Pollutant emissions from IC

Engines
The goal of the human society is to protect and enhance air quality to further protect and promote human health and public
welfare. Until the middle of the 20th century the number of IC engines in the world was so small that the pollution they
caused was tolerable. During that period the environment, with the help of sunlight, stayed relatively clean. As world
population grew, power plants, factories, and an ever-increasing number of automobiles began to pollute the air to the
extent that it was no longer acceptable.

Pollutants from SI and CI Engines:

 Unburnt hydrocarbons (HC)

 Oxides of carbon (COx)
 Oxides of nitrogen (NOx)
 Oxides of sulphur (SOx) and
 Solid carbon particulates

The major causes of these emissions are non-stoichiometric combustion, dissociation of nitrogen, and impurities in the fuel
and air.
Engine emissions are classified as:

 Exhaust emission and

 Non – exhaust emission

Exhaust emission:

 Carbon Monoxide
 Unburnt hydrocarbons (UBHCs)
 Oxides of nitrogen (NO-NOX)
 Oxides of sulphur
 Particulate, soot and smoke

The first four are from both SI and CI engines, where as last two are mainly from CI engines.

Non exhaust emission:

 Fuel tank: Emits fuel vapours into the atmosphere.

 Carburettor: Also gives out fuel vapours.
 Crankcase: It emits blow-by gases and fuel vapours into the atmosphere.
Emissions as a function of equivalence ratio for a SI engine Emissions as a function of equivalence ratio for a CI engine
HYDROCARBON EMISSION:

It is a strong function of 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. This is particularly true during starting, when the air-fuel
mixture is purposely made very rich.

Combustion chamber geometry and engine operating parameters also influence the HC component spectrum.

The causes of hydrocarbon emissions from SI engine are:

 Incomplete combustion
 Crevice volumes and flow in crevices
 Leakage past the exhaust valve
 Valve overlap
 Deposits on walls
 Oil on combustion chamber walls

Because CI engines operate with an overall fuel-lean equivalence ratio, CI engines have only about one-fifth the HC
emissions of an SI engine. In general, a CI engine has combustion efficiency of about 98%. This means that only about 2% of
the HC fuel being emitted.
CARBON MONOXIDE (CO) EMISSION:

 It is generated in an engine when it is operated with a fuel-rich equivalence ratio.

 When there is not enough oxygen to convert all carbon to CO2, some fuel does not get burned and some carbon ends up
as CO.

 Typically the exhaust of an SI engine will be about 0.2 to 5% carbon monoxide.

 Not only is CO considered an undesirable emission, but it also represents lost chemical energy.

 Maximum CO is generated when an engine runs rich. Rich mixture is required during starting or when accelerating under
load. Poor mixing, local rich regions, and incomplete combustion will also be the source for CO emissions.
OXIDES OF NITROGEN (NOX):

 Exhaust gases of an engine can 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). There will also be traces of other nitrogen-oxygen combinations. These are all
grouped together NOx, with x representing some suitable number. NOx is very undesirable.

 Released NOx reacts in the atmosphere to form ozone and is one of the major causes of photochemical smog.

 At low temperatures, atmospheric nitrogen exists as a stable diatomic molecule. However, at very high temperatures that
occur in the combustion chamber of an engine, some diatomic nitrogen (N2) breaks down to monatomic nitrogen (N)
which is reactive.

 Significant amount of N is generated in the temperature range of 2500-3000 K that can exist in an engine. Maximum NOx
is formed at a slightly lean equivalence ratio of about φ = 0.95. At this condition flame temperature is still very high, and
in addition, there is an excess of oxygen that can combine with the nitrogen to form various oxides.

 In addition to temperature, the formation of NOx depends on pressure and air-fuel ratio.

 Combustion duration plays a significant role in NOx formation within the cylinder.
PARTICULATES:

 The exhaust of CI engines contains solid carbon soot particles that are generated in the fuel-rich zones within the
cylinder during combustion. These are seen as exhaust smoke and cause an undesirable odorous pollution.

 Soot particles are clusters of solid carbon spheres. These spheres have diameters from 9 nm to 90 nm (1 nm = 10−9 m).
The spheres are solid carbon with HC and traces of other components absorbed on the surface. A single soot particle
may contain up to 5000 carbon spheres.

 Particulate generation can be reduced by engine design and control of operating conditions, but quite often this will
create other adverse results.

Engine management systems are programmed to minimize CO, HC, NOx, and particulate emissions by controlling ignition
timing, injection pressure, injection timing, and/or valve timing. Obviously, some sort of compromise is necessary. In most
cases exhaust particulate amounts cannot be reduced to acceptable levels solely by engine design and control.
OTHER EMISSIONS:

Apart from major emissions like unburnt hydrocarbon, carbon monoxide and NOx, there are other emissions that come out
of the exhaust.

 Aldehydes

 Sulphur

 Lead

 Phosphorus
EMISSION CONTROL METHODS:

CO and small component hydrocarbons react with oxygen to form CO 2 and H2O and reduce undesirable emissions. The higher
the exhaust temperature, the more these secondary reactions occur and the lower the engine emissions.

In order to reduce emissions, some after-treatments are necessary with add on devices.

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. 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.

 Most thermal converters are essentially an enlarged exhaust manifold connected to the engine immediately outside the
exhaust ports.

 Even though HC and CO emissions can be reduced by oxidation, NOx emissions cannot be reduced using a thermal
converter.
CATALYTIC CONVERTORS:

 The most effective after-treatment for reducing engine emissions is the catalytic converter found on most automobiles
and other modern engines of medium or large size.

 If certain catalysts are present, the temperature needed to sustain the oxidation processes of CO and HC to CO 2 and H2O is
reduced to 250–300 ◦C, making for a much more attractive system.

 Catalytic converters are chambers mounted in the flow system through which the exhaust gases pass through. These
chambers contain catalytic material, which promotes the oxidation of the emissions contained in the exhaust flow.

 Generally, they are called three-way converters because they are used to reduce the concentration of CO, HC, and NOx in
the exhaust.

 It is usually a stainless steel container mounted somewhere along the exhaust pipe of the engine. Aluminium oxide
(alumina) is the base ceramic material used for most catalytic converters.

 Alumina can withstand 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 used are platinum, palladium, and rhodium.
Fig. Catalytic converters for SI engines
Sulphur:

Sulphur offers unique problems for catalytic converters. Some catalysts promote the conversion of SO2 to SO3, which
eventually gets converted to sulphuric acid. This degrades the catalytic converter and contributes to acid rain. New catalysts
are being developed that promote the oxidation of HC and CO but do not change SO2 to SO3. Some of these create almost
no SO3 if the temperature of the converter is kept less than 400 ◦C.

Cold Start-Ups:

Catalytic converters are not very efficient when they are cold. When an engine is started after not being operated for several
hours, it takes several minutes for the converter to reach an efficient operating temperature. A large percentage of
automobile travel is for short distances where the catalytic converter never reaches efficient operating temperature, and
therefore emissions are high.
It is estimated that cold start-ups are the source of 70-90% of all HC emissions. A major reduction in emissions is therefore
possible if catalytic converters could be preheated, at least to light-off temperature, before engine startup.

Methods of catalytic converter preheating include the following:

 by locating the converter close to the engine
 by having super-insulation
 by employing electric preheating
 by using flame heating
 incorporating thermal batteries
Exhaust Gas Recirculation (EGR):

 The most effective way of reducing NOx emissions is to hold combustion chamber temperatures down.

 Probably the simplest and 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 non-reacting gas would work as a diluents.

 The one non-reacting 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. Adding any non reacting neutral gas to the inlet air-fuel mixture reduces flame
temperature and NOx generation, Exhaust gas (EG) is the one gas that is readily available for engine use.

 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 combines with the exhaust residual
left in the cylinder from the previous cycle to effectively reduce the maximum combustion temperature.

 Not only does EGR reduce the maximum temperature in the combustion chamber, but it also lowers the overall
combustion efficiency. Increase in EGR results in some cycle partial burns and, in the extreme, total misfires. Thus, by
using EGR to reduce NOx emissions, a costly price of increased HC emissions and lower thermal efficiency must be paid.

 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.
Measurement of engine emissions:

Emissions may be divided into two groups, viz., invisible emissions and visible emissions.

Carbon dioxide, water vapour, oxides of nitrogen, unburnt hydrocarbons, carbon monoxide, aldehydes are invisible
emissions. Smoke and particulate are visible emissions. Out of the various invisible emissions carbon dioxide and water
vapour are considered harmless compared to others.

Oxides of Nitrogen:

 Internationally accepted method for measuring oxides of nitrogen is by chemiluminescence analyser. The principle of
measurement is based on chemiluminescence reaction between ozone and NO resulting in the formation of excited NO 2.
This excited NO2 emits light whose intensity is proportional to NO concentration. The light intensity is measured by a
photo multiplier tube. The analyser measures only nitric oxide, NO, and not NO 2.

 To analyse all the oxides of nitrogen a converter is usually fitted ahead of the reaction chamber to convert all the oxides of
nitrogen into nitric oxide. Thereby, the light intensity can be taken to be proportional to the oxides of nitrogen
concentration in the sample.
Fig. Chemiluminescence method of
measuring oxides of nitrogen
Carbon Monoxide:

 Non Dispersive Infra-Red analyzer (NDIR) as shown in Fig is the

widely accepted instrument for measuring CO.

 In the NDIR analyzer the exhaust gas species being measured

are used to detect themselves.

 The method of detection is based on the principle of selective

absorption of the infrared energy of a particular wave length
peculiar to a certain gas which will be absorbed by that gas.

Fig. NDIR method of measuring carbon monoxide

Unburned Hydrocarbons:

 Flame Ionization Detector (FID) is used for measuring

hydrocarbons. This instrument as shown in Fig is a well
established and accepted method for measuring HC.

 Ionization is a characteristic of HC compound. This principle

is employed in the FID detector. Formation of electrically
charged particles of ionized carbon atoms from the
hydrocarbons in a hydrogen-oxygen flame is achieved in the
FID analyser. Current flow in micro amperes (amplified for
measurements) is a measure of the concentration of
hydrocarbons.

Fig. Flame ionization method for measuring unburnt

hydrocarbons
VISIBLE EMISSIONS:

Smoke:

Smoke in diesel engine can be divided into three categories viz., blue, white and black. Smoke measurements can be broadly
classified into two groups viz. comparison method and obscuration method.

Comparison Method:

Most ordinances regulating smoke emissions are based on estimation of the density of the smoke as it emerges from the
exhaust. Of the several available methods, the one of the commonly used method is the Ringelmann Chart. The chart shows
four shades of grey, as well as a pure white and an all-black section. To overcome the difficulty of reproducing various shades
of grey, the intermediate shades are built from black lines of various widths The four intermediate charts are printed by the
United States Bureau of Mines on a single 70 cm × 25 cm sheet. They may be reproduced as follows:
0 All white
1 Black lines 1 mm thick, 10 mm apart, leaving white spaces 9 mm square.
2 Lines 2.3 mm thick, spaces 7.7 mm square.
3 Lines 3.7 mm thick, spaces 6.3 mm square.
4 Lines 5.5 mm thick, spaces 4.5 mm square.
5 All black
In use, the chart is set up at eye level in line with the stack at such distances (10 m or more) that the sections appear to be
different degrees of uniform grey shades. The appearance of the smoke at the top of the stack is matched against one of the
shades on the card and reported as a specific Ringelmann number ranging from 0 (no smoke) to No.5 (dense black smoke).
With practice, an observer can estimate smoke density to half a number, particularly in the Nos.2 to 4 ranges. Readings
below No.2 Ringelmann are subject to considerable error.

Fig. Ringelmann chart

Obscuration Method: It is basically divided into light extinction type, continuous filtering type and spot filtering type.

Fig. Obscuration method for measuring smoke

Light Extinction Type: In this method of testing, the intensity of a light beam is reduced by smoke which is a measure of
smoke intensity. A continuously taken exhaust sample is passed through a tube of about 45 cm length which has light
source at one end and photocell at the other end. The amount of light passed through this column is used as an indication
of smoke level or smoke density. The smoke level or smoke density is defined as the ratio of electric output from photocell
when sample is passed through the column to the electric output when clean air is passed through it. The Hartridge smoke-
meter is a very commonly used instrument based on this principle.
Fig. Hartridge smoke-meter
Continuous Filtering Type: In this method provision is made for continuous reading and observing transient conditions.
Measurement of smoke intensity is achieved by continuously passing exhaust gas through a moving strip of filter paper and
collecting particles.

Fig. Continuous filter type smoke-meter

Spot Filtering Type: A smoke stain obtained by filtering a given quantity of exhaust gas through a fixed filter paper is used
for the measure of smoke intensity.

Fig. Spot filtering type smoke-meter

NOISE:

Noise is a mixture of various sounds which is a source of irritation for the listener. Sound is created by a vibrating object. The
vibrations are transmitted to the surrounding air in the form of pressure waves. If the frequency and intensity of the pressure
waves are within specified range they produce sensation of sound (15 to 15000 Hz and 0 to 120 dB intensity). Sound level
meter consists of a microphone, calibrated attenuator, an electronic amplifier and an indicator meter which reads in decibels
(dB) as shown in Fig.15.30. Octave band frequency analyser is suitable for obtaining the frequency distribution in light bands
in frequency region between 20 and 10,000 Hz. The measurement of the noise emitted by motor vehicles is based on a
moving vehicle, since it is the total noise emitted by motor vehicle including gear box and transmission.

Fig. Sound level meter

Bharat Stage Norms:

 Bharat Stage or BS Emission Standards are government-instituted emission standards that all motor vehicles have to
comply with if they are to be sold and driven in India.

 The BS norms are based on the European Emission Standards (Euro norms) and were first set in 2000. Equivalent to the
Euro-1, the first iteration was known as ‘India 2000’, and not BS-I. Subsequent emission standards were called BS-II, BS-
III, and BS-IV.

 With the implementation of the new norms, pollution levels are expected to reduce to a large extent as the particulate
matter (PM) concentration should decrease. About one-third of the air pollution is caused by motor vehicles and cars.

 The volume of particulate matter 2.5 is between 20 to 40 micrograms per cubic metre in BS-VI fuel, whereas, in BS-IV, it
was up to 120 micrograms per cubic metre.

 The sulphur content in the BS-VI compliant fuel is brought down five times when compared to the BS-IV version. (It is 10
ppm of sulphur as against the previous 50 ppm).

 Sulphur in the fuel contributes to fine particulate matter emissions. High sulphur content in the fuel also leads to
corrosion and wear of the automobile engine.
 Under the BS-VI fuel, for 1 KM, a car will emit 80% less PM and almost 70% less nitrogen oxide (in a diesel engine). In a
petrol engine, the emission of nitrogen oxide would be less by 25%.

 BS-VI norms will lead to the reduction of the emission of certain hydrocarbons (that are produced because of the
incomplete combustion of fuel).

 BS-VI fuel contains lesser air pollutants compared to BS-IV fuel.

 The levels of poisonous, highly reactive gases that form when fuel is burned at high temperatures such as NOx, or oxides
of nitrogen, are also expected to reduce.

India 2000 (Euro 1)

BS II (Euro 2)
BS III (Euro 3)
BS IV (Euro 4)
BS V (Euro 5)
BS VI (Euro 6)
 Fuel Type Pollutant Gases BS6 (BSVI) BS4 (BSIV)

Petroleum Distillate Vehicle Nitrogen Oxide (NOx) Limit 60 mg 80 mg

Particulate Matter (PM) 4.5 mg/km -

Limit

Diesel Fuel Vehicle Nitrogen Oxide (NOx) Limit 80 mg 250 mg

Particulate Matter (PM) 4.5 mg/km 25 mg/km

Limit

HC + NOx 170 mg/km 300 mg/km

Thank You