SI Engine Combustion

Emissions From SI Engines

Prof.Dr. Cem Sorubay

Istanbul Technical University

Emissions From SI Engines

Introduction
Exhaust Emissions from SI Engines
NOx Mechanisms

Introduction
In ideal complete combustion of a HC fuel with stoichiometric
air-fuel mixture, exhaust gas would compose of chemical species of
carbon dioxide CO2, water H2O and molecular nitrogen N2 only
For lean mixtures molecular oxygen O2, would also be present
among the products

Cn H m + n +
(O2 + 3.76 N 2 )
4

m
m

n CO2 + H 2O + 3.76 n +
N2
2
4

Introduction
However,
*elementary chemical reactions never proceed completely into
one direction, but always approach an equilibrium state between
Products and Reactants, thus leaving at least small amounts of
reactants,
*local boundary conditions such as mixture distribution,
temperature, turbulence level etc are not ideal
Therefore flame extinction, accompanied with unburned or partially
burned species, or formation of entirely new products such as NOx
or soot may occur
Additional products such as unburned HC, CO, NOx and particulate matter
(PM) are present in exhaust gases.
Depending on the quality of fuel there are also traces of sulphur oxides
SO2 in exhaust gases

Pollutant Formation Local pollutants

IC engine exhaust gases contain
oxides of nitrogen
NO and some amounts of NO2
collectively known as NOx
carbon monoxide
CO
unburned hydrocarbons HC
PM and Soot mainly in Diesel engines and Direct Injection SI engines
The amounts depend on engine design and operating conditions.
These pollutants are measured as concentrations;
CO, CO2, O2 as vol. [%]
NO, NO2, NOx as [ppm] (parts per million)
HC as [ppm] or [ppm C]
eg
1 ppm
propan, C3H8
3 ppm C

Pollutant Formation Global pollutants

Greenhouse gases (GHG)
CO2
Carbon dioxide
CH4
Direct GHGs from transportation
N2O
CO2 , CH4, N2O
HFC
PFC
Indirect GHGs are CO, NOx, NMVOC, SO2
SF6
Kyoto Protocol reduction of total greenhouse gases by %5.4 (ref year
1990) until 2008 - 2012 period
Recent aim is

130 g-CO2/km + 10 g-CO2/km by 2012

95 g-CO2/km by 2020

Greenhouse Gases
1995 2001

in EU-25 countries

CO2 emissions per vehicle reduced by %9.7

(186 168 g-CO2/km)
Total number of vehicles increased by % 24.4

Pollutant Formation

Pollutant Formation
Pollutants
1,1%

CO2
12,3%

SI Engines
Pollutants [%]
PM
0.0008
NOx
0.13
HC
0.09
CO
0.90

H2O
13,8%
O2 and inert
gases
0,7%
N2
72,1%

Diesel Engines
Pollutants [%]
PM soot 0.002
NOx
0.17
HC
0.008
CO
0.008
SO2
0.011

CO2
8,0%

Pollutants
0,2%

H2O
9,0%

O2
9,0%

N2
73,8%

Emission Standards
EURO I (91/44/EEC)
HC + NOx
CO

0.97
2.72

[g/km]

EURO II (94/12/EC)
HC + NOx
CO

0.5
2.2

[g/km]

HC
NOx
CO

0.2
0.15
2.3

[g/km]

2005
HC
NOx
CO

0.1
0.08
1.0

[g/km]

EURO III

EURO IV

Pollutant Formation
There has been a considerable reduction in pollutant emissions from IC
engines over the last three decades
Pre-control (average values)
HC
7
[g/km]
NOx
2.5
CO
50
Present
HC
NOx
CO

2*
1.3*
10*

(0.2)**
(0.2)**
(1.2)**

[g/km]
* engine out
** exhaust out

Temperatures
SI engines
exhaust gas temp 400 600 oC average
300 400 oC at idle and 900 oC at max power
CI engines
200 500 oC average

Emission Control

Nitrogen Oxides
Formation of NO follows extended Zeldovich mechanism
because reactions are slow, amount of NO produced is
controlled by rate of reaction
Lower temperatures greatly reduce reaction rate
reactions freeze below 1800 K during expansion
Time available for the reactions (ignition timing, flame speed),
air-fuel ratio and cylinder temperatures determine
NO emissions from SI engines

Control of Nitrogen Oxides

* EGR (exhaust gas recirculation)

* Exhaust after-treatment : three-way catalysts

Nitrogen Oxide Kinetics

NO play an important role in atmospheric pollution
Combustion products typically contain NO at levels of several
hundred to several thousand [ppm] and NO2 levels in tens of
[ppm]
In atmosphere, in presence of ultraviolet sunlight equilibrium is
established between NO, NO2 and ozone

NO2 + O2 NO + O3
Certain HCs slowly unbalance this reaction, HCs are oxidized, and
products such as nitrates, aldehydes and PAN (peroxyacetyl
nitrate) are formed
NO is converted to NO2

Oxides of Nitrogen Formation

Main sources
* Thermal NO Zeldovich mechanism
oxidation of molecular nitrogen in postflame zone
* Prompt NO Fenimore mechanism
formation of NO in flame zone
* Fuel-bound NO
oxidation of nitrogen-containing compounds in fuel
see Ref.
J.A. Miller and C.T. Bowman, Mechanism and Modelling of
Nitrogen Chemistry in Combustion, Prog in Energy and Comb Sci,
15, 287, 1989

Oxides of Nitrogen Formation

Combustion with excess oxygen in postflame zone (high temperature
combustion) , thermal mechanism dominates (Zeldovich)
Fenimore mechanism is important in rich combustion
N2O intermediate mechanism plays an important role in production
of NO in very lean, low temperature combustion process

Extended Zeldovich Mechanism

O + N 2 NO + N
Forward reaction controls system, has high activation energy thus
slow at low T , therefore not important below 1800 K
Thermal NO is formed in postflame

N + O2 NO + O

N + OH NO + H
Contribution is small for lean mixtures important for rich mixtures
where O2 concentration is low
NO concentrations of 1000 4000 ppm in uncontrolled combustion
systems

Extended Zeldovich Mechanism

d[NO]/dt = kf1 [O][N2] kr1 [NO][N]
+ kf2 [N][O2] kr2 [NO][O]
+ kf3 [N][OH] kr3 [NO][H]
To evaluate rate of NO formation, O, H, N, OH concentrations must
be determined
For high T applications (IC engines) it can be assumed that O,N,OH,H
remain in thermodynamic equilibrium in postflame zone
For moderately high T (furnaces) N does not remain in equilibrium
it remains in steady-state concentration
net rate of change of N is very small -> set zero

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Extended Zeldovich Mechanism

d[N]/dt = kf1 [O][N2] kr1 [NO][N]
- kf2 [N][O2] + kr2 [NO][O]
- kf3 [N][OH] + kr3 [NO][H] = 0

Solving for N at steady-state,

[N] =

( kf1 [O][N2] + kr2 [NO][O] + kr3 [NO][H] )

/ ( kr1 [NO] + kf2 [O2] + kf3 [OH] )

Formation of NO
Methane combustion, initial conditions : 1 atm , 300 K

(Borman and Ragland)

Theoretical air
[%]

NO strongly depend
on excess air

Lean mixture produces more NO than stoichiometric initial rate of NO

formation is higher for = 1
Rich mixture -> NO is lower
NO levels reach equilibrium value in 0.5 to 1.5 [s]
At lower T approach to equilibrium is slower because of back reactions
become more important

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Formation of NO
Stoichiometric mixture of n-octane + air
= 14
10
6

Although final equilibrium value

of NO is only 33% higher for
CR of 14 compared to CR of 6,
initial rate of formation is much higher
After 2.5 [ms] levels are 1000, 2300, 3450 ppm for CR of 6, 10 and 14
NO from SI engines are related to residence time of products in the
cylinder as well as compression ratio (CR)

Formation of NO
Cooling down the cylinder contents lowers NO, but kinetic rates slow
down rapidly as T drops and freeze

2500 ppm

When expansion is faster, (t0 = 0.01 s) less time to form NO,

concentration is frozen at a lower value

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N2O intermediate Mechanism

This mechanism is important in lean mixtures
(eg. gas turbines, < 0.8) and low T

O + N 2 + M N 2O + M
H + N 2O NO + NH
O + N 2 O NO + NO

Prompt NO Mechanism
Small amounts of NO (40 60 ppm) can be produced directly in a
flame front, long before there would be time to form NO
by thermal mechanism
-> HC radicals react with molecular N in the flame

O + N 2 + M N 2O + M
C + N 2 CN + N

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Prompt NO Mechanism
Since the rate-limiting reaction step involves CH radical, NO path
becomes important only under fuel rich conditions
(high CH concentration)
Activation energy is significantly less than rate-limiting step of
thermal NO mechanism (11 060 K to 38 000 K) therefore
T dependency is not as pronounced as thermal NO
mechanism
So it becomes more important for reduced combustion temperatures
Estimation of CH concentration in the flame zone is a challenge
(accuracy problem)

Fuel-bound NO
Produced from the organic nitrogen compounds in the fuel
Crude oil contains 0.1 0.2 % organic nitrogen
Coal contains 1.2 1.6 %
As nitrogen containing fuel burns hydrogen cyanide, HCN or
ammonia, NH3 is formed as intermediate which further reacts with
O, OH, H to form NO in post-flame zone
In practical systems 20 50 % of the fuel nitrogen
is converted to NO

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