Emission Formation in Diesel Engines

Emission Formation in Diesel Engines

Abstract: Emissions formed during burning of the heterogeneous diesel air/fuel mixture depend on the
conditions during combustion, during the expansion stroke, and especially prior to the exhaust valve
opening. NOx emissions are formed manly during the premixed burning. PM, on the other hand, is
generated in diesels primarily during the diffusion flame. The visible smoke emission can be classified into
black smoke, also known as hot or solid smoke, and white smoke also referred to as liquid smoke or fog.

O ntroduction
O ormation of Hydrocarbons in Diesel Engines
O ormation of Carbon Monoxide in Diesel Engines
O ormation of Nitrogen Oxides in Diesel Engines
O ormation of Particulate Matter in Diesel Engines
O $moke in Diesel Engines

ntroduction

Unlike spark-ignited engines where the combustible mixture is predominantly homogeneous, diesel
combustion is heterogeneous in nature. Diesel fuel is injected into a cylinder filled with compressed air of
high temperature. Emissions formed as a result of burning this uneven air/fuel mixture depend on the
prevailing conditions not only during combustion, but also during the expansion and especially prior to the
exhaust valve opening. Mixture preparation during the ignition delay, fuel ignition quality, residence time
in different combustion temperatures, expansion duration, and general engine design features play a very
important role in emission formation. n essence, the concentration of the different emission species in the
exhaust is the result of their formation, and their reduction in the exhaust system. ncomplete combustion
products formed in the early stages of combustion may be oxidized later during the expansion stroke.
Mixing of unburned hydrocarbons with oxidizing gases, high combustion chamber temperature, and
adequate residence time for the oxidation process permit more complete combustion. n most cases, once
nitric oxide (NO)is formed it is not decomposed, particularly in the lean flame region (L#), but may
increase in concentration during the rest of the combustion process if the temperature remains high or
even increases [Henein 1972]. However, some NO decomposition may take place in the fuel-rich regions
unless further oxidation takes place.

$ince combustion is a complex series of chemical reactions and heattransfer processes, the resultant
emissions formation requires further analysis and understanding. A simplified model for heterogeneous
combustion was presented in igure 1 in the paper on diesel combustion. A more developed version of this
model is presented in the following diagram, where the sources of unburned hydrocarbons (HC) and NO in
direct-injected diesel engines are indicated. igure 1 details the species formed in both the premixed and
mixing controlled combustion phases [Heywood 1988].



Pollutant Formation Mechanisms in D Combustion System

Formation of Hydrocarbons in Diesel Engines

Hydrocarbons in diesel exhaust consist of either decomposed fuel molecules or recombined intermediate
compounds. Another source of HC in diesel exhaust is lubricating oil. The sources of HCs in D diesel
engines can be traced mainly to over- or under-mixing of fuel and air, and large fuel droplet sizes at the
end of injection. n general, unburned hydrocarbons are related to the lean flame-out region (LO#),
spray core, portion of fuel injected on the walls, spray tail, and after-injection. Obviously, engine design
and operating variables play a major role in the formation and oxidation of the hydrocarbon molecules.
The effects of some of these variables can be summarized as follows.

Fuel-Air Ratio

n naturally-aspirated diesel engines, if the change in volumetric efficiency is neglected, the mass of air
per cycle is almost constant. Changing power at fixed speed is accomplished by controlling the amount of
fuel injected. njector-to-injector differences may lead to fuel distribution variations, amount of fuel
deposited on the walls, cylinder gas pressure and temperature, and injection duration. n addition, fuel
injected during the ignition delay period (premixed portion) will mix with air and produces a widerange of
equivalence ratios. $ome of these ratios may be too lean to support stabilized combustion, others may be
close to thestoichiometric ratio and ready to combust, and yet others may be too rich and too slow to
evaporate, mix, and engage in the combustion process. At the onset of autoignition, mixtures that are
most likely to burn are those closer to stoichiometric ratio. Combustion will continue unless the localized
A/ ratio decreases rapidly due to over mixing with surrounding air or if the flame is quenched by a
thermal boundary layer [Heywood 1988]. As for the very lean mixture, it may eventually engage in the
combustion process if it meets and mixes with additional evaporated fuel. The opposite is true of the large
droplet sizes injected toward the end of injection duration. Thesedroplets will need both additional air or
lean mixtures and high temperatures to help them evaporate, mix, and subsequently engage in the
combustion process. Evaporation, mixing, and combustion rates must be fast enough to consume most of
the sprayed fuel in advance of significant expansion and cooling off during the expansion stroke, otherwise
excessive unburned hydrocarbons will be found in the exhaust. igure 2, a schematic representation of the
premise presented for the three A/ ratios, describes their influence on forming unburned hydrocarbon
emissions [Heywood 1988]. Theexplanation and the schematic shown in igure 2 are specifically
applicable to the portion of the fuel injected during the ignition delay period.

Hydrocarbon Formation From Fuel njected During gnition Delay

or fuel injected after the start of combustion, fuel pyrolysis or rapid oxidation by mixing with air lead to
complete combustion. Conditions that may slow down the rate of pyrolysis and oxidation will lead to
localized rich mixtures and delays in completing combustion. f such conditions prevail, then exhaust gas
will contain greater concentrations of unburned hydrocarbon. A schematic representation of the formation
of unburned hydrocarbons from post-ignition delay fuel spray is given in igure 3 [Heywood 1988].

Hydrocarbon Formation From Fuel njected After gnition Delay

Effect of Engine Load

At idle and light load conditions, spatial combustion is more likely, meaning that the fuel does not reach
the walls of the combustion bowl, but burns in the space between the nozzle tip and the combustion bowl
perimeter. n addition, the fuel concentration in the spray core is rather small. n this case, unburned
hydrocarbon emissions originate mainly from the LO#. ncreases in local temperatures of this region as
combustion continues are very small, and are associated with slower oxidation reaction rates. These
reaction rates are further reduced due to the very low concentration of fuel molecules as they diffuse in
the air around this region. The ratio of unburned hydrocarbons formed in this region to total fuel injected
is highest at idling [Henein 1972].

As engine load increases, decreasing A/ ratio causes more fuel to be deposited on the walls and produces
higher concentrations in the spray core. The unburned hydrocarbons formed in this case increase;
however, there is sufficient oxygen in the mixture so that, with increased temperature, oxidation reaction
rates are enhanced and hydrocarbon emissions reduced [Burn 1969][Marshall 1968][Perez 1968]. The
effect of load on unburned hydrocarbons is shown graphically in igure 4 [Henein 1972].



Effect of Load on Unburned Hydrocarbon Emissions

At full load as well as overload conditions, further decreases in A/ ratio resulting in more unburned
hydrocarbon molecules in the spray core and near the combustion bowl walls. n this case, the
contribution of the LO# to the total unburned hydrocarbon emissions is very small. The oxidation
reactions are also limited due to the lack of oxygen in the locally rich fuel-air mixture, in spite of the very
high temperatures reached and the overall lean mixture [Marshall 1968].

t is also worth noting that the molecular structure of the hydrocarbon emissions tends to vary with A/
ratio. At idle and light loads, hydrocarbons emitted from D engines are related to the LO# and consist
mainly of the original fuel molecules. At high loads most of the hydrocarbons emitted originate from the
fuel molecules in the spray core and on the combustion bowl walls, where temperatures are fairly high,
and causing decomposition of the original fuel molecules. $ince the A/ ratio in the spray core and near
the combustion bowl walls is generally low (rich condition), there is a great possibility that some
recombination reactions may occur between the hydrocarbon radicals and the intermediate compounds
[ristrom 1965]. This results in higher concentrations of the heavier hydrocarbons. The process of
recombination of the hydrocarbon compounds and radicals also result in compounds having a different
structure than the original fuel [Bascom 1971][Aaronson 1971].

Effect of After-injection and Secondary njection

njection system design problems such as after-injection and secondary injections (see igure 19 in Pump-
Line-Nozzle paper) tend to increase unburned hydrocarbon emissions. The mechanism of unburned
hydrocarbon formation is a combination of slow evaporation rate, since these uncontrolled injections take
place in the expansion stroke while the gas temperature is cooling off, and a mixture too rich to burn.
Modern diesel engines equipped with exhaust emission control devices that require external heating for
their function may use a controlled post-injection pulse of fuel. Unless extra care is taken in designing the
timing and the quantity of this post-injected pulse of fuel, problems in the form of excessive unburned
hydrocarbons, carbon monoxide, and particulate matter can arise. njection system line dynamics as well
as the mass-spring system (injector needle and return spring) must be carefully engineered over a wide
range of engine speeds and loads to avoid these problems [Henein 1972].

Effect of Cold-Start and Misfire

n cold environments, white smoke may form due to misfire. This is a symptom of partially evaporated
fuel that is struggling to evaporate and mix with air. Lack of heat from the cylinder walls, piston crown,
or any of the adjacent engine components makes it difficult for the fuel to evaporate. Unless compression
ratio is raised by design or by control in variable compression engines, misfire is experienced. The
resulting white smoke emission is an ultimate form of unburned hydrocarbons that disappears once the
engine warms up. These problems are generally aggravated by air-to-air charge air cooling, low
compression ratio, injection timing retard, and coolant temperature below 25 to 29 C (77 - 85)
[Heywood 1988][Khair 1987]. This condition is the only operating condition where a diesel engine
experiences misfire. Once warmed up, engine misfire should not be exhibited in diesel engines. $ome
engine designs include an intake charge heater that is energized a few seconds before cranking to assist in
white smoke avoidance or elimination. Other engines, such as the Navistar (nternational Truck and
Engine) 7.3 L, D engine are equipped with a back pressure valve that exerts a light load on the engine
during warmup. This measure is usually combined with an increase in idle speed to increase back pressure
and thus load applied on the engine, as well as increasing friction heat. Both measures combine to provide
heat to aid in fuel spray evaporation and white smoke reduction

Effect of Turbocharging

Turbocharging increases the mass of air inducted into the engine andallows a proportional increase in
injected fuel quantity that leads to higher engine output. Air velocity through the intake port is higher in
turbocharged engines relative to naturally-aspirated engines. t follows that air motion through the intake
port of either a swirl-supported or quiescent combustion system is more likely to enhance mixing and
mixture preparation. n general, better mixing leads to higher reaction and oxidation rates, and results in
higher combustion temperatures which in turn cause a reduction in the concentration of hydrocarbon
emissions. The reduction of hydrocarbonemissions with turbocharging, as observed by Perez and Landen
forboth D and D engines, is shown in igure 5 [Perez 1968].



Effect of F/A Ratio on HC Emissions in D and D
Turbocharged and Naturally-Aspirated Diesel Engines

Effect of Nozzle Opening Pressure

The effect of nozzle opening pressure on performance and emissions was evaluated in a single cylinder
research diesel engine [Henein 1972]. The engine was equipped with a toroidal combustion system and
the results for unburned hydrocarbon emissions are given in igure 6.The data is given for operation at
both rated (2500 rpm) and peak torque (1600 rpm) speeds, full load conditions. t is apparent that by
raising nozzle opening pressure HC emissions are increased, in both cases. Most of the HC increase
however, is seen at nozzle opening pressures below 24 MPa (240 bar). t is believed that raising nozzle
opening pressure improves atomization and widens the lean flame-out region which, as discussed earlier,
is one of the major sources of unburned hydrocarbon emissions.

Effect of Nozzle Opening Pressure on Unburned HC Emissions

Effect of njection Timing

The same single cylinder research engine used in the nozzle opening study, mentioned before, was used
to investigate the effect of injection timing on performance and emissions [Henein 1972]. The results are
shown in igure 7 (the same engine conditions as those in igure 6). njection timing advance appears to
have increased unburned hydrocarbon emissions in both cases. This finding agreed with similar results
reported by Khan and Grigg [Khan 1971]. The mechanism that could explain this phenomenon appears to
be the longer ignition delay which allows more fuel vapor and small droplets to be carried away with the
swirling air, producing a wider LO#. Another factor suggested by Khan and Grigg is the increase in fuel
impingement on the combustion bowl walls.

Effect of njection Timing on HC Emissions

Effect of ntake Swirl

or the purpose of this section, we will define swirl by the term swirl ratio, which is the ratio of the
circumferential speed of air as it enters the cylinder to the engine speed. We will also consider that
increased swirl in D engine generally improves the mixing and the hydrocarbon oxidation processes.
Excessive swirl may, however, produce a wider LO# as discussed above, or an overlap of the sprays
and an increase in unburned hydrocarbon emissions. As explained earlier, swirl in D engines may be
changed by varying the ratio of the bowl diameter to its depth, known as the aspect ratio. The variation in
the aspect ratio has been found by Watts and $cott [Watts 1970] to have little effect on the fuel economy;
it may, however, affect the pollutant formation. $ince combustion bowl sizes and shapes vary widely, it is
difficult to make a general statement concerning how the combustion bowl and its influence on swirl may
affect hydrocarbon emissions.

Sensitivity of HC to the Fuel System

The fuel system plays a major role, not only in engine performance, but also in the formation of emissions
from diesel engines. The point at which the fuel system comes closest to the combustion process is
the injector nozzle hole. t follows then that the nozzle hole design is very important, especially in terms
of their effect on the formation and emission of HC. Nozzle hole diameter, length, surface quality, its
machining process (mechanically-drilled or by electronic discharge machining), as well as the shape and
surface finish of its upstream inlet and downstream discharge side are all factors affecting HC emissions.
These design parameters may directly affect the rate of injection, atomization of the fuel, and the spray
penetration into the combustion bowl. $ac volume, defined as the volume between the needle seat and
the nozzle holes, as shown in igure 8, has particularly strong influence on hydrocarbons emissions.



Cylindrical Versus Conical Sac Volume

t was reported that reducing sac volume greatly reduced unburned hydrocarbon emissions [Merrion
1968]. A conical sac (igure 8b) has a smaller volume than a cylindrical sac (igure 8a). uel accumulating
in the sac leaks out (nozzle dribble) through the injector holes during the expansion stroke. This fuel does
not atomize into the combustion chamber nor mix with the oxidants, and therefore finds its way out to the
exhaust system through the exhaust valves.

$econdary injections and after-injections lead to unburned hydrocarbon emissions, especially at part load
conditions. Careful design of the mass (needle) and spring system dynamics can usually solve this
problem. n addition, delivery valves are often used in conventional pump-line-nozzle systems to maintain
injection line residual pressure at a level that would prevent after-injections and secondary injections from
occurring.


Formation of Carbon Monoxide in Diesel Engines

Carbon monoxide (CO) is an intermediate product in the combustion of hydrocarbons [Challen 1999]. t is
formed mainly due to incomplete combustion, which is exacerbated by lack of oxidants, temperature,
and residence time. As combustion proceeds to completion, oxidation of CO to CO2 occurs through
recombination reactions between CO and various oxidants. f these recombination reactions are
incomplete due to lack of oxidants or due to low gas temperatures, CO will be left without oxidation
[Henein 1972].

Combustion of fuel-rich mixtures usually produces high CO emissions, but since diesel combustion is lean
and has an abundant amount of air, CO from diesel combustion is extremely low.

During the various stages of spray combustion in D diesel engines, conditions that promote high
combustion temperature, high oxygen content, and high mixing rates are responsible for the oxidation of
CO to CO2. However, the main parameter affecting its formation remains a low A/ ratio. igure 9 shows
the relationship between the inverse of A/ (/A ratio) and CO emissions for a turbocharged D and
a naturally-aspirated D diesel engine [Henein 1972].



Effect on F/A Ratio on CO Emissions in Diesel Engines

Formation of Nitrogen Oxides in Diesel Engines

n the exhaust of internal combustion engines, nitrogen oxides (NOx) refer to nitric oxide (NO) and
nitrogen dioxide (NO2). n D diesels, NO typically constitutes 70-90% of the total NOx. Nitric oxide is a
by-product of combustion rather than a compound in transition like CO. Nitrogen makes up over 75% of
the intake charge air by volume. With the balance of the inducted air volume being oxygen and with
help from heat resulting from burning HC fuel, NOx is formed and remains until it is exhausted through
the exhaust valve. uel-borne nitrogen being negligibly small is not a major contributor to the chemical
reaction process. The formation of NO is well understood. t is accepted that NO is formed by the
extended (or modified) Zeldovich mechanism:

1) O2 + N2 NO + N

2) N + O2 NO + O

3) N + OH NO + H

Essentially, when a molecule of O2 is exposed to high temperature in an N2 environment, NO is formed
and an atom of nitrogen is left in an energetic and unstable state, Equation (1). The nitrogen atom tries
to reach a stable state by combining with oxygen present in the cylinder, while enough energy is available
in the form of heat from the combustion process. This reaction, once again forms more nitric oxide and
leaves an atom of oxygen in an unstable state, as shown in Equation (2). n the modified Zeldovich
mechanism, scientists suggested that radicals, such as OH, are formed and react with the nitrogen atoms
to form more NO and an atom of hydrogen as given by Equation (3). t follows that all three equations
show mechanisms by which NO can be formed and that the longer the residence time in this high NO
formation regime, the greater the NOx concentration.
According to this mechanism, atomic nitrogen does not start the chain reaction because its equilibrium
concentration during the combustion process is relatively low compared to the equilibrium concentration
of atomic oxygen [Henein 1972]. Therefore, in diesel combustion the local NO formation in the spray is
related to the local oxygen atom concentration and the local temperature. NO2 forms from NO by reaction
with excess oxygen and quenching by excess air in the cylinder can freeze NO levels at well above
equilibrium concentrations. As the temperature decreases during the expansion stroke, the NO
concentration does not decrease to the equilibrium concentration, because it is stable under these
conditions. t is believed that in reciprocating engines the NO removal processes during the expansion
stroke are very slow, and thus NO concentration remains nearly constant during expansion [Lavoie
1970][$tarkman1967]. This is particularly true in fuel-lean combustible mixtures [Komiyama 1973].

The premixed portion of the fuel (mixed during the ignition delay), which burns before the time of peak
cylinder pressure, is articularly important for NO formation. After it has burned, it is compressed to a
higher pressure and temperature and so reaches the highest temperature of any portion of the cylinder
charge. or this reason, techniques to control NOx focus on this early phase of combustion. Unfortunately,
most of these techniques resort to reducing combustion temperatures. n so doing, they lead to penalties
in hydrocarbon emissions, particulate emissions, and fuel consumption.

t is common to refer to the NOx/PM trade-off or the NOx/fuel consumption trade-off in diesel engines.
These expressions point in part to the admission that means to reduce NOx emissions would invariably
lead to increases in particulate emissions as well as fuel consumption, and vice versa. Most factors
affecting the initial rate of heat release will affect the NOx formation rate in the same direction [Challen
1999]. Many control schemes attempt to reduce the amount of fuel burned in the premixed burning
phase. These schemes include rate-shaping using a lower injection rate early in the injection period
followed by a considerable injection rate increase after the start of combustion. They also include pilot
injection, which has a separate small injection to initiate combustion with a minimum of fuel followed by a
main injection after combustion initiation.
Having reviewed NOx formation, it is perhaps time to study the effects of some engine variables and other
parameters on NOx emissions.


Fuel-air ratio

ncreasing load in naturally-aspirated diesel engines implies an increase in fuel for the same mass of air
inducted at a constant speed. As more fuel is burned, more heat is generated and an increase
in combustion temperature is experienced. The availability of high combustion temperature provides
adequate energy to help the chemical reactions described by the Zeldovich and modified Zeldovich
mechanisms, thus causing more NOx formation as long as N2 and O2 are present. t was suggested by
Henein and Patterson that a reduction in /A ratio to below 0.02 would actually reduce NOx formation due
to the drop in combustion temperature by air dilution [Henein 1972]. igure 10 shows the increase in
maximum combustion pressure (Pmax), exhaust temperature (Texh), brake mean effective pressure
(BMEP), and observed NO as a function of /A ratio. t is worth noting that smoke also increases as /A
ratio increases, but NO, corrected to an equivalence ratio of 1, decreased as a function of /A ratio within
the test range. The increase in observed NO emission did not appear to be proportional to /A ratio,
indicating that there are other factors affecting NO formation.

Effect of F/A Ratio on NO Formation

Effect of Nozzle Opening Pressure

ncreasing nozzle opening pressure tends to improve atomization. With smaller fuel particles due to
improved atomization, combustion efficiency improves, releasing higher heat and raising combustion
temperature. n general, higher combustion temperatures lead to higher NO formation [Henein 1972].

Effect of njection Timing

njection timing advance appears to extend the ignition delay. The reason for this observation is that fuel
is injected into a lower pressure medium having lower temperature. The longer the ignition delay, the
greater the portion of fuel injected during that period, and the better the chance for it to mix with air. n
other words, the earlier the fuel is injected, the longer the ignition delay (igure 11), and the greater the
premixed portion of the fuel prior to ignition [Henein 1972]. Higher NO formation is usually related to the
premixed portion of the fuel.

Effect of njection Timing on NO and Other Parameters

As injection timing is retarded, the opposite effect is experienced. gnition delay tends to be shorter and
ultimately, the premixed portion of the fuel is reduced. #educing the premixed fuel portion leads to lower
NO formation and is illustrated in igure 11. $ince retarding injection timing has a desirable effect on NO
formation, it has become an effective means to control NOx emissions. An important side effect to this
action is the increase in fuel consumption, as shown in the diagram, unless other measures are taken to
avoid this loss in fuel economy.

Effect of Cetane Number

uels with high cetane number are easier to evaporate and quick to ignite. Therefore, they are
characterized with shorter ignition delay periods. Consequently, they have smaller premixed fuel portions
and lower NO emissions for the same BMEP compared to fuels having lower cetane number [Challen
1999]. With low cetane fuel, ignition delay is usually long and more fuel is present in the L# when
combustion starts. This larger quantity of premixed fuel produces a higher gas temperature upon
combustion early in the cycle, and more NO is formed in the L#.

Effect of Swirl

Air motion in the cylinder affects fuel and air mixing rates. While high swirl, or a high degree of air motion
is generally desirable, over-swirling can be experienced. A good indication of over-swirling is a
deteriorating fuel economy and an increase in HC, CO, and particulate matter emissions. Generally, an
increase in air swirl improves mixing and promotes efficient combustion and more NO formation. The
mechanism responsible for the increased NO formation is the higher initial heat release rate [Challen
1999].

Effect of ntake Charge Dilution

ntake air charge dilution is accomplished through several methods including nitrogen, water, and exhaust
gas recirculation. The effect of charge air diluents is usually reduced NO formation. Two mechanisms are
referred to when explaining the reason for reduced NO formation. The first is simply oxygen displacement,
meaning that the normal oxygen inducted through the fresh air charge is reduced or displaced by a diluent
that is inert or has less oxygen than fresh air. #educing oxygen in the cylinder leads to sluggish
combustion (lower rate) and therefore, lower peak pressure and temperature as well as NO emission. The
second explanation is that the diluent acts as a heat-sink in the combustion process. Diluents with high
specific heat, such as water, N2, or CO2, are most effective in reducing NO formation. Their high specific
heat combined with their much lower temperature (relative to combustion temperature) causes them to
absorb heat from combustion, thus lowering combustion temperature and reducing NO emissions. This is
one of the principles underlying the application of EG# in diesel engines.

Formation of Particulate Matter in Diesel Engines

Perhaps the most controversial of all regulated emissions, particulate matter (PM) is defined as any matter
in the exhaust of an internal combustion engine that can be trapped on a sampling filter medium at 125
(52C) or less. As such, the diesel PM is not a well defined physical species. #ather, it is a complex
emission, including a number of components, which is discussed in more detail in the paper on diesel
particulates.

The above definition of PM uses the all-encompassing term "any matter" to describe what can be
considered part of total PM. n general, particulate matter originates from the organic and inorganic
substances inducted into the engine along with the fuel and air. One of the major constituents of PM is the
carbonaceous matter resulting from the heterogeneous combustion process in diesel engines. $mall
particles or combustion nuclei form as a result of both diffusion and premixed flames, and in the case of
premixed flames by both rich and lean conditions. #esearch on these particles, including when they are
formed in the flame and their chemical composition, is ongoing. Dust (in air) or inorganic material (in the
fuel or fuel additives) may appear as particulates in the exhaust (ash, oxides, etc.). Trace metals from
engine component wear may be carried by the lube oil and eventually migrate to the exhaust where they
can be trapped on the particulate sampling filter.

The presence of sulfur in the fuel and lube oil contributes to the formation of sulfate particulates. An
added problem associated with sulfates is their retention of humidity which may more than double
their mass.

inally, high boiling hydrocarbons and their derivatives are also included in the PM. This material, referred
to as the soluble organic fraction ($O), is composed mainly of lube oil derived hydrocarbons. Loss of oil
control resulting from improper cylinder bore honing or piston ring wear can be a major source of oil
consumption and contribution to unburned oil content in particulate matter [Khair 2001]. Other soluble
organic constituents include unburned fuel, in spite of the high combustion efficiency displayed by diesel
engines.

Carbonaceous Particulate Release and Oxidation

igure 12 presents a summary of diesel engine variables affecting soot particle formation and oxidation,
after Broome and Khan [Broome 1971]. The first part of the chart represents the mechanisms leading
to carbonaceous particulate formation, while the second part of the chart represents the mechanisms of
their oxidation. The underlined parameters on the right hand side of the chart are means that help
$olve the observed symptom. The top line of the chart shows that an increase in the amount of
incompletely mixed fuel and its equivalence ratio is one of the causes of net carbonaceous particulate
release. A good example of incomplete combustion is partially combusted carbon in the form of soot. n
other words, carbonaceous particulate results from diffusion burning rather than combustion of a well-
mixed fuel and air mixture whose equivalence ratio is close or equal to stoichiometric. Diffusion burning
would obviously be enhanced when more fuel is injected after the start of ignition. Another possibility for
more diffusion burning is through a greater unmixed portion of the fuel injected during the ignition delay
period. actors that may affect diffusion burning are therefore, the ignition delay period and the physical
and chemical events that take place in it as well as the rate and duration of injection. Higher initial
injection rates tend to increase the premixed portion of the fuel and reduce carbonaceous particulate.
Longer injection durations tend to increase diffusion combustion by increasing the fuel injected after
the start of ignition. Designers of diesel combustion systems may have a few tools to avoid excessive
diffusion combustion and carbon release. ncreasing cetane number improves the evaporation and mixing
processes and in turn reduces diffusion burning and particulate formation. Another design parameter that
could help is compression ratio, since increasing it would provide more heat that could be used by the
injected fuel to evaporate, mix with air, and burn as premixed rather than diffusion combustion.

Another approach to the particulate control issue is its oxidation following its formation. The second part
of the chart in igure 12 presents a few tools to enhance the oxidation of carbon after its release during
combustion. ncreasing the time available for the combustion process may give additional opportunity for
incomplete combustion products to find extremely lean pockets with which to mix. n the presence of high
temperature in the cylinder, oxidation is then enhanced and exhaust carbonaceous particulate emissions
are reduced. Providing more time for the combustion and oxidation process can be achieved through
reduced engine speed.



Diesel Engine Variables Affecting Soot Particle Formation
and Oxidation

Other Sources of Particulate Matter

Loss of oil control, combustion quality, cold starting emission of white smoke, unburned fuel, and general
fuel quality problems are among common sources of particulate matter. n general, the sources of
particulate matter in diesel engines can be categorized as follows (the sources are listed randomly and not
necessarily in order of contribution to the total particulate matter problem):


1. Loss of oil control
2. Black smoke from excessive richness

* over fueling
* poor combustion
* transients

3. White smoke

* cold start
* misfire

4. Other hydrocarbon origins

* nozzle dribble
* secondary injections
* after injections

5. Fuel quality

* sulfur content
* aromatic content
* cetane number

Loss of oil control can result from many areas within the internal combustion engine. mproper cylinder
liner honing, lack of piston ring pack sealing, lube oil seeping through excessive valve guide and stem
clearances, turbocharger lubrication and bearing malfunction, extended diesel engine idling, and excessive
piston-to-liner clearances are all contributors to high oil consumption. Lube oil jets are usually an integral
part of heavy-duty diesel engine applications. These jets are aimed at the underside of the combustion
bowl to cool the entire piston crown area. Excessive flow through these jets has been shown to cause high
oil consumption. n addition, sudden accelerations or changes from low to high loads are prone to
generate more unburned lube oil, since ring pack sealing may be less than desirable. At low load,
combustion pressure is low and causes a decrease in the sealing force applied to the back of the piston
ring. The lower the sealing force, the lower the sealing and the higher the oil consumption.
Lack of Piston Ring Sealing

Particulate formation may be also encouraged by a number of engine operational reasons. or instance,
hard accelerations are performed by an instantaneous increase in engine fueling. n general, the available
air to efficiently mix with this increased fuel is less than is required. n naturally aspirated engines, the
ability of quickly filling the cylinder with charge air may be hindered by reduced volumetric efficiencies;
while the turbocharger lag in turbocharged engines may cause an instantaneous drop in charge air.
n both engine configurations, a momentary lack of charge air is experienced and this leads to additional
carbonaceous particulate emission.

n cold ambients, compression heat in most D engines with 17 or 18:1 compression ratio is unable to
raise the compressed air temperature enough to help the fuel evaporate, mix with air, and burn.
Therefore, fuel is partially evaporated and exits the exhaust port and system in the form of white smoke.
This problem is especially aggravated by additionally retarding injection timing and over-cooling charge
air, and is primarily caused by misfire.

The contribution of unburned hydrocarbons to particulate matter has been already mentioned. Nozzle
dribble, after injections, and secondary injections are all major sources of hydrocarbon-based particulate.
Yet, besides lube oil, fuel itself is the main source of particulate if it does not have the right ingredients to
support good combustion or it is not being used properly. High sulfur and aromatic content together with
low cetane number is the best list of ingredients for high particulate formation and tailpipe emissions.

Smoke in Diesel Engines

$moke in diesel engine exhaust is an indication of poor combustion, resulting from an over-rich A/ ratio
or partially evaporated fuel during cold start conditions. $moke emission, especially if it is black, is diesel's
worst enemy since it is emitted in plain view of the public, giving the diesel its reputation of being a dirty
engine. $ocial and environmental pressures are leading diesel engine manufacturers to design and
produce engines that are nearly smoke-free. Most industrialized countries have therefore introduced
regulations of varying degrees of complexity to control smoke emission from road vehicles.

$moke may be in the form of particles, either solid or liquid suspended in the exhaust gases (aerosols). t
obstructs, reflects, or refracts light and causes soiling of structures as well as limiting visibility. Diesel
engine exhaust smoke can be classified as follows:


1. White in appearance under direct illumination, consisting of a mixture of fuel and lubricating oil
particles in an unburned, or partly burned state. This form of smoke is sometimes referred to as
liquid smoke or fog.
2. Black in appearance, consisting of solid particles of carbon from otherwise complete combustion of
fuel. This form of smoke is often referred to as hot or solid smoke.

A classification of the sources of diesel smoke is shown in igure 14. or the sake of clarity of
presentation, the chart has been split into two parts, which describe
(a) "cold smoke", both liquid and
solid, and
(b) "hot smoke".

Smoke Sources in Diesel Engines

n cases where excessive lube oil consumption is experienced, smoke emitted takes on a shade of blue or
grey. Blue or grey smoke is therefore an indication that an engine has reached the point where major
maintenance is required. However, unburned fuel can also appear as blue smoke if the droplet size is
about 0.5 micron. The white component, on the other hand, is mainly a result of too low a temperature in
the combustion chamber during the fuel injection period. t has a droplet size of about 1.3 micron. This
phenomenon is mainly experienced during cold starting, in low ambient temperatures or at high altitude.
White smoke disappears as the engine warms up. igure 15 shows a photograph of white smoke emitted
from an experimental truck in cold start mode [Khair 2001].

White Smoke Emitted During Cold Start

White smoke can also result from fuel injected too late in the combustion cycle or can even be an
indication of a design fault, in the sense that the compression ratio is too low, or has beenoptimized for an
inappropriate combination of operating conditions [Challen 1999]. A few manufacturers opted to use
electric inlet or intake manifold heaters. These are typically turned on perhaps 30 seconds before cranking
the engine in cold start conditions. They also cycle between being on and off until the water
jackettemperature indicates 25 to 27C (77 - 80). Limits imposed on NOx emission in the 1990's have
dictated that injection timing be retarded and that air-to-air intercooling be used. Both measures lead
to increased likelihood of white smoke formation. There are no regulations in place limiting white smoke
even though it is quite visible and widespread at truck stops especially in colder climates.

The main causes of excessive black smoke emission are either poor maintenance of air filters and/or fuel
injectors, or incorrect setting of the fuel injection pump/system. $uch smoke consists mainly of carbon
particles or coagulates of a wide range of sizes, from 0.02 microns to over 0.12 microns mean diameter
[Challen 1999]. This size distribution depends to some extent on the type of combustion system, which
also affects the onset of smoke emission as fuel input quantity is increased. igure 16 gives an example of
black smoke emitted under accelerating conditions [Khair 2001].


Black Smoke Emitted Under Accelerating Conditions