IIT Kanpur Kanpur, India (208016)

Engine Exhaust Emissions: Formation and Control Techniques
Date- 20/3/2013 & 21/3/2013

Course Instructor Dr. Avinash Kumar Agarwal Professor Department of Mechanical Engineering Indian Institute of Technology Kanpur, Kanpur

 Introduction of Engine Exhaust Pollutants  Issues Related with Engine Exhaust Pollutants  Health Effects  Environmental effects  Classification of Engine Exhaust Pollutants  Regulated Emission  Unregulated Emission  Types of Regulated Pollutants  Oxides of Nitrogen (NOx)  Hydrocarbons (HC)  Carbon Monoxide (CO)  Particulate Matter (PM)  Summary


 Diseases like bronchitis and asthma are aggravated by a high concentration of SO2 Carbon-monoxide (CO)  It has a strong affinity (200 times) for combining with the hemoglobin of the blood to form carboxyhemoglobin.  Besides IC engines other sources such as electric power stations.  They are major contributors to eye and respiratory irritation caused by photochemical smog Breathing Mechanism 2 . Issues related with Engine Exhaust Emission: Health Effects Sulphur dioxide (SO2)  It is an irritant gas and affects the mucous membrane when inhaled.  Air pollution can be defined as an addition to our atmosphere of any material which will have a deleterious effect on life upon our planet. in recent years. Hydrocarbon (HC)  They are primarily irritating.  CO affects the central nervous system.  In the presence of water vapor it forms sulphurous and sulphuric acids acids. These acids cause severe bronchospasma at very low levels of concentration. that the IC Engines are responsible for too much atmospheric pollution.  Thus concerted efforts are being made to reduce the responsible pollutants emitted from the exhaust system without sacrificing power & fuel consumption. industrial and domestic fuel consumers also add pollution.4/1/2013 Air Pollution and Engine Exhaust Emission  There has been a great concern.  It is also responsible for heart attacks and a high mortality rate. which is detrimental to human health & environment. This reduces the ability of the hemoglobin to carry oxygen to the blood tissues.

asthma Compounds of Incomplete combustion  Exhaust discharge from IC engines carry compounds of incomplete combustion (polycyclic organic compounds and aliphatic hydrocarbons). 3 .  Ground-level ozone can lead to reductions in agricultural crop and commercial forest yields. Lead  Inorganic lead compounds (discharged from vehicles using leaded petrol) cause a variety of human health disorders. reduced growth and survivability of tree seedlings.a phenomenon known as global warming. Crop and Forest Damage  Air pollution can damage crops and trees in a variety of ways. Smoke  It is visible carbon particles. Issues related with Engine Emission: Environmental Effects Acid Rain due to NOx and SO2 Emission  Acid rain is rain consisting of water droplets that are acidic because of atmospheric pollution.  As a result. including carbon dioxide and methane.  The effects include gastrointestinal damage. liver and kidney damage. and visibility reduction. and pulmonary discomfort after brief exposure to 25 ppm of nitrogen oxide. causing the Earth's average temperature to rise . the Earth's atmosphere appears to be trapping more of the sun's heat. which act as carcinogenic agents and are responsible for lungs cancer.4/1/2013 Issues related with Engine Exhaust Emission: Health Effects Oxides of nitrogen (NOx)  These are known to cause occupational diseases.  It also aggravates diseases like bronchitis and asthma. causes other h respiratory i di diseases. It also. abnormality in fertility and pregnancy etc.  Acid deposition can occur via natural sources like volcanoes but it is mainly caused by the release of sulfur dioxide and nitrogen oxide during fossil fuel combustion. It is estimated that eye and nasal irritation will be observed after exposure to about 15 ppm of nitrogen oxide.  Humans have disturbed the natural balance by producing large amounts of some of these greenhouse gases. Global Climate Change  This "greenhouse effect" keeps the Earth's temperature stable. It causes irritation in eyes and lungs.

(1) Regulated Emission  Carbon monoxide (CO). the distinction is generally made between regulated and unregulated constituents. Classification of Engine Exhaust Emission Air pollutants are classified as either primary or secondary contaminants.  General unregulated compounds can be given as (individual hydrocarbons. aldehydes and ketones. Fuel Vapour (20%) – chemicals that enter the air as fuel evaporate.  A primary air contaminant. (2) Unregulated Emission  Unregulated exhaust constituents are defined as emitted compounds that are not specified by law.  Secondary emissions are emitted as gases and can combine with other airborne substances to form particles once in the atmosphere. or particles of unburned fuel.). nitro-PAH. atmosphere  When discussing exhaust emissions from vehicles.blown out the tailpipe when engine burns a hydrocarbon based fuel. hydrocarbons (HC). nitrogen oxides (NOx. and soluble organic fraction of particulate matter) 4 . for diesel-fueled cars. Engine Exhaust (60%).4/1/2013 Sources of Vehicle Emissions Engine Crankcase Blow-by Fumes (20%)– heating oil and burning of fuel that blows past piston rings and into the crankcase. such as carbon monoxide gas. ethanol. a group that consists of several thousands of compounds. and. is added to the atmosphere as a by-product of burning gasoline or diesel in an internal combustion engine. particulates are regulated exhaust constituents from vehicles. polynuclear aromatic hydrocarbons (PAH).

can cause pollution. in certain environments. N2O. which is an inert gas and. Hence high temperature and availability of O2 are the main reason for the formation of NO and NO2. because it reacts to the atmosphere to form ozone and causes photochemical smog  NOx is mostly created from nitrogen of air.N2O5 are also formed in low concentration but they decompose spontaneously at ambient conditions of NO2. The major pollutants emitted from the exhaust due to incomplete combustion are:  Carbon monoxide (CO)  Hydrocarbons (HC)  Oxides of nitrogen (NOx)  Particulate Matter (PM)  If. NC.  Combustion duration plays a significant role in NOx formation within cylinder.  Oxides of nitrogen and other obnoxious substances are produced in very small quantities and.  These are generally formed at high temperature.4/1/2013 Regulated Engine Exhaust Emission  Pollutants are produced by the incomplete burning of the air-fuel mixture in the combustion chamber. Due to fast-burn combustion chamber the modern engines have less NOx emission. while prolonged exposure is dangerous to health. combustion is complete.  The maximum NOx levels are observed with A:F ratios of about 10% above stoichiometric. the only products being expelled from the exhaust would be water vapor which is harmless. however. N2O3 . HCN) 5 . Some times the fuel contains nitrogen in compound form (for example NH3. as such it is not directly harmful to humans. Oxides of Nitrogen (NOx)  Oxides of N2 generally occur mainly in the form of NO and NO2 .  Many other oxides like N2O4. and carbon dioxide. emission  NOx emission is very undesirable.

it can be said that petrol engine exhaust is free of CO if the air fuel ratio is 15.  CO is generally formed when the mixture is rich in fuel. while large concentration will kill.  In general there are two types of NOx emission takes place in engine exhaust as.  The majority of NO formed will however decompose at the low temperature of exhaust. CO + ½ O2 CO2 + heat 6 . (2) Fuel NOx: formed from combustion of fuels containing organic nitrogen in the fuel.  Not only CO is considered undesirable emission.  Small amounts of CO concentrations. slow down physical and mental activity and produces headaches.  Theoretically .  It is far in excess of the equilibrium composition at that temperature as t formation of NO freezes at low exhaust temperatures. when inhaled. when breathed in.  The NO formation will be less in rich mixtures than in lean mixtures. But due to very low reaction rate at the exhaust temperature a part of NO formed remains in exhaust. dependent on local combustion conditions and nitrogen content in the fuel.  Fast cooling rate freezes formed Nox. it also represent loss of chemical energy. the following chemical reactions take place behind the flame:  Chemical equilibrium q calculations show that a significant g amount of NO is formed the end of combustion. The amount of CO formed increases the mixture becomes more and more rich in fuel. replaces the oxygen in the blood stream so that the body’s metabolism can not function correctly.  It is a poisonous gas which.  Some CO is always present in the exhaust even at lean mixture and can be as high as 1%. Carbon Monoxide (CO)  It is a color less gas of about the same density as air. CO behave as fuel that can be combusted to supply additional thermal energy. fuel  Small amount of CO will come out of the exhaust even when the mixture is slightly lean in fuel. (1) Thermal NOx: formed by reaction between N2 and O2 in the air.4/1/2013 Oxides of Nitrogen (NOx)  At high combustion temperatures. sensitive to temperature  Fast formation rate at high temperature.  CO is intermediate product of combustion remains in exhaust if the oxidation of CO to CO2 is not complete.

4/1/2013 Carbon Monoxide (CO)  A small amount of CO will come out of the exhaust even when the mixture is slightly lean in fuel.  This is due to the fact that equilibrium is not established when the products pass to the exhaust.  In improper mixing the air-fuel mixture is not homogeneous and that causes the HC emission. operating variables and engine condition. major part of CO reacts with oxygen form CO2 However.  At the high temperature developed during the combustion. Higher the S/V ratio.  As the products cool down to exhaust temperature. higher the HC emission Incomplete combustion  Even if fuel air mixture enter in stoichiometric condition perfect combustion does not occur because of improper mixing and flame quenching. and the following reactions take place before the equilibrium is established.  The Surface to volume ratio greatly affects the HC emission.  In flame quenching the flame near the wall quenched leaving a small volume of unreacted fuel-air mixture Crevice volume and flow in crevices  In I compression i stroke k the h air i and d fuel f l compressed d into i crevice i volume l of f the h combustion b i chamber h b  During expansion process the air and fuel come out of crevice volume because of pressure difference  Upto 80% of all HC emission can come from this source Leakage past the exhaust valve  During compression some of fuel air mixture forced into the volume around edges of exhaust valve and between the valve and valve seat 7 . Hydrocarbon Emission from SI Engines  The emission amount of HC (due to incomplete combustion) is closely related to Design variables. the products formed are unstable. a relatively small amount of CO will remain in exhaust. its concentration creasing with rich mixtures.

CI engine have only one-fifth of HC emission of an SI engine. that means only 2% of HC fuel is emitted. and a thick film of lubricating oil is left on the walls. HC emission from CI engine  As CI engine operate with an overall fuel-lean equivalence ratio.4/1/2013 Unburned Hydrocarbon (HC): Formation Mechanism  A small amount even leak past the valve into the exhaust manifold  When exhaust valve open this trapped fuel air mixture carried out to exhaust manifold and increase the HC emission Valve overlap  Valve overlap p is a must to obtain satisfactory yp performance from the engine g  During valve overlap some fresh fuel air mixture directly flows to the exhaust manifold increasing the HC emission Deposits on walls  Gas particles including fuel vapor absorbed by the deposits on the wall of combustion chamber  The maximum absorption occur during compression and combustion (high pressure)  Later in the cycle when exhaust valve opens the particles get desorbed back into the cylinder and comes out from exhaust manifold increasing the HC emission Oil on combustion chamber walls  As an engine gets old the gap between piston rings and cylinder walls becomes greater. Oil is high molecular weight hydrocarbons  Some of this oil get scraped during compression and burned during combustion  Oil does not burn easily and hence some of them come out from exhaust manifold increasing the HC emission.   In general CI engine has 98% combustion efficiency. In CI engine the HC emission occurs mainly because of:        Heterogeneous mixture condition Under mixing of fuel with air (lean mixture) Over mixing of fuel with air (rich mixture) Trapping of fuel in tip of nozzle Crevice volume (Same as SI engine) Wall deposit absorption (Same as SI engine) Oil film absorption (Same as SI engine) 8 .

fumes.  The Th emission i i rates t are typically t i ll 0. some is contributed by the lubricating oil. aerosols.  Particles originate from a variety of mobile sources and may be directly emitted (primary emissions) or formed in the atmosphere (secondary emissions) by transformation of gaseous emissions. soot. and sulfuric acid (sulfates). the individual particles are principally clusters of many small spheres or spherules of carbon (with a small amount of hydrogen) with individual spherule diameters of about 15 5 to 3 30 nm. and polynuclear aromatic hydrocarbons. ethers.6 6 g/km /k for f light-duty li ht d t diesels di l in i an automobile. smoke. esters.  Most particulate material results from incomplete combustion of fuel hydrocarbons.5 to 1. 9 . fly ash. oxygenated hydrocarbons (ketones.  The temperatures above 5000C. Characteristics of Diesel Particulates  Diesel particulates consist principally of combustion generated carbonaceous material (soot) on which some organic compounds have become absorbed.  As temperatures decrease below 5000C. mists and condensing vapors that can be suspended in the air for extended periods of time.2 to t 0. t bil In I larger l direct-injection engines. organic acids). the particles become coated with adsorbed and condensed high molecular weight organic compounds which include: unburned hydrocarbons.  The condensed material also includes inorganic species such as sulfur dioxide. particulate emission rates are 0.4/1/2013 Particulate Matter (PM)  Components of particulate matter (PM) include finely divided solids or liquids such as dust.5 g/ kWh. nitrogen dioxide.  The composition of the particulate material depends on the conditions in the engine exhaust and particulate collection system.

atypical rust and scale from the exhaust system. also.  These not emitted directly as such. as this mode includes. of an accumulation-mode particle. and not because the spherules themselves vary in size 10 . research suggests that nucleation-mode particles consist of volatile material  Other research suggests that some nucleation-mode particles are in fact solid.  Accumulation-mode particles vary in size because they contain greater or fewer numbers of spherules. or backbone. which forms the skeleton. but not all. another and then re-enter the exhaust stream as much larger. or at least possess minute solid kernels Motor Vehicle Particulate Size Wise Classification Coarse Mode Particles  Coarse-mode particles are of varying nature.  This storage–release process makes the coarse mode an inconsistent emission – one that proceeds in a random and unpredictable manner Accumulation Mode Particles  Accumulation mode particles are constructed from a solid core of carbonaceous building blocksp spherules  Size of spherules is typically 20–50 nm  This assemblage of spherules. system become attached to one another. but formed from the other two modes  These predecessors lodge somewhere within the exhaust system. is an ‘agglomerate’ or an ‘aggregate’. composite particles.4/1/2013 Motor Vehicle Particulate Size Wise Classification Nucleation Mode Particles  Nucleation-mode l i d particles i l were obscure b prior i to mid id 1990 as they h lie li at the h detection d i limit li i of f many instruments  Admittedly this situation is changing rapidly  Most.

8 HC emission increase due to poor combustion and misfire.  For φ <0.  NOx emission is steadily increase with φ due to high temperature and pressure.  NOx emission is highest near stoichiometric condition because NOx emission is a function of temperature.  For rich mixture (φ>1) the HC and CO emission increased. CO and NOx emission with respect p to equivalence q ratio for a four stroke diesel engine.4/1/2013 Engine Exhaust Emission in SI Engines  The Th figure fi above b shows h th variation the i ti of f HC. 11 .  CO emission is very low at all equivalence ratio since excess air is always available.  HC initially increase slightly with increase in φ due to high cylinder temperature make it easier to burn up any over-mixed or under mixed fuel mixture. . HC CO and d NOx NO emission i i as a function f ti of f equivalence i l ratio ti for an SI engine. Engine Exhaust Emission in CI Engines  The above figure g shows the HC.

Emission Chart from IC Engines A: Major contributor Type of Pollution Lead Carcinogens Acid Rain Principal Sources Anti-knock compounds Diesel exhaust Sulfur dioxide Oxides of nitrogen Unburned hydrocarbons Carbon monoxide Global warming CFCs Carbon dioxide Methane Photochemical smog Carbon monoxide Unburned hydrocarbons Sulfur dioxide Oxides of nitrogen Ozone depletion CFCs Unburned hydrocarbons Oxides of nitrogen B: Secondary influence Relevance of I.  Fuel tank: The furl tank emits the fuel vapor p into the atmosphere.  Carburetor: The carburetor also gives out fuel vapor.4/1/2013 Non-Exhaust Emission Sources of emission (SI Engine)  Apart from exhaust emission IC engine have following non exhaust emissions.  ELCD control the evaporative emission by capturing the vapors and recalculating them at the appropriate time.  To control the non exhaust emission ELCD (Evaporation loss control device) is used. p .C. Engine A (for the SI Engine) A B (for the CI Engine) A A (for the SI Engine) A (for the SI Engine) B (for car with AC) B (may be even A) B (may be A if CNG used) A (for the SI Engine) A (for the SI Engine) B (for the CI Engine) A B (for car with AC) A (for the SI Engine) A 12 .  Crankcase: It emits blow-by gases and fuel vapors into the atmosphere.

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