UNIT III ENGINE EXHAUST EMISSION CONTROL

Formation of NOx, HC/CO mechanism, Smoke and Particulate emissions, Green house effect, Methods of controlling emissions, Three way catalytic converter and Particulate Trap, Emission (HC,CO, NO and NOx) measuring equipments, Smoke and Particulate measurement, Indian driving cycles and emission norms

AICE

Topics covered:
Formation of NOX Formation of HC/CO Formation of Smoke and Particulate emissions Methods of controlling emissions Three way catalytic convertor Particulate Trap Measuring HC emissions Measuring CO emissions Measuring NO emissions Measuring NOx emissions Measuring Particulate and Smoke emissions Indian Driving cycles and Emission norms

AICE

AICE

AICE

AICE

AICE

Formation of Nitrogen Oxides

Nitric oxide is the major component of NOx emissions from the

internal combustion engines. During combustion, three probable sources of NO formation are: (i) Thermal NO : By oxidation of atmospheric (molecular) nitrogen at high temperatures in the post-flame burned gases. (ii) Prompt NO : Formed at the flame front within the flame reaction zone. (iii) Fuel NO : Oxidation of fuel-bound nitrogen at relatively low temperatures.
AICE

 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.
Kinetics of Thermal NO Formation

The following three reactions commonly referred to as the extended Zeldovich mechanism govern the formation of thermal NO: (2.1) (2.2) (2.3) k1, k2 and k3 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.

AICE

 Prompt NO
In the flame reaction zone NO may be formed rapidly. The prompt NO is formed in the flame by reaction of intermediate chemical species of CN group with O and OH radicals. The hydrocarbon radicals CH, CH2, C, C2 etc. formed in the flame front react with molecular nitrogen to give intermediate species such as HCN and CN by the reactions shown below. Large concentrations of HCN near the reaction zone in fuel rich flames have been observed and rapid formation of NO has been seen to be associated with rapid decay of HCN.

AICE

 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.

10

AICE

FORMATION OF CARBON MONOXIDE

Carbon monoxide is formed during combustion of fuel-rich mixtures due to deficiency of oxygen. Combustion of hydrocarbon fuels may be considered as a two-step process leading to complete combustion when carbon dioxide is the final product. 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) RH represents a hydrocarbon where R stands for the hydrocarbon radical Step 2 Conversion of CO to CO2 : when sufficient oxygen is available. Hydroxyl radical OH is one the principal oxidizing species and converts CO to CO2, (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.
11 AICE

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 . These CO values may be considered as partial equilibrium values. Detailed investigations have shown:

For rich mixtures (>1), the average exhaust CO concentrations are close to equilibrium concentrations during expansion. For near stoichiometric mixtures ( 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.
AICE

12

CO emissions in real engines:

Mixture mal-distribution in multi cylinder engines causes cylinder-to-cylinder

variation in air-fuel ratio. It results in significant increase in the average CO emissions. This is especially prominent in the carburetted or single point throttle body-injected (TBI) engines.
Another contributing factor to higher CO emissions is non-uniform mixture

distribution within the cylinder.

During cold start of engine and acceleration rich mixtures are used resulting in higher

CO emissions
Overall, the air-fuel ratio is the most important engine parameter affecting CO

emissions. Other factors influence CO mostly indirectly through changes in mixture composition and/or promotion of slow oxidation reactions resulting in incomplete combustion.

13

AICE

 HC Emissions from Wall Quenching

Single wall quench layer thickness typically varies from 0.05 to 0.1 mm. It decreases with increase of engine load as higher wall temperature results at higher engine loads, which reduces heat loss to the walls from the reaction zone, and consequently a smaller quench layer thickness is obtained.
However, at top dead centre the surface to volume ratio of the combustion chamber is at its maximum and at this point the wall quench layer may comprise of 0.1 to 0.2 percent of the total charge inducted into the cylinder. Studies on combustion of pre-mixed fuel air mixtures in combustion bombs show that when all the crevices in the bomb are eliminated by filling with solid material, unburned HC concentrations were just about 10 ppmC only. Such low concentrations result as after flame quenching the hydrocarbons in the quench layer thickness on the single walls diffuse in the hot burned gas quite early and get oxidized. Typically, most hydrocarbons would get oxidized on diffusion in the high temperature burned gases within 2-3 milliseconds of the flame quench. These studies showed that the contribution of single wall quench layers to the total unburned HC emission is quite small.
14 AICE

 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 following figure.

15

AICE

16

AICE

 HC Emissions from CI Engines The unburned hydrocarbons in diesel exhaust consist of original fuel molecules,

products of pyrolysis of fuel compounds and partially oxidized hydrocarbons, in all numbering to almost 400 organic compounds ranging from methane to heaviest fuel components. In diesel engines, several events like liquid fuel injection, fuel evaporation, fuel-air mixing, combustion, and mixing of burned and unburned gases may take place concurrently and combustion is heterogeneous in nature. Thus, several processes are likely to contribute to unburned hydrocarbon emissions as below;
Overmixing of fuel and air beyond lean flammability limits during delay period, Under-mixing of fuel injected towards the end of injection process resulting in fuel-

air ratios that are too rich for complete combustion,

Impingement of fuel sprays on walls due to spray over-penetration, Poorly atomized fuel from the nozzle sac volume and nozzle holes after the end of

injection, and
Bulk quenching of combustion reactions due to cold engine conditions, mixing with

cooler air or during expansion.

17

AICE

18

AICE

 SOOT AND PARTICULATE EMISSIONS: Soot is a carbonaceous particulate matter and is produced during combustion of the

rich fuel - air mixtures.

Appearance of black smoke emissions in the exhaust indicates high concentration of

soot in the exhaust gases.

Soot is mostly produced in the diffusion combustion systems, but overly rich

premixed combustion also produces soot.

As the spark ignition engines generally operate close to stoichiometric air-fuel ratio,

soot emissions from these engines are not significant. With the use of unleaded gasoline, lead particulates from the SI engines have been eliminated.
Here, we will discuss particulate emissions only from the diesel engines as these are

of major health concern and are more difficult to control. Soot emissions have been associated with respiratory problems and are thought to be carcinogenic in nature. The particle size is important as the particles smaller than 2.5 can reach lungs along with the inhaled air and cause health problems. The particles smaller than 2.5 constitute more than 90 percent mass of the total particulate matter in the diesel exhaust. The fuel composition also is an important factor in soot production and emissions. For diffusion combustion soot-forming tendency is generally in the following order;
19 AICE

20

AICE

Diesel particulate matter has two main components;

Dry soot or solid carbon material

Dry soot is mainly the carbonaceous fraction of the particulate and its typical chemical formulae are C8H, C9H and C10H. About 5 to 10 % by mass oxygen and 0.5% nitrogen are also present. Typical empirical formula of dry soot would be CH0.11O0.065N0.005. Dry soot results from several processes like pyrolysis, dehydrogenation and condensation of fuel molecules.
Soluble organic fraction (SOF)

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 C17 to C40 are present in particulate SOF phase, the C23 C24 being close to the mean. Typically, SOF has an empirical formula CH1.65O0.1N0.007. 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
21 AICE

Diesel Smoke
Visible black smoke emissions from diesel engine result on account of high

concentration of soot in the exhaust gas. All the diesel engine design and operating variables that affect soot formation and oxidation also influence black smoke intensity. Initially, smoke emission standards for production diesel vehicles were in force to control black smoke. Smoke emissions increase with increase in engine load due to overall richer fuel-air ratios and hence, the rated engine power was specified based on the maximum permitted smoke density to curb black smoke emissions during engine operation. The rated power was also known as smoke limited power. Poor control of fuel injection rate during acceleration also increases smoke. Use of EGR reduces combustion temperatures and oxygen concentration in the burned gases. EGR also reduces oxidation of soot and hence overall effect of EGR is to increase smoke. Smoke emissions can be reduced by accelerating combustion. Higher combustion rates are obtained by increasing fuel air mixing through use of high swirl rates, by increasing injection rate and improving fuel atomization. Advancing injection timing increases combustion temperatures and allows more time for oxidation of soot thereby reducing smoke emissions. Smoke is measured by measurement of light absorbed (opacity) in a defined specific length of column of exhaust gas. The smokemeters employing this principle are known as light extinction type of smokemeter such as Hartridge or AVL smokemeters. Smoke has also been measured by filtering a fixed volume of exhaust gases through a filter paper and the smoke stain thus formed is evaluated on a grayness scale by a light reflectance meter (Bosch smokemeter).
AICE

22

23

AICE

Catalytic Convertors 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.
AICE

24

The oxides of base metals such as copper, chromium, nickel, cobalt etc. have been studied. The base metal oxides are effective only at higher temperatures. In addition, they sinter and deactivate when subjected to high exhaust gas temperatures experienced at high engine loads. Their conversion efficiency is severely reduced by sulphur dioxide produced by sulphur in fuel. The noble metals platinum (Pt), palladium (Pd) and rhodium (Rh) were found to meet the above mentioned performance requirements. In practice, only the noble metals are used although these are expensive. Mixtures of noble metals are used to provide higher reactivity and selectivity of conversion. Following are typical formulations; Pt : Pd in 2:1 ratio for oxidation catalysts (Pt + Pd): Rh in ratio of 5 :1 to 10: 1 for simultaneous oxidation and reduction such as in 3-way catalysts Palladium has higher specific activity than Pt for oxidation of CO, olefins and methane. For the oxidation of paraffin hydrocarbons Pt is more active than Pd. Platinum has a higher thermal resistance to deactivation. Rhodium is used as a NOx reduction catalyst when simultaneous conversion of CO, HC and NOx is desired as in the 3-way catalytic converters.
25 AICE

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 Ceramic monoliths Metal monoliths
26 AICE

27

AICE

28

AICE

29

AICE

Oxygen Sensor The exhaust gas oxygen sensor (EGO) also called, as -sensor' or lambda sensor' is used to control air-fuel ratio within about 1% of stoichiometric value for operation of 3way catalysts. The sensor is fitted in the exhaust pipe just upstream of the catalytic converter. EGO operates on the principle of electro-chemical cell. Lambda-sensor is used to detect the presence or absence of free oxygen in the exhaust gas. Typical construction of an EGO is shown in Figure. Solid zirconium oxide (ZrO2 ) stabilized with yttrium oxide (Y2O3 ) is used as electrolyte. The outer and inner surfaces of the hollow cylindrical are coated with porous platinum to form inner and outer electrodes. The outer electrode is exposed to the exhaust gas while the inner electrode to air having a fixed oxygen concentration. Due to catalytic effect of platinum electrode the exhaust gas reaches equilibrium composition very rapidly.. The electrochemical reactions at the electrodes produce oxygen ions that carry current through solid electrolyte producing a voltage signal. The e.m.f. voltage, e 0 produced is a function of the ratio of partial pressures of oxygen at the two electrodes and is given by Nernst equation :

30

AICE

31

AICE

DIESEL PARTICULATE FILTERS

Diesel particulate filters (DPF) also called as particulate traps have been developed to filter out PM from the diesel exhaust gases to meet very stringent emission limits. Alumina coated wire mesh, ceramic fiber, porous ceramic monoliths etc., have been studied as filtration media. Presently, ceramic monolith of honeycomb type structure is used to trap the particulate matter as the gas flows through its porous walls. These filters are also termed as ceramic wall flow filters.
A ceramic honeycomb type particulate filter is shown in Figure. In this cellular structure, alternate cells are plugged at one end and open at the opposite end. The exhaust gas enters the cells that are open at the upstream end and flows through the porous walls to the adjacent cells. The adjacent cells are open at the downstream end from where the filtered gas exits .to the atmosphere. Flow path of gas through walls of the filter is also shown on Figure.

32

AICE

33

AICE

CO and CO2 NDIR Analyzers Beer-Lambert's Law is used for operation of NDIR analyzers by measuring the degree of absorption of infrared (IR) radiations when they pass through a column of gas. The fraction of incident radiations absorbed is given by,

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

34

AICE

NDIR analyzer is shown schematically in Figure: As the absorption of IR radiations is measured only in a narrow range of wavelengths (not the entire range of wavelength of IR radiations) which has specifically a high absorbance for the particular gas, the technique is called as Non-dispersive infra-red'. For example carbon monoxide has a strong absorbance in the wavelength band of 4.5-5 m. The analyzer measures differential in absorption of energy from two columns of gas; (i) the gas to be analyzed in the sample cell' and (ii) a gas of fixed composition like N2 contained in the reference cell which is free of the gas of interest and relatively nonabsorbing in the infrared region. The infrared beam from a single source is usually split into two beams of the same intensity, one each for the sample and reference cells. The detector is divided in two compartments separated by a flexible diaphragm; one section receives transmitted IR energy from the sample cell and the other from the reference cell. The detector is filled with the gas of interest, so that the energy transmitted to the detector is fully absorbed. The flexible diaphragm of the detector senses the differential pressure between the two sections of the detector caused by the difference in the amount of transmitted IR energy absorbed. The deflection in the diaphragm is used to generate an electrical signal that determines the concentration of the gaseous species of interest. A rotating interrupter in the path of IR beam is put to generate AC signal output that can be amplified.
35 AICE

36

AICE

Flame Ionization Detector (FID) Pure hydrogen-air flames are practically ion-free but on introduction of even little amount of hydrocarbons the flame causes considerable ionization and becomes electrically conducting. The ionization current is proportional to the number of carbon atoms present in the hydrocarbon molecules. Thus, FID is effectively a carbon atom counter e.g., one molecule of propane generates three times the response generated by one molecule of methane. The measurement of HC by FID is expressed as parts per million of methane i.e. as ppmC 1 i.e., ppm of hydrocarbon containing equivalent of one carbon atom. The HC concentration is commonly written as ppmC. HC concentration measured as ppm propane (C3 ) is to be multiplied by a factor of 3 to convert it to ppmC. All classes of hydrocarbons i.e., paraffin, olefins, aromatics, etc. show practically the same response to FID. Oxygenates, e.g. aldehydes and alcohols however, have a somewhat lower response. FID essentially consists of a hydrogen-air burner and an ion collector assembly as shown in Figure. Sample gas is introduced with hydrogen in the burner assembly and the mixture is burned in a diffusion flame. An electric potential is applied between the collector plates that makes the ionization current to flow and generate signal proportional to HC concentration in the sample gas. This current is amplified and the output signal is measured. A well-designed burner will generate ionization current that is linearly proportion to hydrocarbon content over a dynamic range of almost 1 to 10 6 . The commercial AICE FID analyzers have the most sensitive range set at about 0-50 ppmC and 37 the maximum range reaching 0-100,000 ppmC.

Hydrogen is mixed with helium in ratio of 40:60 to decrease flame temperature that increases flame stability. The FID analyzer is calibrated with propane or methane mixtures in nitrogen. For the measurement of hydrocarbons in diesel exhaust, sampling line and FID are heated to a temperature of 191 11C to minimize condensation of heavy hydrocarbons present in the diesel exhaust in the sampling system.

38

AICE

Chemiluminescence Analyzer (CLA) When NO and ozone (O3 ) react a small fraction (about 10% at 26.7 C) of excited NO2* molecules is produced as per the following reactions: (4.2) (4.3) As the excited molecules of NO2 * decay to ground state, light in the wavelength region 0.6-3.0 m is emitted. The quantity of excited NO2 produced is fixed at a given reaction temperature and the intensity of light produced during decay of excited NO2 is proportional to the concentration of NO in the sample.

39

AICE

A schematic diagram of the chemiluminescence NOxanalyzer is shown in Figure: The sample containing NO flows to a reactor where it reacts with ozone produced from oxygen in ozonator' .In the reactor NO is converted to NO2 . A photomultiplier tube detects the light emitted by the excited NO2 . The signal is then amplified and fed to recorder or indicating equipment.

For the measurement of nitrogen oxides (NOx ), NO2in the sample is first converted to NO by heating in a NO2- to-NO converter prior to its introduction into the reactor. At 315 C, about 90 percent of NO2 is converted to NO2. The total concentration of NOx in the sample is thus, measured as NO. When the sample is introduced in the reactor bypassing the NO2 - to- NO converter, concentration of NO alone is determined. The difference between the two measurements provides the concentration of NO2in the sample.
The response of the instrument is linear with NO concentration. The technique is very sensitive and can detect up to 10-3 ppm of NOx. The output signal is proportional to the product of sample flow rate and NO concentration. As the method is flow sensitive an accurate flow control is necessary. The calibration and operation are done at the same flow rate and reactor temperature.
40 AICE

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 Figure.

41

AICE

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 opacityis 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, ks 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. In the full flow type smokemeters, 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, ks for different exhaust pipe diameter or path lengths are made available for the full flow smoke meters.
42 AICE

43

AICE

44

AICE

Description
1992 Euro 1

Vehicle Type
All

CO
2.72 (3.16)

HC
-

NO x
-

HC+NO x
0.97 (1.13)

PM
0.14 (1) (0.18) (2) 0.08 0.10 -

1996 Euro 2

Gasoline Diesel IDI Diesel DI

2.2 1.0 1.0 2.3

0.20

0.15

0.50 0.70 0.90 -

2000 - Euro 3 (3)

Gasoline

Diesel
Gasoline 2005 Euro 4 Gasoline Diesel

0.64
1.00 1.00 0.50

0.10 0.10 -

0.50
0.08 0.08 0.25

0.56
0.30

0.05
0.025

2009 - Euro 5

Gasoline
Diesel

1.0
0.50 1.0
0.50

0.10 (4)
0.10 (4) 0. 08

0.06
0. 18 0.06 0.17

0.23 0.17

0.005 (5,6)
0.005 (6) 0.005 (5,6) 0.005 (6)

2014 Euro 6

Gasoline Diesel

45

AICE

(1)PM limits apply only to diesel cars.

(2)Values in parentheses are conformity of production (COP) limits. From Euro 2 standards type approval and COP limits are the same

(3)40s idle phase preceding test eliminated

(4)0.068 g/km NMHC (non-methane hydrocarbons) (5)applicable only to lean burn gasoline direct injection engines (6)Likely to be reduced to 0.003 with new measurement method .

46

AICE