Pollutant Formation in

Combustion Systems
Pollutant Formation in Combustion Systems
NO
x
Formation
Thermal NO
x
Prompt NO
x
Fuel NO
x
Carbon Monoxide (CO)
Volatile Organic Compounds (VOC)
Polycyclic Aromatic Hydrocarbons (PAH), Soot and
Submicron Particulates (solid-phase pollutants)
Sulphur Compounds
NOx formation
What is NO
X
?
NO
x
= Oxides of Nitrogen which are produced by
combustion:
Nitric Oxide (NO)
Nitrogen Dioxide (NO
2
)
Nitrous Oxide (N
2
O)

Nitric Oxide (NO)
Highly reactive due to lone electron at N atom
Not particularly toxic
Major precursor of photochemical smog (NO NO
2
)
It is produced by most of combustion systems
Nitrogen Dioxide (NO
2
)
Brown, poisonous gas
Emissions of NO
2
from most combustion < 10% of
NO
X
Adverse health effects include: lung irritation,
bronchitis, pneumonia and a lowering respiratory
resistance
Ambient limit = 120ppb [NEPC, 1998]
Significant direct emissions of NO
2
occur from
processes involving premixed flames:
- Indoor gas appliances (20-100% of NO
x
)
- Gas turbines yellow/brown plumes
Nitrous Oxide (N
2
O)
Relatively inert
Uses: Dental anaesthetic
Strong absorber of infrared radiation (~300 x CO
2
)
Stability = long atmospheric residence times (~150
yrs)
Hence, potentially significant greenhouse gas
Long life-time also allows its transportation into
stratosphere and participates in ozone depletion
Only significant from low-temperature processes (eg.
Fluidised bed combustion)
combustion
activities
chemical
reactions
Sources of Nitrogen
Formation of NO
X
requires a source of nitrogen
Two sources of nitrogen:
a. Molecular nitrogen from air (1/2 N
2
(from air) +1/2
O
2
NO)
Thermal or Zeldovich Mechanism.
Prompt-Fenimore Mechanism (HC + N
2
).
Other minor mechanisms
b. Nitrogen chemically bound within fuel
Fuel NO
x
,
Most of NO
x
in the form of NO
Thermal NO
One of the most important issues for combustion
engineers is: 'What are my NO
x
emissions?'
In most cases, unusually high NO
x
emissions are due to
NO formed by the Thermal (Zeldovich) mechanism
Thermal NO mechanism involves the attack of molecular
nitrogen (N
2
) and atomic nitrogen (N) by oxygen (O
2
)
and oxygen-containing radicals (O, OH). This can occurs
in oxygen rich mixture.
First identified by Zeldovich (1946) and extended by
Fenimore and Jones (1957)
Described by the following reactions:
N
2
+ O NO + N (R.1)
N + O
2
NO+O (R.2)
N + OH NO + H (R.3)
Westenberg (1971) invoked the steady-state
approximation and determined that the maximum NO
formation rate is given by:


Hence, [NO] depends on:
Temperature (the higher the temp, strongly the
higher the NO formed) high temp environment
O
2
concentration (the higher the oxygen conc, the
higher the NO formed) oxygen-rich
environment
Residence time
| |
( )
| | | |
1/ 2
17 1/ 2 3
2 2
69460
1.45 10 exp . . / .
eq eq
d NO
x T O N mol cm s
dt T K

=
(
(

Fenimore (1971) observed an additional formation of
NO which could not be explained by the thermal
mechanism
NO formed close to the burner (hence - "prompt' NO)
Effect is not observed under very fuel-lean conditions
or in systems with H
2
or CO as fuel
Mechanism involves the attack of N
2
by hydrocarbon
fuel fragments, mainly CH radicals and C-atoms.
The Prompt-Fenimore mechanism is initiated mainly
by R.4 (the formation of HCN) with a lesser
contribution from R.5:
CH + N
2
HCN + N (R.4)
C + N
2
CN + N (R.5)
Prompt NO
HCN is subsequently oxidised to NO (see diagram)
Prompt mechanism dominates for hydrocarbon
combustion in fuel-rich, in both premixed and diffusion
flames

Minor Mechanisms
1. N
2
O-Intermediate Mechanism:
It occurs under fuel-lean, low-temperature conditions
Minor source of NO in most practical combustors
Mechanism is given by:
O + N
2
+ M N
2
O + M (R.6)
O + N
2
O NO + NO (R.7)
H + N
2
O NO + NH (R.8)
2. NNH-Intermediate Mechanism:
It is observed under laboratory conditions
H
2
and CH
4
(high H) fuel-rich, laminar premixed
flames
Yet to be definitely observed in practical combustors
Mechanism is given by:
H + N
2
NNH (R.9)
NNH + O NO + NH (R.10)
1. The Nature of Fuel-Nitrogen:
Nitrogen in coal (and oil) originates in the plant
material from which the fuel is formed

Plants contain nitrogen in the form of proteins, amino
acids, alkaloids, chlorophyll and porphyrins

These were transformed, during the coalification
process, into polycyclic aromatic compounds with
pyridinic, pyrrolic or other functional groups

Nitrogen content of coals typically vary between
1-2.5 wt% and is largely independent of rank
Fuel-NO
2. Coal Combustion and the Release of Fuel-Nitrogen:
First stage of coal combustion is rapid devolatilisation
of the coal
Devolatilisation: volatile components such as light
hydrocarbons and tars are released and then oxidised in
the gas~phase at very short timescales (< 10 ms)
The solid product of coal pyrolysis is the char which is
oxidised at much slower timescales (~ 1s)
Fuel-nitrogen is released during both pyrolysis and char
combustion but in very different ways
Partitioning of fuel-nitrogen between the volatiles and
char depends on pyrolysis conditions (normally approx.
equal)
3. Nitrogen released with the volatiles:
Nitrogen contained within the volatiles is released as,
or rapidly converted to compounds such HCN, NH
3

or HNCO
These simple nitrogenous species then react in the gas
phase to form either NO, N
2
O or, under fuel-rich
conditions to N
2
(see next slide)
Relative amounts of NO, N
2
O and N
2
depends
strongly on the local O
2
concentration during
pyrolysis and temperature
NO
X
formation is reduced if volatiles are released
under fuel-rich conditions
Pulverised-fuel combustors - NO
X
control techniques
include: low-NO
X
burners, flue gas recirculation
(fuel-lean) and air staging
NO emissions are reduced in these techniques by
changes in stoichiometry and/or temperature near the
burner thus reducing both volatile-NO and
thermal-NO (important to take into account in
combustion)
4. Char combustion and the Fate of Char-Nitrogen:
The fate of char-nitrogen is still leading edge research
Primary product of char-N oxidation is NO
However, both HCN and HNCO are observed at low
temperatures (Ashman et al., 2000)
NO may be reduced to N
2
by direct reaction with the
char surface or by a char-catalysed reaction with CO
Effective techniques aimed specifically at controlling
char-NO are not available
5. In principle, NOx is reduced if it is reacted with C or
CxHy concept of reburn
Summary of NOx Formation
References
Ashman, P1, Haynes, B.S., Nicholls, P.M. and
Nelson, P.F. (2000). Interactions of gaseous NO with
char during the low temperature oxidation of coal
chars. 28th Symp. (Int.) on Combustion,
Bowman, C.T. (1992). Conrol of combustion-
generated nitrogen oxide emissions: technology
driven by regulation, 24th Symp. (Int.) on
Combustion, The Combustion Institute, pp 859-878.
Fenimore, C.P. (1971). Formation of nitric oxide in
premixed hdrocarbon fames. 13th Symp. (Int.) on
Combustion, The Combustion Institute, pp 373-379.
Fenimore. C.P. and Jones, G.W. (1957). The water
catalysed oxidation of carbon monoxide by oxygen at
high temperatures. J. Phys. Chem, 61, pp 651-654.
Pershing, D.W. and Wendt, LO.L. (1976). Pulverized
coal combustion: the influence of flame temperature
and coal composition on thermal and fuel NOx, 16th
Symp. (Int.) on Combustion, The Combustion
Institute, pp 389-399.
Westenberg, A.A. (1971). Kinetics of NO and CO in
lean premixed hydrocarbon air flames, Combust. Sci.
Technol., 4, pp 59-64.
Zeldovich, Ya.B. (1946). The Oxidation of nitrogen
in combustion explosions. Acta Physiochimica,
USSR, 21, pp 577-628.
Further Reading
Turns, S.R. (1996). "An Introduction to combustion
concepts and applications", McGraw-Hill, Chapter 15
and pp143-146 (1st Edition)
Borman, G.L. and Ragland, KM. (1998).
"Combustion Engineering", WCB/McGraw-Hill, pp
125-138
Wendt, LO.L. (1995). Combust. Sci. Tech., 108, pp
323-344
van der Lans, R.P., Glarborg, P. and Darn-Johansen,
K. (1997). Prog. Energy Combust. Sci., 23, pp
349-377
All hydrocarbon fuels are converted to CO
2
via CO
CH
4
CH
3
CH
2
O CHO CO CO
2
Conversion of CO to CO
2
occurs largely downstream
of the flame-zone and is an equilibrium process
which occurs relatively slowly
Emission of CO as a stable product is minimised if
CO CO
2
is allowed to proceed to completion
There are 3 processes leading to incomplete
combustion:
Insufficient Oxygen (low O
2
)
Aerodynamic Quenching (low temp)
Impingement Quenching (low temp)
CO (carbon monoxide) formation
1. Insufficient Oxygen
In this case, there is simply not enough O
2
present in
the downstream gases to fully oxidise the CO to CO
2
Usually as a result of poor design or operation and, in
flames, often related to inadequate mixing of
secondary air
2. Aerodynamic Quenching
Caused by a rapid decrease in the temperature of the
postflame gases, either by expansion of the gases or
by mixing with ambient air
Rapid decrease in temperature results in kinetic
"freezing" of the CO at the equilibrium condition
Aerodynamic quenching is a serious problern for
spark-ignition engine when too much air used (not
really for open-flame systems)
3. Impingement Quenching
Quenching occurs as a result of the hot postflame
gases impinging on a relatively cold surface
Again, a problem in internal combustion engines
CO Toxicity
Balance between CO and NO
We have seen that CO is largely a product of
insufficient combustion (low O
2
, rapid cooling, etc)
In comparison, the formation of NO which is
enhanced by conditions which could be termed as
over-aggressive combustion (high O
2
, high temp, etc)
There is a fine balance between the formation of NO
and CO such that control measures which are
effective against one species often result in an
increase in the other species
Fortunately, the two mechanisms are decoupled
somewhat since NO formation occurs primarily in the
near-burner zone and CO consumption occurs in the
postflame gases.
Volatile Organic Compounds (VOCs)
Volatile organic compounds (VOC's) are also
products of incomplete combustion
VOC consist of various unburned fuel fragments,
aliphatic and aromatic hydrocarbons and partially
oxidised fuel fragments
The formation and destruction of VOC's occurs much
closer to the flame front (higher temp zone) than does
CO and hence greater extents of incomplete
combustion cause the emission of VOC's
VOC's play a key role in photochemical smog cycles
(reactions in atmosphere triggered by photon of the
sunray)
PAH's, Soot & PM10 (solid phase pollutants)
What are PAH's, Soot & PM10?
PAH's (polycyclic aromatic hydrocarbons) are
clusters of aromatic rings up to about 4 rings in size.
Soot is formed when, under appropriate conditions,
PAH's grow in size until they reach approximately
20-50 nm
PM10 is a general term given to all air-borne
particulates which have a size < 10 microns
PAH's (polycyclic aromatic hydrocarbons):
PAH's are formed in, and may be emitted from,
combustion processes under very fuel-rich conditions
The main cause of concern with PAH's is that many
species are known mutagens, co-carcinogens, or
carcinogens
While PAH's are oxidised quite rapidly in the urban
atmosphere, they may be stabilised considerably by
adsorption to the surface of particulate (e.g. soot)
PAH's then become quite long-lived and are capable
of penetrating deep into the human lungs
Soot:
The health effects of soot are serious and are related
to the transport of fine particles within the lungs
PM10 is the environmental standard used to quantify
airborne particulates from all sources
Soot particles also contribute to visible pollution and
haze within the urban environment
Soot formation is encouraged within some
combustion applications on the basis of the
significantly enhanced radiative heat transfer obtained
from sooting flames
PAH & Soot Formation:
PAH's and soot are formed mainly in diffusion flames
and in diesel engines (also from I.C. engines with
lubricant oil leakage)
A precursor species (believed to be acetylene) is
formed under fuel-rich conditions
Acetylene and other hydrocarbon fragments combine
through pyrolytic (without oxygen) reactions to form
progressively larger ring structures (PAH's)
Without competition with oxidation reactions, which
break ring structures, the clusters continue to increase
in size
Small particles of a critical size are formed by the
growth of these aromatic clusters by both chemical
and physical means, i.e. coagulation
At this point, the molecules are identifiable as
primary soot particles
The soot particles continue to grow by both chemical
(surface growth) and physical (particle
agglomeration) processes whilst they remain within
the bath of precursor species, clusters and adolescent
soot particles
Sulphur Compounds
All of the sulphur contained within various fuels is
emitted from combustion processes as either SO
2
or
SO
3
The ultimate fate of oxides of sulphur in the
environment is transformation to H
2
SO
4
(acid rain)
Only two possible abatement procedures:
remove S before combustion (from the fuel)
remove SO
X
after combustion (from the flue
gases)
Most common technique is the reaction of SO
2
in the
flue gas with limestone (CaCO
3
) or lime (CaO)
A slurry of limestone or lime is sprayed in an aqueous
absorption tower through which the flue gas is passed
References
Muzio, L.J. and Quartucy, G.C. (1997).
Implementing NOx control: Research to Application,
Prog. Energy Cornbust. Sci., 23, pp 233-266.
Wendt, LO.L. (1995). Mechanisms governing the
formation and destruction of NO
x
and other
nitrogenous species in low NO
x
Coal Combustion
Systems, Combust. Sci. Tech., 108, pp 323-344

Further Reading
Turns, S.R. (1996). "An Introduction to combustion
concepts and applications", McGraw-Hill, chapter 15,
pp 291-293 and ppl43-146 (1
st
Edition)
Borman, G.L. and Ragland, KM. (1998).
"Combustion Engineering", WBIMcGraw-Hill, pp
125-138 and pp 413-421
Wendt, J.0.L. (1995). Combust. Sci. Tech., 108, pp
323-344
van der Lans, R.P., Glarborg, P. and Darn-Johansen,
K. (1997). Prog. Energy Combust. Sci., 23, pp
349-377