Pollutant Formation

Pollutant Formation and Control
2103471 Internal Combustion Engine
Pollutant Formation and Control All IC engines produce undesirable emissions as a result of combustion. The emissions of concern are unburned hydrocarbons (UHC), carbon monoxide (CO), oxides of nitrogen such as nitric oxide and nitrogen dioxide (NOx), sulfur dioxide, and solid carbon particulates. These emissions pollute the environment and contribute to acid rain, smog odors, and respiratory and other health problems. HC emissions from gasoline-powered vehicles include a number of toxic substances such as benzene, polycyclic aromatic hydrocarbons (PAHs), 1,3-butadiene and three aldehydes (formaldehyde, acetaldehyde, acrolein). Carbon dioxide is an emission that is not regulated but is the primary greenhouse gas responsible for global warming.
Emissions Control The current emission limits for HC, CO and NOx have been reduced to 4%, 4% and 10% of the uncontrolled pre-1968 values, respectively. Three basic methods used to control engine emissions: 1) Engineering of combustion process - advances in fuel injectors, oxygen sensors, and on-board computers. 2) Optimizing the choice of operating parameters - two NOx control measures that have been used in automobile engines since 1970s are spark retard and EGR. 3) After treatment devices in the exhaust system - catalytic converter
Historical Perspective During the 1940s air pollution as a problem was first recognized in the Los Angeles basin. Two causes of this were the large population density and the natural weather conditions. Smoke and other pollutants combined with fog to form smog. In 1966 HC and CO emission limits were introduced in California. All of North America usually follows Californias lead (all US in 1968). By making more fuel efficient engines and with the use of exhaust after treatment, emissions per vehicle of HC, CO, and NOx were reduced by about 95% during the 1970s and 1980s. Automobiles are more fuel efficient now (2x compared to 1970) but there are more of them and the trend is to larger SUVs, as a result fuel usage is unchanged over this period.
Ontario Drive Clean Program In Ontario every vehicle must undergo a tail pipe emission test every other year to check compliance with regulation: Nitrogen Oxide 984 ppm @ 3000 rpm Carbon Monoxide 0.48% @ 3000 rpm and 1.0% @ 800 rpm Unburned hydrocarbons 86 ppm @ 3000 rpm and 200 ppm @ 800 rpm Particulates (diesels only at present) 30% opacity Evaporative Emissions (SI only at present)
Ontario Drive Clean Program Stats
Test results between 1999 and March 2004 Light-Duty Program*: Heavy-Duty Diesel**: 14.6% failed test 4% failed test
Heavy-Duty Non-Diesel**: 27.3% failed test * 6 million vehicles (automobiles, vans, SUVs, pick-ups) in program ** 200,000 vehicles in program
Emission Formation In S.I. Engine

This section provides an introduction to vehicle emissions components.
Principle S.I. Engine Exhaust Constituents

The chemical reaction that takes place in the engine cylinder when air is mixed with fuel and ignited is called combustion. Although combustion has been studied for many years, scientists and engineers are still unable to fully predict the behavior of this complicated process. Several variables must be considered in determining the correct levels of fuel, air, and ignition required for efficient combustion. Port or direct fuel injection has improved the distribution of the fuel in the cylinders; mass air flow meters accurately determine the amount of air flowing into an engine; and distributor-less electronic ignition systems have improved the reliability and accuracy of ignition systems. The entire power-producing process has considerably reduced emissions and improved driveability over the last 20 years.

Consider the combustion of octane, C8H18. Under ideal conditions, all of the hydrocarbon fuel consumed by the engine would be converted to CO2, H2O, and N2. Since ambient air contains approximately 21% oxygen and 78% nitrogen by volume, each mole of oxygen consumed involves (78/21) = 3.7 moles of N2. With this information, the ideal combustion equation for a fuel such as octane can be written by balancing the number of moles of each constituent on either side of the combustion equation: C8H18 + (12.5)O2 + (12.5)(3.7)N2 --> (8.0)CO2 + (9.0)H2O + (47.0)N2

Hence, ideal combustion of octane produces approximately 13% carbon dioxide, 14 % water vapor, and 73 % nitrogen. However, actual vehicle exhaust gas also contains unburned hydrocarbons (HC), carbon monoxide (CO), oxides of nitrogen (NOx), aldehydes, and various other constituents. The emissions in exhaust as it leaves the engine are called engine-out or feedgas emissions; they are carried through a catalytic converter, and the net output to the air is called tailpipe emissions. The ratio of air mass to fuel mass is called air fuel ratio (A/F). The stoichiometric or theoretical A/F is defined as the minimum amount of air that supplies sufficient oxygen for the complete combustion of all the carbon, hydrogen and any other elements in the fuel that may oxidize. For example, the stoichiometric A/F for the ideal combustion of octane can be calculated as follows:

On a molar basis: (A/F)mole = (12.5 moles O2 + 47.0 moles N2) (1 mole of fuel) (A/F)mole = 59.5 mole air/mole fuel On a mass basis: (A/F)mass = (59.5 mole air/mole fuel)*(28.97 kg/mole air) (114.2 kg/mole fuel) (A/F)mass = 15.0 kg air/kg fuel

In current combustion control systems, air flow is controlled by throttle position. Closing the throttle plate restricts airflow, thereby reducing power output. Fuel flow is regulated by electronic control of the amount of time the solenoid fuel injectors are open. The electronic engine control system measures airflow and adjusts the injector control to maintain A/F within fairly narrow limits around the stoichiometric A/F. A/F ratio data is often presented as fuel to air ratio, F/A, or as the equivalence ratio, commonly defined in the two forms shown below: = (A/F)/(A/Fstoich) = (F/A)/(F/Astoich)

It is important to define what measure is being used in describing the relationship between A/F and other parameters. Keys for remembering the trends in each measure of A/F is:
Measure A/F F/A Leaner Combustion Bigger Smaller Bigger Smaller Richer Combustion Smaller Bigger Smaller Bigger

Under normal operating conditions, stoichiometric operation is maintained by control electronics. When the control system is operating in closed-loop mode, it utilizes feedback signals from the heated oxygen sensors. These signals provide a means for determining how close the vehicle is to stoichiometric operation. When the control system is operating in open loop mode, this feedback signal is not used. In open loop mode, the control electronics uses default operation parameter values for determining correct operation.
Emission Formation Mechanisms

This section discusses the formation of HC, CO, NOx, CO2, and aldehydes and explains the effects of design parameters.

(i) Hydrocarbon Emissions Hydrocarbon emissions result from the presence of unburned fuel in the engine exhaust. HC emissions are various compounds of hydrogen, carbon, and sometimes oxygen. They are burned or partially burned fuel and/or oil. HC emissions contribute to photochemical smog, ozone, and eye irritation. However, some of the exhaust hydrocarbons are not found in the fuel, but are hydrocarbons derived from the fuel whose structure was altered do to chemical reaction that did not go to completion. For example: cetaldehyde, formaldehyde, 1,3 butadiene, and benzene all classified as toxic emissions.

(i) Hydrocarbon Emissions There are several formation mechanisms for HC, and it is convenient to think about ways HC can avoid combustion and ways HC can be removed; we will discuss each below. Most of the HC input is fuel, and most of it is burned during normal combustion. However, some HC avoids oxidation during this process. About 9% of the fuel supplied to the engine is not burned during the normal combustion phase of the expansion stroke. Only 2% ends up in the exhaust the rest is consumed during the other three strokes. As a consequence hydrocarbon emissions cause a decrease in the thermal efficiency, as well as being an air pollutant.

(i) Hydrocarbon Emissions The processes by which fuel compounds escape burning during normal S.I. combustion are: 1. 2. 3. 4. 5. Fuel vapor-air mixture is compressed into the combustion chamber crevice volumes. Fuel compounds are absorbed into oil layers on the cylinder liner. Fuel is absorbed by and/or contained within deposits on the piston head and piston crown. Quench layers on the combustion chamber wall are left as the flame extinguishes close to the walls. Fuel vapor-air mixture can be left unburned if the flame extinguishes before reaching the walls.

(i) Hydrocarbon Emissions 6. 7. Liquid fuel within the cylinder may not evaporate and mix with sufficient air to burn prior to the end of combustion. The mixture may leak through the exhaust valve seat.
Each of these seven processes allows some fraction of the fuel to escape normal combustion. However, there are a number of hurdles which the HC must pass before it can make it into the exhaust system

(i) Hydrocarbon Emissions The processes by which HC can oxidize or exit the cylinder are: 1. 2. 3. 4. Outflow of unburned mixture from the crevices, mixing with the hot burned gases; some of this will oxidize. Diffusion of HC vapor from oil layers and deposits into the burned gases; some will oxidize. Mixing of wall quench and burned gases; some will oxidize. Exhaust blowdown process carries some HC into the exhaust.

(i) Hydrocarbon Emissions 5. 6. Displacement of gases by the piston during the exhaust stroke will transport an additional fraction into the exhaust. Unburned HC leaving the cylinder mixes with hot exhaust gases; some of this will oxidize in the port and manifold.
The formation and exhausting of HC is very complex. No rigorous models of HC emissions exist today, although many labs are working on the problem.

(i) Hydrocarbon Emissions
Hydrocarbon Emission Sources for SI Engines The six principal mechanisms are believed to be responsible for hydrocarbon emissions: Source Crevices Oil layers Deposits Liquid fuel Flame quench Exhaust valve leakage Total % fuel escaping normal combustion 5.2 1.0 1.0 1.2 0.5 0.1 9.0 % HC emissions 38 16 16 20 5 5 100

(i) Hydrocarbon Emissions Crevices these are narrow regions in the combustion chamber into which the flame cannot propagate because it is smaller than the quenching distance. Generally, any volume with a dimension less than one millimeter across will form a crevice. Crevices are located around the piston, head gasket, spark plug and valve seats and represent about 1 to 2% of the clearance volume. With walls so close together, the flame cannot burn into the crevice, so mixture in the crevices escapes primary combustion.

(i) Hydrocarbon Emissions Figure 1 illustrates the various crevice volumes which exist in an engine.
Figure 1 Crevice Volume Sites.

(i) Hydrocarbon Emissions The crevice around the piston is by far the largest. Crevices typically amount to about 2% of the cylinder clearance volume. Fuel-air mixture is compressed into the crevices during the compression stroke and also during combustion (density higher than cylinder gas since gas is cooler near walls) and released during expansion.
Crevice
Piston ring

(i) Hydrocarbon Emissions At peak pressure, calculations suggest as much as 6-8% of the mixture may be trapped in the crevices. This is much higher than the crevice volume fraction because the gases in the crevices cool rapidly to something close to wall temperature, which is much lower than cylinder temperature at peak pressure. As a result of the lower temperature, their density is 3-4 times higher than the burned gases. As the piston travels downward, pressure in the cylinder decreases and mixture comes back out of the crevices. Crevices are estimated to cause roughly 40% of HC emissions.

(i) Hydrocarbon Emissions The second HC mechanism is related to the thin layer of oil which is always present on the cylinder walls. Since the piston ring is not 100% effective in preventing oil migration into the cylinder above the piston, oil layers exist within the combustion chamber. This oil layer traps fuel and releases it later during expansion. Although the rings scrape off most of the oil, there must be a tiny layer to provide lubrication for the rings on the up strokes. This thin layer (on the order of tens of microns in thickness) absorbs HC. Oil layers are thought to cause roughly 10-30% of HC emissions.

Figure 2 shows the effect on HC of fuel solubility in oil. Oils with higher fuel solubility increase HC emissions. Unfortunately, practical oils - i.e., those which prevent mechanical wear acceptably, have a very limited range of solubilities so that we cannot do too much about this mechanism.
Figure 2 Unburned Hydrocarbon Solubility in Oil.

Deposits - With continued use carbon deposits build up on the valves, cylinder and piston head. These deposits are porous with pore sizes smaller than the quenching distance so trapped fuel cannot burn. Deposits can absorb fuel in a manner similar to oil. However, deposits are not present on new engines but accumulate with mileage. The fuel is released later during expansion. Operating conditions also affect the deposition and removal of deposits. As a result, the effect of deposits on HC emissions is rather difficult to identify.

When the exhaust valve opens the large rush of gas escaping the cylinder drags with it some of the hydrocarbons released from the crevices, oil layer and deposits. During the exhaust stroke the piston rolls the hydrocarbons distributed along the walls into a large vortex that ultimately becomes large enough that a portion of it is exhausted.
Blowdown
Exhaust Stroke
Hydrocarbon Exhaust Process

The first peak is due to blowdown and the second peak is due to vortex roll up and exhaust (vortex reaches exhaust valve at roughly 290o)
Exhaust valve opens
Exhaust valve closes
BC
TC
Hydrocarbon Exhaust Process

(i) Hydrocarbon Emissions Liquid fuel For some fuel injection systems there is a possibility that liquid fuel is introduced into the cylinder past an open intake valve. The less volatile fuel constituents may not vaporize (especially during engine warm-up) and be absorbed by the crevices or carbon deposits.

(i) Hydrocarbon Emissions Flame quenching It has been shown that the flame does not burn completely to the internal surfaces, the flame extinguishes at a small but finite distance from the wall. Most of this gas eventually diffuses into the burned gas during expansion stroke. Flame quenching is another HC producing mechanism but one not very well understood. Under extreme conditions of lean A/F, high exhaust gas recirculation (EGR), or high residual gas fraction, the flame may not propagate fully across the chamber. Very severe decelerations may produce such conditions. Figure 3 summarizes the path of HC through the engine. The percentages are rough estimates of the percent of the input fuel which goes through each path for a typical partial load condition.
Figure 3 Hydrocarbon Path Through Engine.

(i) Hydrocarbon Emissions HC emissions are also dependent on several other parameters such as spark advance, A/F ratio, and EGR. High advance generally increases HC emissions, primarily because the temperature of the charge is lower during the expansion stroke. This reduces oxidation during expansion as the HC comes off the walls and out of the crevices. Lower A/F ratios (richer combustion) cause more HC emissions because there is less O2 to oxidize fuel. Very lean A/F ratios cause HC emissions to increase due to misfires, partial burns, and reduced temperature during expansion.
Figure 4 EGR Effect on Hydrocarbon Formation.
Figure 4 depicts HC formation versus EGR rate. High EGR causes an increase in HC emissions. The increase is gradual at first, but the curve becomes steep as the combustion degrades. In fast burn engines, the combustion degradation sets in at higher EGR rates than in slow burn engines.

(ii) Carbon Monoxide Formation of CO is well established. Under some conditions, there is not enough O2 available for complete oxidation and some of the carbon in the fuel ends up as CO. The amount of CO, for a range of fuel composition and C/H ratios, is a function of the relative air-fuel ratio. Even when enough oxygen is present, high peak temperatures can cause dissociation - chemical combustion reactions in which carbon dioxide and water vapor separate into CO, H2, and O2. Conversion of CO to CO2 is governed by reaction CO + OH CO2 + H Dissociated CO may freeze during the expansion stroke. Figure 5 shows CO production as a function of A/F ratio.
Figure 5 Air/Fuel Ratio Effects on Carbon Monoxide Concentration.

(iii) Oxides of Nitrogen NOx is a generic term for the compounds nitric oxide (NO) and nitrogen dioxide (NO2). Both are present to some degree in the exhaust, and NO oxidizes to NO2 in the atmosphere. NOx contributes to acid rain and photochemical smog; it is also thought to cause respiratory health problems at atmospheric concentrations found in some parts of the world. To understand NOx formation, we must recognize several factors that affect NOx equilibrium. Remember that all chemical reactions proceed toward equilibrium at some reaction rate.

(iii) Oxides of Nitrogen In SI engines the dominant component of NOx is NO forms as a result of dissociation of molecular nitrogen and oxygen. Since the activation energy of the critical elementary reaction O+N2NO+N is high the reaction rate is very temperature dependent, w'' ~ exp (-E/RT) Therefore NO is only formed at high temperatures and the reaction rate is relatively slow. At temperatures below 2000K the reaction rate is extremely slow, so NO formation not important. Equilibrium NO (which comprises most of the NOx formation) is formed at a rate that varies strongly with temperature and equivalence ratio, as shown in Figure 6.
Figure 6 Temperature and Equivalence Ratio Effects on NO Formation Rate.

(iii) Oxides of Nitrogen Since the cylinder temperature changes throughout the cycle the NO reaction rate also changes. In figure 6, much of the mixture in the cylinder is burned essentially adiabatically (without loss or gain of heat). As we can see, more NO will be formed rapidly during the engine cycle when the peak temperature is highest and/or when the equivalence ratio is slightly lean of stoichiometry. During the combustion process, O2 and N2 are heated to high temperatures, and NO is formed very rapidly at the peak temperatures. Then, during expansion, the temperature drops so rapidly that the reaction rate slows before the concentration can go all the way down; the NO concentration freezes at a level typical of equilibrium at an elevated temperature.
SI Engine In-cylinder NO Formation Each fluid element burns to its AFT based on its initial temperature, elements that burn first near the spark plug achieve a higher temperature. Since the chemistry is not fast enough the actual NO concentration tends toward but never achieves the equilibrium value.
If NO concentration is lower than equilibrium value NO forms If NO concentration is higher than equilibrium value NO decomposes
Once the element temperature reaches 2000K the reaction rate becomes so slow that the NO concentration effectively freezes at a value greater than the equilibrium value. The total amount of NO that appears in the exhaust is calculated by summing the frozen mass fractions for all the fluid elements: x = 1 x dx
NO
NO
x=0
x=1
-15o (x = 0)
25o (x = 1)
(assuming no mixing of fluid elements)
x=0
Equilibrium concentration: based on the local temperature, pressure, equivalence ratio, residual fraction Actual NO concentration: based on kinetics
x=1

(iii) Oxides of Nitrogen
Figure 7 Air/Fuel Effect on NO Formation.
One would expect the peak NO concentrations to coincide with highest AFT. Figure 7 shows feed-gas emission of NOx versus A/F ratio. A peak occurs at about 16:1 A/F. Under rich conditions, the amount of available O2 is less than optimal for NOx formation. Under leaner conditions, the peak temperatures drop.

(iii) Oxides of Nitrogen Typically peak NO concentrations occur for slightly lean mixtures that corresponds to lower AFT but higher oxygen concentration.
Effect of Equivalence Ratio on NO Concentration

(iii) Oxides of Nitrogen Exhaust NO Concentration Reduction Since the formation of NO is highly dependent on cylinder gas temperature any measures taken to reduce the AFT are effective:
increased
residual gas exhaust gas recirculation (EGR) moisture in the inlet air In CI engines the cylinder gas temperature is governed by the load and injection timing
IDI/NA indirect injection naturally aspirated DI/NA direct injection naturally aspirated

(iii) Oxides of Nitrogen Exhaust Gas Recirculation is used to reduce NOx. By recirculating a fraction of the exhaust into the intake charge, the heat capacity (Cp) of the mixture in the cylinder is increased. This means that the temperature of the charge increases less during compression (including the compression of unburned charge during combustion). As we have seen, even a small drop in peak temperature can have a dramatic effect on NO formation. Thus, EGR has a strong effect on NO, as shown in Figure 8. A 2:1 reduction is obtained with as little as 10% EGR.

(iii) Oxides of Nitrogen
Figure 8 EGR Effect on NO Formation.

(iii) Oxides of Nitrogen Unfortunately, EGR also reduces flame speed. Excessive EGR rates can slow burn rate so drastically as to cause surge, misfire, and other combustion problems. However, EGR can increase fuel economy. When used optimally, EGR can reduce NO and improve fuel economy while avoiding rough engine operation. This optimum varies with speed, load, and engine design. NOx also varies with spark timing. More spark advance means that parts of the mixture spend more time at high temperatures, so more NO is formed.

(iii) Oxides of Nitrogen Effect of Various Parameters on NO Concentration Increased spark advance and intake manifold pressure both result in higher cylinder temperatures and thus higher NO concentrations in the exhaust gas
Pi= 658 mm Hg Pi= 354 mm Hg
= 0.97
= 0.96
= 1.31 = 1.27

(iv) Carbon Dioxide While not normally considered a pollutant, CO2 may contribute to the greenhouse effect. Proposals to reduce CO2 emissions have been made. CO2 controls strongly influence fuel economy requirements. (v) Aldehydes Aldehydes are the result of partial oxidation of alcohols. They are not usually present in significant quantities in gasoline-fueled engines, but they are an issue when alcohol fuels are used. Aldehydes are thought to cause lung problems. So far, little information of engine calibration effects on aldehyde formation is available.
Fuel and Combustion Control For S.I. Engine

Fuel Injection Technology Fuel injectors are solenoid valves which deliver and atomize precisely controlled amounts of fuel into an air intake system. The operation of fuel injectors is controlled by the powertrain control module (PCM) or engine control unit (ECU). Use of fuel injection provides for better cold-driveability, lower emissions, and eliminates dieseling when the key ignition is turned off.
Fuel Injection Technology

The three principle fuel injection systems are as follows: Central Fuel Injection (CFI)--Injector delivers fuel above the throttle plate. Multiport Fuel Injection (MFI)--Injector placed near each intake valve; injectors arranged on common fuel rails open and close simultaneously. Sequential Electronic Fuel Injection (SEFI)-Injector placed near each intake valve; injector operation matched to operation of corresponding Intake valve. SEFI is also called SFI (Sequential Fuel Injection). SEFI provides better performance, driveability, and lower emissions than CFI and MFI.
Fuel Injection Technology

Figure 9 shows the various components of a fuel injector. Pressurized fuel enters the fuel injector at the top, then passes through a filter and into the injector body, where a needle blocks it from passing out the injector orifice. When the solenoid activates, it pulls back the needle, thus allowing fuel to pass out of the injector through the metering plate. When the coil is de-energized a spring pulls the needle back to its seated position, thereby closing off the exit orifice to further fuel flow. The amount of fuel delivered depends on how long the injector is open. Typical fuel injection "pulse width"--the amount of time the fuel injector is delivering fuel--is between one and fifteen milliseconds, depending on what the PCM commands.
Heated Oxygen Sensors

The Heated Oxygen Sensor (HO2S, formerly known as HEGO), shown in Figure 10, is located in the exhaust manifold and monitors the oxygen content in the exhaust. This information is used by the PCM to control the fuel metering to keep the desired air-fuel mixture entering the cylinder chamber. An HO2S has a ceramic surface coated in platinum. This ceramic surface can conduct oxygen ions when exposed to a gas of at least 300 oC, and when the oxygen sensor is internally heated it is functional for exhaust gas temperatures as low as 200 oC. When the surface is exposed to both the exhaust gas and ambient air, a voltage signal is generated indicative of how much oxygen is in the exhaust.

The Heated Oxygen Sensor (HO2S, formerly known as HEGO), shown in Figure 10, is located in the exhaust manifold and monitors the oxygen content in the exhaust. This information is used by the PCM to control the fuel metering to keep the desired air-fuel mixture entering the cylinder chamber. An HO2S has a ceramic surface coated in platinum. This ceramic surface can conduct oxygen ions when exposed to a gas of at least 300 oC, and when the oxygen sensor is internally heated it is functional for exhaust gas temperatures as low as 200 oC. When the surface is exposed to both the exhaust gas and ambient air, a voltage signal is generated indicative of how much oxygen is in the exhaust.
Figure 9 Fuel Injector.
Figure 10 Heated Oxygen Sensor.

HO2S are located in the exhaust pipe both before and after the catalytic converter. The HO2S before the catalytic converter gives the feedback necessary to keep the desired air-fuel mixture. The output of the HO2S after the catalyst is compared to the output of the HO2S before the catalyst as an indication of catalytic converter efficiency with respect to oxygen. This is used in the On-Board Diagnostics to determine catalyst burnout.
Powertrain Control Module

The powertrain control module (PCM) controls a vehicle's powertrain (P/T) by monitoring electronic signals generated by various sensors in order to ascertain current powertrain conditions. Based on these P/T conditions, the PCM's microprocessing unit will signal various actuators to perform certain control functions according to a computer program referred to as the vehicle's engine control calibration. This calibration is composed of smaller programs called strategies.

Different strategies are used to control engine operation for the following: Engine Cranking; Cold Start/Warm Up; Cold Driveaway; Warm Driveaway; Warm Cruise; Part-Throttle Acceleration; Full-Throttle Acceleration; Deceleration; and Warm-Idle. The strategies, stored in the PCM's Programmable Read Only Memory (PROM) chip, contain the logic to control the powertrain. Strategy development is an integral part of the development of a powertrain.

Within each strategy there exists a vast quantity of variables used by the logic. Certain variables, referred to as Random Access Memory (RAM) variables, are set by calibrators during vehicle operation to reflect current signal status. Other variables, referred to as Read Only Memory (ROM) variables, are set by calibrators during development for use as references in the logic. We can significantly enhance a powertrain's performance by setting the ROM variables at optimum values during strategy development. We refer to this process as engine calibration.
Exhaust Gas Recirculation (EGR)

The EGR system, shown in Figure 11, is mainly used to reduce nitrogen oxides (NOx) which are formed in the combustion chamber at high temperatures.
Figure 11 EGR System.

The EGR system recirculates already combusted exhaust from the exhaust manifold back to the air-fuel mixture and is drawn into the cylinder chamber. This reduces the peak combustion temperature in the cylinder chamber. This temperature reduction in turn reduces NOx formation. The EGR flow is directed by a solenoid valve that is controlled by the Powertrain Control Module (PCM). The PCM uses inputs such as engine speed, intake-manifold pressure, and engine temperature to determine how much exhaust flow to meter back to the air-fuel mixture.

Disadvantages of EGR are increases in hydrocarbon emissions and fuel consumption. Consequently, EGR is not used during conditions of low NOx formation such as idle. EGR is also not used during wide open throttle (WOT) when full power is needed for acceleration.
Emission Formation In C.I. Engine

For many years, diesel engines have had a reputation of giving poor performance and producing black smoke, an unpleasant odor, and considerable noise. However, it would find it difficult to distinguish todays modern diesel car from its gasoline counterpart. For diesel engines the emphasis is to reduce emissions of NOx and particulates, where these emissions are typically higher than those from equivalent port injected gasoline engines equipped with three-way catalysts. Catalyst of diesel exhaust remains a problem insofar as research has not yet been able to come up with an effective converter that eliminates both particulate matter (PM) and oxide of nitrogen (NOx).
Principle C.I. Engine Exhaust Constituents

Acquired load of diesel engines is accomplished by modifying the fuel quantity supplied, whereas the air quantity per work cycle is drawn in without any throttling. The air to fuel mixture ratio is therefore adjusted to achieve load required. This means that the mixture in its working range is made leaner or richer, respectively. Depending on friction power and the combustion process of the engine, the mixture setting, as shown in Figure 12,may made leaner up to levels of = 10. This diesel-engine processes is referred to as quality management.
Figure 12 Excess air ratio map of a diesel engine.

In the same manner as with SI engines, the air/fuel ratio of the diesel engine has a significant impact on the level of pollutant concentrations but this parameter is not freely available for minimizing pollution. Figure 13 shows an example of the dependence of major pollutant concentrations on the air /fuel ratio in the case of a direct-injection diesel engine.
Figure 13 Exhaust concentrations as a function of air/fuel ratio.

Carbon monoxide: The mean air-fuel mixture present in the combustion chamber per cycle is far leaner in the diesel engine than in the SI engine. Due to a lack of homogeneity of the mixture built up by stratification, however, extremely rich local zones are exist. This produces high CO concentrations that are reduced to a greater or lesser extent by post-oxidation. When the coefficient increases, i.e. when the excess-air ratio increases, dropping temperatures cause the postoxidation rate to be reduced. The reactions freeze up. The CO concentrations of diesel engines therefore are far lower than in SI engines. The basic principles of CO formation, however, are the same as in SI engine.

Carbon Monoxide
Carbon monoxide appears in the exhaust of fuel rich running engines. For fuel rich mixtures there is insufficient oxygen to convert all the carbon in the fuel to carbon dioxide.
C8H18-air

Carbon Monoxide
The C-O-H system is more or less at equilibrium during combustion and expansion. Late in the expansion stroke when the cylinder temperature gets down to around 1700K the chemistry in the C-O-H system becomes rate limited and starts to deviate from equilibrium. In practice it is often assumed that the C-O-H system is in equilibrium until the exhaust valve opens at which time it freezes instantaneously. The highest CO emission occurs during engine start up (warm up) when the engine is run fuel rich to compensate for poor fuel evaporation. Since CI engines run lean overall, emission of CO is generally low and not considered a problem.

Unburned hydrocarbons: Since the air-fuel mixture is not homogeneous throughout, extremely too lean (high excess air ratios) are present in certain zones during the diesel combustion process. The leaner the air-fuel mixture, the lower is the local temperature. This means that chemical reactions proceed fairly slowly or may even freeze up, thus leading to increased HC emissions. On the whole, HC concentrations of diesel engines are lower than those of SI engines.
Emission Formation Mechanism

Unburned hydrocarbons:
Crevices - Fuel trapped along the wall by crevices, deposits, or oil due to impingement by the fuel spray (not as important as in SI engines). Undermixing of fuel and air - Fuel leaving the injector nozzle at low velocity, at the end of the injection process cannot completely mix with air and burn. Overmixing of fuel and air - During the ignition delay period evaporated fuel mixes with the air, regions of fuel-air mixture are produced that are too lean to burn. Some of this fuel makes its way out the exhaust. Longer ignition delay more fuel becomes overmixed.
Exhaust HC, ppm C
Emission Formation Mechanism

Unburned hydrocarbons:
Note for the direct injection diesel the hydrocarbon emission are the worst at light load (long ignition delay)

Nitrogen oxides: NOx concentrations are lower than in SI engines; the share of NO2 in the NOx emissions is slightly higher. When comparing an SI engine with three-way closedloop catalytic converter with a diesel engine with oxidation catalyst, it is found that NOx concentrations of the SI engine are lower. The type of combustion process has a significant effect on nitrogen oxide formation.

Nitrogen oxides: Diesel engine with IDI combustion chamber: In engines with an IDI combustion chamber, combustion initially occurs in the pre-chamber or swirl chamber under conditions of extreme oxygen deficiency. This generates high temperatures, but NOx levels are low due to a lack of oxygen. This process is reversed in the main combustion chamber. Extreme excess air ratios and, hence, low temperatures also result in low NOx formation.

Nitrogen oxides: Diesel engine with DI combustion chamber: The direct-injection diesel engine does not have the above features that keep NOx emissions low. As a result, NOx formation is approximately twice as high as with an IDI combustion chamber engine. When exhaust recirculation (EGR) systems are used, both systems show virtually identical NOx levels as the direct-injection diesel engine is far more compatible with large re-circulated exhaust quantities (more than 50% of the fresh charge).

Sulphur compounds: Sulphur compounds are caused by the sulphur content of the diesel fuel. According to modern world-wide fuel regulations, this content may have to be reduced to below 0.05 weight percent. When combined with the water produced during the combustion process, SO2 produces sulphuric acid. Sulphur compounds cause problems with regard to acid rain and particulate formation via sulphates.

Particulates: A high concentration of particulate matter (PM) is manifested as visible smoke in the exhaust gases. Particulates are any substance other than water that can be collected by filtering the exhaust, classified as:
1) solid carbon material or soot 2) condensed hydrocarbons and their partial oxidation products
Diesel particulates consist of solid carbon (soot) at exhaust gas temperatures below 500oC. HC compounds become absorbed on the surface. Particulate can arise if leaded fuel or overly rich fuel-air mixture are used. Burning crankcase oil will also produce smoke especially during engine warm up where the HC condense in the exhaust gas.

Particulates: According to the California Air Resources Board (CARB), particulate matter is defined as all exhaust components that are deposited on a defined filter after having been diluted with air to a temperature below 51.7oC. Basically, soot emissions also are part of particulate emissions. Soot formation occurs at extreme air deficiency. This air or oxygen deficiency is present locally inside diesel engines. It increases as the air/fuel ratio approaches a value = 0.

Particulates: Most particulate material results from incomplete combustion of fuel HC which occurs in fuel rich mixtures. Based on equilibrium the composition of the fuel-oxidizer mixture at the onset of soot formation occurs when x 2a (or x/2a 1) in the following reaction:
C x H y + aO2 2aCO + y H 2 + ( x 2a )C ( s ) 2
i.e. when the (C/O) ratio exceeds 1. Experimentally it is found that the critical C/O ratio for onset of soot formation is between 0.5 and 0.8 The CO, H2, and C(s) are subsequently oxidized in the diffusion flame to CO2 and H2O via the following second 1 stage CO + 1 O CO C ( s ) + O CO H + O H O
2
2 2 2 2 2

Particulates: Any carbon not oxidized in the cylinder ends up as soot in the exhaust! Soot is produced by thermal cracking of long-chain molecules at oxygen deficiency. A separation of hydrogen leads to C-structures showing an increasing lack of hydrogen. Acetylene and other polymerization processes lead to formation of molecules rich in carbon that form soot particulates. Once soot has formed, it can be oxidized only to a limited extent. The process described here is shown schematically in Figure 14. The logarithm of the molecular mass is shown as a function of the hydrogen contents of the hydrocarbon components. Soot formation produces molecules with an increasingly low hydrogen content and higher weight that will finally agglomerate to form soot particulates.

Particulates:
Figure.14 Potential soot formation process.

Particulates: Particulates consist of solid (organically insoluble) and liquid (organically soluble) phases. The solid phase consists of Soot in the form of amorphous carbon, ash, oil additives, corrosion products and abrasion products. Sulphates and its molecule-bound water. The liquid phase consists of fuel and lubricant contents that are, usually, combined with soot. The hydrocarbons contained in the hot exhaust still are largely gaseous and are converted into a liquid, organically soluble phase (particulates) only after having been cooled by turbulent intermixing with air.

Particulates: The size of such particulates is approx. 0.01 to 1m and above. Most particulates have a size below 0.3m and some of them can therefore penetrate into the lungs. Particulate composition is largely dependent on the operating point and the combustion process. Figure 15 shows a typical particulate composition of diesel engine exhaust gas.

Particulates:
Figure 15. Particulate composition of diesel engine exhaust.
Particulates and CI Engines Particulates are a major emissions problem for CI engines. Exhaust smoke limits the full load overall equivalence ratio to about 0.7
= 0.7
= 0.5 = 0.3
One technique for measuring particulate involves diluting the exhaust gas with cool air to freeze the chemistry before measurements
An outstanding problem for diesel engine designers is that in order to reduce NOx one wants to reduce the AFT but this has the adverse effect of decreasing the amount of soot oxidized, or increases the amount of soot in the exhaust.
Particulates and CI Engines An example of this dilemma is changing the start of injection, e.g., increasing the advance increases the AFT
Crank angle bTC for start of injection
Fuel and Combustion Control For C.I. Engine

Increasingly stringent emission legislation means that the high speed CI engine will have to employ advanced fueling technologies to meet these requirements principally by employing systems which use very high fuel injection pressures with electronic control of injection timing and fueling. These large pressure differences across the injector nozzle are required so that the injected liquid fuel enters the chamber at sufficiently high velocity to: Atomize into small-sized droplets to enable rapid evaporation. Traverse the combustion chamber in the time available and fully utilize the air charge.
Electronic Fuel Injection Technology

DI diesel engines will use electronic fuel injection systems. Replacing traditional mechanical systems, which are now approaching the end of their effective life. In what are termed full authority fuel injection systems, the benefits include emission reduction, improved driveability. Smoother idling, integration with other vehicle systems, self-diagnostics, and performance checks. The benefits of higher injection pressure on particulates and smoke are shown in Figure 16.
Electronic Fuel Injection Technology
Figure 16 Benefits of higher mean injection pressure on particulate and smoke.
Electronically Controlled Distributor Pumps

The fuel injection pumps are able to vary the fueling and injection timing using electro-hydraulic devices. The cam ring is rotated to vary injection timing using a hydraulic actuator. The working fluid is diesel fuel, the pressure being regulated by a solenoid valve acting on a pulse width modulation (PWM) signal from the electronic control unit (ECU). Fueling is varied by moving the rotor mechanism axially using a second actuator. Or a solenoid-operated spill valve Injection timing is still set by rotating the cam ring the use of the solenoid-operated spill valve may allow rate shaping and pre-injection.
Electronically Controlled Distributor Pumps

If the cam profile has a varying rate of rise, the injection rate can be varied by using the appropriate section of the cam. Errors in the timing of the valve operation will influences start of injection timing, injection rate, and injected quantity. In addition to controlling the fuel pump, the ECU supervises a EGR control, inlet throttle control (if fitted), and turbocharger wastegate or variable geometry turbocharger (if fitted). The ECU will generally have other abilities including onboard diagnostics (OBD), cruise control, and networking with other controllers. The advent of electronic control has opened up a variety of alternative approaches.
Electronic Unit Injector (EUI) System

The EUI is a fueling system. Both pump and injector are combined in a single unit for each cylinder (Figure 17). Each pumping plunger is driven directly by the engines camshaft, and this enables very high injection pressures (in the region of 1500-2000 bar) to be obtained. The main benefits of these very high injection pressure are smaller droplet sizes, better fuel-air mixing, and reduced ignition delay.
Figure 17 Schematic of EUI system.

The timing and quantity of fuel can be adjusted to give optimum conditions over the complete engine operating profile. The system also has the capability to act as a pilot injection device to reduce NOx and engine noise. Sensors provide information to the electronic control unit (ECU) on the relevant functions of engine operation, which are:
Acceleration position Engine speed Camshaft position Inlet manifold temperature and pressure Coolant temperature
This information is continuously compared with the optimum values stored in the ECU memory. The result of that comparison is translated into signals instructing the unit injector solenoid-actuated spill valve system to deliver the fuel at the timing required by the engine.
Caterpillar HEUI System

This hydraulic electronic unit injector (HEUI) requires no mechanical actuation or mechanical control devices Inherent features of the HEUI fuel system include injection pressure control independent of engine speed or load, totally flexible injection timing, and full control of injection parameters. High-pressure oil from the pump flows to a manifold or rail, which is connected to the injectors. A solenoid operates a control valve to start and end the injection process. Initial injection rate shaping is achieved with a Ported spill control device in the plunger and barrel; this is called PRIME (preinjection metering). The HEUI system is time based, so injection characteristics are independent of engine speed.
Caterpillar HEUI System
Figure 18 caterpillar HEUI system.
The Common Rail System

The common rail system in which high-pressure fuel is fed into a manifold (or rail), which then serves individual injector (Figure 19).
Figure 19 Schematic of a common rail system

The injector is simply a solenoid-actuated nozzle, which is opened under the control of the ECU when injection is required. In principle the system is very simple, a low-drive torque mechanical pump pressurizes the distribution rail with diesel fuel at the desired injection pressure Short pipes connect the rail to each injector. There is no pressure intensification within the injector. The injection process is controlled by a solenoid valve in each injector. The final fuel injected quantity being dependent on the opening period and system pressure. The solenoid is controlled by the ECU, as is the rail pressure via a pressure sensor.

The key advantage of the common rail fuel system compared to a traditional pump-line-nozzle system, is that injection pressure is independent of engine speed and load. Injection timing, rate, and duration can be varied precisely over the operating range. At part load the higher injection pressure available gives a reduction of particulate emissions. The lower particulate emissions allow higher EGR rates, so the NOx emissions can be reduced, leading to a superior NOx particulates trade off. Pilot injection for combustion noise control is feasible with common rail. Small fuel quantities of 1 to 2 m3 / stroke can be injected before the main injection.

The high-pressure pump acts continuously and so has a more uniform drive torque than the highly cyclic loads imposed by distributor and unit injector pump. A comparison between the capabilities of pump-linenozzles systems, EUIs, common rail systems is shown in Figure 20.
Figure 20 Comparison of different electronic fuelling system capabilities.
Exhaust Gas Recirculation

Exhaust gas recirculation (EGR) is a well-proven technique for the effective suppression of NOx emissions. The reductions in emissions due to the influence of EGR are shown in Figure 20.
Figure 20 General trend on emissions due to the influence of EGR in DI diesel engine.
Control of EGR
EGR systems consist of an electronically controlled, vacuum-operated poppet valve mounted mounted ont eh exhaust or the intake manifold. A current-to-vacuum transducer (CVT) controls the amount of vacuum applied to the EGR valve diaphragm, which in turn lifts the poppet off its seat. The engine ECU contains schedules (look-up tables), which relate engine speed, fueling rate, and mass air flow (MAF). The MAF sensor is located in the air intake system and provides the information to determine EGR valve position and, hence, EGR mass flow is calculated by implication.
Control of EGR
There are a number of disadvantages with this method, namely: Volumetric characteristics of the engine can drift with time due to wear and tear and the build-up of deposits The flow capacity of the EGR system can be affected by partial blocking through deposit build-up (i.e., soot, particulates, and so on and wear of the EGR valve) Blockages in the inlet air filter can seriously affect EGR mass flow Blockages in the exhaust can cause increased exhaust pressure
After Treatment Devices
Catalytic Converter All catalytic converters are built in a honeycomb or pellet geometry to expose the exhaust gases to a large surface made of one or more noble metals: platinum, palladium and rhodium. Rhodium used to remove NO and platinum used to remove HC and CO.
Lead and sulfur in the exhaust gas severely inhibit the operation of a catalytic converter (poison).
Three-way Catalytic Converter A catalyst forces a reaction at a temperature lower than normally occurs. As the exhaust gases flow through the catalyst, the NO reacts with the CO, HC and H2 via a reduction reaction on the catalyst surface. e.g., NO+CON2+CO2 , NO+H2 N2+H2O, and others The remaining CO and HC are removed through an oxidation reaction forming CO2 and H2O products (air added to exhaust after exhaust valve). A three-way catalysts will function correctly only if the exhaust gas composition corresponds to nearly (1%) stoichiometric combustion. If the exhaust is too lean NO are not destroyed If the exhaust is too rich CO and HC are not destroyed A closed-loop control system with an oxygen sensor in the exhaust is used to determine the actual A/F ratio and used to adjust the fuel injector so that the A/F ratio is near stoichiometric.
Effect of Mixture Composition
Since thermal efficiency is highest for slightly lean conditions it may seem that the use of a catalytic converter is a rather severe constraint. The same high efficiency can be achieved using a near stoichiometric mixture and diluting by EGR
Effect of Temperature The temperature at which the converter becomes 50% efficient is referred to as the light-off temperature. The converter is not very effective during the warm up period of the engine
Catalytic Converter for Diesels For Diesel engines catalytic converters are used to control HC and CO, but reduction of NO emissions is poor because the engine runs lean in order to avoid excess smoke. The NO is controlled by retarding the fuel injection from 20o to 5o before TC in order to reduce the peak combustion temperature.
This has a slight negative impact, increases the fuel consumption by about 15%.

Pollutant Formation

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Pollutant Formation

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Pollutant Formation and Control

2103471 Internal Combustion Engine

Ontario Drive Clean Program Stats

Emission Formation In S.I. Engine

Principle S.I. Engine Exhaust Constituents

Principle S.I. Engine Exhaust Constituents

Principle S.I. Engine Exhaust Constituents

Principle S.I. Engine Exhaust Constituents

Principle S.I. Engine Exhaust Constituents

Principle S.I. Engine Exhaust Constituents

Principle S.I. Engine Exhaust Constituents

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Figure 1 Crevice Volume Sites.

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Figure 2 Unburned Hydrocarbon Solubility in Oil.

Emission Formation Mechanisms

Emission Formation Mechanisms

Hydrocarbon Exhaust Process

Emission Formation Mechanisms

Exhaust valve opens

Exhaust valve closes

Hydrocarbon Exhaust Process

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Figure 3 Hydrocarbon Path Through Engine.

Emission Formation Mechanisms

Emission Formation Mechanisms

Figure 4 EGR Effect on Hydrocarbon Formation.

Emission Formation Mechanisms

Emission Formation Mechanisms

Figure 5 Air/Fuel Ratio Effects on Carbon Monoxide Concentration.

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Figure 6 Temperature and Equivalence Ratio Effects on NO Formation Rate.

Emission Formation Mechanisms

(assuming no mixing of fluid elements)

Emission Formation Mechanisms

Figure 7 Air/Fuel Effect on NO Formation.

Emission Formation Mechanisms

Effect of Equivalence Ratio on NO Concentration

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Figure 8 EGR Effect on NO Formation.

Emission Formation Mechanisms

Emission Formation Mechanisms

Emission Formation Mechanisms

Fuel and Combustion Control For S.I. Engine

Fuel Injection Technology

Fuel Injection Technology