Sustainable Mobility

Technical and environmental challenges for the automotive sector

Week 3 Session 4 Emissions and After-treatment

systems : Pollutant formation
Prakash Chandra Dewangan

IFPEN / IFP School 2014

Here, we will be continuing the discussion on the topic of engines with focus on pollutants. This
topic will be dealt with in three parts. The first part includes the introduction and pollutant
formation; then reduction of these pollutants at their source will be discussed. Finally, we will
discuss after-treatment technologies for pollutant reduction in the last part of this lecture.

Introduction
To start with the reasons which make pollutants important. Firstly, Global warming. Certain gases
called greenhouse gases, in majority carbon dioxide or CO2, are the primary cause of global
warming. The transportation sector is a significant contributor to the greenhouse gases.
Secondly, air pollution, below you can see two caricatures of the famous Eiffel Tower: on the left a
beautiful blue sky with a clear view of the tower and on the right, a grayish environment filled with
particles and smog. You saw during the first week that the transportation sector is also a significant
contributor to the emission of gases that are dangerous for our health.

Lastly, Emission Regulations. To control the two points above mentioned, legislation has imposed
emission regulations which have been discussed in earlier lectures. Due to all these reasons, it is
important to control emissions from engines or vehicles.
Before we can think of how to reduce the emissions, we must understand their origin.
So, let's try to understand the Emissions from Engines
As you already know by now, the engine takes Air and Fuel as input. Air, which is largely a mixture
of N 2 and O 2 , while the Fuel, as you have seen in previous lectures could be gasoline, diesel, CNG,
bio fuels etc. Basically, a chemical mix of mostly carbon and hydrogen and maybe oxygen. After
combustion in the engine, at the exhaust, the engine produces a mix of various gases. Significantly
it consists of nitrogen (N 2 ), oxygen (O 2 ), water vapor (H 2 O), carbon dioxide (CO 2 ), unburned fuel or
HC, carbon monoxide (CO), Nitrogen Oxides (NOx), particulate matters, sulfur dioxide (SO 2 ),
Polycyclic Aromatic Hydrocarbons (PAH), Ammonia and aldehydes. There may also be traces of
other gases in the exhaust. I would like to remind you that in diesel engines, the combustion is by
auto-ignition while in gasoline, the combustion is initiated with a spark plug.

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Coming back to the exhaust gases, we can classify them in greenhouse gases , for example, CO2,
methane & sulphur dioxide, pollutants which are regulated by legislations as in HC, CO, NOx, PM
and other gases which are not yet regulated. Please note that Particulates or PM are also known
as soot.
Also, note that, SO2 comes from the sulfur in the fuel. As has already been discussed in the lecture
on fuels, a lot of effort has been made to remove the sulfur from the fuel itself.

Among the two types of engines, the principal emissions for gasoline are HC, CO and NOx while for
Diesel engines, it is the NOx and soot. By principal emission, I mean the emission which is produced
in the larger quantity and imposes bigger constraints. The question that comes to mind is why is
this so? Although both the engines are based on the combustion principle why is their emission
behavior different?
And, to answer this question, we will have to understand HOW these gases are formed in the
engine.

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Pollutant Formation
To reply to the why and the how, we must understand the combustion.
During combustion in the engine, fuel reacts with air. Fuel molecules contain Carbon & Hydrogen; it
may contain Oxygen in some cases; while air is largely a mix of O 2 and N 2 . Theoretically, if
combustion is complete, it will produce CO 2 & H 2 O; and N 2 remains unreacted.

However, the real combustion in the engine is incomplete; and with CO 2 and H 2 O, it also produces
CO, HC and nitrogen oxides, generally called NOx. Here, HC is a gaseous mix of unburned and
partially burned fuel. Please note that HC and CO are the products of incomplete combustion while

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NOx is a by-product of the combustion due to the reaction of N 2 with O 2 . Also note these small red
arrows representing heat transfer during combustion.
As we see that combustion depends on the gases present in the system and also on the heat
exchanged, it can be concluded that combustion is a function of chemical variables and thermal
variables.
To better understand combustion in general, we need to characterize the chemical and thermal
variables. For the chemical part, we must characterize gas composition. The first question to ask is
which are the gases present? Secondly, if we know which are the gases present, we need to ask
what are the relative concentrations of these gases?
Lastly, even if we know relative concentrations, we should know, how is the mixture in the volume?
Is it homogeneous meaning even distribution everywhere; or heterogeneous meaning the gases are
unequally distributed in the volume?
In the same way, we need to know the temperature range and how it varies in the volume. You see
the image of a typical cross section of an engine's combustion chamber showing temperature
variation during combustion (in the figure below). As you can imagine, the red are the hotter zones
and blue are relatively colder zones.
Overall, we can say that Gas composition governs the availability of the reactants while the
temperature governs their reactivity. The two factors together guide the combustion.

Now, in the particular case of the engine, as we have already seen, a mix of a variety of gases is
present during combustion, especially notice air containing O 2 and N 2 and Fuel.
At any moment during the combustion, the amount of each gas relative to the unit amount of fuel
will give us their relative concentrations in the mix.

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Gas composition can be summarized in the engines with a single parameter called the Equivalence
Ratio, also known as RICHNESS. It is the ratio of the mass of fuel to that of air with respect to the
stoichiometric Fuel to Air ratio. Stoichiometric ratio is the ratio of mass of fuel to that of air
required for complete combustion.
Sometimes, Air to Fuel Ratio or AFR is used which is the inverse of the Equivalence Ratio.

The Equivalence ratio plays the central role in the combustion. Equivalence ratio equal to 1 means
there is enough air to burn the fuel completely. If more than 1, then we have an excess of fuel with
respect to the air in the mix or we can say the mix is rich in fuel. Also, because there is too much
fuel, the combustion is incomplete.
In the same way, if the equivalence ratio is less than 1, that means there is an excess of air with
respect to the fuel available. Or, we can say, less fuel than needed for a given amount of air.
Meaning the mix is lean.
When the mix is rich, incomplete combustion produces HC, CO and soot as we have already seen.
Do note that Soot is partially burnt solid residue of the fuel in the form of small particles, while

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HC is gaseous. On the other hand, NOx production is favored in lean conditions due to an
excess of O 2 .
Finally, at equivalence ratio 1, in reality, the combustion is not complete and it gives NOx, HC and
CO.

Please note that, in Diesel, the mix is always lean while gasoline functions mostly at equivalence
ratio 1 and sometimes in rich conditions.
If we review the earlier table of pollutants for diesel and gasoline, we have already understood why
HC, CO and NOx are the main emissions for gasoline; why more NOx is produced in diesel while HC
and CO are low for diesel. Still, we havent yet found the answer to why soot is produced in diesel
although the mix is lean and on the contrary, why not much soot is produced for gasoline?
Here, I would like you to remember what we said about gas composition. For diesel, the mixture is
highly heterogeneous and there are pockets of very rich zones and very lean zones. Richness could
be higher than 4 in these rich pockets, producing a high quantity of soot. In fact, this is the reason
for the black smoke you see coming out of old diesel trucks. In contrast, in gasoline, the mix is
homogenous and the equivalence ratio remains close to 1 everywhere in the volume; hence the
mix is not rich enough to produce much soot.
In fact, this is why diesel engines were considered more polluting than gasoline in the past because
it produced more black smoke.

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To summarize all we have said about pollutant formation, I emphasize again that HC and CO are
products of incomplete combustion. On the graph below, you can see zones of formation of soot
and NOx. Soot is produced by a very rich mixture at high temperature while NOx is produced in the
lean mixture at a very high temperature.
The orange rectangle shows the zone of conventional combustion. You can conclude that, in
gasoline, the mixture being at richness 1, a large quantity of NOx is produced. While for diesel, due
to rich and lean pockets, both soot and NOx are produced.

In order to reduce NOx and Soot, alternative combustion technologies have been invented which
help to avoid both the zones, of soot as well as NOx formation. However, we will not go into detail

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about these alternative combustion technologies which is an advanced subject and is outside of this
introductory coursework.

A practical example of diesel combustion had been explained in the video lecture.
It was observed that NOx is produced at places with lean mix and high temperature while soot is
produced at reasonably reach mix and high temperature. Also, the NOx and soot are not produced
at the same place at any instance just like it was observed in the diagram previously.

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