Nitrogen oxide chemistry in

combustion processes

Mikko Hupa
 Background - NOx

• Nitrogen oxides, ”NOX” = NO + NO2

• In combustion flue gases >95% NO and <5% NO2
• NO2 formed via NO
• In the atmosphere NO reacts to NO2, and further to
compounds such as HNO3 and nitrates (acidification)
• NO2 + hydrocarbons → photochemical ”smog”

• In some special cases also emissions of N2O

 Background – NOx (ii)

• In some special cases also emissions of N2O

• N2O stable in the atmosphere – not part of the
acidification
• However, N2O is green-house gas and upper
atmosphere ozone destructor

• Nitrogen oxide chemistry in combustion complicated

– and fascinating!
Emissions are expressed in a
variety of units – be aware!

100 ppm (3 % O2)

= 72 ppm (8 % O2)
= 83 ppm (8 % O2, dry gas)
= 237 mg NO2/m3 (3 % O2, dry)
= 71 mg NO2/MJ (LHV)
= 0.104 gr/DSCF (3 % O2, dry)
= 0.00116 gr/BTU (LHV)
 Background
-Nitrogen oxide emissions from various combustion
processes without reduction measures

(Hupa et al.)
 Nitrogen oxide chemistry in combustion
processes – Terms and concepts

• Chemical equilibrium and NO

• Thermal-NO (Zeldowich NO) and kinetics
• Fuel-NO
• Volatile-NO – HCN, NH3
• Char-NO
• Staged Combustion: Low Nox Technologies
• NO formation tendency characterization
• (NO chemistry in fluidised bed combustion)
Nitrogen species in a typical flue gas
under chemical equilibrium conditions
Temperature Temperature
Equilibrium concentration
Nitrogen species in a typical flue gas
under chemical equilibrium conditions

• Most abundant ones

λ=1.1: N2, NO, NO2, N2O
λ=0.9: N2,HCN, NH3
• Equilibrium conc. of NOx decreases with temp.:
data from flue gas with λ=1.1:
T=1800 K 1200 ppm
T=500 K <1ppm
NO – Chemical equilibrium vs. Kinetics
Schematic view of NO formation in a boiler
Time

NO concentration

Equilibrium concentration
(λ=1.1)

Typical measured
concentration

Furnace Superheaters
Temperature
 Nitrogen chemistry in boilers

• At equilibrium: high temperatures -> high NO, low temperatures ->

no NO
• Formation of NO determined by kinetics – not equilibrium
• Decomposition at lower temperatures kinetically ”frozen”
• Great variations in NO emissions. Which factors influence NO-
formation kinetics?
• Major research activities to understand mechanisms of NO formation
since 1970’s
• NO emissions brought detailed chemistry into combustion engineering
 Thermal-NO (i)

• NO formed from N2 in combustion air

• Direct reaction N2 + O2 → 2NO
very slow even at high temperatures (N2
• Zeldowich (1946): atomic oxygen needed to react with N2:
O + N2 → NO + N (1)
• The N atom reacts further to yield a second NO
N + O2 → NO + O (2)
• d(NO)/dt = k1 · (O) · (N2)
 Thermal-NO (ii)
O + N2 → NO + N (1)
Kinetic rate to this reaction:
d(NO)/dt = k1 · (O) · (N2)
Conc. of atomic oxygen significant only at high temp.:
O2 = 2 O
K = (O)2/(O2)
 (O) = K1/2 · (O2)1/2

 d(NO)/dt = k1 · K1/2 · (O2)1/2 · (N2)

K and k strongly dependent on temperature
Thermal-NO (iii)
Estimated rates of thermal-NO formation
10-3 1000

atm/s ppm/s

10-4 100

10-5 10

10-6 1
1700 1800 1900 2000 2100 K
Temperature
 Thermal NOx - Summary

• Molecular nitrogen in air reacts to form NO

• Reaction kinetically possible with atomic
oxygen
• Significant only if T > 1400 C
• Formation steeply dependent on temperature
• Main contributor to NO formation in gasolin
engines and gas combustion systems
 Fuel-NO:

Gradual Exploration of the Mechanisms

Fuel NOx – Fuel Oil with Organic Nitrogen Addition

NO concentration (λ=1.0)
Oil + pyridine
(0.5% N)

Pure Oil
(<0.01% N)

Air factor λ
Based on Martin and Berkan, Air pollution and its control,
AICHE symp. Series 68, Nr 126, 45, 1972
 Fuel-NO
Amines
• NO formed from N in fuel
• Fuel-N organically bound - reactive Pyridine Pyrrole Quinoline

• Until the 1970’s fuel-N was not

considered a source of NO

(1 (2

(3

1) Calculated as CaO
2) Calculated as Na
3) Not organic-N, but molecular-N, N2
NO formation – Fuel Oil Containing N

Thermal
N2 NO

N2
NO
Nfuel Nvol
Ntar HCN
NH3
N2
NO formation – Fuel Oil Containing N

Thermal
N2 NO
Which
one is
more
N2 important?
NO
Nfuel Nvol
Ntar HCN
NH3
N2
Thermal-NO vs. Fuel-NO in Oil Firing

NO concentration
Air

Thermal-NO

Ar+CO2+O2

Fuel-NO

Air factor λ
When burning heavy fuel oil or pulverized coal.
Based on
- Pershing et al., Influence of design variables on the production of thermal and fuel
NO from residual oil and coal combustion, 66th annual AICHE Meeting, Philadelphia, 1973
- Pershing and Wendt, Effect of coal composition on thermal and fuel NOx production from pulverized coal combustion,
The Combustion Institute Control States Section Spring Meeting, Columbus, Ohio, USA, 1976
- Wendt and Pershing, Combust. Sci. Technol. 16, 11, 1977
- Wendt, Prog. Energy Combust. Sci. 6, 201, 1980
Thermal-NO vs. Fuel-NO in Coal Firing

NO concentration (λ=1.0)

NO from volatiles

NO from char

Air factor λ
When burning pulverized coal.
Based on Wendt and Pershing, Combust. Sci. Technol. 16, 11, 1977
 NO formation

Thermal
N2 NO

N2
NO
Nvol
HCN, NH3
N2
Nfuel
N2
Nchar
NO
 Schematic view of NO emission
distribution by source

500
NOx-emissions, mg NO2/MJ

400
Thermal-NO

300
(Combustion
200 air)

(Volatiles) Fuel-NO
100
(Char)
Prompt-NO
0
1000 1200 1400 1600 oC
 Fuel NOx – How to Control?

• Traditional efficient combustion: Maximize the

three T’s: Temperature, Turbulence, Time
• Gives low CO and CxHy
• ...but effective conversion of Fuel-N to NO!
• ”Low NOx” concept: staged combustion to
convert Fuel-N to N2
• A variety of novel burner and furnace
technologies with Low-NOx
 Conventional Burner for Solid Fuels

Fuel powder
+
Transport air

Combustion air

Devolatilization
Char
and Ash
combustion
gas combustion
 Low-NOx Burner for Solid Fuels

Secondary air

Fuel powder Primary Secondary

+
zone zone,
Transport air
l<1 “Burn-out
Primary air zone”
Secondary air l>1
How to Characterize Fuels with Respect to
their NO Formation Tendency?

Thermal
N2 NO

N2
NO
Nvol
HCN, NH3
N2
Nfuel
N2
Nchar
NO
Experimental procedure #1
• 2-step burning of fuel in 5 vol-% O2 +Ar
- Pyrolysis: Ar through bed + secondary O2
- Char ox: Ar + O2 through bed
• Release curves integrated to
obtain cumulative CO2 and NO (NO I + NO II)

European bark

Tbed=850°C
Volatile NO and Char NO – Laboratory Tests
(NO results given as weight-% N per original fuel)

Fuel-N
Vol NO (NO I)
Total NO (NO I + NO II)
Volatile NO and Char NO – Laboratory Tests
(NO results given as weight-% N per original fuel)

Fuel-N

Vol-NO (NO I)

Total NO (NO I + NO II)

 Fuel NOx Summary
• Fuel-N very reactive: 20-60 % conversion to NO
• Not very sensitive to temperature (cf thermal NO)
• Main contributor to NO in solid fuel combustion
• Different fuels have different fuel N bahavior
• Staged air combustion reduces fuel NO
 Special Case:

NO chemistry in FBC
 Nitrogen Oxides with Coal and Wood
(Leckner et al.)

Coal Wood

Volatile, % db 40 80
N(fuel), % db 1.6 0.14

CFBC NO, ppm 50 60

 NO Profiles in CFBC
(Leckner at al.)

500
Secondary air
400
NOx ppm

300

200 Wood

100

0
0 2 4 6 8 10 12
Reactor height, m
 NO Profiles in CFBC
(Leckner et al.)

500
Secondary air
400
NOx ppm

300

200 Wood

100
Coal
0
0 2 4 6 8 10 12
Reactor height, m
 NO formation for solid fuels

Thermal
N2 NO

N2
NO
Nvol
HCN, NH3
N2
Nfuel
N2
Nchar
NO
NO formation for solid fuels in CFBC

Thermal
( N2 NO )
N2
N2
NO
Nvol
HCN, NH3
N2
Nfuel
N2
Nchar
NO
NO Profiles in CFBC (Leckner et al.)
Modelling Attempts (Goel et al.)
500
Secondary air
400
NOx ppm

300

200 Wood

100
Coal
0
0 2 4 6 8 10 12
Reactor height, m
 NO Nchar NH3 HCN N2O

N2 16 N2 15

N2O14

NO 8
NO13 N2O12 NO10 N2O7

N2 11 N2 9
6
N2
NH35
NH33 HCN4
Hupa & Kilpinen (1995)

Nchar1
Nvol 2

Nfuel

Fuel-N Conversion in CFBC, Coal

17th FBC Conference, May 21, 2003, Jacksonville, Fl.
 NO Nchar NH3 HCN N2O

N2 16 N2 15

N2O14

NO10 9 NO 8
NO13 N2O12 N2 N2O7

N2 11 N2 6

NH35
Hupa & Kilpinen (1995)

NH33 HCN4
Nchar1
Nvol 2

Nfuel

Fuel-N Conversion in CFBC, Wood

17th FBC Conference, May 21, 2003, Jacksonville, Fl.
 NO Emission with Wood-Coal
(Leckner et al.)

150
Nitric
oxide
100
ppm
(6% O2)

50

0
Wood 50% Coal
(Energy)
 NO Emission with Wood-Coal
(Leckner et al.)

150
Nitric
oxide
100
ppm
(6% O2)

50

0
Wood 50% Coal
(Energy)
NO Emission with W&C (Leckner et al.)

150
Nitric
oxide
100
ppm
(6% O2)

50

0
Wood 50% Coal
(Energy)
NO Emission with W&C (Leckner et al.)
and Modelling Attempts (Engblom et al.)
150
Nitric
oxide
100 Measured
ppm
(6% O2) Case 2

Case 1
50

0
Wood 50% Coal
(Energy)
 Nitrogen oxide chemistry in combustion
processes – Terms and concepts

• Chemical equilibrium and NO

• Thermal-NO (Zeldowich NO) and kinetics
• Fuel-NO
• Volatile-NO – HCN, NH3
• Char-NO
• Staged Combustion: Low Nox Technologies
• NO formation tendency characterization
• (NO chemistry in fluidised bed combustion)