1. Purpose of Experiment
The primary purpose of emissions testing is obviously to lower polluting emissions into the
environment. Many of these pollutants are the result of unburned or partially burned fuel passing
through the combustion system of an engine, while others are simply naturally occurring
chemical reactions the occur from the temperatures and air mixtures in vehicular operation. The
primary pollutants that adversely affect human, animal, and plant welfare are:
2. Theory of Experiment
The major causes of these emissions are nonstoichiometric combustion, dissociation of
nitrogen, and impurities in the fuel and air. The emissions of concern are hydrocarbons (HC),
carbon monoxide (CO), oxides of nitrogen (NOx), sulfur, and solid carbon particulates. Ideally,
engines and fuels could be developed such that very few harmful emissions are generated, and
these could be exhausted to the surroundings without a major impact on the environment.
2.1. Hydrocarbons (HC)
Exhaust gases leaving the combustion chamber of an SI engine contain up to 6000 ppm of
hydrocarbon components, the equivalent of 1-1.5 % of the fuel. About 40% of this unburned
gasoline fuel components the other 60% consist of small no equilibrium molecules that are
formed when large fuel molecules break up during the combustion reaction. It is often convenient
to treat these molecules as if they contained one carbon atom, as CH1.
When hydrocarbon emissions get into the atmosphere, they acts as irritants and odorants;
some are carcinogenic. All components expect CH4 react with atmospheric gases to from
photochemical smog.
Causes of HC Emissions
Nonstoichiometric Air-Fuel Ratio. With a fuel-rich mixture, there is not enough oxygen to
react with all the carbon, resulting in high levels of HC and CO in the exhaust products. If AF is
too lean poorer combustion occurs, again resulting in HC emissions.
Incomplete Combustion. Even where the fuel and air entering an engine are at the ideal
stoichiometric mixture, perfect combustion does not occur and some HC ends up in the exhaust.
Maximum CO is generated when an engine runs rich, such as when starting or when
accelerating under load. Even when the intake air-fuel mixture is stoichiometric or lean, some CO
will be generated in the engine.
2.3. Oxides of Nitrogen (NOx )
Exhaust gases of an engine have up to 2000 ppm of oxides of nitrogen. Most of this will
be nitrogen oxide (NO), with a small amount of nitrogen dioxide (NO2), and traces of other
nitrogen-oxygen combinations. These are all grouped together as NOx .It is a very undesirable
emission, and regulations that restrict the allowable amount continue to become more stringent.
Released NOx reacts in the atmosphere to from ozone and is one of the major causes of
photochemical smog.
NOx is created mostly from nitrogen in the air. Nitrogen can also be found in fuel blends,
which may contain trace amounts of NH3, NC, and HCN, but this would contribute only to a
minor degree.
2
O+ N 2 NO+ N
N +O2 NO+O
N +OH NO + H
(2)
NO, in turn, can then further react to from NO2 by various means, including
NO+ H 2 O NO2 + H 2
NO+O2 NO 2+O
(3)
2.4. Carbon Dioxide (CO2)
At moderate levels of concentration, carbon dioxide is not considered an air pollutant.
However, it is considered a major greenhouse gas and, at higher concentrations, is a major
contributor to global warming. CO2 is am major component of the exhaust in the combustion of
any hydrocarbon fuel. Because of growing number of motor vehicles, along with more factories
and other sources, the amount of carbon dioxide in the atmosphere continues to grow. At upper
elevations in the atmosphere, this higher concentration of carbon dioxide, along with other
greenhouse gases, creates a thermal radiation shield.
2.5. Aldehydes
A major emission problem when alcohol fuel is used the generation of aldehydes, an eye
and respiratory irritant.
3. After treatment
After the combustion process stops, those components in the cylinder gas mixture that
have not fully burned continue to react during the expansion stroke, during exhaust blow down,
and into the exhaust process. Up to 90% of the HC remaining after combustion reacts during this
time either in the cylinder, near the exhaust port, or in the upstream part of the exhaust manifold.
CO and small component hydrocarbons react with oxygen to from COz and HzO and reduce
undesirable emissions. The higher the exhaust temperature, the more these secondary reactions
occur and the lower the engine emissions. Higher exhaust temperature can be caused by
stoichiometric air-fuel combustion, high engine speed, retarded spark, and/or a low expansion
ratio.
3.1. Thermal Converters
Secondary reactions occur much more readily and completely if the temperature is high,
so some engines are equipped with thermal converters as a means of lowering emissions.
3
Thermal converters are high-temperature chambers through which the exhaust gas flows. They
promote oxidation of the CO and HC which remain in the exhaust.
CO+O z CO z
(4)
For this reaction to occur at a useful rate, the temperature must be held above 700C
C x H y + z Oz x CO z +h H z O
(5)
So thermal converter systems include an air intake which provides additional oxygen to
react with the CO and HC. This increases the complexity, cost, and size of system.
4. Catalytic Converters
A catalytic converter is a device used to convert toxic exhaust emissions from an internal
combustion engine into non-toxic substances. Inside a catalytic converter, a catalyst stimulates a
chemical reaction in which noxious byproducts of combustion are converted to less toxic
substances by dint of catalyzed chemical reactions. The specific reactions vary with the type of
catalyst installed. Most present-day vehicles that run on gasoline are fitted with a "three way"
converter, so named because it converts the three main pollutants in automobile exhaust: an
oxidizing reaction converts carbon monoxide (CO) and unburned hydrocarbons (HC), and a
reduction reaction converts oxides of nitrogen (NOx) to produce carbon dioxide (CO2), nitrogen
(N2), and water (H2O).
The first widespread introduction of catalytic converters was in the United States market,
where 1975 model year automobiles were so equipped to comply with tightening U.S.
Environmental Protection Agency regulations on automobile exhaust emissions. The catalytic
converters fitted were two-way models, combining carbon monoxide (CO) and unburned
hydrocarbons (HC) to produce carbon dioxide (CO2) and water (H2O). Two-way catalytic
converters of this type are now considered obsolete except on lean burn engines.[citation needed]
Since most vehicles at the time used carburetors that provided a relatively rich air-fuel ratio,
oxygen (O2) levels in the exhaust stream were in general insufficient for the catalytic reaction to
occur. Therefore, most such engines were also equipped with secondary air injection systems to
induct air into the exhaust stream to allow the catalyst to function.
Catalytic converters are still most commonly used on automobile exhaust systems, but are
also used on generator sets, forklifts, mining equipment, trucks, buses, locomotives, airplanes and
other engine fitted devices. This is usually in response to government regulation, either through
direct environmental regulation or through Health and Safety regulation.
The surface of the ceramic passages contains small embedded particles of catalytic
material that promote the oxidation reactions in the exhaust gas as it passes. Aluminum oxide is
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the base ceramic material used for most catalytic converters. Alumina can with stand the high
temperatures, it remains chemically neutral, it has very low thermal expansion, and it does not
thermally degrade with age. The catalyst materials most commonly used are platinum and
rhodium, with other noble metals (palladium and iridium) sometimes used as well.
Palladium and platinum promote the oxidation of CO and HC as in equations (4) and (5)
with platinum especially active in the hydrocarbon reaction. Rhodium promotes the reaction of
NOx in one or more of the following reactions:
1
NO+CO N 2 +CO2
(6)
2
2 NO +5 CO+3 H 2 O 2 NH 3 +5 CO2
(7)
2 NO +CO N 2 O+CO 2
(8)
1
NO+ H 2 N 2 + H 2 O
2
(9)
2 NO +5 H 2 2 NH 3 +2 H 2 O
(10)
2 NO + H 2 N 2 O+ H 2 O
(11)
Also often used is cerium oxide, which promotes the so-called water-gas shift:
CO+ H 2 O CO 2+ H 2
(12)
This reduces CO by using water vapor as an oxidant instead of O2, which is very
important when the engine is running in a rich manner.
Instead of ceramics, the interior chamber of some catalytic converters is filled with a very
thin corrugated metal foil wrapped into a monolith structure the exhaust gases pass between the
rolls of foil, the surface of which is embedded with catalytic material. The active surface area of a
2
larger converter of this type can be as great as 70.000 m
poison the catalyst material. These include lead and sulfur from fuels, and zinc, phosphorus,
antimony, calcium, and magnesium from oil additives. Figure 9-12 shows how just a small
amount of lead one catalyst site can reduce HC reduction by a factor of two or three. Small
amounts of lead impurities are found in some fuels, and 10-30% of this ends up in the catalytic
converter. Up until the early 1990s, leaded gasoline was quit common, and it was imperative that
it not be used in engines equipped with catalytic converters; such use was unlawful. Two fuel
tanks of leaded gasoline would completed the poison a converter and make it totally useless.
5. Exhaust Gas Recycle- EGR
The most effective way of reducing NOx emissions is to hold combustion chamber
temperatures down. Although practical, this is a very unfortunate method in that it also reduces
the thermal efficiency of the engine. We have been taught since infancy in our first
thermodynamics course that for maximum engine thermal efficiency, Qin should be at the highest
possible.
Probably the simplest practical method of reducing maximum flame temperature is to
dilute the air-fuel mixture with a non-reacting parasite gas. This gas absorbs energy during
combustion without contributing any energy input. The net result is a lower flame temperature.
Any no reacting gas would work as a diluent, as shown Figure-4. Those gases with larger specific
heats would absorb the most energy per unit mass and would therefore require the least amount;
thus less CO2 would be required than argon for the same maximum temperature. However, neither
CO2 nor argon is readily available for use in an engine. Air is available as a diluent but not totally
nonreacting. Adding air changes the AF and combustion characteristics. The one nonreacting gas
that is available to use in an engine is exhaust gas, and this is used in all modern automobile and
other medium size and large engines.
Exhaust gas recycle (EGR) is done by ducting some of the exhaust flow back into the
intake system, usually immediately after the throttle. The amount of flow can be as high as 30%
of the total intake. EGR gas combines with the exhaust residual left in the cylinder from the
previous cycle to effectively reduce the maximum combustion temperature. The flow rate of EGR
is controlled by the EMS. EGR is defined as a mass percent of the total intake flow:
m
Figure-4: Reduction of NOx generation by adding noncombustible diluent gas to intake mixture
After EGR combines with the exhaust residual left from the previous cycle, the total
fraction of the exhaust in the cylinder during the compression stroke is
EGR
X cx =
( 1x r ) + x r
100
(14)
Where
Not only does EGR reduce the maximum temperature in the combustion chamber, but it
also lowers the overall combustion efficiency.
The amount of EGR is controlled by the EMS. By sensing inlet and exhaust conditions
the flow controlled, ranging from 0 up to 15-30 %. Lowest NOx emissions with relatively good
fuel economy occur at about stoichiometric combustion, with as much EGR as possible without
adversely affecting combustion. No EGR is used during WOT (Wide Open Throttle), when
maximum power is desired. No EGR is used at idle and very little at low speeds. Under these
conditions, there is already a maximum exhaust residual and grater combustion inefficiency.
Engines with fast-burn combustion chambers can tolerate a greater amount of EGR.
A problem unique to CI engines when using EGR is the solid carbon soot in the exhaust.
The soot acts as an abrasive and breaks down the lubricant. Greater wear on the piston rings and
valve train results.
5.1. In Diesel Engines
If 3% more diesel is being burned, that means theres also a 3% increase in all the
pollutants being expelled out the exhaust pipe. While emission controls are clearly a good thing,
8
it isnt clear if the EGR is causing more good than harm by burning off the trace amount of
nitrogen oxides. Furthermore, it may not be good for the diesel engine itself.
m
exhaust ,intake
EGR [ ]=
(15)
5.2.
Advantages of EGR
Reduced NOx
Potential reduction of throttling losses on spark ignition engines at part load
Improved engine life through reduced cylinder temperatures (particularly exhaust valve life)
5.3.
Since EGR reduces the available oxygen in the cylinder, the production of particulates
(fuel which has only partially combusted) is increased when EGR is applied. This has
traditionally been a problem with diesel engines, where the trade-off between NOx and
particulates is a familiar one to calibrators.
The deliberate reduction of the oxygen available in the cylinder will reduce the peak
power available from the engine. For this reason the EGR is usually shut off when full power is
demanded, so the EGR approach to controlling NOx fails in this situation.
The EGR valve can not respond instantly to changes in demand, and the exhaust gas takes
time to flow around the EGR circuit. This makes the calibration of transient EGR behavior
particularly complex- traditionally the EGR valve has been closed during transients and then reopened once steady state is achieved. However, the spike in NOx / particulate associated with
poor EGR control makes transient EGR behavior of interest.
The recirculated gas is normally introduced into the intake system before the intakes
divide in a multi-cylinder engine. Despite this, perfect mixing of the gas is impossible to achieve
at all engine speeds / loads and particularly during transient operation. For example poor EGR
distribution cylinder-to-cylinder may result in one cylinder receiving too much EGR, causing
high particulate emissions, while another cylinder receives too little, resulting in high
NOx emissions from that cylinder.
Although the term EGR usually refers to deliberate, external EGR, there is also a level
of internal EGR. This occurs because the residual combustion gas remaining in the cylinder at
the end of the exhaust stroke is mixed with the incoming charge. There is therefore a proportion
of internal EGR which must be taken into account when planning EGR strategies. The
scavenging efficiency will vary with engine load, and in an engine fitted with variable valve
timing a further parameter must be considered.
Slightly worse fuel economy. Exhaust gases dont re-burn all that well because it contains
very little that is useful to the combustion process. So when you reintroduce exhaust back into
the diesel engine, you are displacing fresh air that has more oxygen with exhaust gasses that
dont. As a result, the engine doesnt burn the fuel as well because there is less oxygen.
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Diesel exhaust by its very nature has pollutants in it, including soot in the form of carbon.
By re-introducing the untreated exhaust back into the combustion chamber, soot will start to
buildup in the oil and on other internal engine parts, including the intake turbo. This cannot be
good, but its debatable how bad it is. Im of the opinion that the cleaner the air going into the
engine, the better it will run and the less problems youll have in the long run. This is the whole
reason why vehicles have air filters. The EGR system does not pass the exhaust back through the
air filter because there is too much soot which would clog the filter in a matter of minutes. So if
the EGR process is too dirty to pass the exhaust through a filter, think of all that black soot that is
going directly into the engine.
Because exhaust is hot, it must first be cooled prior to re-mixing it with new air. Piping
700F gasses into the engine is a recipe for disaster. Therefore, an EGR cooler is needed. It is
basically a second radiator that reduces the exhaust gas temperatures before they are re-burned. If
the cooler fails, the temperatures in the engine can skyrocket quickly causing permanent damage
to your engine.
5.4. Is the EGR needed?
The answer is no, if you dont mind breaking the law. Federal emission laws state you are
not allowed to tamper with the emission control system on a vehicle, which the EGR is a part of.
And since EPA regulations require it, you cannot remove it. If caught, you could face a penalty.
However, the EGR provides no benefit to the diesel engine and can be removed with no ill
effects. In fact, many have reported that their diesel engine runs better with it removed. On the
dodge Ram forums, most people report anywhere from a 1 to 2 mpg increase in fuel efficiency
once the EGR system has been disabled or removed. Some also report a little better response in
acceleration. Almost all said their oil was in much better condition when they changed it.
oxides of carbon
nitrogen
water
aldehydes
oxides of nitrogen
oxides of sulfur
Polycyclic aromatic hydrocarbons.
12
Oxides of nitrogen
NO is formed by the combustion of air-fuel mixture near the stoichiometric ratio. Increased of the
NO production is the gas temperature and oxygen concentration.
Oxides of sulfur
End of the combustion SO3 it become, then this SO3 is combined with condensed water and
sulfuric acid (H2SO4) becomes.
Aldehydes
Partly burned hydrocarbons in emissions as a result of not complete combustion of hydrocarbons
used as fuel that aldehydes occurs.
CnHm.CHO this is form of the aldehydes.
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Blue smoke (mainly oil and unburnt fuel) which indicates a poorly serviced and/or tuned
engine;
Black smoke (soot, oil and unburnt fuel) which indicates a mechanical fault with the
engine;
White smoke (water droplets and unburnt fuel) which is produced when the engine is
started from cold and disappears when the engine warms up.
With older engines, the white smoke produced has a sharp smell which may cause
irritation to your upper respiratory system.
Affecting Factors of the Exhaust Emissions
Compression Ratio
Air / Fuel Ratio
Advance ignition
14
Fuel Quality
Engine Friction
Assistant Systems Used in Motor
Firing chamber design
Vehicle Design
ma m
= a
f
ma m
(17)
FA=
mf m
1
= f=
ma ma AF
(18)
Where
ma=mass of air
mf =mass flow rate of air
The ideal stoichiometric AF for many gasoline-type hydrocarbon fuels is very close to
15:1, with combustion possible for values in the range of 6 to 25. AF less than 6 is too rich to
sustain combustion and AF greater than 25 is too lean. A vehicle will often be operated with a
rich mixture when accelerating or starting cold, rich mixtures having better ignition.
15
Equivalence ratio is defined as the actual ratio of fuel-air to ideal or stoichiometric fuel-air:
=
( FA )act ( AF ) stoich
=
( FA ) stoich ( AF )act
(19)
Some literature uses lambda value instead of equivalence ratio, lambda value being the reciprocal
of the equivalence ratio:
1
=
(20)
8. Data/Results
8.1. Assignments
%vol O2=0,9
%vol CO=0,12
%vol C O2=6,77
%vol
HC=74 ppm
C6 H 14 +O 2 Heat +C O2 +CO+ HC + N O x
( ) )
R HC
3.5
R
[CO ]
[ NO]
4
C
O
+
+
O
+
+
O C ( [ C O2 ]+ [ CO ] )
[ 2] 2 [ 2] 2
2
[ CO ]
3.5+
[C O2 ]
II
=
1+
R H C ROC
( [ C O 2 ] + [ C 0 ] + ( n[ HC ] ) )
4
2
( ))
14
6
3.5
[0.12]
4
0
[ 6.77 ] +
+ [ 0.9 ] +
( [ 6.77 ] + [ 0.12 ] )
2
[ 0.12 ] 2
3.5+
[ 0.9 ]
III
=
14
6 0
1+
( [ 6.77 ] + [ 0.12 ] + ( 6[ 74106 ] ) )
4 2
16
IV
11.72891
=1.075074
10.90986
8.2. Conclusion
17
is decrease
When the carbon dioxide increase is decrease
9. References
[1]
<ref> [www.cambustion.com/products/egr], EGR<ref>
[2]
<ref> [ http://www.weatherimagery.com/blog/diesel-engine-egr-bad/.] , Emission of Diesel
Engines <ref>
[3]
<ref> [http://kth.diva-portal.org/smash/get/diva2:305816/FULLTEXT01.]<ref>
[4]
<ref>[http://megep.meb.gov.tr/mte_program_modul/moduller_pdf/Egzoz%20Emisyon
%20Kontrol%C3%BC.pdf ]<ref>
[5]
[6]
[7]
18