Pollutant Formation control

Pollutant sources and types

2 categories
1. Exhaust emission
2. Non- Exhaust emission

Exhaust emission

Unburnt hydrocarbons (HC)

Oxides of carbon (CO and CO2 )
Oxides of nitrogen (NO and NO2 )
Oxides of sulphur (SO2 and SO3 )
Particulates
Soot and smoke

NOx formation
What is NOX?
NOx = Oxides of Nitrogen which are produced by
combustion:
Nitric Oxide (NO)
Nitrogen Dioxide (NO2)
Nitrous Oxide (N2O)
Nitric Oxide (NO)
Highly reactive due to lone electron at N atom
Not particularly toxic
Major precursor of photochemical smog (NO NO2)
It is produced by most of combustion systems

Nitrogen Dioxide (NO2)

Brown, poisonous gas
Emissions of NO2 from most combustion < 10% of
NOX
Adverse health effects include: lung irritation,
bronchitis, pneumonia and a lowering respiratory
resistance
Ambient limit = 120ppb [NEPC, 1998]
Significant direct emissions of NO2 occur from
processes involving premixed flames:
- Indoor gas appliances (20-100% of NOx)
- Gas turbines yellow/brown plumes

Nitrous Oxide (N2O)

Relatively inert
Uses: Dental anaesthetic
Strong absorber of infrared radiation (~300 x CO2)
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)

chemical
reactions

combustion
activities

Sources of Nitrogen
Formation of NOX requires a source of nitrogen
Two sources of nitrogen:
a. Molecular nitrogen from air (1/2 N2 (from air) +1/2
O2 NO)
Thermal or Zeldovich Mechanism.
Prompt-Fenimore Mechanism (HC + N2).
Other minor mechanisms
b. Nitrogen chemically bound within fuel
Fuel NOx,
Most of NOx in the form of NO

Thermal NO
One of the most important issues for combustion
engineers is: 'What are my NOx emissions?'
In most cases, unusually high NOx emissions are due to
NO formed by the Thermal (Zeldovich) mechanism
Thermal NO mechanism involves the attack of molecular
nitrogen (N2) and atomic nitrogen (N) by oxygen (O2)
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:
N2 + O NO + N
(R.1)
N + O2 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
O2 concentration (the higher the oxygen conc, the
higher the NO formed) oxygen-rich
environment
Residence time

 HCN is subsequently oxidised to NO (see diagram)

Prompt mechanism dominates for hydrocarbon
combustion in fuel-rich, in both premixed and diffusion
flames

Prompt NO
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 H2 or CO as fuel
Mechanism involves the attack of N2 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 + N2 HCN + N (R.4)
C + N2 CN + N
(R.5)

Minor Mechanisms
1. N2O-Intermediate Mechanism:
It occurs under fuel-lean, low-temperature
conditions
Minor source of NO in most practical combustors
Mechanism is given by:
O + N2 + M N2O + M
(R.6)
O + N2O NO + NO
(R.7)
H + N2O NO + NH
(R.8)

2. NNH-Intermediate Mechanism:
It is observed under laboratory conditions
H2 and CH4 (high H) fuel-rich, laminar premixed
flames
Yet to be definitely observed in practical combustors
Mechanism is given by:
H + N2 NNH
(R.9)
NNH + O NO + NH
(R.10)

Fuel-NO
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

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, NH3 or
HNCO
These simple nitrogenous species then react in the
gas phase to form either NO, N2O or, under fuel-rich
conditions to N2 (see next slide)
Relative amounts of NO, N2O and N2 depends
strongly on the local O2 concentration during
pyrolysis and temperature

 NOX formation is reduced if volatiles are released

under fuel-rich conditions
Pulverised-fuel combustors - NOX control techniques
include: low-NOX burners, flue gas recirculation (fuellean) 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 N2 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