Fuel 87 (2008) 3579–3585

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Fuel
journal homepage: www.elsevier.com/locate/fuel

High-temperature reduction of nitrogen oxides in oxy-fuel combustion

Fredrik Normann *, Klas Andersson, Bo Leckner, Filip Johnsson
Department of Energy and Environment, Chalmers University of Technology, SE-412 96 Göteborg, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: The possibility of high-temperature reduction of nitrogen oxides (NOx) in oxy-fuel combustion is inves-
Received 13 February 2008 tigated. A detailed gas-phase model identifies the effect of temperature, stoichiometric ratio, residence
Received in revised form 16 June 2008 time and composition of the oxidizer on NOx reduction. It is concluded that an efficient high-temperature
Accepted 23 June 2008
reduction of NOx is achieved with high-purity oxygen, negligible amount of air ingress, presence of a sub-
Available online 16 July 2008
stoichiometric combustion zone, and relatively long residence time. The temperature should be high but
decreasing along with the NOx concentration throughout the reaction zone. The influence of these param-
Keywords:
eters is discussed, also with regard to combustion efficiency, corrosion and ash handling.
NOx
Oxy-fuel
Ó 2008 Elsevier Ltd. All rights reserved.
Coal
High-temperature combustion
Thermal NO

1. Introduction nism to reduce NO at high temperature, opposite to air-firing

Oxy-fuel (O2/CO2) combustion is considered a promising option
to capture carbon dioxide (CO2) from power plants. Fig. 1 gives the
principle of the oxy-fuel combustion in which a mixture of nearly
pure oxygen (O2) and recycled flue gas (RFG) serve as oxidizer in-
stead of air; nitrogen (N2) is eliminated from combustion and the
flue gas consists of highly concentrated CO2, which is required
for cost-effective storage. In many present proposals on the oxy-
fuel process, the combustion conditions are chosen similar to those
in a conventional air-fired process to use existing knowledge and
technology, thereby gaining an easier implementation of the new
process. The oxy-fuel process, however, offers opportunities to
optimize the combustion process with respect to temperature
and composition of the oxidizer. Higher combustion temperature
can be achieved with higher oxygen concentration (lower recycle
ratio) or different burner design, and thereby the dimensions of
the furnace can be reduced. In general, at high combustion temper-
atures melting of ashes and formation of nitrogen oxides (NOx) are
favored, with the former handled by furnace design and the latter
being the focus of this work.
Recently, emissions of nitric oxide (NO) in oxy-fuel combustion
were investigated [1] in a 100 kW oxy-fuel test unit with flue gas
recycle. It was concluded that the emission of NO is drastically re-
duced during oxy-firing compared to air-firing, caused by reduc-
tion of formed and recycled NO. Furthermore, it was shown that,
theoretically, the absence of air-N2 enables the Zeldovich mecha-
* Corresponding author. Tel.: +46 31 772 1000.
E-mail address: fredrik.normann@chalmers.se (F. Normann).
where NO is formed at high temperatures. In the present work,
these results are further examined with focus on the gas-phase
nitrogen chemistry. Parameters affecting the NOx chemistry are
investigated and the boundaries for the high-temperature NOx
reduction are identified. Present techniques to limit emissions of
NOx from coal-fired power plants and for combustion with higher
oxygen concentration and temperature are discussed. Finally, the
findings on the NOx chemistry in oxy-firing are exploited to dem-
onstrate the effects on oxy-fuel firing strategies and boiler design.
2. NOx emissions and principal reduction measures
In a boiler NOx consists mostly of NO. Therefore the interest is
focused on this species. NOx is formed along three routes: thermal
and prompt formation from N2 and from fuel-bound nitrogen
(Fuel-N). Thermal NO evolves from gas-phase reactions between
molecular N2 and O2, as described by the extended Zeldovich
mechanism,
N2 þ O $ NO þ N ð1Þ
N þ O2 $ NO þ O ð2Þ
N þ OH $ NO þ H ð3Þ
which is strongly temperature dependent and becomes important
only at high temperatures (>1500 °C). Prompt NO is formed in the
reaction between free nitrogen and hydrocarbon radicals that
occurs mostly under fuel-rich conditions. Fuel-N is split into
volatile- and char-N during the devolatilization. The volatile-N (an
intermediate gaseous compound, e.g. HCN or NH3) then transforms
through a series of subsequent reactions to form either NO or N2,

0016-2361/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.06.013
3580 F. Normann et al. / Fuel 87 (2008) 3579–3585
Fig. 1. A simplified oxy-fuel combustion scheme.
while char-N reacts through a set of heterogeneous reactions along
with the oxidation of the char. The split between N2 and NO de-
pends on qualities like nitrogen content, coal rank and volatility,
and varies with type of coal and combustion conditions. The funda-
mental aspects of fuel nitrogen conversion in solid fuel fired sys-
tems are reviewed by Glarborg et al. [2].
NOx is reduced by primary (in-combustion) and secondary (post
combustion) measures. Secondary measures including conven-
tional techniques, such as selective catalytic reduction (SCR) and
selective non-catalytic reduction (SNCR), and innovative proposals
particularly for the oxy-fuel process, such as separation by distilla-
tion [3], the Lead-chamber concept [4] or co-storage with CO2, are
not the focus of this work and are not further discussed. The con-
ventional techniques for NOx reduction are reviewed by Soud and
Fukasawa [5]. Fig. 2 illustrates common primary measures to re-
duce NOx: fuel-staged (reburning) and air-staged (staged) combus-
tion. Reburning, (Fig. 2a) is carried out by introducing fuel, forming
a sub-stoichiometric flame downstream of the primary combus-
tion zone yielding hydrocarbon radicals, which reduce the NO pro-
duced in the primary zone. After the reburning zone, additional
oxidizer is introduced into the furnace to ensure sufficient burnout
of the fuel.
In air-staged combustion, the oxidizer is staged to create an ini-
tial oxygen-lean zone followed by an oxygen-rich zone by intro-
ducing parts of the oxidizer above the main combustion zone in
the furnace (overfire) (Fig. 2b) and/or in a burner (Fig. 2c), where
the zones are created by controlling the flows of fuel and oxidizer
through the burner registers. In both cases, the purpose of the pri-
mary zone is to reduce the supply of oxygen in areas that are crit-
ical to NO formation and also to reduce the amount of fuel burnt at
the peak temperature. The secondary zone ensures a good burnout
of the fuel. Air staging is the central technique in low-NOx burners.
The design of burners is important in reducing the emission of NOx
and several burner configurations have been developed. The state-
of-the-art burners of today are optimized with respect to residence
time, temperature and stoichiometric ratio to minimize NOx
emissions.
Most parameters with a positive effect on NOx emissions (oxy-
gen lean conditions and low temperature) have a negative effect in
the form of a loss of unburned carbon (UBC) and, thus, on the com-
bustion efficiency. The design of a burner must be optimized
regarding both NOx emissions and UBC. A stable flame with good
mixing between fuel and oxidizer is an important element in
reducing NOx and UBC. This is promoted by flame holders and
swirling flows. High-temperature corrosion, by mainly sulfur and
Fig. 2. Schematic figures showing low-NOx firing strategies: (a) fuel-staging (reburning), (b) air-staging in furnace (overfire), and (c) air-staging in burner (low NOx burner). (k
is the stoichiometric ratio).
chlorine species, is also an issue enhanced by low-NOx burners.
In the reducing atmosphere prevailing in low-NOx flames, no pro-
tective oxide layers are formed on boiler tubes and corrosion may
be accelerated. Normally, this problem is solved by designing the
burners to maintain a layer of oxidizing atmosphere along the boi-
ler walls.
3. Oxy-combustion
Combustion with elevated concentrations of oxygen is a com-
mercially available technique for air-fired systems known as oxy-
gen-enriched combustion, applied, for example, in the glass and
cement making industry [6,7]. The primary effect of oxygen-en-
riched combustion is a reduction of the mass flow through the fur-
nace. Furthermore, the flame temperature and the burning velocity
are higher; whereas the ignition temperature is lower [6].
The techniques employed in oxygen-enriched combustion are
suitable for the oxy-fuel process, as the oxidizer is pure oxygen di-
luted with recycled flue gas. Fig. 3 illustrates the effects of O2 con-
centration on the adiabatic flame temperature for methane oxy-
fuel combustion (in CO2) as an example. For comparison, the adia-
batic flame temperature for methane in air is 1950 °C, which corre-
sponds to 27 vol% of O2 in oxy-fuel combustion. Locally, a furnace
could have higher O2 fraction and higher temperature than what
corresponds to the global O2 fraction. It is also possible to raise
the adiabatic flame temperature by increasing the inlet tempera-
ture to the burner, which is 25 °C in the calculated case.
Besides the higher operation temperature, the concentration of
oxygen has an important effect on the gas residence time in the
combustor. The amount of RFG per mole of fuel is controlled by
the stoichiometric ratio (k) and the concentration of O2 in the oxi-
dant according to,
kmð1  ½O2 oxidant Þ
RFG ¼ ð4Þ
½O2 oxidant
with m being the stoichiometric coefficient for the fuel burnt (m = 2
for methane used in the simulations). In Fig. 3, the influence of
the amount of RFG on the total volume flow through the reactor
is illustrated, independent of temperature and at a temperature
change corresponding to the adiabatic flame temperature. A rise
in the oxygen concentration increases the flame temperature and
reduces the gas flow through the system. Lower gas flow means
smaller equipment (boiler, recirculation loop and related compo-
nents). In oxy-fuel combustion the once-through residence time
of gas in the furnace (sonce) must be distinguished from the effective
residence time (stot), where the recycle of gas is included also. The
difference between sonce and stot for a simplified oxy-fuel system
(cf. Fig. 1) is illustrated by the following relationships,
VC
sonce ¼ ð5Þ
F O2 þ F RFG
 
F O þ F RFG VC VC
stot ¼ 2 ¼ ð6Þ
F O2 F O2 þ F RFG F O2
 F. Normann et al. / Fuel 87 (2008) 3579–3585
Fig. 3. The influence of O2 concentration on an adiabatic equilibrium methane O2/
CO2 flame at constant atmospheric pressure, inlet gas temperature 25 °C and k = 1.1.
Left: flow at constant temperature (lower curve) and at the adiabatic temperature
that corresponds to the oxygen concentration (upper curve). Right: adiabatic flame
temperature.
where F is the volumetric flow of oxygen (index O2) and recirculated
flue gas (index RFG) through the volume of the combustion cham-
ber (VC). Only the once-through residence time, of importance for
the combustion process, is affected by the amount of RFG (or oxy-
gen concentration), whereas the total residence time, of importance
for the nitrogen chemistry, is only affected by the oxygen flow. If
the equipment is designed to accommodate the combustion pro-
cess, and the single-pass residence time sonce is maintained (re-
duced furnace volume), the effective residence time for NOx
reduction stot is reduced. In addition, at increased oxygen concen-
tration, the combustion process in the flame becomes more intense
and is completed faster.
4. Combustion model
The focus of this investigation is on the potential for gas-phase
reduction of NOx during high-temperature oxy-fuel combustion.
Therefore, heterogeneous reactions are omitted. This is a useful
simplification when investigating NOx mechanisms employed in
many investigations, e.g. [8,9]. The fuel is represented by methane
being a simple hydrocarbon gas with no major difference estab-
lished to other hydrocarbons in the present context [10]. HCN
and NH3 are introduced to represent the fuel-bound nitrogen found
in coal. The fuel is burnt in an O2/RFG mixture. The RFG has an ini-
tial content of CO2, H2O, N2 and NO. The amount of RFG is calcu-
lated with Eq. (4). The gas-phase reactions involving nitrogen
oxides are treated, applying a detailed chemical kinetic scheme to-
gether with the associated thermodynamic library [9]. The scheme
involves 73 species in 520 elementary gas-phase reactions and in-
cludes mechanisms for combustion of light hydrocarbons (C1–C2)
and the nitrogen mechanisms relevant for staged combustion and
reburning (CxHyOz + nitrogen species). The furnace is modeled as
an isothermal and isobaric plug-flow reactor with the SENKIN
[11] code for kinetic calculations and with the EQUIL [12] code
for equilibrium calculations implemented in the CHEMKIN-II [13]
software, an approach applied also in previous work [1]. Even
though the boiler geometry and detailed mixing behavior is impor-
tant to NOx emission, the plug-flow reactor description is used to
focus the investigation on nitrogen chemistry in an oxy-fuel com-
bustion environment. The modeling is divided into two parts. First
3581
the reduction of NO is studied independently, with an initial con-
tent of NO in the input gas, but without fuel-N. In the second set
of simulations, the features of gas-phase NOx chemistry in oxy-fuel
combustion are exploited to find firing strategies to minimize the
emissions of NOx.
5. Impact of combustion parameters on high-temperature NOx
reduction
The sensitivity of high-temperature NOx reduction to critical
parameters is investigated. A large span of parameter variation is
applied in order to illustrate the behavior of nitrogen chemistry
in oxy-fuel combustion under both conventional and non-conven-
tional combustion conditions, see Table 1. The amount of total
fixed nitrogen (TFN), i.e. NO + NO2 + HCN + NH3, quantifies the
NO reduction. In most cases without fuel-N (like in Table 1) TFN
consists exclusively of NO according to the calculations.
To illustrate the relative importance of the Zeldovich mecha-
nism (forward and backward reactions 1–3) to the reduction of
NOx in oxy-fuel combustion, it is isolated from the remaining reac-
tions involving NOx (reburning, cyanide and H/N/O reactions [9]) in
Fig. 4a. At temperatures below 1400 °C the Zeldovich mechanism is
not active, and the reburning mechanism is dominant. At higher
temperatures the reverse Zeldovich mechanism dominates the
NO reduction, even though the complete reaction scheme is used
in the calculations. High-temperature combustion only reduces
NOx when the nitrogen concentration is low, as during oxygen com-
bustion. The influence of N2 concentration is shown in Fig. 4b; at
sufficiently high N2 concentration, the thermal mechanism no long-
er acts in the reverse direction. Instead NO is formed, such as under
normal air-fired conditions. The efficiency of the Zeldovich mecha-
nism also decreases with lower initial NO concentration: The tem-
perature for the critical equilibrium concentration decreases and
the reduction of NO is lower. It should be noted that the outlet con-
centration of NO is still lower at lower initial NO concentration.
In Fig. 5a, the concentration of NO is plotted as a function of res-
idence time at three temperatures. The initial gap between 1000
and 950 ppm NO is due to the reburning mechanism, which is fast
at the time scale used. The residence time is critical for the reduc-
tion of NO by the reverse Zeldovich mechanism. The reduction rate
increases with temperature, but the limit of achievable reduction,
the equilibrium concentration of NO, rises with temperature as
marked by the filled symbols in Fig. 5a. Fig. 5b further illustrates
the dependence of the equilibrium concentrations on temperature
at different N2 contents in the flue gas and stoichiometric ratios (k).
It is important to keep the amount of N2 and O2 low to achieve a
high reduction. The calculated concentrations below 1500 °C will
never be reached in combustion due to the low reaction rate at
such temperatures (cf. Fig. 5a).
In summary, Fig. 4 and 5 show a complex temperature depen-
dence of the NO reduction, due to the trade-off between reaction
rate and equilibrium concentration. To find the optimal reactor
Table 1
Investigated parameters in the gas-phase reaction model
Base case Variation span
Temperature Varied 800–2100 °C
Pressure 1E5 Pa Constant
Stoichiometric ratio 0.9 0.9, 1.1
Residence time 1s 0–3 s
Initial fraction in oxidizer
NO 1000 ppm 300, 1000 ppm
N2 0% 0–10%
H2O 25% 0–75%
O2 25% 25–100%
3582 F. Normann et al. / Fuel 87 (2008) 3579–3585

Fig. 4. The NO reduction ratio for: (a) isolated reduction mechanisms and (b) for various combinations of nitrogen and nitric oxide contents in the inlet flow.

Fig. 5. (a) NO concentration as a function of residence time. The filled symbols are the equilibrium concentration at each temperature. (b) Equilibrium concentration of NO.

Fig. 6. The rate of NO reduction at different NO concentrations and temperatures.

The solid line is the maximum rate of reaction at the current NO concentration. Fig. 7. Ratio of NO reduction at different composition of the oxidizer.
 F. Normann et al. / Fuel 87 (2008) 3579–3585 3583

temperature with regard to NO emissions, the NO reduction rate

was calculated as a function of NO concentration for different tem-
peratures, with the results shown in Fig. 6. As the NO concentration
approaches the equilibrium corresponding to the reactor tempera-
ture, the reaction rate suffers and will eventually benefit from a
lower temperature, with a lower equilibrium concentration. Hence,
to achieve maximum NO reduction in the combustor via the re-
verse Zeldovich mechanism, the temperature profile should ideally
fall throughout the combustion zone, according to the solid line in
Fig. 6. The optimal temperature profile depends on parameters like
residence time, oxygen concentration (k), and amount of nitrogen
supplied by fuel, oxygen and air ingress into the combustion
chamber.
The oxygen and water contents of the oxidizer (oxygen + RFG)
are crucial design parameters for the oxy-fuel process. To investi-
gate the influence of the composition of the oxidizer on the high-
temperature NOx reduction, the two major components of the
RFG, CO2 and H2O, are changed from a dry recycle case (pure
CO2) to a hypothetical case of pure steam as a diluent, and the
O2 concentration in the oxidizer is varied from 20% up to pure oxy-
gen combustion. The results are presented in Fig. 7. Both water and
oxygen have positive effects on the reduction of NO under other-
wise constant conditions. Increase in concentration of diluents
gives lower concentrations of the chain-carrier radicals, i.e. O, H,
and OH, of importance for the Zeldovich mechanism. Steam is a
source of these radicals, and the decrease in reduction ratio is
not as significant in the case of steam addition with a high H2O
content in the RFG as in dry gas when the CO2 content is high. Sim-
ilar effects have been seen previously by, for example, Park et al.
[14] when investigating the influence of diluents on flame temper-
atures. Combustion of a fuel with a moisture content of around 10%
and 25% O2 in the RFG mixture generates a flue gas with around
25% H2O during wet recycling and ten percentage points higher
reduction of NO compared to the dry recycle case, according to
the calculations.
6. Design considerations for an oxy-fuel combustion boiler
6.1. Comparison of firing strategies
The gas-phase chemistry of four firing strategies is simulated
(Table 2 and Fig. 2): (1) conventional, (2) high temperature, (3)
staged combustion, and (4) reburning. The moisture content of
the fuel is 10.2 wt% and the nitrogen content 0.6 wt% d.a.f. of which
60% is represented by HCN and the rest by NH3, values typical for
pre-dried lignite [15]. The composition of the recycled flue gases is
matched with the furnace outlet concentrations. The furnace gas
residence time (sonce) is 2.5 s in all cases. The global oxygen
Table 2
Simulated combustion cases and the properties used
Case Description Temperature O2 Stoichiometric Residence
concentration ratio (k) time
in oxidant (%) (sonce) (s)
1 Conventional 1500 °C 30 1.1
(reference)
2 High temperature Optimized 40 1.1
3 Staged
Primary zone Optimized 40 0.8
Secondary zone Optimized 100 1.1
4 Reburning
Primary zone Optimized 40 1.1
Reburning zone Optimized 0.8
Burnout zone Optimized 100 1.1
Fig. 8. NO concentration as a function of residence time in the combustor in the
four calculated cases of Table 2. The circles indicate the inlet concentration of NO
and the arrows indicate a temperature drop of 100 °C. The jump in the curve of Case
3 is due to the introduction of reburning fuel containing nitrogen.
concentration is set to 40% in Cases 2 to 4, but, locally, the oxygen
concentration could be higher to achieve the desired temperatures.
In Fig. 8, the concentration of NO in the reactor is shown as a
function of residence time, for the firing strategies of Table 2. The
inlet concentration of NO from the recycled flue gases is marked
with a circle and case number. The difference between the inlet
and maximum concentrations of NO arises from the conversion
of volatile-N to NO, which is fast at the time scale used. The
high-temperature cases (Case 2–4) have a higher volatile-N to
NO conversion. In the reference case (Case 1) the temperature
(1500 °C) is too low for the Zeldovich mechanism and no reduction
of NO is seen. In Case 2–4 the temperature profile is optimized in
line with Fig. 6. A change in temperature is indicated with an ar-
row. The high-temperature case (Case 2, 2000 °C to 1800 °C) has
a relatively modest reduction during combustion. The importance
of sub-stoichiometric zones in the combustor is evident in Cases
3 and 4: The reduction is much faster in the oxygen-lean zones.
Staged combustion (Case 4) with 2000 °C to 1800 °C in the primary
and 1600 °C in the secondary zone has an outlet concentration of
NO below the equilibrium concentration due to the change of stoi-
chiometric ratio and the slow reaction rate in the secondary zone.
There is no significant increase in reduction due to the introduction
of hydrocarbons downstream of the primary flame (Case 3). In-
stead, the low stoichiometric ratio is the important reason for NO
reduction also in the reburning case. To achieve an effective NO
reduction zone, sub-stoichiometric combustion should be initiat-
ing. The oxygen-lean conditions should be sustained at least until
approaching the equilibrium concentration at 1900 °C, while the
reduction is efficient. Reduction of NO below 1800 °C is costly in
the form of extra residence time in the combustor. Lower equilib-
rium concentration and further reduction could be achieved with
even lower stoichiometric ratio and concentrations of nitrogen,
but the possibility of improvement decreases at low equilibrium
concentrations (see Fig. 5b).
2.5
6.2. Application to oxy-fuel boiler design
2.5
Techniques for combustion at the high temperatures suggested
2.0
0.5 here for oxy-fuel combustion have long been available. Before the
awareness of the NOx issue (before about 1970), development of
1.0 burner system focused on maximizing the heat input per unit of
1.0 volume to design compact and cost-effective boilers. This resulted
0.5
in burners (for air combustion) with rapid mixing and high flame
3584 F. Normann et al. / Fuel 87 (2008) 3579–3585
Fig. 9. Schematics of: (a) cell burner boiler, (b) cyclone-fired u-shaped WBB, and (c) downshot-fired WBB.
temperatures (even above 2000 °C), which gave high emissions of
NOx. Although these burners performed well, today’s boilers are
of low-NOx design, and all high-temperature boilers have been ret-
rofitted or closed down to obey NOx reduction regulations. Oxy-
fuel combustion brings those techniques to the fore by eliminating
thermal NOx formation and by making oxygen production feasible
for thermal power production.
To reach the high combustion temperatures proposed, the fuel
has to be burnt in relatively high concentrations of oxygen
(>50%), and preferably with a burner design allowing rapid mixing
in the furnace. Three formerly common techniques with high com-
bustion temperatures are cell burners, cyclone- and downshot-
fired boilers, illustrated in Fig. 9. A cell burner (Fig. 9a) is an assem-
bly of two or three closely coupled burners forming one cell. The
tight burner spacing and rapid mixing between oxidizer and fuel
result in a compact and intense flame. A cyclone burner (Fig. 9b)
is a horizontal, cylindrical furnace mounted outside the main boi-
ler, to which the gases are passed on. The intensive turbulence of
cyclone combustion makes the fuel burn off quickly, developing a
high flame temperature. In a downshot-fired boiler (Fig. 9c) the
burners are facing downwards, so that the flames go toward the
bottom and then turn back, up through the centre of the furnace.
This design achieves longer residence time in the flame zone,
which is suitable for high-temperature NOx reduction; longer res-
idence time at high combustion temperature gives higher reduc-
tion of NOx.
The previous chapter investigates the effect of high operation
temperature in the furnace on gas-phase reactions. Although the
homogeneous reactions dominate the combustion process, the
behavior of the solids and the heterogeneous interactions are also
important. At higher temperature, the devolatilization rate is in-
creased and burnout is enhanced. More nitrogen is released as vol-
atiles [2], which promotes the conversion of fuel-N to N2. Another
effect of increased temperature is that the ashes will melt and a
technique to handle the molten ash is required to prevent slagging.
The temperature around the bottom and walls of the furnace
should be kept below the ash melting temperature. This could be
achieved with an outer layer of recycled flue gases with low con-
centrations of oxygen. The alternative is a wet-bottom (or slag-
tap) boiler (WBB), where the ash is removed from the bottom of
the furnace in a molten state. Cyclone, downshot and u-shaped
boilers (Fig. 9b and c) are common WBB. There is less fly-ash and
convective-pass slagging with a WBB, but there are demands on
the properties (e.g. volatile matter content and slag viscosity) of
the coal used.
Besides high temperature, the design should aim at achieving
low concentrations of nitrogen and a sub-stoichiometric atmo-
sphere during a relatively long time for the reverse Zeldovich
mechanism to be efficient. Air-staging in the burner alone (Fig.
2c) would not generate sufficient time under oxygen-lean condi-
tion and a boiler design with staging in the furnace is called for
(Fig. 2b). The overfire air should be added as pure oxygen (as in
Case 3, Table 2) to avoid introduction of recycled NOx at a late stage
in the combustor without reduction possibilities, a technique
known as oxygen-enriched air-staging, which is used in the glass
making industry [6]. A protective layer of oxidizing atmosphere
along the boiler walls may be needed to resist high-temperature
corrosion.
The sources of air-borne nitrogen in oxy-fuel combustion are air
ingress to the furnace and impurities in the oxygen. The purity of
the oxygen is a question of energy consumption and investment
in the air-separation unit, but production of O2, in principle free
from N2, is a common technique. For safety reasons most of today’s
coal-fired furnaces operate at slight sub-atmospheric pressure and
have to be made gas-tight to avoid air ingress. However, even for a
pressurized oxy-fuel boiler there are possibilities for air ingress,
e.g. in the particle separation, in the recycle fan, and in the coal-
feeding system. To maintain a low level of impurities in the result-
ing flue gas pays off, not only for NOx reduction, but also in the
form of a positive effect on CO2 compression and purification
downstream of the furnace [16].
The increase in oxygen concentration enables a further reduc-
tion of the furnace volume for oxy-fuel combustion compared with
high-temperature air combustion; as the flow through the furnace
is lower (Fig. 3). The residence time is also of importance for the
NOx chemistry, which could be limiting. Other effects of reduction
of the furnace volume (e.g. heat transfer and combustion) need to
be further investigated.
7. Conclusion
The focus of this work is on the gas-phase nitrogen chemistry of
oxy-fuel combustion and the possibility for high-temperature
reduction of nitrogen oxides. The boundaries of crucial parameters
for this reduction are identified, and the reduction effect is demon-
strated on possible oxy-fuel firing strategies by modeling.
It is concluded that the high-temperature reduction of NOx is
dominated by the Zeldovich mechanism and that this reduction
can be made far more powerful than the reduction at combustion
temperatures below 1500 °C; in the latter case the reduction is
mainly by reburning mechanisms. However, the high-temperature
reduction is limited by the equilibrium concentration of NO and
the reaction rate of the mechanism. A low equilibrium concentra-
tion is achieved at negligible air ingress, high oxygen purity, sub-
stoichiometric combustion zones in a furnace, and low tempera-
ture. Sufficient conversion rate by the relatively slow Zeldovich
mechanism requires long residence time and high temperature
(>1800 °C) in the reaction zone. As a consequence of these two con-
tradictory temperature conditions for a maximum reduction rate,
the temperature profile should be decreasing throughout the fur-
 F. Normann et al. / Fuel 87 (2008) 3579–3585
nace from an initially high level in order to lower the equilibrium
concentration while NO is being reduced.
The possibility of high-temperature reduction of NOx avoids the
traditional trade-off between low NOx and low UBC in boiler and
burner design. Instead, issues related to high-temperature corro-
sion and melting of ashes become of importance. This could, how-
ever, be handled with conventional techniques by creating a colder
oxidizing gas layer along the boiler walls to protect these from cor-
rosion and ash deposits or with a wet-bottom boiler design.
To reach the high temperatures suggested in this work, the fuel
has to be burnt in high fractions of O2, at least locally. Except high-
er temperature, the primary effect of higher oxygen concentration
is a decrease in recycle ratio and mass flow through the combustor.
This offers an opportunity to downsize the oxy-fuel boiler and the
equipment used in the recycle loop, given that a sufficient resi-
dence time for the NOx reduction is maintained.
Acknowledgment
This work is financed by the Swedish Energy Agency.
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