engine operation, CO emissions are also
lower. With the use of electronic engine and fuel management and emission control technology,
natural gas vehicles complying with the US Tier 2 and ULEV standards can be built more easily
compared to gasoline vehicles. Emission results for two vehicles operating on gasoline and natural
gas vehicles are compared in Table 8.16. Natural gas cars gave more than 50% lower non-methane
hydrocarbons, 10 to 50% lower CO and 10 to 80% lower NO x .

Table 8.16
Emissions and Performance of a SI Natural gas Heavyduty Engine with 3-Way Converter, European Transient
Test Cycles, g/kWh

Test Cycle Fuel

CO

NMHC

CH4

NOx

PM

ETC limits

3.0

0.40

0.65

2.0

0.020

NG Engine

1.10

0.04

0.15

0.57

0.008

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 39:Alternative Fuels
Liquefied Petroleum Gas
Liquefied petroleum gas (LPG) is a mixture of commercial propane and butane. It is obtained either
from the natural gas processing or during petroleum refining. Composition of LPG varies very widely
from country to country depending on the use and demand of butane. LPG is a gas at normal ambient
temperatures and pressures (the boiling point of propane and butane at atmospheric pressure is about
- 45 C and -2 C, respectively). When subjected to pressure of 4 to 20 bars mixture of propane and
butane becomes liquid. The pressure at which it becomes liquid at room temperature depends upon
propane to butane ratio. The LPG is usually fed to the engine in gas phase.
Most LPG vehicles operate on bi-fuel systems for operation either on gasoline or LPG. It is
important as the number of LPG filling stations is usually small.
One drawback with a bi-fuel system is that the engine is neither optimised on LPG nor on
gasoline.
Better cold start and warm-up characteristics due to its gaseous state compared to gasoline
hence lower HC emissions.
HC emissions from LPG vehicles have significantly lower potential of smog formation compared
to gasoline and diesel fuels.
Negligible PM emissions compared to diesel.
Small reductions in CO compared to gasoline as no enrichment of mixtures during warm up or
acceleration phase is required.
No significant difference in NO x emissions.
Variation in propane/butane ratio in LPG poses problem as the octane number of the two main
constituents; propane (RON is 112) and butane (RON is 94) is quite different.
For bi-fuel vehicles specific technological development will be necessary to ensure compliance
with the stringent emission standards.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 40:Alternative Fuels (contd.)
The Lecture Contains:
BIODIESEL
Biodiesel Production Esterification of Oils
Properties of Biodiesel
Emissions
Hydrogen
Greenhouse Gas Emissions with Alternative Fuels
Questions

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 40:Alternative Fuels (contd.)
BIODIESEL
In a 1912 speech, Rudolf Diesel said, "the use of vegetable oils for engine fuels may seem
insignificant today, but such oils may become, in the course of time, as important as petroleum and
the coal - tar products of the present time". The revival of biodiesel derived from vegetable oils started
as a result of agricultural surplus in some European countries and under Kyoto protocol the need of
reducing greenhouse gas CO 2 emissions.
Biodiesel is a renewable fuel that is produced from a variety of edible and non-edible vegetable oils
and animal fats.
The term biodiesel is commonly used for methyl or ethyl esters of the fatty acids in natural oils and
fats, which meet the fuel quality requirements of compression-ignition engines.
Straight vegetable oils (SVO) are not considered as biodiesel. The straight vegetable oils have a very
high viscosity that makes flow of these oils difficult even at room temperatures. Moreover, presence
of glycerine in the vegetable oil causes formation of heavy carbon deposits on the injector nozzle
holes that results in poor and unacceptable performance and emissions from the engine even within a
few hours of operation.

Biodiesel Production Esterification of Oils


Biodiesel is produced by reacting vegetable oils or animal fats with an alcohol such as methanol or
ethanol in presence of a catalyst to yield mono-alkyl esters. The overall reaction is given in Fig. 8.6.
Glycerol is obtained as a by-product.

Figure
8.6:

Esterification reaction for vegetable oils and


fats.

Properties of Biodiesel
A variety of vegetable oils such as soybean, rapeseed, safflower, jatropha-curcas, palm, and
cottonseed oils have been used for production of biodiesel. Waste edible oils left after frying/cooking
operation etc., have also been converted to biodiesel for study of their performance. The biodiesel
are also known as fatty acid methyl esters [FAME]. Recently non-edible oil produced from jatrophacurcas seeds has gained interest in India as this plant can be easily grown on wastelands. The
properties of methyl esters of rapeseed and jatropha oils are given in Table 8.18.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 40:Alternative Fuels (contd.)

Table 8.18
Properties of Biodiesel Derived from Some
Vegetable Oils

Properties

Rapeseed
Jatropha
methyl ester methyl
ester

Molecular weight
Hydrogen/carbon ratio, m/m
Oxygen content, % m/m
Relative density @ 15 C
Kinematic viscosity @ 40 C, mm2/s
Cetane number
Lower heat of combustion, MJ/kg
Sulphur content, %m/m

300
0.15
9-11
0.882
4.57
51.6
37.7
<0.002

293
0.157
10.9
0.88
4.4
57.1
38.45
< 0.020

The vegetable oil esters are practically free of sulphur and have a high cetane number ranging from
46 to 60 depending upon the feedstock. Due to presence of oxygen, biodiesels have a lower calorific
value than the diesel fuels. European specifications for biodiesel or fatty acid methyl esters (FAME),
EN 14214 have been issued in 2003.

Emissions
The influence of biodiesel on emissions varies depending on the type of biodiesel (soybean,
rapeseed, or animal fats) and on the type of conventional diesel to which the biodiesel is added due
to differences in their chemical composition and properties. The average effects of blending of
biodiesel in diesel fuel on CO, HC, NO x and PM emissions compared to diesel as base fuel are
shown in Fig.8.7.The Table 8.19 gives change in emissions with 20 % blend of biodiesel in diesel and
100% biodiesel compared to diesel alone. These show the average of the trends observed in a
number of investigations.
Use of biodiesel results in reduction of CO, HC and PM, but slight increase in NO x emissions is
obtained.
Reduction in CO emissions is attributed to presence of oxygen in the fuel molecule.
A slight increase in NO x emissions results perhaps due to advancement of dynamic injection
timing with biodiesel. The methyl esters have a lower compressibility, which results in
advancement of dynamic injection timing with biodiesel compared to diesel.
Lower SOF with biodiesel and advanced injection timing also results in lower PM emissions.
Volumetric fuel consumption with biodiesel is higher than diesel due to its lower heating value.
An increase of 10-11 % in fuel consumption compared to diesel may be expected when
comparing their heating values. An increase in volumetric fuel consumption by 0.9-2.1% with
20% blends has been obtained.

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Figure
8.7:

Average effect on diesel engine emissions resulting from


addition of biodiesel in diesel fuels

Table 8.19
Average reduction in emissions with use of biodiesel and 20% biodiesel
blends compared to diesel alone

Emission

B100

B20

HC
CO
PM
NOx
PAH
Sulphates

- 93
- 50
- 30
+13
- 80
- 100

-30
-20
-22
+2
-13
-20

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 40:Alternative Fuels (contd.)
Hydrogen
Interest in hydrogen as a potential alternative automotive fuel has grown due to need of reducing
greenhouse gas, CO 2 emissions and to minimize dependence on fossil fuels. Hydrogen can be
produced from a variety of fossil and non-fossil sources.
Hydrogen is a colourless, odourless and non-toxic gas. It burns with an invisible and smokeless
flame. The combustion products of hydrogen consist of water and some nitrogen oxides. The major
hurdles in the use of hydrogen as a fuel are lack of production, distribution and storage infrastructure.
On board storage of hydrogen is another major challenge. Hydrogen has very low boiling point (
253 C) and very low volumetric energy density.
Volumetric energy density of compressed hydrogen is just one-third of energy density of natural gas.
Liquid hydrogen also has a very low volumetric energy density, which is about one-fourth of gasoline.
Hydrogen can be stored as compressed gas, as iron, magnesium, titanium or nickel hydride, or in
liquefied form. The liquid, hydride and compressed hydrogen storage methods are compared in Table
8.20 for storing 19 litres of gasoline equivalent in energy. Hydrogen storage space required is at least
10 to 12 times higher than for gasoline. Storage and fuel weight for hydrides is 27 times and for
compressed H 2 is 4 to 5 times of gasoline.

Table 8.20
Comparison of Hydrogen Storage
Methods

Gasoline
Energy (LHV) stored, MJ
600
Fuel mass, kg
14
Tank mass, kg
6.5
Total Fuel System mass, kg 20.5
Volume, l
19

Liquid H 2

Hydride Fe- Compressed


Ti (1.2%)
H 2 (70MPa)

600
5
19
24
178

600
5
550
555
190

600
5
85
90
227

Combustion characteristics of hydrogen and its impact on emissions are given below;
Hydrogen octane rating is 106 RON making it more suitable for spark-ignited engines.
The laminar flame speed of hydrogen is 3 m/s, about 10 times that of gasoline and methane.
Hydrogen has very wide flammability limits ranging from 5 to 75% by volume (f = 0.07 to 9),
which may lead to pre-ignition and backfiring problems.
Its adiabatic flame temperature is higher by about 110 C compared to gasoline.
If inducted along with intake air, the volume of hydrogen is nearly 30% of the stoichiometric
mixture decreasing maximum engine power.
Hydrogen on combustion produces water and there are no emissions of carbon containing
pollutants such as HC, CO and CO 2 and air toxics.
Trace amounts of HC, CO and CO2 however, may be emitted as a result of combustion of
lubricating oil leaking into engine cylinder.
NO x is the only pollutant of concern from hydrogen engines. Very low NO x emissions can be
obtained with extremely lean engine operation (f < 0.05) and/or injection of water into intake
manifold or exhaust gas recirculation which in this case consists primarily of water vapours.

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NO x emissions of 0.013 g/km have been obtained which are about 1/10th of the US Tier 2
regulations.
Hydrogen fuelled engines produces almost no CO 2 and its global warming potential is
insignificant.
Hydrogen fuelled IC engines however are not considered a long term option when compared to fuel
cell. Hydrogen fuel-cell vehicles are expected to have more commercial potential in the long run.
Though it is believed that significant production volumes for customers will not be available until the
2017-2020 time frame.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 40:Alternative Fuels (contd.)
Greenhouse Gas Emissions with Alternative Fuels
Fossil fuels currently supply about 80% of all primary energy and are expected to remain fundamental
to global energy supply for at least the next 20 to 30 years. . Presently, it is estimated that power
generation accounts for about 40% and surface transport contributes nearly 20% of global CO 2
emissions.
The Kyoto Protocol signed in December 1997 commits the industrialized countries to legally binding
reductions in emissions of greenhouse gases by 2008-2012. Strategy to achieve reduction in CO 2
emissions from transport sector involves essentially the following:
Reduction in fuel consumption of vehicles.
Increased use of low carbon alternative fuels and bio fuels.
European Union countries

have introduced CO 2 emission regulations for the automobiles. A


voluntary target of 140 g/km average CO 2 emissions for new car sales to be met in 2008 was set that

had to be relaxed. By the year 2012, a goal of 130 g/km of CO 2 to be achieved by engine and
vehicle technology, and further reduction to 120g/km by use of renewable fuels has been set by
European Union.
When comparing different fuel and power plant alternatives, life cycle CO 2 equivalent GHG emissions
are to be considered. It should account for CO 2 and other GHG emissions generated during
production, transportation and use in the vehicles. Lifecycle CO 2 emissions for liquid petroleum fuels,
LPG, natural gas and biodiesel for heavy vehicle application are compared in Fig 8.8. The CO 2
emissions yielded during fuel production and during fuel utilization stage in engines are shown
separately. Among the alternative fuels, natural gas having lower carbon content in the fuel molecule
has advantage over gasoline and diesel fuels as far as CO 2 emissions are concerned. From natural
gas vehicles, the greenhouse effect of the fugitive methane emissions as a result of leakage from the
transportation and distribution systems is also to be accounted for as methane is nearly 20 times
more potent than CO 2 in causing global warming. LPG lies in between the natural gas and liquid
petroleum fuels. The bio fuels such as ethanol and biodiesel have much lower lifecycle CO 2
emissions as the carbon dioxide produced on their combustion would be the same that has been fixed
from atmosphere during growth of the agriculture crops. These fuels do contribute to net CO 2
emissions resulting from manufacture of fertilizers and other ingredients used for crops and, during
processing of these fuels and making them suitable for use in the engines.

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Figure
8.8:

Lifecycle GHG carbon dioxide emissions with different transport


fuels.

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Module8:Engine Fuels and Their Effects on Emissions


Lecture 40:Alternative Fuels (contd.)
Example 8.2: Calculate GHG carbon dioxide (CO2 ) emissions per unit release of energy when
methane is completely burned.
Solution:
Complete or stoichiometric combustion reaction of methane in air is;

Mass of reactants
Methane + Air
= CO2 + Water + Nitrogen
16
+ 2 (32 + 3.76 x28) = 44
+ 2x 18 + 2 x3.76x 28
16

+ 274.56

44

+ 36

+ 210.56

From Example 1 the energy released when 1 kg of methane is burned = 50 MJ/kg the above
CO 2 produced per kg of methane burned = 44/16 = 2.75 kg CO 2 /kg of methane
CO 2 produced = 2.75/50 = 0.055 kg/MJ or 55 g/MJ of energy released.

Ans

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Module8:Engine Fuels and Their Effects on Emissions


Questions
(8.1) A diesel fuel when tested has the same ignition characteristics as the mixture of 40% ncetane and 60% hepta-methyl nonane. What is its cetane number? The fuel at 15 C has
density of 825 kg/m 3 and mid-boiling point (T 50 ) of 240 C. Find

the calculated cetane

index of the fuel. How much error results in using CCI instead of CN?
(8.2) What are the changes in volumetric efficiency for a gasoline (C8 H 15 ) engine when it is
converted -by retro- fitment for operation on methane or hydrogen? Assume inlet conditions
as 1 bar, 298 K and the engine size and geometry remain unchanged. Gasoline also enters
the engine cylinder mostly as liquid.
(8.3) Calculate energy content of 1 m3 of stoichiometric mixtures with air of gasoline (C H ),
8 15
ethyl alcohol, methanol and hydrogen. Compare your results with those in Table 8. 13.
Take standard conditions of 1 atmosphere (101 kPa) and 298K.
(8.4) Rate the fuels methane, ethanol, gasoline, high aromatic gasoline, and diesel in terms of
their potential to produce NO emissions based on adiabatic flame temperature data.
(8.5) Calculate mass of CO 2 per MJ of energy for gasoline, diesel, propane and ethanol when
burned as stoichiometric mixtures. Check your results with the data given in Table 8.13.
(8.6) Find the contribution of 0.1% sulphur in fuel to PM as percentage of Euro 1 to Euro 4 heavy
duty PM emission limits.
(8.7) Discuss why Supreme Court of India could have ordered replacement of all the diesel buses
by CNG buses in early 2003? How the CNG buses could meet those goals?

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