What are the main NOx formation

processes in combustion plant?

A Combustion File downloaded from the IFRF Online Combustion Handbook

ISSN 1607-9116
Combustion File No: 66
Version No: 1
Date: 10-Dec-01
Author(s): Gerry Hesselmann and Marta Rivas
Source(s): See CF
Referee(s): Mikko Hupa
Status: Approved
Sponsor: Mitsui Babcock Energy Ltd - MBEL

1. Background
In order to present a clear background to the continuously developing range of Nitrogen
Oxides (NOx) control techniques and equipment, it is essential to understand NOx
formation chemistry.
There are a number of nitrogen oxides, but only three of these are of interest for
combustion processes:
Nitrogen monoxide, or nitric oxide, NO
Nitrogen dioxide, NO2
Di-nitrogen oxide, or nitrous oxide, or "laughing gas", N2O
The first two, NO and NO2 are collectively referred to as NOx and they are essential
contributors to the acid rain or smog problems.
The NOx content in the combustion gases from conventional power plant boilers and
many industrial heating process contains some 90 % NO with the remainder NO2.
The third oxide, N2O, is found in flue gases from, among others, Fluidised bed
combustors, and from engine exhaust gases after the catalytic converting system.
N2O is not an acidic oxide, and is normally not included in the abbreviation NOx.
However, N2O is a gas, which contributes to the destruction of the stratospheric ozone.
This Combustion File gives a brief overview on this subject and gives a platform for
more detailed Combustion Files both on NOx formation and reduction chemistry.
There are basically three recognized mechanism on NOx formation Thermal, Fuel and
Prompt. These are outlined below.
2. Thermal NOx formation
Thermal NOx is produced by the reaction of atmospheric oxygen and nitrogen at
elevated temperatures, and is reputed to contribute about 20% of the total NOx
emission in pulverised coal firing, but is the dominant mechanism when the fuel contains
little or no inherent nitrogen (i.e. gas firing). Where high air preheat temperatures are
employed, for example in cement kilns, thermal NOx can also contribute considerably to
the overall NOx emission.
The reactions are described by the Zeldovich mechanism as follows:
N2 + O = NO + N .(1)
N + O2 = NO + O .(2)
N + OH = NO + H .(3)
The first step is rate limiting, and due to its high activation energy (314 KJ/mol)
requires high temperatures to proceed. Reaction (3) is only significant under reducing
conditions.
By kinetic analysis it is possible to derive an overall expression for the rate of thermal
NOx formation (Bowman, 1975), viz:

d [NOx ] 6.0 x10

16
69090
[N 2] [O 2]
0.5
= exp (4)
dt T 0.5 T
Where T = absolute temperature (K)
[N2], [O2] = concentration of nitrogen, oxygen (mol/cm3)
d[NOx]/dt = rate of NOx formation (mol/cm3/s)
In practise the control/minimisation of thermal NOx is accomplished primarily by
measures, which reduce temperature, but dilution of the available oxygen is also
beneficial.

3. Fuel NOx formation

Fuel NOx arises from the reaction of the organically bound nitrogen in the fuel with
oxygen. The process is complex (reaction schemes typically consider of the order of 50
intermediate species and several hundred separate reversible reactions, and there is
still considerable uncertainty as to the true value of the various rate constants, etc.),
but can be simply expressed as follows:
ii) Volatile fuel nitrogen is evolved mainly as HCN (and NH3) during the processes.
iii) The HCN reacts with various free radical species (O, OH) to form intermediates
such as CN, NCO, HNCO and ultimately with reaction with H to produce NH,
NH2.
Fuel NOx can be most effectively minimised by burning the fuel by staged combustion,
which implies delayed mixing between the fuel gas and air.
4. Prompt NOx formation
Prompt NOx is formed by the reaction of hydrocarbon radicals with atmospheric
nitrogen to produce HCN and hence NOx via a complex series of gas phase reactions.
The contribution of the prompt NOx to the total emission in pulverised coal combustion
is small (about 5%). Measures, which are effective in minimising thermal and fuel NOx,
are also effective in minimising prompt NOx.

Glossary terms
Nitrogen Oxides (NOx) Gaseous atmospheric pollutant Mixture of oxides of Nitrogen
comprising NO and NO2

Keywords
combustion; emissions, NOx formation reactions, NOx control; fuel NOx; nitrogen oxides
NOx; prompt NOx; thermal NOx.

Related Combustion Files

CF56 What are the available NOx control technologies for fossil fuel fired utility
boilers based on combustion modification?
CF127 What is the current status of low NOx burners for fossil fuel wall fired utility
boilers?
CF126 What are the general principles of low NOx burner design for fossil fuel fired
utility boilers?

Sources
[1] Bowman CT, Kinetics of Pollutant Formation and Destruction on Combustion, Prog
Energy Combust Sci 1 33-45, (1975).
[2] Beltagui SA, Kenbar AMA & McCallum NRL, NOx Generation and Control in Confined
Swirling Flames Review and Parametric Study, HTFS Paper No RS 827, (1989)

Acknowledgements
None

File Placing
[Emissions] [NOx] [Formation]
[Modelling]; [Mathematical]; [Emissions]
[Basics]; [Chemistry]; [Nitrogen Oxides]

Access Domain
[Open Domain]
The information contained in this Combustion File is derived from the IFRF Combustion
Handbook (http://www.handbook.ifrf.net)
IFRF 1999 - 2001