11.

Combustion & Pollutants 1 AER 1304LG

11. Combustion & Pollutants
I ntroduction:
Pollutant emission control is a major factor in de-
sign of modern combustion devices.
11. Combustion & Pollutants 2 AER 1304LG
Control of emissions may sometime involve
a
compromise of thermal efficiency (fuel
consump
tion).
(Pollutants of concern include: Particulate
mattersoot, ash, aerosols); oxides of nitrogen;
sulphur
11. Combustion & Pollutants 3 AER 1304LG
oxides; carbon monoxide; unburned hydrocarbons;
nitrous oxide, and carbon dioxide.
Local/Regional Air Quality Concerns:
Combustion generated and regulated
pollutantsare:
- Particulate matter; PM
10
and PM
2.5

- Oxides of nitrogen; NO
x
(NO and NO
2
) -
Ozone; O
3
(air quality standards).
- Carbon monoxide; CO
11. Combustion & Pollutants 4 AER 1304LG
- Lead
- Unburned and partially burned hydrocarbons
- Sulphur dioxide
Regulated emissions:
Gasoline engines (SI):
- NO
x
, CO, unburned HC
Diesel engines (CI):
- NO
x
, CO, unburned HC, Particulate Matter
Gas Turbines (Stationary and aircraft, limited):
11. Combustion & Pollutants 5 AER 1304LG
- NO
x

Power plants:
- NO
x
, CO, Particulate Matter, SO
2

11. Combustion & Pollutants 6 AER 1304LG
SI engine:
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11. Combustion & Pollutants 8 AER 1304LG
SI engine 3-Way Catalytic converter Air
Toxics/Hazardous Air Pollutants:
Close to 200 substances are listed as air toxics:
- Selected aliphatic, aromatic, and polycyclic
aromatic hydrocarbons
- Selected halogenated hydrocarbons
- Various oxygenated organic compounds
- Metals and metal compounds
- Polycyclic aromatic hydrocarbons with
nitrogen atoms in the structure
11. Combustion & Pollutants 9 AER 1304LG
- A list of other compounds
Greenhouse Gases tied to Global Warming:
Kyoto Protocol identifies the following as
theGreenhouse gases:
- Carbon dioxide, CO
2

- Methane, CH
4

- Nitrous oxide, N
2
O
- Particulates, soot, aerosols
- Stratospheric H
2
O
11. Combustion & Pollutants 10 AER 1304LG
- Tropospheric and stratospheric ozone, O
3

- Sulphates
Stratospheric Ozone Destruction:
Montreal (1987), London (1990) and
Copenhagen(1992) Protocols cap the following:
- Methane, CH
4

- Nitrous oxide, N
2
O
- Methyl chloride, CH
3
Cl
- Methyl bromide, CH
3
Br - Stratospheric H
2
O
11. Combustion & Pollutants 11 AER 1304LG
- Stratospheric ozone, O
3


11. Combustion & Pollutants 12 AER 1304LG
Chlorine loading of earths atmosphere
Stratospheric ozone shields earth from
ultravioletradiation.
Most of this ozone is contained in a layer
between20 and 50 km altitude.
Three mechanisms control the level of ozone con-
centration:
11. Combustion & Pollutants 13 AER 1304LG
- HO
x
cycle (H, OH, HO
2

- NO
x
cycle (NO, NO
2
)
- ClO
x
cycle [halomethanes: CFCl
3
(Freon-11),
CF
2
Cl
2
(Freon-12); and CH
3
Cl)]
11. Combustion & Pollutants 14 AER 1304LG

Ozone removal in lower stratosphere NO
x
formation in combustion:
11. Combustion & Pollutants 15 AER 1304LG
- Thermal NO: oxidation of molecular nitrogen in the
postflame zone.
- Prompt NO: formation of NO in the flame zone
(Fenimore mechanism).
- N
2
O-intermediate mechanism.
- Fuel NO: oxidation of nitrogen-containing
compounds in the fuel.
Relative importance of these three are dependent on the
operating conditions and fuel. In most practical
combustion devices the thermal NO is the main source.
11. Combustion & Pollutants 16 AER 1304LG
The basic mechanism for thermal NO production
is given by six reactions known as extended
Zeldovich mechanism:
k
3r

- The
O + N2 uD1kf1r NO + N (N.1)
k
N + O2 uD2kf2r NO + O
(N.2)
k
N + OH uD
3
k
f
NO + H
(N.3)
11. Combustion & Pollutants 17 AER 1304LG
contribution of reaction 3 is small for lean
mixtures, but for rich mixtures it should be
considered. Forward reaction 1 controls the system,
but it is slow at low temperatures (high activation
energy). Thus it is effective in post-flame zone
where temperature is high and the time is available.
- Concentrations of 1000 to 4000 ppm are typically
observed in uncontrolled combustion systems.
- From reactions 1-3, the rate of formation of thermal
NO can be calculated:
d[NO]dt = k1f[O][N2] k1r[NO][N] + k2f[N][O2]
11. Combustion & Pollutants 18 AER 1304LG
k
2r
[NO][O] + k
3f
[N][OH] k
3r
[NO][H] (5.14)
- To calculate the NO formation rate, we need the
concentrations of O, N, OH, and H.
- In detailed calculations, these are computed using
detailed kinetic mechanisms for the fuel used.
- For very approximate calculations, these may be
assumed to be in chemical equilibrium.
- At moderately high temperatures N does not stay at
thermodynamic equilibrium. A better
approximation could be to assume N to be at
steady-state.
11. Combustion & Pollutants 19 AER 1304LG
[ ] N
ss
=
1 f
[ O][N
2
]+
2 r
NO][O ]+ [
3 r
k [ ]+ NO k [ O ]+ k [ ] OH
- From reactions 1-3, we have
d[N]
dt = k
1f
[O][N
2
]
k
1r
[NO][N] k
2f
[N][O
2
]
+k
2r
[NO][O] k
3f
[N][OH] + k
3r
[NO][H] = 0 k k
k [NO][H]
1r 2f 2 3f
(5.15)
- The reaction rate constants, in [m
3
/ kmol s], for 1-3
are as follows:
11. Combustion & Pollutants 20 AER 1304LG
10
kkk1
1
f
r
= 1= 3..88
1010
11
10
7
Texp(exp(exp(425384680,370/T/T)/T)
) (5.16)
10
kk2
32
f
f
r = 1= 3= 7...818
1010
6
Texp(exp(45020,/T820)/T)
11. Combustion & Pollutants 21 AER 1304LG

k3r = 1.7 10
11
exp(24,
560
/T)
Nlean combustion (2O-intermediate mechanism

<
0.8). This mechanism canis important in verybe
represented by:
11. Combustion & Pollutants 22 AER 1304LG
O + N O + M (N.4) H + N NO + NH
(N.5) O + N NO + NO (N.6)
- This mechanism is important in NO control
strategies in lean-premixed gas turbine combustion
applications.
It has been shown that some NO is rapidly pro-
duced in the flame zone long before there would
be
time to form NO by the thermal mechanism. This is
also known as the Fenimore mechanism:
11. Combustion & Pollutants 23 AER 1304LG
- The general scheme is that hydrocarbon radicals
form CN and HCN
CH + N HCN + N (N.7) C + N CN + N (N.8)
- The conversion of hydrogen cyanide, HCN, to
form NO is as follows
HCN + O uD NCO + H (N.9)
NCO + H uD NH + CO (N.10)
NH + H uD N + H
2
(N.11)
N + OH uD NO + H (N.3)
11. Combustion & Pollutants 24 AER 1304LG
- For equivalence ratios higher than 1.2,
chemistry becomes more complex and it
couples with the thermal mechanism.
NO
x
emissions from SI engines:
Nitric oxide forms in the high temperature
burnedgases during the combustion
process. During expansion, as the burned
gas temperature falls, NO freezes out as the
11. Combustion & Pollutants 25 AER 1304LG
decomposition chemistry becomes
extremely slow.
The burned gas temperature, and the
amount of
oxygen in the burned gases, are
11. Combustion & Pollutants 26 AER 1304LG
the primary vari
ables affecting NO
formation.
NO
x
emissions from SI engines (Contd):
Dilution of the unburned mixture with
EGR leadsto lower burned gas temperature
11. Combustion & Pollutants 27 AER 1304LG
due to increased heat capacity of the
mixture per unit mass of fuel.
Dilution with air also increases the heat
capacity,but increasing the oxygen content
has a greater impact on NO formation rate.
11. Combustion & Pollutants 28 AER 1304LG

it reduces peak cylinder pressures and
burned gas
Spark retard reduces NO
formation rate because temperatures.
Unburned HC emissions from SI engines:
11. Combustion & Pollutants 29 AER 1304LG
Unburned HC emissions are various
compounds ofhydrogen and carbon.
a lessor extent, oil.They are unburned or
partially burned fuel, and to
About 1000-3000 ppm under normal
operatingconditions (before catalyst).
11. Combustion & Pollutants 30 AER 1304LG
flow into the engine.This corresponds to
about 1 to 2 % of the fuel
CO emissions from SI engines:
Carbon monoxide (CO) is the incomplete
oxida-tion product of the fuel carbon. It is
present in
significant amounts in fuel-rich combustion
products, and in high-temperature burned gases.
Effectively determined by fuel-air ratio.
11. Combustion & Pollutants 31 AER 1304LG
Although in chemical equilibrium during
combus-tion, recombination with oxygen is
slow and CO
levels freeze during expansion and exhaust strokes.
Unburned HC emissions from CI engines:
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The unburned hydrocarbons in the diesel
exhaustcome from fuel which escapes
combustion because it is:
- too lean to burn due to over-mixing with air
- too rich to burn because it did not mix with
enough air
mass HC which condense on the soot particlesThe
lubricating oil contributes high molecular
11. Combustion & Pollutants 33 AER 1304LG
in the exhaust and contribute to the particulates.
What is Particulate Matter?
Soot:- Carbonaceous particles produced through
gasphase combustion process
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Coke or cenospheres:
-
Carbonaceous particles
formed as a result of direct pyrolysis of liquid
hydrocarbon fuels
Particulate Matter (PM):
-
Particles that can be
collected on the probes
of measuring instruments such as filters
- Originate from a variety of sources
11. Combustion & Pollutants 35 AER 1304LG
Soot formation in combustion:
Conversion of a hydrocarbon fuel with
moleculescontaining a few carbon atoms into a
carbonaceous agglomerate containing some
millions of carbon atoms in a few milliseconds
11. Combustion & Pollutants 36 AER 1304LG
Transition from a gaseous to solid phase
Smallest
detectable solid particles are about 1.5
nm in diameter
(about 2000 amu)
mixed systems soot does not form unless theIt is an
artifact of diffusive combustion. In preequivalence
ratio is richer than 1.7-2.0
11. Combustion & Pollutants 37 AER 1304LG

11. Combustion & Pollutants 38 AER 1304LG
Combustion soot Soot/particulates
in gas turbine and diesel engines:
The soot particles form in the extremely fuel-rich
zones of the burning fuel spray as the fuel
molecules pyrolyze and break down and then form
increasingly higher molecular mass polycyclic
aromatics and polyacetylenes.
These eventually form nuclei for soot
particleswhich grow and agglomerate.
11. Combustion & Pollutants 39 AER 1304LG
within the combustion chamber (more than 90-95A
substantial fraction of the soot formed oxidizes
%).
Soot/particulates in gas turbine and diesel engines:
PM emissions from diesel engines and gas tur-
bines
consist of soot particles and volatile organics

(hydrocarbons and sulfates) absorbed into the
particles in the exhaust.
11. Combustion & Pollutants 40 AER 1304LG
Particles are agglomerates of 5 to 30 nm
diameterprimary soot particles. Aerodynamic
dimensions of agglomerates range from 10 to 1000
nm.
11. Combustion & Pollutants 41 AER 1304LG
as mass of matter that can be collected from aFor
regulatory purposes, PM emissions are defined
diluted exhaust stream on a filter kept at 52
o
C.
Reading Assignment
Study Chapter 15 in the Textbook