IC Engine Exhaust Emissions Section 7

Pollutant Formation and Control All IC engines produce undesirable emissions as a result of combustion, including hydrogen fuelled engines. The emissions of concern are: unburned hydrocarbons (HC), carbon monoxide (CO), nitric oxide and nitrogen dioxide (NOx), sulfur dioxide (SO2), and solid carbon particulates (particulate matter). These emissions pollute the environment (smog, acid rain) that contribute to 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 (CO2) is an emission that is not regulated but is one of the primary greenhouse gases, water vapour and methane are the others, believed to be responsible for global warming.
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Global Warming vs Climate Change Global warming occurs because the greenhouse gases are transparent to the high frequency solar radiation that heat up the earths surface but absorb the lower frequency radiation from the earths surface.

Carbon Dioxide and Global Warming CO2 is a gas in earths atmosphere and is currently at a globally averaged concentration of approximately 383 ppm by volume Atmospheric concentration of CO2 has increased by about 31% since the beginning of the industrial revolution (mid1700s). About three-quarters of this is due to the burning of fossil fuel, the other quarter is mainly due to deforestation Transportation accounts for about 14% of global greenhouse gas emissions and 19% of the CO2 emissions

Carbon Dioxide and Global Warming

In the US a new law requires automakers to increase the average fuel economy of their entire fleets by 40% by 2020 (motor vehicles would be required to meet an average 6.7 L/100 km within 12 years). Canadian govt will soon follow suit.

Emissions - Historical Perspective During the 1940s air pollution as a problem was first recognized in the Los Angeles basin. Problem is due to the large population density, geography, natural weather pattern and affinity to cars. Classic smog results from large amounts of coal burning in an area and is a mixture of smoke and sulfur dioxide (London). Photochemical smog is due to chemical reaction of sunlight, NOx and HC in the lower troposphere producing airborne particles and ground-level ozone (O3) In 1966 California introduced HC and CO emission limits for new vehicles. These limits were set nationally for vehicles in 1968 as part of Clean Air Act. 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 has been towards larger SUVs (e.g. Hummer, Navigator, Escalade) as a result fuel usage is unchanged over this period.6

Photochemical Smog Recipe for smog: sunlight (h), NO, HC NO (small amount of NO2) and hydrocarbons generated by combustion leads to the formation of many biological irritants

Peroxylacetyl Nitrate (PAN) Production NO2 + hv NO + O O + O2 + M O 3 + M NO + O3 NO2 + O2 O + H2O 2OH RH - hydrocarbon R* - HC radical R - methyl CH3 Produce O, O3

O PAN CH3
RC(O)O2NO2

C O O

NO2
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North American Emission Standards (g/mile)

* Phased in by 2009, NLEV - National Low Emission Vehicle voluntary program

EU Emission Standards for Passenger Cars (g/km)

Diesel Euro 1 Euro 2, IDI Euro 2, DI Euro 3 Euro 4 Euro 5 Euro 6 Date 1992.07 1996.01 1996.01 2000.01 2005.01 2009.09 2014.09
b a

CO 2.72 (3.16) 1.0 1.0 0.64 0.50 0.50 0.50

HC -

HC+NOx 0.97 (1.13) 0.7 0.9 0.56 0.30 0.23 0.17

NOx 0.50 0.25 0.18 0.08

PM 0.14 (0.18) 0.08 0.10 0.05 0.025 0.005 0.005

e e

Petrol (Gasoline) Euro 1 Euro 2 Euro 3 Euro 4 Euro 5 Euro 6 1992.07 1996.01 2000.01 2005.01 2009.09
b

2.72 (3.16) 2.2 2.30 1.0 1.0 1.0

0.20 0.10 0.10 0.10

c c

0.97 (1.13) 0.5 -

0.15 0.08 0.06 0.06

0.005 0.005
d,e d,e

2014.09

Values in brackets are conformity of production (COP) limits a - until 1999.09.30 (after that date DI engines must meet the IDI limits) b - 2011.01 for all models c - and NMHC = 0.068 g/km d - applicable only to vehicles using DI engines e - proposed to be changed to 0.003 g/km using the PMP measurement procedure

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Regulation on Sulphur Content of Diesel Fuels The average sulphur content in Canadian Diesel fuel in 2000 was 350 parts per million (ppm) Starting 2009 ultra-low sulphur diesel (ULSD) with 15 ppm sulphur is mandatory in North America for highway vehicles. This is a critical complement to the stringent new Tier II emission standards. Since 2005 EU standards require diesel fuel to have less than 50 ppm sulphur content. In 2009 all vehicles will run on Sulphur-free 10 ppm sulphur diesel, including off-road. EU also requires that diesel fuel have a minimum Cetane number of 48

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Ontario Drive Clean Program In Ontario every vehicle must undergo a tail pipe emission test every other year to check compliance with emission regulations: 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 from gas refuelling cap (SI only at present)

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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

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Nitrogen Oxides (NOx) NOx includes nitric oxide (NO) and nitrogen dioxide (NO2), in SI engines the dominant component of NOx is NO NOx forms as a result of dissociation of molecular nitrogen and oxygen. Zeldovich mechanism O+N2NO+N N+O2NO+O

N 2 + O2 2( NO )

since the activation energy (E) of the first reaction is very high the reaction rate, '' ~ exp (-E/RT), is very temperature dependent NO is only formed at high temperatures (>2000K) and the reaction rate is relatively slow.

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SI Engine In-cylinder NO Formation Since the cylinder temperature changes throughout the cycle the NO reaction rate also changes. 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 cools to 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:
1 x NO = 0 x NO dx

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x0 x1

-15o (x 0)

25o (x 1)

(assuming no mixing of fluid elements)

x0

Equilibrium concentration: based on the local temperature, pressure, equivalence ratio, residual fraction Actual NO concentration: based on kinetics

x1

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Effect of Equivalence Ratio on NO Concentration One would expect the peak NO concentrations to coincide with highest AFT. Typically peak NO concentrations occur for slightly lean mixtures that corresponds to lower AFT but higher oxygen concentration.

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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

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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 fraction exhaust gas recirculation (EGR) moisture in the inlet air run fuel lean 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

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Hydrocarbons Hydrocarbon emissions result from the presence of unburned fuel in the engine exhaust. However, some of the exhaust hydrocarbons are not found in the fuel, but are hydrocarbons derived from the fuel whose structure was altered due to chemical reaction that did not go to completion. For example: acetaldehyde, formaldehyde, 1,3 butadiene, and benzene all classified as toxic emissions. 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.

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Hydrocarbon Emission Sources for SI Engines There are six primary mechanisms believed to be responsible for hydrocarbon emissions: % fuel escaping normal combustion 5.2 1.0 1.0 1.2 0.5 0.1 9.0

Source Crevices Oil layers Deposits Liquid fuel Flame quench Exhaust valve leakage Total

% HC emissions 38 16 16 20 5 5 100

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Hydrocarbon Emission Sources Crevices these are narrow regions in the combustion chamber into which the flame cannot propagate because it is smaller than the quenching distance. Crevices are located around the piston, head gasket, spark plug and valve seats and represent about 1 to 2% of the clearance volume. The crevice around the piston is by far the largest, during compression the fuel air mixture is forced into the crevice (density higher than cylinder gas since gas is cooler near walls) and released during expansion.

Crevice

Piston ring

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Hydrocarbon Emission Sources Oil layers - Since the piston ring is not 100% effective in preventing oil migration into the cylinder above the piston, an oil layer exists within the combustion chamber that traps fuel. Deposits - Carbon deposits build up on the valves, cylinder and piston crown. These deposits are porous with pore sizes smaller than the quenching distance so trapped fuel cannot burn. 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 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.

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Hydrocarbon Exhaust Process 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 (near BC)

Exhaust Stroke

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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

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Hydrocarbon Emission Sources for CI Engines 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.
air Exhaust HC, ppm C

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Note for the direct injection diesel the hydrocarbon emission are worse at light load (long ignition delay)

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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. In properly adjusted SI engines soot is not usually a problem 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.
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Particulates (soot) Most particulate material results from incomplete combustion of fuel HC for fuel rich mixtures. Based on equilibrium the composition of the fuel-oxidizer mixture 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 of reactants exceeds 1. Experimentally the critical C/O ratio for onset of soot formation is 0.5 - 0.8 The CO, H2, and C(s) are subsequently oxidized in the diffusion flame to CO2 and H2O via the following second stage
1 CO + O2 CO2 2 C ( s ) + O2 CO2 1 H 2 + O2 H 2O 2

Any carbon not oxidized in the cylinder ends up as soot in the exhaust!
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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

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Particulates and CI Engines In order to reduce NOx one wants to reduce the AFT but that has the adverse effect of decreasing the amount of soot oxidized and thus increases the amount of soot in the exhaust. 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

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Carbon Monoxide Carbon monoxide appears in the exhaust of fuel rich running engines, there is insufficient oxygen to convert all the carbon in the fuel to carbon dioxide.

C8H18-air

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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.

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Emission 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 engine control unit (ECU). 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

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Catalytic Converter The catalytic converter uses a reduction catalyst and an oxidation catalyst to remove CO, NO, and HC from the exhaust stream Both consist of a ceramic honeycomb coated with a metal catalyst, usually platinum, rhodium and/or palladium.

Lead and sulfur in the exhaust gas severely inhibit the operation of a catalytic converter (poison). 36

Three-way Catalytic Converter A three-way catalysts will function properly only if the exhaust gas composition corresponds to nearly (1%) stoichiometric combustion. If the exhaust is too lean NO is not destroyed If the exhaust is too rich CO and HC are not destroyed

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Three-way Catalytic Converter 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 with EGR to reduce NOx Reduction catalyst: In the first stage platinum and rhodium are used to remove NOx. The NO molecule dissociates on the catalyst surface producing molecular oxygen and nitrogen that are released 2NO N2 + O2 or 2NO2 N2 + 2O2

Oxidation catalyst: In the second stage platinum and palladium are used to oxidize the CO and the unburned hydrocarbon (HC) using the oxygen in the stream. 2CO + O2 2CO2 2CxHy + (2x+y/2)O2 2xCO2 + yH2O

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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

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Emission Control A closed-loop control system with an oxygen (lamda) sensor in the exhaust is used to control the fuel delivery so that the A/F ratio is near stoichiometric. The narrow-band oxygen sensor when hot (800oC) produces a voltage that varies according to the amount of oxygen in the exhaust compared to the ambient oxygen level in the outside air. Sensor output is very nonlinear ranging from 0.2 VDC (lean) to 0.8 VDC (rich), a stoichiometric mixture gives an average reading of around 0.45 Volts. The sensor can contain a heater to bring it quickly up to temperature and is located before the catalytic converter Wide-band sensor output is linear and can be used to measure the O2 in the gas stream. Is used for tuning, only used in a few vehicles
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Bosche LSU-4 wide band sensor

Diesel Exhaust Treatment Diesel engines run fuel lean (reduce soot) so a 3-way catalytic converter is not useful, also particulate matter (PM) consisting of C needs to be removed. Oxidizer catalysts used for reducing HC and CO Diesel Particulate Filters (DPF) are used for removing PM. Active DPFs: raise temperature of the filter by periodically adding fuel to the exhaust stream that combusts in the filter raising the DPF temp cleans the DPF by oxidizing the collected PM with O2, requires >600oC (regeneration). Passive DPF:

Non catalyst

(reaction requires > 250oC)

Johnson Matthey CRT

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Diesel Exhaust Treatment NO can be reduced by retarding fuel injection from 20o to 5o before TC in order to reduce the peak combustion temperature at the expense of efficiency. Selective Catalytic Reduction (SCR) used to convert NOx into N2 and H2O. In a lean burn engine, it is necessary to add a reductant like ammonia (NH3) to the gas stream to enable this reaction over a catalyst. 4NH3 + 4NO + O2 4N2 + 6H2O 2NH3 + NO + NO2 2N2 + 3H2O 8NH3 + 6NO2 7N2 + 12H2O Typically an aqueous solution of urea (NH2)2CO is added to the exhaust stream to produce ammonia: (NH2)2CO HNCO + NH3 HNCO + H2O CO2 + NH3 Mercedes-Benz BlueTEC ML320 has a 7 gal urea based Addblue tank
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