Proceedings of

2000 International Joint Power Generation Conference

Miami Beach, Florida, July 23-26, 2000

IJPGC2000-15103
OBSERVATIONS OF NO2 FORMATION IN TWO LARGE NATURAL GAS FIRED BOILERS

Verle V. Bland
Stone and Webster Engineering Corporation
7677 East Berry Avenue
Englewood, Colorado 80111
Phone: 303 741 7684
Email: verle.bland@stoneweb.com

John P. Guarco & Tom V. Eldredge

Todd Combustion / John Zink Co.
2 Armstrong Road, 3rd Floor
Shelton, Connecticut 06484
Phone: 203 925 0380
Email: guarcoj@kochind.com
Email: eldredgt@kochind.com
ABSTRACT
Nitrogen oxides (NOx), a major source of ozone pollution, are
comprised of two major components; nitrogen oxide (NO) and
nitrogen dioxide (NO2). The formation of nitrogen dioxide (NO2) in
combustion systems has attracted considerable attention over the last
several years because of relatively high levels of NO2 measured in
the exhaust of some combustors. The formation of NO2 has been
studied in small scale combustors, and reactions for the formation
and destruction of NO2 have been postulated. This paper describes
the results of measured NO2 and NO emissions on two 24 burner
natural gas fired boilers. For the first boiler, data was recorded over a
range of excess oxygen (02) levels and over-fire air (OFA) settings.
Other staging methods, such as burner out of service (BOOS)
operation and fuel biasing were also investigated on the first boiler.
For the second boiler, data was recorded for a range of excess oxygen
(02) levels, separated over-fire air (SOFA) settings, and flue gas
recirculation (FGR) levels. These results suggest that NO2 formation
is a strong function of OFA setting as well as a strong function of 02
level. This is consistent with published data from a laboratory scale
combustor, which found NO2 emissions to increase significantly as
the equivalence ratio was raised above one, to create a fuel rich
environment near the flame. The presented data do not indicate that
NO2 formation was strongly affected by FGR levels. The presented
data also indicate that there may be an upper limit on the amount of
NO2 created in a fuel rich flame.

INTRODUCTION

The formation of nitrogen dioxide (NO2) in combustion systems

has attracted considerable attention over the last several years
because of relatively high levels of NO2 measured in the exhaust of
practical combustors, such as gas turbines, natural gas furnaces,
diesel and spark ignition engines, and laboratory combustion systems.
Generally, in relatively unstaged commercial combustors, NO2
accounts for between 5 and 10 percent of total NOx emissions, with
NO accounting for the remainder. NO2 is more toxic than NO,
therefore NO 2 emissions are of concern for unflued space heaters.
NO2 emitted by combustors also has a direct impact on smog
formation; and if concentrations are high enough, NO2 can impart a
coloration to the stack plume.
Under certain operating conditions for natural gas-fired furnaces
the fraction of NOx that is NO2 can be significantly more than 10
percent. In order to understand why certain boiler operating settings
produce significant amounts of NO2, it is important to understand the
physical mechanisms by which NO2 is produced. Hori (1986)
conducted chemical kinetics calculations using 29 gas phase
reactions, and found that NO2 was formed and destroyed by the
following reactions:

Reaction

of Formation
NO + HO2 = NO2 + OH (1)

NOMENCLATURE
BNF - Burners not firing - no fuel, air doors closed.
BOOS - Burners out of service- no fuel, air doors open.
FGR - Flue gas recirculation.
NO, NO2 - Nitrogen oxide, nitrogen dioxide respectively.
NOx - Nitrogen oxides (total).
02 - Excess oxygen.
OFA - Over-fire air.
SOFA - Separated over fire air, no FGR mixed with the OFA.

Reactions for Destruction

NO 2 + H = NO + OH

NO2 + O = NO + 02

(2)
(3)

A study by Merryman and Levy (1975) showed significant

NO 2 levels in the flame front followed by the apparent conversion of

Copyright (C) 2000 by ASME

NO2 back to NO in the near post flame region. At typical flame

temperatures the ratio of NO2/NOx should be negligibly small,
because the reaction rates for destruction are high, even at relatively
low temperatures. Therefore, NO: exists only as a transient species at
flame temperatures. However, studies have shown that rapid cooling
of hot combustion gas by mixing with cold air can result in
significant levels of NO2. Cernansky (1977) indicated that a possible
reason for the NO2 in practical combustors is the NO-NO2 conversion
during rapid quenching of turbulent eddies. Sano (1984) computed
NO2 concentrations in the mixing region of hot gas and cold air, and
maximum values of NO2 were found in the temperature range of 800
to 900K. Hori (1986, 1988) conducted experiments on double
concentric jets and on a swirl burner, and claims that his
measurements prove that NOz can be formed by turbulent mixing of
hot combustion gases and cold air.
These findings may suggest that there are two effects resulting
from the quenching. First, the NO2 formation reaction may occur
more readily, because quenching may result in a more abundant
supply of the HO2 radicals, because reactions, other than (1) above,
which use up HO2 do not proceed below a threshold temperature.
Secondly, quenching the hot combustion gases likely "freezes" the
NO2. That is, the destruction reactions, (2) and (3) above, do not
proceed because the temperature is below a critical threshold value.
The most important result of this discussion is that it is known that
NO2 can result in practical combustors from quenching of hot
combustion gases.
Hori (1988) also observed two other results, which are
noteworthy. He found that the NOE/NO~ ratio was highest under fuelrich and fuel-lean extremes. Hori (1988) concluded that the relatively
high initial concentration of NO is the primary reason for increased
NO2 levels under fuel-lean conditions. Under fuel-rich conditions it
was concluded that the additional supply of radicals and unbumt
species (CO, H:, and hydrocarbons) result in higher levels of the HO2
radical which in turn results in higher levels of NO:.

operated at 345 MW. The NOx and NO2 data were corrected to a 3%
02 level on a dry basis.

~'-a.
m

J
c a m o~A m

RUUe--UNm~ ~ JJO ;

Figure 1 - 345MW Boiler

Figure 2 shows the effect of the flow through the OFA ports on
both NOx and NO2. As expected, opening the OFA ports was very
effective at reducing overall NOx. It should be noted that the OFA
ports were supplied with a combustion air/FGR mixture. The % OFA
flow represents the percentage of the total combustion air/FGR
mixture that was passed through the OFA ports.

C A S E S T U D Y #1

Unit D e s c r i p t i o n
The first unit on which the magnitude of the NO2 phenomenon
has been investigated was a Babcock & Wilcox "El Paso" style,
opposed wall-fired, natural circulation, forced draft design, rated to
supply steam to a 345 MW turbine generator. This unit is depicted in
Fig. 1. The combustion equipment was comprised of 24 bumers and
12 over-fire air (OFA) ports. Each wall had two elevations of six
burners below one elevation of six over-fire ports. Natural gas, the
primary fuel, is fired in the 24 TODD Combustion Dynaswirl-LNR
low NOx burners. These 24 burners using advanced steam atomizer
sprayer plates can also inject residual fuel oil, the secondary fuel. The
results, which form the subject of this paper, were obtained firing
natural gas only.

45

40
35
30

25

L
4 0-

g 2o

L ..oxo.o

2ppmo t

15
10
1

5
0

Results and D i s c u s s i o n
As stated above, N O 2 and NO emissions were measured for a
range of excess oxygen (02) levels, over fire air settings, and flue gas
recirculation (FGR) levels. The data were taken with the unit

I
0%

5%

I
10%

I
15%

I
20%

I
25%

0
30%

OFA%

Figure 2 - Effect of OFA Flow on NOx and NO2

Copyright (C) 2000 by ASME

0
z

Figure 3 shows the effects of 02 on total NOx and NO2

emissions. It should be noted that for the O2 tests there were various
levels of OFA flow, which provided quenching of the hot combustion
gases. As expected, lowering the 02 level decreased total NOx
emissions.

on lowering total NOx emissions and on increasing NO2 formation.

Opening the OFA dampers had two effects, one it created a fuel rich
environment in the flame front and the near-flame region. Secondly,
it provided quenching of the hot combustion gases by the mixing of
the relatively cool OFA flow. Therefore, the recorded effect of
opening the OFA dampers on increasing NO2 is consistent with
Hori's (1986, 1988) findings.
With the OFA ports set to deliver 18-24% OFA flow, further
staging of the fuel and air was investigated. The techniques
implemented to further stage the boiler were burner out of service
(BOOS) operation (no fuel, burner air doors open), burners not firing
(BNF) operation (no fuel, burner air doors closed) and fuel biasing.
Figure 5 shows the effect of 02 on NOx and NO2 formation when
these further staging techniques were implemented. Figure 5
indicates that NO and NO2 formation have relatively similar
reactions to 02 when further staging was implemented as when
operated under the 18-24% OFA "only" baseline condition.

45

40

Ae.

35
~. 3 0 e
O 25Z

~< 20
~o 15
z

I NOx ppmc NO2 I

10

I[~

-&

ILl
1.00

,
I

1.50

.It

2.00

2.50

3.00

45.

3.50

4O

Excess 0 2 . %

35

Figure 3 - Effect of O2 Level on NOx and NO2

re'#W

30-

"

o.
0
z

Figure 4 shows that decreasing O2 level increased the NO2/NOx

ratio. It was expected that the NOJNOx ratio would increase due to
the NO decreases, but as shown in Fig. 3, lowering the 02 level also
raised the NO2/NOx ratio because NO2 increased. Lowering the O2
level created a more fuel-rich environment which results in more
NO2, consistent with Hori's (1986, 1988) findings.

25
20-

,~ BOOS/BNF NOx
O BOOS/BNF NO2

FUEL BIAS NOx

Q FUEL BIAS NO2

18-24%OFA NOx /
z~18-24%OFA NO2

~ 15z
10

~'$

"C~b''~- ~. . . . . ?

0
0.40

0.00

0.30
0.25

".

0.20
O
Z
0.15

1.50

2.00

2.50

3.00

3.50

Figure 5 - Effect of 02 Level on NOx and NO2 with Further

Staging.

2-" " \
\,~,

1.00

Excess 02, %

"'"'"""..~..,.,
%.
"'",.

0.35

0.50

0.50
0.45

".,,.

0.40
0.10

BNF

= FUEL BIAS

& 18-24%OFA

oBOOS }

0.35
0.05
0.00
0.00

"&

x 0.30
o

0.25

0.50

1.00

1.50

2.00

2.50

"L

3.00

Z 0.20

~'~.,.~ o """ .?..

Excess 02, %

0.15

Figure 4 - Effect of 02 Level and OFA % on NO2/NOx

%...."

0.10
0.05

Figure 4 also shows the effect of opening the OFA ports on the
NO2/NOx ratio. With the OFA dampers closed, the fraction of NOn
that was NO2 was less than 10 percent, but with 18-24 percent OFA
flow, the fraction of NOx that was NO2 was approximately 30
percent. Prior to analysis of the data, it was expected that the
NO2/NOx ratio would increase as NO decreased when the OFA flow
was raised,; but as shown in Fig. 2, raising the OFA flow also raised
the NO2/NOx ratio because NO2 is increased, even though overall
NOx levels are reduced. Therefore, OFA flow had a significant effect

0.00
0.00

0.50

1.(30

1.50

ZOO

2.50

3.00

3.50

Excess 02, %

Figure 6 - Effect of O= Level on NOzlNOx with Further

Staging.
Figure 6 shows the effect of 02 on NO2/NO x when these further
staging techniques were implemented. Figure 6 indicates that while

Copyright (C) 2000 by ASME

BNF operation and fuel biasing did not increase the level of
NO2/NO~ as compared to the baseline condition, BOOS operation did
in fact increase the level of NO2/NO~ for a give O2, as compared to
the baseline condition,. This is indicated by the dashed line.
An important note should be inserted here regarding the
minimum levels of O2 for each curve. During this testing, as well as
all subsequent testing, the minimum O2 level for each operating
condition was dictated by the level of carbon monoxide (CO)
formation. The testing was conducted in such a way that the CO
generally remained in a "controlled" region of below 400 ppm. With
this in mind, Fig. 6 indicates that for BOOS operation, while the
curve of the NO2/NOx ratio as a function of 02 did increase, the
overall maximum level did not increase, the curve was just shifted
rightward along the O2 axis. This indicates that there may be a
maximum NOz/NOx level that is created while keeping CO under
control.

NO2/NOx ratio because NO2 is increased. Therefore, as with Case

Study #1, SOFA flow has a significant effect on lowering total NOx
emissions and on increasing NO2 formation. Opening the SOFA
dampers had the same two effects, one it created a fuel rich
environment in the flame front and the near-flame region. Secondly,
it provided quenching of the hot combustion gases by the mixing of
the relatively cool SOFA flow. Therefore, the effect of opening the
SOFA dampers on increasing NO2 is consistent with Hori's (1986,
1988) findings. Comparing Figures 4 and 9, there was no noticeable
difference between the effects of OFA or SOFA on NOJNOx.

CASE S T U D Y #2

Unit Description
The second unit investigated was a Babcock & Wilcox "El
Paso" style, opposed wall-fired, natural circulation, forced draft
design, rated to supply steam to a 325 MW turbine generator. The
unit is depicted in Fig. 7. The combustion equipment was comprised
of 24 burners and 8 separated over-fire air (SOFA) ports. SOFA
differs from OFA in that OFA has FGR mixed with the combustion
air flow, whereas with SOFA flow the SOFA air is separated from
the combustion air upstream of the FGR mixing station, therefore
there is no FGR in the SOFA flow. Each wall had three elevations of
four burners below one elevation of four SOFA ports. Natural gas,
the primary fuel, was fired in the (24) TODD Combustion DynaswirlLNR low NOx burners. These 24 burners using advanced steam
atomizer sprayer plates can also inject residual fuel oil, the secondary
fuel. The results, which form the subject of this paper, were obtained
firing natural gas only.

NClNA POW[R ~ - - U ~ I T
NO 4
CALIF~NI&
"
OGW ~"rR,SCT NO IqB-477

E-456

Results and Discussion

Figure 7 - 3 2 5 M W B o i l e r

As stated above, NO2 and NO emissions were measured for a

range of O2 levels, over fire air settings, and FGR levels. The data
were taken with the unit operated at 290 MW, except for a few tests
conducted at 212 MW. The NOx and NO2 data were corrected to a
3% 02 level on a dry basis.
Figure 8 shows the effect of the flow through the SOFA ports on
NOx emissions for various 02 and FGR levels. As expected, opening
the SOFA ports was very effective at reducing overall NOx. It should
be noted that the SOFA dampers were supplied with
pure
combustion air, there was no FGR mixed with the SOFA flow. The
%SOFA flow represents the percentage of the total combustion air
that was passed through the SOFA ports. Figure 5 shows the effect of
opening the SOFA ports on NO2 formation. With the SOFA dampers
closed, the fraction of NOx that was NO2 was less than 10 percent,
but with 18 percent SOFA flow, the fraction of NO~ that was NO2
was approximately 30 percent. It is expected that the NO2/NO~ ratio
will increase because NO decreased as the SOFA flow was raised,
but as shown in Fig. 9, raising the SOFA flow also raises the

70

60

5O

,~ 4o
=
2

30

20
Econ. 0 2 : 1 . 6 5 - 1.88% FGR: 24.7 - 25.8%

&Econ 0 2 : 2 . 4 7 - 2,66% FGR: 22.8 - 2 3 . 4 %

10

0
5

10
% SOFA

15

Flow

Figure 8 - Effect o f S O F A F l o w on NOx

Copyright (C) 2000 by ASME

20

SOFA levels. Therefore, these data do not suggest a strong effect of

FGR on total NO2 emissions, since the change in NO2/NOx ratio
observed is due to the affect of FGR on the NO emissions level.

0,35

0.3

0.25

0.2

0.35

Effect if 0 2 Only Increases NO

and NO2 remains constant

Effect if S O F A Only= Lowers NO

0.3

z
Oz 0 . 1 5

0.25

0.1

Effect if 0 2 Only Increases N O ~ "

end NO2 remains c ~ s t a n t & \ % ~

0.2

" " " "

z
0.05

zO 0 . 1 5

eEcon.

O2:1.65-1,88%
AEcon 02:2.47 -2.66%

FGR:24.7-25.8%
FGR:22.8 -23.4%

10

15

0.1

20

Flow

% SOFA

SOFA: 17.5% FGR: 2 3 - 28.6%

- B - S O F A : 15.8 - 16,3% FGR: 15.1 - 15.8%
- ~ r SOFA: 10% FGR: 22.8 - 24.7%

0.05

Figure 9 - Effect of S O F A F l o w on NOz/NOx

0

0.5

1.5

2.5

3.5

Economizer 02 (%)

Figures 10 and 11 show the effects of 02 on total NOx and NO2

emissions. It should be noted that for the 02 tests there were various
levels of SOFA flow, which provided quenching of the hot
combustion gases. As expected, lowering the 02 level decreased total
NOx emissions. Figure 11 shows that decreasing 02 level increased
the NOE/NOx ratio. It is expected that the NO2/NOx ratio would
increase because NO decreases, but as shown in Fig. I l lowering the
02 level also raised the NOE/'NOx ratio because NO2 increased.
Lowering the 02 level creates a more fuel-rich environment which
results in more NO2, consistent with Hori's (I 986, 1988) findings.

Figure 11 - Effect o f 02 level o n NO21NOx

70
-a=-290 MW SOFA: 16.3% 0 2 : 2 . 6 9 - 3.06%
--11-212 MW SOFA: 1.4 - 1.8% 0 2 : 1 . 5 6 - 1.75%
-11-212 MW SOFA: 9.8 - 10.6% 0 2 : 1 . 4 5 - 1,64%

60

5O

~ 4o

50
O 30
z

45

20

4O
35

10

o 30
0

o. 25
ff
o
z 20

10

15

20

25

30

35

% FGR

15

Figure 12 - Effect of FGR level on NOx

10

SOFA: 17,5% FGR: 23 - 25.8%

IISOFA: 15.8 - 18.3% FGR: 15.1 - 15.8%
& S O F A : 10% FGR: 22,8 - 24.7%

10-

-e-290 MW SOFA: 16.3% 02:2.89 - 3.06%

-11--212 MW SOFA: 1.4 - 1.8% 02:1.56-1.75%
-ilk- 212 MW SOFA: 9.8 - 10.6% 02:1.45 - t.64%
- e - 315 MW SOFA: 19.8-21.4% 02:1,92-2.17%

0
0.5

1.5

2.5

3.5

8-

E c o n o m i z e r 0 2 (%)

Figure 10 - Effect o f O2 level on NOx

Q.
O

Figures 12 and 13 show the effects of FGR level on total NOx

and NO2 emissions respectively. As expected, raising the FGR level
lowers total NOx emissions, but there appears to be very little effect
on NO2 emissions. Some of the data presented in Fig. 13 appear to
show some small changes in NO2 as the FGR level is increased, but
the observed changes were essentially within the accuracy range of
the instrument. The ratio of NO2/NO was typically observed to
increase with increasing FGR level because NO2 essentially remained
constant while NO decreased, as presented in Fig. 14. This effect is
also shown in Fig. I 1 by comparing results for the first two data
series ( and symbols), which were collected at comparable

0
0

10

15

20

25

30

% FGR

Figure 13 - Effect of F G R level on NO2

Copyright (C) 2000 by ASME

35

03[

(International) on Combustion, p. 1175-1181, The Combustion

Institute
Merryman, E. L. and Levy, A., 1975, Fifteenth Symposium
(International) on Combustion, p. 1073, The Combustion Institute
Sano, T., 1984, Combustion Science and Technology, 38, 129

0.35

-A-290
-e-212
-11-212
-4-- 315

MW
MW
MW
MW

SOFA: 16.3% 0 2 : 2 . 8 9 - 3.06%

SOFA: 1.4 - 1.8% 0 2 : 1 . 5 6 - 1.76%
SOFA: 9.8 - 10,6% 0 2 : 1 . 4 5 - 1.64%
SOFA: 19.8 - 21.4% 0 2 : 1 . 9 2 - 2.17%

0.25

0.2

O 0.15
z

0.1

0.05
0
0

10

15

20

25

30

35

% FGR

Figure 14 - Effect of FGR level on NO2/NOx

CONCLUSIONS

Two large scale natural gas fired boilers were investigated as to

the effect of different operating parameters on NO2 formation and
NO2/NOx ratio. The findings presented show that OFA flow, whether
mixed with the FGR flow or not, and excess 02 level both have
significant effects on NO2 formation, due mainly to the localized
effects of fuel rich combustion. Our data show that raising the
OFA/SOFA flow significantly increases NO2 emissions and the
NO2/NOx ratio. Opening the OFA/SOFA dampers has two effects,
one it creates a fuel rich environment in the flame front and the nearflame region. Secondly, it provides quenching of hot combustion
gases by the mixing of relatively cool OFA/SOFA flow.
When operating at 18-24% OFA flow, further biasing
techniques, such as BOOS, BNF and fuel biasing, show little
noticeable difference in either the overall NOx or the NO2 emissions.
However, BOOS operation did tend to further increase the NO2/NOx
ratio for a given 02 level, but the maximum value recorded did not
increase. The curve had just shifted rightward along the excess 02
axis. This indicates that there may be an upper limit on the amount
of NO2 created in a fuel rich flame when keeping CO under control.
Lowering the 02 level creates a more fuel-rich environment,
which results in more NO2. Therefore, the effects of opening the
OFA/SOFA dampers and lowering excess O2 both were observed to
increase NO2 emissions and the NO2/NOx ratio, which is consistent
with Hori's (1986, 1988) findings.
The data suggest that FGR has a negligible effect on NO2
emissions. The NO2/NOx ratio increases with increasing FGR
because of the affect of FGR on reducing NO emissions.

REFERENCES

Cernansky, 1977, N. P., Pro~;ress in Astron. and Aeron., Vol. 53,

(B. T. Zinn, Ed.), p. 83, AIAA
Hori, M., 1986, "Experimental Study of Nitrogen Dioxide
Formation in Combustion Systems", Twenty First Symposium
(International) on Combustion, p. 1181-1188, The Combustion
Institute
Hori, M., 1988, "Nitrogen Dioxide Formation by the Mixing of
Hot Combustion Gas with Cold Air", Twenty Second Symposium

Copyright (C) 2000 by ASME