NITROGEN OXIDES FORMATION

in combustion processes

COMBUSTION AND FUELS

NITROGEN OXIDES FORMED DURING COMBUSTION

N2O - nitrous oxide

NO - nitric oxide
NO2 - nitrogen dioxide

N = 14, O2 =16, NO = 30, NO2= 46

COMBUSTION AND FUELS

 CONTRIBUTION OF PARTICULAR NITROGEN
OXIDES IN TOTAL NOX PRODUCTION

the biggest contribution has nitric oxide (NO)
 its content in flue gas is in the range of: 100 1000 mg/m3

next is nitrogen dioxide NO2 in proportion 5-10% of NO
 its content in flue gas is in the range of: 10 100 mg/m3

N2O has the least contribution:
 its content in flue gas is in the range of: 110 mg/m3

COMBUSTION AND FUELS

WHAT DOES NOX MEAN ?

COMBUSTION AND FUELS

 DEFINITION OF NOX

NOX means the sum of NO and NO2 contents

in flue gas recalculated on NO2

NOx = NO + NO2
(expressed in NO2)

COMBUSTION AND FUELS

UNITS OF NOX

COMBUSTION AND FUELS

 Units of NOx content in flue gas

mg/m3

ppm (emission)

g/m3 (imission)

g/GJ
Remarks:
1. The NOx content in flue gas is given for a certain content of
oxygen (O2) in flue gas.
2. The NOx content in flue gas is given for normal conditions.
3. ppm - unite part per million (x10-6)

COMBUSTION AND FUELS

NOX emissions conversion chart
ppm:
NOx [ppm] = NO [ppm] + NO2 [ppm]

ppm mg/m3
NO [mg/m3] = 1.3387 NO [ppm]
NOx [mg/m3] = 2.0525 NOx [ppm]

mg/m3 GJ (dla NOx)

1 g/GJ = 2.7 [mg/m3] for bituminous coal
1 g/GJ = 2.35 [mg/m3] for lignite

COMBUSTION AND FUELS

NOX emission units which are in use in the power
generation industry

In Poland (and in EU) NOx is expressed as

follows:
[mg NO2/m3]
for 6% O2 in dry flue gas
at normal conditions

COMBUSTION AND FUELS

 NOX FORMATION
IN
COMBUSTION PROCESSES

COMBUSTION AND FUELS

COMBUSTION CHEMISTRY OF NITROGEN OXIDES

The chemical mechanism of NOx (NO and NO2)

formation during combustion obeys hundreds of
elementary chemical reactions.
Depending on the temperature range, stoichiometric
ratio and type of nitrous species present in the combustion
zone, it is possible to distinguish predominant groups of
chemical reactions, which are called the mechanisms of
nitrogen oxides formation.
Usually the type of flame determines the conditions
of the predominant mechanism of NOx formation.

COMBUSTION AND FUELS

MAJOR SOURCES OF NOX FORMATION DURING
COMBUSTION
1. Air nitrogen (N2)

thermal NOx

prompt NOx

2. Fuel nitrogen (NF)

fuel NOx

COMBUSTION AND FUELS

MAJOR MECHANISMS OF NITRIC OXIDE (NO)
FORMATION DURING COMBUSTION

Thermal

Prompt

Fuel

COMBUSTION AND FUELS

THERMAL NITRIC OXIDE
MECHANISM

COMBUSTION AND FUELS

ZELDOVICHs MECHANISM OF NO FORMATION
O2 + M = O + O + M (3) (dissociation)
Where M is stable molecule of high energy necessary to break
the bounds of O2 [10].
The liberated O atoms can react with N2 through a relatively
slow reaction:

O + N2 NO + N, (4)
the N atoms liberated in this reaction quickly react with O2

N + O2 NO + O (5)
also giving NO.

COMBUSTION AND FUELS

 RATE OF NOX FORMATION via ZELDOVICH MECHANISM
Rate of NOx formation by thermal mechanism
d[NO]/dt = kp[O2]1/2[N2]
where kp 2K31/2k2, which is in accord with the experimental.

50000 1,0E+05

czas do 0,5 [NO]r, s

40000 1,0E+03
[NO]r, ppm

30000 1,0E+01
Equilibrium concentration of
20000 1,0E-01 NO, [NO]r, and time to reach
0,5[NO]r versus the temperature
10000 1,0E-03

0 1,0E-05
1000 1500 2000 2500 3000
T, K

It shows that the Zeldovich mechanism becomes important when the temperature reaches the
range of 1600-1800 K. COMBUSTION AND FUELS
PROMPT NITRIC OXIDE
MECHANISM

COMBUSTION AND FUELS

REACTIONS OF HYDROCARBON RADICALS
WITH N2
There are many hydrocarbon radicals in flame (CH, CH2, CH3, C2H4, C2H5,
C3H7, C, C2...), which can react with molecular nitrogen (N2).

CH2 + N2 HCN + NH
CH + N2 HCN + N
C + N2 CN + N
general
CHx + N2 HCN and other radicals (CN, NH, N...)

As a result: HCN, NH i CN are easily oxidized to NO in flame.

COMBUSTION AND FUELS

FUEL NITRIC OXIDE
MECHANISM

COMBUSTION AND FUELS

WHAT IS A SOURCE OF FUEL NITRIC OXIDE

1. The source of fuel NO are nitric compounds in fuel, often

called fuel nitrogen (denoted NF).

2. The content of fuel nitrogen in fuels is very different!!!!

3. Fuel nitrogen can be a very important source of nitric

oxides.

COMBUSTION AND FUELS

FUEL NITROGEN (NF) IN FUELS

COMBUSTION AND FUELS

 FUEL NITROGEN IN GAS

Natural gas practically doesnt have

fuel nitrogen.

COMBUSTION AND FUELS

 FUEL NITROGEN IN LIQUID FUELS

Crude oil has fuel nitrogen in the range of

0.01 do 0.3% wt.

Only exceptionally NF content excess 0.9%.
Major groups of nitric compounds are: pyridyne, indoles, chinolines,
tetrahydrochinolines, carbazoles i pyroles.

Nitric compounds in oil are relatively stable in the elevated temperature,

therefore during crude oil destillation they are cumulated in heavy
fractions of oil. For example, the content of NF in asphaltes reaches 1.5%.

COMBUSTION AND FUELS

 FUEL NITROGEN IN HEATING OILS
Content, %
Wd Va, min Tcomb
Fuel
MJ/kg m3/kg C
C H S N O

Gas 85 15
47 11,57 2263

Heating oil 86,4 12,5 0,05 0.05 1 45,2 11,18 2258

1
Heating oil 85,5 13 0,4 0.3 0,8 43,6 11,96 2210
2
Heating oil 87 11,4 0,5 0.6 0,3 43,1 10,74 2262
3

COMBUSTION AND FUELS

THE INFLUENCE OF NF CONTENT ON NOX EMISSION

COMBUSTION AND FUELS

 FUEL NITROGEN IN COAL
The origin of fuel nitrogen in coal is organic material of coal, these
are vegetables, bacteria and fungi containing amines, alkaloid and
chlorophyll being source of nitrogen.

NF in different coals:
Bituminous coal: 0.6 - 2.8% N (85% C)
Anthracite <1% N
Lignite: 0.6 - 2% N.

COMBUSTION AND FUELS

SELECTED NITRIC COMPOUNDS IN COAL

COMBUSTION AND FUELS

Major nitric compounds in coal

COMBUSTION AND FUELS

 CONVERSION OF
FUEL NITROGEN
DURING COAL COMBUSTION

COMBUSTION AND FUELS

CONVERSION OF FUEL NITROGEN DURING
COAL PARTICLE BURNING

Pirolysis Rapid Slow burning

combustion of char
of v.m.

Coal
particle

Products: Conversion of v.m. into Gasification of char, releasing of: CO, CO2,
HCN, NH3, tar, CO, CO2, H2O, N2, N2, N2O, NO etc.; reduction of NO on the
aromatic compounds N2O, NO etc. surface and in the pores of char

COMBUSTION AND FUELS

EVALUATION OF FUEL NITROGEN DURING
COAL PYROLYSIS

COMBUSTION AND FUELS

 NITRIC OXIDE FORMATION
DURING COAL COMBUSTION

COMBUSTION AND FUELS

FUEL NITRIC OXIDE FORMATION DURING
COAL COMBUSTION
OH, O, O2 C(s)
NH3 NO N2
nitrogen in
volatile matter
nitrogen in C(s)
N, czci lotne char residue N koks.

OH, O, O2
nitrogen in fuel HCN NO
2

N paliwowy
nitrogen in
char residue N koks.

O2
N poz. koks. NO
nitrogen in
char residue

COMBUSTION AND FUELS

CONVERSION OF GAS-PHASE FUELN TO NO

COMBUSTION AND FUELS

CONVERSION OF CHAR FUELN TO NO

COMBUSTION AND FUELS

NITRIC OXIDE REDUCTION ON CHAR

COMBUSTION AND FUELS

NITROGEN DIOXIDE (NO2)
FORMATION IN FLAMES

COMBUSTION AND FUELS

CONDITIONS OF NITROGEN DIOXIDE (NO2)
FORMATION IN FLAMES

NO2 is a secondary product, and is formed by oxidation
of NO in combustion processes.

NO2 is formed in cooler regions of flame, in the
temperature range of:

T < 800 C

NO2 undergoes destruction on tat higher temperatures:

T > 1200 C

COMBUSTION AND FUELS

BASIC MECHANISM OF NITROGEN DIOXIDE
(NO2) FORMATION IN FLAMES

The major reaction of NO2 formation is with
hydroperoxide radical HO2 :

NO + HO2 NO2 + OH
(where from HO2: H + O2 + M HO2 + M)

The temperature range of this reaction:

T < 1000 K

COMBUSTION AND FUELS

 ADDITIONAL MECHANISM OF NO2
FORMATION

Hydrocarbonperoxides RO2 plays a considerable part in
NO2 formation:

NO + RO2 NO2 + RO
(where from RO2: R + O2 + M ROO + M)

where R are alkil radicals:

CH3, C2H5 and higher

COMBUSTION AND FUELS
 NITROGEN DIOXIDE FORMATION IN
REACTION WITH ATOMIC OXYGEN

The three body reaction:

NO + O + M NO2 +M
NO2 also is generated, but the contribution of this
reaction is not important.
The temperature range: T < 800 K.

COMBUSTION AND FUELS

CONTRIBUTION OF NITROGEN DIOXIDE NO2
TO THE TOTAL NOX

The NO2 contribution to the total NOx formation during
pulverized coal combustion is minor:

[NO2]/[NOx]100% 5%

More important contribution to the total production of
NOx NO2 introduces during combustion in gas turbines:

[NO2]/[NOx]100% 10-15%
COMBUSTION AND FUELS
 NITROUS OXIDE (N2O)
FORMATION IN FLAMES

COMBUSTION AND FUELS

 CONDITIONS OF NITROUS OXIDE (N2O)
FORMATION

NO2 is produced in flames due to:

1. Oxidation of amine radicals (mainly Nhand

less significant CN2).

2. In lean regions of gas flames.

3. In fluidized bed furnaces (T approx. 850 C)

COMBUSTION AND FUELS

MAJOR SOURCES OF NIROUS OXIDE N2O
IN FLAMES
Major reaction

NH + NO N2O + H

NH amine radical

Where is from NH? Mainly, from decomposition of

ammonia (NH3, perhaps also hydrogen cyjanide (HCN).

COMBUSTION AND FUELS

NIROUS OXIDE N2O FORMATION IN LEAN
FLAMES (<1)

O + N 2 + M N 2O + M
The temperature range of the chemical reaction:

T < 1500 C

COMBUSTION AND FUELS

 NIROUS OXIDE N2O FORMATION IN
FLUIDIZED BEDS
In catalytic reaction:

2NO N2O + 0.5O2

Catalysts in fluidized bed:

1. char

2. Limestone

COMBUSTION AND FUELS

HOW IMPORTANT IS NITROUS OXIDE N2O?

N2O is known is the as laughing gas.

N2O has contribution to the stratospheric ozone destruction

In combustion processes N2O is formed mainly in fluidized
beds (N2O content in flue gas up to 50 ppm).

N2O has also some contribution to NO emission, by chemical
reactions with radicals O i OH:

N2O + O NO + NO

COMBUSTION AND FUELS

DOMINATING MECHANISMS
OF NOx IN FLAMES

COMBUSTION AND FUELS

MAJOR FACTORS INFLUENCING NOx
FORMATION

fuel nitrogen NF

flame temperature

air excess ()

residence time in flame

COMBUSTION AND FUELS

NOX FORMATION IN PULVERIZED COAL
FLAME

COMBUSTION AND FUELS

SOURCES OF NOX EMISSION IN PULVERIZED
COAL FLAME

COMBUSTION AND FUELS

 CONTRIBUTION OF PARTICULAR NITRIC
OXIDES IN TOTAL NOX EMISSION FROM PF
Fuel NOx is dominating NOx

lN O
tota
O
m al N
the
r
Bituminous coal (Tp = 1650 C)

volatile matter NO

Lignite (Tflame = 1250 C):

approx.95% of NOx is fuel NOx
NO from char

COMBUSTION AND FUELS

NOx EMISSION vs. FURNACE TYPE (PF BOILERS)

Power NOx
Furnace type Coal type
MWe mg/m3

Tangencial 650750 bituminous 71060

Tangencial 465490 bituminous 7501000
Tangencial 200360 bituminous 500900
Wall fired 425460 bituminous 1360110
FBB 110 bituminous 40080
FBB 160 bituminous 52080
FBB 230 lignite 280 50

COMBUSTION AND FUELS

 OIL FLAMES
Heavy heating oil has much of fuel nitrogen NF > 0,5%.
NOx emission from oil burners operating on heating oils nr 2 and 3 is in
the range:

300-700 mg/m3
(mainly fuel NOx).
Fuel nitrogen NF is a dominating factor.

Light heating oil has less fuel nitrogen NF < 0,05%

NOx emission form oil burners operating on light heating oil (nr 1) is in
the range:

180-220 mg/m3
(mainly thermal NOx).
COMBUSTION AND FUELS
 GAS FLAMES
No fuel nitrogen NF in gas.
Industrial gas burners (flames).

Range of NOx emission: 100-300 mg/m3

Dominating mechanism: thermal

Small gas burners (flames):

Range of NOx emission: 10-100 mg/m3

Dominating mechanism: thermal + prompt (20%)

COMBUSTION AND FUELS