Professional Documents
Culture Documents
Department Mechanical
Engineering
IIT Kanpur
Instructor
Prof. BP Pundir
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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
1878
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
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
1981
1988
1989-1990
1990
1994
Direct injection stratified charge (DISC) engine powered cars came in production by
Mitsubishi and Toyota
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Figure
1.1
Table 1.2
Sequence of Events in 4-Stroke SI
Engine Cycle
Event
60 -40
stroke
Spark ignition
45 -15
stroke
CA
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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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Table 1.3
Sequence of Events in 4-Stroke CI
Engine Cycle
Event
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CI Engines
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
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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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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
Figure1.6 (adapted
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Table 1.4
Photochemical Reactivity of
Hydrocarbons (General Motor Scale)
Hydrocarbon
Relative Reactivity*
10
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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Table 1.5
Adverse Health Effects of IC Engine
Generated Air Pollutants
Pollutants
Short-term health
effects
Carbon
monoxide
Nitrogen
dioxide
Oxidants
Ozone
Sulfates
TSP/Respirable
Increased
susceptibility
suspended
other pollutants
particulate
to
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Table 1.6
Engine Emission Control A
Historical Perspective
Year
1952
1965
1968
The exhaust emission standards set for the first time throughout the USA
1970
1974
1981
1992
1994
Catalytic emission control for engines under lean mixture operation introduced
1994
2000-2005
Widespread use of diesel particulate filters and lean de-NOx catalyst systems
on heavy duty vehicles
2004
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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
Evaporative Emissions
HC
NO x
*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
HC
20 to 500 ppmc1
NO x
PM
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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
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Figure.
2.3
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Prompt NO
Fuel NO
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(i)
Thermal NO
(ii)
Prompt NO
(iii)
Fuel NO
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.
(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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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;
(i)
(ii)
(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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(2.7)
(2.9)
Eliminating [N] and [H] using equations 2.7 and 2.8, the equation 2.6 gives,
(2.10)
and
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(2.11)
where w = R 1 /( R 2 + R 3 )
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(2.12)
(2.13)
(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 (
(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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x [N2]e 0.71
(2.18)
Time
Fig. 2.4
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
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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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(2.19)
(2.20)
(2.21)
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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NO Formation in SI Engines
Effect of Addition of Diluents on NO Formation
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(a)
(b)
(c)
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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Figure
2.5
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
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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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Figure
2.8(a)
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)
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NO Formation in CI Engines
NO 2 Formation
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(2.23)
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the (EINO x ) data normalized with emissions obtained for standard air (without diluents) for several
engines had linear correlation with the reciprocal of
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
Figure 2.9
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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(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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(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
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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)
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
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(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
Exhaust valveleakage,and
(viii)
In the vehicles, fuel evaporation from fuel tank and fuel system is another source of unburned HC emissions.
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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
Quench distance,
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(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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is proportional to the
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
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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
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Percent
44
100
0.51
1.32
0.32
0.86
0.40
0.88
0.32
0.86
1.55
3.5
0.20
0.45
0.20
0..45
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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Ans.
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(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)
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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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Figure 2.13
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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(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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Figure
2.14
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Figure 2.15
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Figure 2.16
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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
Figure 2.18
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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Figure 2.19
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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Soot Structure
Diesel Smoke
Soot Formation Stoichiometry
Conceptual Models of Soot Formation
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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.
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Figure 2.21
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Figure 2.22
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(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.
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Figure2.23
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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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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(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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(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)
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diameter.
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In the beginning of oxidation we may assume x =1. Hence, the soot oxidation rate is,
For
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Figure 2.25
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Figure 2.26
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Questions
2.1 Show the effect of overall fuel-air equivalence ratio,
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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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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Figure
3.1
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Fig
3.2(a)
Fig
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3.2(b)
emissions.
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Figure
3.3
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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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
Engine speed
Engine load
Coolant temperatures
EGR
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Operating Variables
Compression Ratio
Direct Injection (DI) versus Indirect Injection (IDI) Engines
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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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Figure
3.4
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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Table 3.2
Volume Distribution of Combustion Chamber at
TDC
Piston bowl
55%
6%
7%
Head gasket
2%
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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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Figure
3.6
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Figure 3.7
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Figure
3.8
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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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Figure 3.9
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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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
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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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
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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Figure 4.1
chassis dynamometer
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ECE-15 cycle
EUDC Cycle
Distance, km
4.052
6.955
Time, s
780
400
19
62.5
50
120
Acceleration, %time
21.16
0.833
Deceleration, % time
13.8
-1.389
Idle, % time
35.4
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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Cycle Details:
56.7 mph
(91.2
km/h)
Length
Max. Speed :
Time
Idle
Av. Speed
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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13-mode steady state cycle (ESC) with a dynamic load response (ELR) smoke test
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
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Figure 4.5 European ELR dynamic response test for smoke emissions.
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Figure 4.6
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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Figure 4.6
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
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EMISSION STANDARDS
Light Duty Vehicles
Heavy Duty Engines
Motorcycle Emission Standards
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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
0.018
(7)
(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)
LEV, 2000
0.075 (0.090)
3.4 (4.2)
0.2 (0.3)
(0.08)
ULEV, 2001
0.04 (0.055)
1.7 (2.1)
0.2(0.3)
(0.04)
LEV 2, 2004
0.075(0.090
3.4 (4.2)
0.05 (0.07)
(0.01)
ULEV2,2004
0.040(0.055)
1.7(2.1)
0.05(0.07)
(0.01)
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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Description
1992 Euro 1
All
CO
2.72
HC
-
NO x
-
(3.16)
1996 Euro 2
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)
(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)
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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Figure 4.8
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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
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
15.5
0.14
(3)
(1)
(2)
(3)
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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
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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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
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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
2003
2005
2010
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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
12.0
1.0
12,000-30,000
> 280 CC
12.0
1.4
6,000 -18,000
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
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
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Table 4.9
Measurement Principles of Exhaust
Gas Analyzers
Gas component
Measurement Principle
CO
HC
NO x
(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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Figure
4.11
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(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
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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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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
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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Figure 4.14
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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Figure 4.15
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Figure
4.16
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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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Fig 5.1
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Fig
5.2(b)
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Figure 5.3
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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Figure
5.4
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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Fig 5.5
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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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Figure
5.7
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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
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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
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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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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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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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
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Parameter
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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Ceramic Monolith
Cells
Figure
5.11
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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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
16 - 186
16 - 186
89- 91
67 -75.0
area
3.2
2.4-2.8
14-22
0.1-0.8
0.4- 0.5
0.75-1.05
Density, g/cm 3
7.4
2.2-2.7
15
1275-1375
1400
900-1150
1200
680
340
Characteristics
Geometric 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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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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(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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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
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Table 5.3
Possible Reactions for Reduction of
NO x
1.
NO + CO
2.
3.
4.
NO + H2
5.
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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Figure
5.14
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Figure 5.15
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(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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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
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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(a)
Figure 5.16
(b)
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Figure 5.17
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Figure
5.18
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Figure
5.19
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Figure
5.20
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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Figure
5.21
Typical layouts of the hydrocarbon adsorber/trap and main catalysts are shown in Fig 5.22 .
Figure
5.22
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
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Figure
5.24
Schematic of a NSR
Catalyst (NO x trap).
(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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(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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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
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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Thermal Deactivation
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-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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Figure
5.26
..
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
1500
1400
Cordierite phase changes to Mullite
1300
1100
900
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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
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Table 5.4
Summary of Developments in Emission Control Technology for Gasoline
Passenger Cars
Year
Model
Technology
1963
1968
1973
1975
1977
1981
1988
1990
1994
1996
1999
2004
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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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, 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
(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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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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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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Table 6.2
Comparison of Performance and Emissions of Pilot Injection and
Conventional
Injection with Retarded
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
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Figure
6.5
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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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high-pressure pump
(ii)
(iii)
injectors, and
(iv)
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
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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Figure 6.7
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Figure 6.8
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Figure
6.9
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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
(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
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SO 2 + O2 SO 3
(6.3)
Sulphate storage:
SO3 +MO (washcoat metal oxide) MSO4
(6.4)
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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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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.
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(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)
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Figure
6.12
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Figure
6.13
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Table 6.3
Comparison of SCR and NSR de-NO x
Technologies
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
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Figure
6.14
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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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.
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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.
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Figure
6.16
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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Figure
6.17
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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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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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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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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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Figure 7.1
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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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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
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.
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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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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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Figure 7.4
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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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
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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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.
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Figure 7.6
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Valve timings and lift using residual gas trapping method for CAI
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
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Figure 7.8
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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Figure 7.9
=0.77) and SI
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Figure
7.10
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Figure
7.11
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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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Fig 7.12
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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
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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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Figure
7.14
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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Figure 7.15
Schematic of
cell.
H2 O2 fuel
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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
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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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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Table 7.4
Fuel Cell Types and their
Characteristics
Temperature
Electrolyte
operation, C
Type
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
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
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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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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
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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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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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Table 8.1
Important Characteristics of Liquid Petroleum
Fuels
Gasoline
Diesel
Distillation
Ignition quality
number)
(Cetane
index, Cetane
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Heat of combustion*
Heat of combustion*
Density
Density
Antiknock
number)
quality
(Research
and
Motor octane
Viscosity
Oxidation stability
Aromatic content
Sulphur content
Lead content
Storage stability
Sulphur
Benzene
Sediments
Sediments
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Table 8.2
Requirements of Automotive
Fuels
Fuel Quality
Combustion characteristics
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
Material Compatibility
Flow characteristics
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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
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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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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Table 8.4
Engine Test Conditions for ASTM Research and Motor
Methods
Operating Conditions
Research Method
Motor Method
600
900
Inlet temperature, C
52
149
Inlet Pressure
Atmospheric
Atmospheric
0.0036-0.0072
0.0036-0.0072
Coolant Temperature, C
100
100
13 (constant)
Air-fuel ratio
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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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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Figure 8.1
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.
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Figure 8.2
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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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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.
Ethanol, stabilizing
necessary
agents
may
be
Isopropyl 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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Table 8.6
Summary of Effects of Gasoline Properties on Emissions from
Catalyst Cars
Property
Change
Reduce Lead
0.013 0.005
g/l
Butadiene
Aldehydes
-0
-0
-0
Lead CO
0-
+0
Reduce
Aromatics
50 20% v/v
+0
+0
Reduce
Benzene
3 2 % v/v
+0
-0
-0
0 - *
Reduce RVP
70 60 kPa
-0
Increase E100
35 65%
0-
-0?
0 -
Increase E150
85 90%
0-
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Table 8.7
Performance Targets of US Reformulated Gasoline
Programme
RFG Programme
Performance Target
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
50
46
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Winter
79
T50, C
94
94
T90, C
158
145
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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Figure 8.3 catalyst equipped cars with those with regular grade unleaded
gasoline
Table 8.9
Indian Specifications for Euro IV/Bharat Stage IV Emmission Norms
Compliant Motor Gasoline
Characteristics
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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40-70
40-70
75
75
210
210
91
95
81
85
40
40
50
50
0.005
0.005
60 (67)
60 (67)
21
18
360
360
35
35
2.7
2.7
Nil
Nil
c) Iso-Propyl alcohol
10
10
d) Iso-butyl alcohol
10
10
15
15
e) Tertiary-butyl alcohol
f) Ethers containing 5 or more 'C' atoms
per molecule
g) Other Oxygenates
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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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(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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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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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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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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Table 8.10
Trends in Diesel Fuel Sulphur in Some
Countries
Country/Region
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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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%;
Table 8.12
Diesel Fuel Specifications in Some
Countries
Property
Europe (EN590:
1999)
51
51
46
46
Density @ 15 C, kg/m3
820-845
820-845
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2.0 -4.5
2.0-5.0
0.035
BS III: 0.035
BS IV: 0.005
-
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
55
35
0.30
0.30
200
200
25
25
Particulates, mg/l
24
460
460
0.6
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Table 8.13
Properties of Various Fuels for
Vehicles
Property
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
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
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Energy content per unit volume of stoichiometric mixture = 800/258.07 = 3.10 MJ/m3
Ans.
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Table 8.14
Advantages and Disadvantages of Alcohol Motor Fuels Compared to Gasoline
and Diesel
Performance
Parameter
Advantages/Disadvantages
Flame temperature
Lower
Vapour pressure
Lower
PM emissions
Lower
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Lower
Lower benzene
emissions
and
1,3 butadiene
Similar
Aldehyde emissions
Higher
Formaldehyde
and
emissions are higher
Nature of sources
acetaldehyde
emissions.
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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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Table 8.16
Emissions and Performance of a SI Natural gas Heavyduty Engine with 3-Way Converter, European Transient
Test Cycles, g/kWh
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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Figure
8.6:
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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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:
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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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
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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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:
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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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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?