Fuel 363 (2024) 130996

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Fuel
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Full Length Article

Experimental study on the effects of ammonia cofiring ratio and injection

mode on the NOx emission characteristics of ammonia-coal cofiring
Yan Xie a, Jingwen Yan a, Jun Li a, Chaoqun Zhang b, Xin Liu a, b, Wenzhen Zhang a, b,
Heyang Wang a, *
a
School of Mechanical Engineering, Tianjin University, Tianjin 300350, China
b
Yantai Longyuan Power Technology Co. Ltd., Yantai, Shandong Province 264006, China

A R T I C L E I N F O A B S T R A C T

Keywords: Ammonia (NH3) cofiring is a promising approach to reduce the CO2 emissions from coal-fired power plants.
Ammonia/coal cofiring However, the potential drastic increase of NOx emissions may inhibit the wide implementation of NH3 cofiring.
NOx To explore the potential NOx control strategies, the effects of NH3 cofiring ratio (RNH3 ), NH3 injection mode and
Ammonia slip
overfire air (OFA) rates on the NOx emission characteristics of NH3/coal cofiring are studied in a test furnace that
Reduction of CO2 emission
allow for flexible control of the injection positions and combustion environment of NH3. The results show that
when NH3 is injected with coal stream (top mixing mode), the NOx emissions increase and then decrease with the
increase of RNH3 under all OFA rates. However, when NH3 is fed through the side port of furnace separately (side
mixing mode), the NOx emissions exhibit distinct trends under different OFA rates. Under lower OFA rates, the
NOx emissions show monotonical decrease with the increase of RNH3 , while under higher OFA rates the NOx
emissions first decrease and then increase with the increase of RNH3 . Consequently, higher OFA rates could
produce higher NOx emissions than lower OFA rates. This indicates that air-staging is not always effective in the
NOx reduction of NH3 cofiring. Thus, although the side mixing mode of NH3 cofiring exhibits overall better
performance in NOx control, caution is needed to accommodate the OFA rate with NH3 cofiring ratio. Although a
variety of trends of NOx emissions were observed in this study, the results demonstrate that all these trends are in
fact governed by the same mechanism – the competition between the NO-formation and NO-reduction reactions
of NH3 in the varying O2 environment in the furnace. By creating appropriate O2 environment in the furnace, the
NOx emissions of NH3/coal cofiring could be substantially lower than that of pure coal combustion. The findings
of these paper are instrumental in the design and operation of NH3 cofiring system in full scale coal-fired boilers
to achieve effective NOx control.

1. Introduction promising option to be widely used as a carbon-free fuel in coal-fired

Coal combustion is the world’s largest source of carbon dioxide
(CO2) emissions. The greatest use of coal worldwide is by coal-fired
boilers for electric power generation. The resulting CO2 emissions
have caused global concerns with the severe global warming problems.
A practical solution to reduce CO2 emissions from existing coal-fired
power plants is cofiring coal with low carbon alternative fuels [1].
Ammonia (NH3), because of its carbon-free characteristics and high
hydrogen density, provides an attractive option as a carbon-free fuel. In
comparison to hydrogen (H2), NH3 has higher volumetric energy den­
sity, much lower transportation and storage costs, and well-established
utilization and safety procedures. Thus, it has been considered a more
boilers [2,3].
Despite the above advantages of NH3, cofiring NH3 in coal-fired
boilers still faces considerable challenges. Particularly, the potential
drastic increase of NOx emissions due to the high nitrogen content of
NH3 remains the greatest challenge hindering the application of NH3 as
a carbon-free fuel [4–6]. Significant increases of NOx emissions have
been observed when NH3 was cofired with hydrocarbon fuels in a va­
riety of combustion devices [7–12]. At present, majority of the in­
vestigations on NH3 cofiring were based on gas turbines and internal
combustion engines [13–15], and only a handful of studies were con­
ducted on the cofiring characteristics of NH3 with coal. Specifically, Xia
et al. [16] and Hadi et al. [17] investigated the turbulent flame

* Corresponding author.
E-mail address: heyang.wang@tju.edu.cn (H. Wang).

https://doi.org/10.1016/j.fuel.2024.130996
Received 12 November 2023; Received in revised form 22 December 2023; Accepted 14 January 2024
Available online 23 January 2024
0016-2361/© 2024 Elsevier Ltd. All rights reserved.
Y. Xie et al.
propagation behavior of NH3/coal co-combustion in a small spherical
combustion chamber. The results showed that co-combustion of NH3
and bituminous coal could promote each other, and consequently, the
flame propagation speed of NH3/coal particle mixture could be faster
than both the pure coal combustion and pure NH3 combustion cases
under NH3 lean conditions. The Central Research Institute of Electric
Power Industry (CRIEPI) of Japan [18] conducted experimental studies
on NH3/coal cofiring in a 760 kWth horizontal test furnace equipped
with a single coal burner. The results showed that when NH3 was
injected from the burner the NOx emissions increased with the increase
of NH3 cofiring ratio, while when more NH3 was injected through the
port on the furnace side wall, the NOx emissions could be reduced to the
level close to that of coal combustion. Tamura et al. [19] investigated
the effects of NH3 injection methods on NOx emissions in a 1.2 MWth
horizontal coal-fired furnace. The results showed that when NH3 was
injected from the coal burner, the NOx emissions did not exhibit sig­
nificant increase until NH3 cofiring ratio was increased above 30%.
However, when NH3 was injected from the side wall, considerable in­
crease of NOx emissions was observed even under low NH3 cofiring ra­
tios. Ma et al. [20] investigated the cofiring characteristics of NH3 with
coal and biomass in a 25 kW quasi-one-dimensional down-fired furnace
with a swirl-stabilized burner, and NH3 was injected through the central
tube of the burner. It was observed that the NOx emissions increased
almost linearly with NH3 cofiring ratio for both coal and coal/biomass
cofiring cases. Tan et al. [21] studied NH3/coal cofiring in a 6 kW drop
tube furnace with staged combustion. The results showed that staged
combustion plays a key role in reducing NOx emissions. When NH3 was
injected with the staging air 300 mm downstream of the coal injection,
the NOx emissions first decreased until the cofiring ratio reached 20%,
and then increased monotonically with the increase of NH3 cofiring
ratio. As a result, when the cofiring ratio was below 30%, the NOx
emissions could be controlled at approximately the same level as the
pure coal combustion case. Chen et al. [22] carried out experimental
studies in the same 6 kW drop tube furnace under different NH3 injection
modes. It was shown that under lower furnace temperature (1000 ◦ C)
within the SNCR reactions temperature window, the NOx emissions
overall decreased with the increase of NH3 cofiring ratio. Under higher
temperatures (1200 ◦ C, 1400 ◦ C), however, the NOx emissions exhibited
distinct behavior under different NH3 injection modes. When NH3 was
premixed with coal, the NOx emissions exhibited an overall increasing
trend with NH3 cofiring ratio. However, when NH3 was injected with the
staging air downstream of coal injection, the NOx emissions first
increased and then decreased with NH3 cofiring ratio showing peak
values at approximately 20% cofiring ratio.
In terms of numerical studies, Ishihara et al. [23,24] investigated the
effects of NH3 injection positions in a 1000 MW pulverized coal-fired
boiler using a zero-dimensional reactor network model with detailed
chemistry. The results showed that lower NOx emissions could be ob­
tained when NH3 was injected directly into flame zone, while the NOx
emissions would be the highest when NH3 was mixed with the main
combustion air. Zhang et al. [25] simulated NH3/coal cofiring in an 8.5
MW furnace equipped with a single swirl burner using three-
dimensional CFD model. The results showed that the NOx emission
first increased and then decreased monotonically with the increase of
NH3 cofiring ratio due to the DeNOx effect of unreacted NH3 under
higher cofiring ratio. Lyu et al. [26] simulated NH3/coal cofiring in a
600 MW utility boiler and investigated the influences of NH3 cofiring
ratio, O2 enrichment in combustion air, and deep air staging on the heat
transfer and combustion characteristics of the boiler. The results indi­
cated that high temperature and strong reducing atmosphere created by
combining the O2 enrichment and deep air staging could help reduce the
NOx emission by 50%.
The above studies investigated the cofiring characteristics of NH3
with coal in different combustion facilities and divergent trends of NOx
emissions regarding the critical influences of NH3 cofiring ratio and
injection methods were reported in those literatures. So far, there still
2
Fuel 363 (2024) 130996
lack of reasonable mechanistic explanations on these divergent obser­
vations. It is known that the amount of NOx formation is strongly
affected by the combustion environment of NH3 [27,28]. An O2-defi­
cient reducing environment would greatly suppress the formation of
NOx. Note that many of these studies involved the use of swirl burners of
different designs to feed coal and NH3 into the furnace [18,19]. These
burners would create complex aerodynamics in the furnace and affect
the mixing process of NH3 with air, and hence, would strongly affect the
amount of NOx formation. Thus, even under similar experimental con­
ditions (e.g. NH3 cofiring ratio, injection position, staging air ratio etc.)
the actual combustion environment of NH3 in these studies may be
substantially different resulting in different NOx emissions. Therefore, in
order to elucidate the NOx emission characteristics of NH3/coal cofiring,
it is critical to exclude the effects of complex aerodynamics on the
mixing process of NH3 and be able to realize accurate control of the
combustion environment of NH3. Therefore, in this paper experimental
studies were conducted in a one-dimensional drop tube furnace that was
specially designed to allow for flexible control of the injection positions
and combustion environment of NH3. The effects of NH3 cofiring ratio,
injection location and staging air ratio on NOx formation were system­
atically investigated. A variety of trends of variation of NOx emissions
with NH3 cofiring ratio were observed under different NH3 injection
modes and staging combustion conditions. However, it is found in this
paper that all these trends are governed by the same mechanism – the
net NOx formation of NH3 cofiring is determined by the competition
between the NO-formation and NO-reduction reaction pathways of NH3
over the entire furnace space, as will be discussed in detail in this paper.
2. Experimental facility and conditions
2.1. Experimental facility
A one-dimensional (1D) drop tube furnace was designed for the NH3/
coal cofiring experiments to realize flexible control of the combustion
environment of NH3. Fig. 1 shows the schematic and in-situ picture of the
experimental facility. The experimental system consists of a furnace, a
gas supply system, a coal feeder, a burner, and a gas analyzer (Testo 350,
Germany). The furnace is 75 mm in diameter and 2.1 m long, including
three segments of 0.7 m long (Zone 1 to 3). Each segment is lined with
refractory material and installed with MoSi2 heating elements for pre­
cise furnace temperature control. Nine ports are opened along the
furnace. Each port is equipped with a branch pipe with a spherical valve
that can be linked to the overfire air (OFA) pipe, NH3 gas pipe or gas
sampling pipe. By switching the valves, each port can be used to inject
overfire air or NH3 or sample the combustion gas to measure the con­
centrations of key species.
A burner consisting of two air ducts is placed on the top of the
furnace. The primary air (PA) is injected into the furnace through the
inner duct of the burner, while the secondary air (SA) is injected through
the outer duct. A screw coal feeder with maximum feeding rate of 200 g/
h is used to feed pulverized coal to the PA duct of the burner, and the
coal particles are then carried into the furnace by the PA stream. The
overfire air (staging air) is fed into the furnace through the side ports of
the furnace. The NH3 gas can be fed into the furnace through the burner
with the PA/coal stream or through the side ports of the furnace. The
flow rates of PA, SA, OFA and NH3 are controlled by flow controllers.
The concentrations of O2, CO, CO2, and NOx in flue gas are measured by
a Testo 350 gas analyzer. The NOx is mainly composed of NO and a small
amount of NO2. The maximum errors of O2, CO, CO2, and NOx con­
centration measurements were 0.8%, 5%, 1%, and 5% of the measure­
ment values, respectively. The SHL-6000 ammonia analyzer is used to
measure the NH3 slip, and the measurement error is ± 0.1 ppm. All
species concentrations are measured on dry basis. The sampled gas is
first passed through a gas dryer to remove water vapor and then fed into
the gas analyzer. Each test is carried out at least three times to ensure the
consistency of the experimental results.
Y. Xie et al. Fuel 363 (2024) 130996

Fig. 1. NH3/coal cofiring experiment system.

3
Y. Xie et al.
As described above, this experimental system allows for flexible
control of the injection locations of NH3 and overfire air. Particularly,
NH3 can be fed from the top of the furnace with PA/coal stream or
injected separately through the side ports of the furnace. The overfire air
can also be injected into the furnace through different side ports creating
a reducing reaction zone with different length. Hence, this system can
imitate the air-staging combustion process in real coal-fired boilers and
realize flexible control of the combustion environment of NH3 by
injecting NH3 into different positions of the furnace. The side ports on
the furnace also provide the ability to monitor the distributions of major
species along the furnace to reveal the effects of NH3 cofiring on the
combustion and NOx formation processes.
2.2. Experimental conditions
Both pure coal combustion and NH3/coal cofiring cases were tested
in this study. The coal used in the experiments is a bituminous coal. Its
ultimate and proximate analyses data are given in Table 1. Before each
test, the coal particles were first vacuum-dried for one hour and sieved to
the particle size below 200 µm.
NH3 cofiring under two different NH3 injection modes were inves­
tigated in this study. As shown in Fig. 2, the first is referred to as the top
mixing mode (TM, Fig. 2(a)) under which NH3 and the PA/coal stream
are mixed in the burner and fed into the furnace simultaneously. The
second is the side mixing mode (SM, Fig. 2(b), (c)) under which NH3 was
injected into the furnace separately through the side port of the furnace.
Hereafter, NH3 injection through port 1 and port 3 are respectively
referred to as SM-P1 and SM-P3 cases. Note that under the side mixing
mode, NH3 was injected into the furnace later than the coal particles so
that the combustion of NH3 may take place in a more O2-deficient
environment due to the consumption of O2 by the initial combustion of
coal particles.
The key experimental parameters are listed in Table 2. The coal flow
rate of pure coal combustion case is 200 g/h and the thermal input is
thus 5.34 MJ/h calculated based on the lower heating value (LHV) of
coal. Under NH3 cofiring cases, a portion of coal is replaced with NH3 of
the same heating value so that the total thermal inputs are maintained at
5.34 MJ/h. For all cases the excess air ratio is 1.15, and the rate of PA is
fixed at 20% of the total air. Overfire air is fed into the furnace through
the side port 5, and its flow rate varies in the range of 10% ~ 30% of the
total air flow. The furnace temperature is maintained at 1473 K. The
present study is mainly concerned with the fuel NOx of NH3/coal
cofiring which is sensitive to the atmosphere of the combustion envi­
ronment and less sensitive to the temperature [22,23]. For this reason,
this paper is mainly focused on the influences of NH3 cofiring ratio under
different combustion atmosphere created by different NH3 injection
modes and OFA rates. The furnace temperature of this study (1473 K) is
above the temperature window of Selective Non-Catalytic Reduction
(SNCR). It was shown by Chen et al. [22] that the trends of NOx emis­
sions would not be affected by furnace temperature above this range.
The PA, SA, and OFA are preheated to 350 K, 423 K and 423 K,
respectively, before being fed into the furnace.
NH3 cofiring ratio is one of the key parameters studied in this paper.
It is defined as the percent of NH3 in terms of the total thermal input,
ṁNH3 × QNH3
RNH3 = × 100% (1)
ṁNH3 × QNH3 + ṁcoal × Qcoal
Table 1
Coal proximate and ultimate analyses data (wt%, as received).
Proximate analysis Ultimate analysis
(wt%) (wt%)
Moisture Ash Volatile Fixed carbon C H
6.21 9.14 30.19 54.46 69.30
4
Fuel 363 (2024) 130996
where RNH3 denotes NH3 cofiring ratio, ṁNH3 and ṁcoal are the mass flow
rates of NH3 and coal (g/h), and QNH3 and Qcoal are their lower heating
values (MJ/kg), respectively. In this paper NH3 cofiring ratio RNH3 varies
in the range of 10–30%.
3. Results and discussion
3.1. Effects of NH3/coal cofiring on CO2 reduction
Fig. 3 shows the variations of CO2 emissions (@6% O2) at the furnace
outlet with NH3 cofiring ratio under different NH3 injection modes. The
theoretical CO2 concentrations (estimated assuming complete combus­
tion of coal and NH3) are also shown in Fig. 3 for comparison. Since NH3
is a carbon free fuel, the coal flow rate decreases proportionally with the
increase of NH3 cofiring ratio under the same thermal input. As a result,
it is seen that the CO2 emissions exhibit linear reduction with the in­
crease of NH3 cofiring ratio and that experimental and theoretical results
are in close agreement.
3.2. CO and NOx emission characteristics under the top mixing mode
Fig. 4 shows the variations of CO concentrations measured at
different ports along the furnace under different NH3 cofiring ratios (top
mixing mode). There are no measurements at port 5 because overfire air
is injected through this port. The OFA rate is 30% of the total air under
which the overall air/fuel stoichiometric ratio (SR) in the upper furnace
is 0.805. As a result, it is seen that the CO concentrations increase
quickly in the upper furnace because of the incomplete combustion of
coal. The high CO from the upper furnace is then nearly completely
consumed by the overfire air in the burnout zone such that the CO
emissions at the furnace outlet are at very low levels (<30 ppm). The CO
emissions under higher NH3 cofiring ratios (20% and 30%) are lower
than those of 10% cofiring ratio and pure coal combustion cases. This is
attributed to the reduced coal feeding rate under higher NH3 cofiring
ratios. Moreover, NH3 was not detected at the furnace outlet under all
NH3 cofiring ratios. This indicates complete burnout of NH3 in the
furnace. This is primarily attributed to the following reasons: 1) the
furnace temperature is much higher than the ignition temperature of
NH3 (924 K [1]) which ensures instant ignition of NH3 as it enters the
furnace; 2) the residence time of the gas mixture in the furnace is
approximately 2.6 s which ensures sufficiently long time for the burnout
of NH3 [29]; 3) the results of Xia et al. [16] and Hadi et al. [17] showed
that the combustion of NH3 could be enhanced by co-combustion of
bituminous coal which consequently would promote the burnout of
NH3.
Since NH3 is carbon-free, all the CO should originate from the
incomplete combustion of coal. However, it is seen in Fig. 4 that the CO
concentrations in the main combustion zone (before the OFA port) in­
crease with the increase of NH3 cofiring ratio. The CO concentration at
the location of port 4 is 2601 ppm under pure coal combustion case,
while it increases to 6825 ppm as NH3 cofiring ratio increases to 20%.
This is in opposite trend with the amount of coal fed into the furnace.
Note that under the top mixing mode, the coal and NH3 are fed into the
furnace with the PA and SA simultaneously. Hence, the combustion
reactions of coal and NH3 are going to compete with the available O2 in
the PA and SA in the main combustion zone. The increase of CO with
NH3 cofiring ratio in the upper furnace then implies that NH3 burns
Lower heating value (MJ/kg)
O N S
4.38 9.65 0.78 0.54 26.71
Y. Xie et al. Fuel 363 (2024) 130996

Fig. 2. NH3 injection modes for NH3/coal cofiring experiments.

Table 2
Operational conditions of experimental studies.
Operation parameters Unit Values

Thermal input MJ/h 5.34

Excess air ratio
Total air flow rate
Coal mass flow rate
NH3 cofiring ratio (RNH3 )
NH3 mass flow rate
NH3 injection mode
Rate of PA
Rate of OFA
PA temperature
SA and OFA temperature
OFA injection port
Furnace temperature
– 1.15
m3/h 1.76
g/h 200; 180; 170; 160; 150; 140
% 0; 10; 15; 20; 25; 30
g/h 0; 29.6; 44.4; 59.2; 74.0; 88.8
– TM; SM-P1; SM-P3
% 20
% 10; 20; 30
K 350
K 423
– Port 5
K 1473

faster than the coal particles so that the available O2 for coal combustion
becomes increasingly deficient with the increase of NH3 cofiring ratio.
This is because NH3 has been well mixed with O2 in the PA stream, and
hence, would readily undergo prompt combustion when being fed into
the high temperature environment of furnace, while coal combustion Fig. 3. Variations of CO2 emissions (@6% O2) with NH3 cofiring ratio under
involves sequential processes of particle heating, moisture evaporation, different NH3 injection modes.
devolatilization, and combustion of volatile and char. Consequently,
under the top mixing mode more O2 tends to be quickly consumed by the
the furnace, and at the location of port 4 the NOx concentrations are
NH3 combustion, leading to a more O2-deficient environment for coal
reduced to only 46.30% (20% OFA) and 29.26% (30% OFA) of their
combustion. This leads to increased CO concentration in the main
peak values, respectively. The OFA is injected through port 5.
combustion zone with the increase of NH3 cofiring ratio.
Downstream this port, the NOx concentrations exhibit a slight in­
Fig. 5 shows the distributions of NOx concentrations along furnace
crease at port 6 and then remain nearly invariant along the furnace.
under different OFA rates and 15 % NH3 cofiring ratio. The following
2) The distribution of NOx along furnace under 10% OFA shows a
observations can be made from Fig. 5.
similar but slightly different trend with those of 20% and 30% OFA
cases. It is seen that under 10% OFA rate the NOx concentration
1) Under 20% and 30% OFA rates the NOx concentrations increase
reaches the peak value at the location of port 2 which is a little later
quickly as the fuels enter the furnace and reach their highest level at
than the 20% and 30% OFA cases, and then decreases monotonically
the location of port 1. The NOx concentrations then decrease along

5
Y. Xie et al.
Fig. 4. Variations of CO concentrations (@6% O2) along furnace under
different NH3 cofiring ratios (TM, OFA = 30 %).
Fig. 5. Variations of NOx concentrations (@6% O2) along furnace height under
different OFA rates (TM, RNH3 =15 %).
along the furnace without showing a slight increase across the OFA
port 5.
3) Comparing the NOx curves under different OFA rates, it is seen that
the NOx concentrations are greatly reduced by increasing the OFA
rate. This suggests that air-staging combustion is still an effective
way to reduce the NOx emissions of NH3/coal cofiring.
The mechanism underlying the above trends can be obtained from
the following analysis.
Firstly, it is noted that although the combustion of NH3 may cause
Fig. 6. Schematic of the major reaction pathways of NH3 combustion [28].
6
Fuel 363 (2024) 130996
high NOx formation due to its high nitrogen content, NH3 can also
convert NOx to N2 acting as a reducing agent of NOx. Fig. 6 shows the
major reaction pathways of NH3 combustion. It is seen that NH3 and its
intermediate species NHi (i = 0, 1, 2) involve two major competing re­
action pathways. They can either react with O2 or oxygen-bearing rad­
icals (O, OH) forming NO, or react with NO reducing them to N2
[27,28,30,31]. The NO-formation and NO-reduction reaction pathways
of NH3 coexist and which one takes a superior role is mainly dependent
on the O2 concentration in the combustion environment. In an O2-rich
environment the NO-formation pathway is superior and cofiring NH3
may lead to increase of NOx emissions, while in an O2-deficient
(reducing) environment the NO-reduction pathway can become supe­
rior, and as a result, the net formation of NO would be reduced. The
competition between the two reaction pathways of NH3 forms the basis
for the discussion throughout the paper.
Secondly, as seen in Fig. 7, the O2 concentration drops quickly in the
main combustion zone because of the continuous O2 consumption by the
combustion reactions of NH3 and coal. Thus, the combustion of NH3
takes place in a constantly varying O2 environment along the furnace.
During the early stage of combustion at the top region of the furnace, the
O2 is abundant so that the NO-formation pathway of NH3 is dominant
leading to a significant amount of NO formation, as evidenced by the
high NO concentrations at the location of port 1 in Fig. 5. During the
later stage of combustion downstream of port 1, the NO-reduction
pathway becomes increasingly important with the decrease of O2 con­
centration along the furnace. Thus, a portion of the NO generated during
the early stage of combustion would be reduced during the later stage of
combustion by the residual NH3 in the main combustion zone, as evi­
denced by the much lower NO concentrations at the location of port 4 in
Fig. 5.
Lastly, with the increase of OFA rate, the combustion environment in
the main combustion zone becomes increasingly O2-deficient. Thus, the
NO-reduction pathway becomes more important leading to decreased
NO concentrations under higher OFA rates, as seen in Fig. 5. Moreover,
the SR in the upper furnace is 0.92 and 0.805 under 20% and 30% OFA
rates, respectively. This means that there would be a considerable
amount of unburned fuel in the main combustion zone. When they
encounter the overfire air from port 5, a small amount of NO would be
generated by the combustion of these unburned fuel. This leads to a
slight increase of NO concentrations across the OFA port 5 under 20%
and 30% OFA rates. In comparison, under 10% OFA rate the SR in the
upper furnace is 1.035 indicating that there would be sufficient O2 for
the fuels to achieve complete combustion. One consequence is that the
oxidation reactions of NH3 would last longer so that the NO concen­
tration reaches its peak value at a downstream location (port 2) of the
furnace. In addition, there would be little residual fuels left in the main
combustion zone. Thus, little NO would be generated by the residual
Fig. 7. Variations of O2 concentrations along furnace height under different
OFA rates (TM, RNH3 =15 %).
Y. Xie et al.
fuels with overfire air. The overfire air from port 5 in fact dilutes the NO
from the main combustion zone. This is the reason why the NO con­
centration exhibits a monotonical decease along furnace downstream of
port 2 under 10% OFA.
The above discussion demonstrates an important property of NH3
cofiring − the net formation of NO depends on the competition between
the NO-formation and NO-reduction reaction pathways of NH3 over the
entire furnace space. Because of the continuous consumption of O2 by
the combustion reactions, the NO-reduction reaction pathway will
become increasingly dominant during the later stage of combustion by
which a significant amount of the NO generated during the initial stage
of combustion will be reduced. Understanding this property of NH3
cofiring, the following interesting and important results would be easier
to be illustrated.
Fig. 8 shows the variations of NOx emissions at the furnace outlet
with NH3 cofiring ratio under different OFA rates. Thess result address
one of the major concerns regarding cofiring NH3 with coal – high NOx
emissions. It is seen that although the amount of fuel nitrogen into the
furnace increases dramatically with NH3 cofiring ratio, the NOx emis­
sions do not exhibit a corresponding monotonical increase. Instead, they
first increase and then decrease with the increase of NH3 cofiring ratio.
Consequently, under high NH3 cofiring ratios (RNH3 = 30%) the NOx
emissions can drop to the level close to those of coal combustion cases
under 20% and 30% OFA rates. Moreover, it is noted that the maximum
NOx emission occurs atRNH3 = 15% under 10% OFA rate, and it gradu­
ally shifts to a lower value ofRNH3 = 10% under 30% OFA rate. The
mechanism underlying these trends can be obtained from the following
analysis.
Firstly, under lower NH3 cofiring ratios the amount of fuel nitrogen
into the furnace increase quickly compared to the pure coal combustion
cases. This leads to significant increase of NO formation during the early
stage of combustion. Moreover, as the NH3 cofiring ratio is low, there
would be little residual NH3 survived from the initial stage of combus­
tion to participate the NO-reduction reactions that are more dominant
during the later stage of combustion. Thus, the amount of NO formation
by the NH3 is overall greater than its reduction leading to increase of
NOx emissions under low NH3 cofiring ratios. With further increase of
NH3 cofiring ratio, the amount of residual NH3 survived from the initial
stage of combustion increase continuously and they tend to reduce the
NO formed at the initial stage of combustion. When NH3 cofiring ratio
increases beyond a certain value (e.g. 15% under 10% OFA rate), the
reduction of NO by NH3 begins to surpass its formation and the NOx
Fig. 8. Variations of NOx emissions (@6% O2) with NH3 cofiring ratio under
different OFA rates (TM).
7
Fuel 363 (2024) 130996
emissions begin to decrease with further increase of NH3 cofiring ratio.
Under high NH3 cofiring ratios (e.g. 25% and 30%), the NOx emissions
can be reduced to the level close to, or even lower than, those of coal
combustion cases, as seen in Fig. 8.
Secondly, note that with the increase of OFA rate the main com­
bustion zone becomes more O2-deficient. Consequently, the initial for­
mation of NO decreases and there would be more residual NH3 to reduce
the NO at the later stage of combustion. Thus, the NOx emissions are
greatly reduced under higher OFA rates, as seen in Fig. 8. Furthermore,
since there would be more residual NH3 to reduce the NO under higher
OFA rate due to the more O2-deficient environment, the NO reduction
reactions of NH3 can surpass the formation reactions at relatively lower
NH3 cofiring ratio. This is the reason why the occurrence of maximum
NOx emissions gradually shifts fromRNH3 = 15% under 10% OFA rate
toRNH3 = 10% under 30% OFA rate, as seen in Fig. 8.
3.3. NOx emission characteristics under the side mixing mode
The above results demonstrated the O2 environment in the furnace
plays a critical role to the NOx emissions of NH3 cofiring. Under the top
mixing mode, the O2 environment in the upper furnace was mainly
controlled by means of varying the OFA rates. The O2 environment of
NH3 combustion can also be modulated by varying the injection posi­
tions of NH3. For example, NH3 can be injected separately through the
side ports into the furnace, as shown in Fig. 2. Under this side mixing
mode, because the combustion of coal particles would first consume a
portion of O2 upstream of the injection location of NH3, the combustion
reactions of NH3 would take place in a more O2-deficient environment in
the main combustion zone comparing to the top mixing mode. This is
going to have significant effects on the net formation of NOx, as will be
detailed thereafter.
Fig. 9 shows the variations of NOx emissions with NH3 cofiring ratio
under different OFA rates when NH3 is injected into the furnace through
the side port 1 and 3, respectively. It is seen in Fig. 9 (a) that as NH3 is
injected through port 1 the NOx emissions decrease monotonically with
the increase of NH3 cofiring ratio under 10% and 20% OFA rates. This is
a remarkable result indicating that the NOx emissions of NH3/coal
cofiring can be substantially lower than the pure coal combustion cases
under high NH3 cofiring ratios (e.g. RNH3 = 30%). This is attributed to the
more O2-deficient environment of NH3 combustion in the upper furnace
under the side mixing mode so that the NO-reduction pathway of NH3
plays a more significant role in comparison to the top mixing mode.
Under 10% and 20% OFA rates, the NO reduction by NH3 exceeds NO
generation and a portion of NO formed from the fuel nitrogen content of
coal is also reduced by NH3. With the increase of NH3 cofiring ratio, the
amount of NH3 participating the NO-reduction reactions increases.
Thus, the NOx emissions decrease monotonically with the increase of
NH3 cofiring ratio under 10% and 20% OFA rates, and they are lower
than the pure coal combustion cases under all NH3 cofiring ratios.
It is noted that under 30% OFA rate the NOx emission exhibits a
different trend. It tends to first decrease and then increase with the in­
crease of NH3 cofiring ratio. This is because the available O2 in the upper
furnace under higher OFA rates will become insufficient for NH3 to
achieve complete combustion. Then there would be increasing amount
of residual NH3 from the main combustion zone under higher NH3
cofiring ratios. When the residual NH3 encounters the overfire air from
port 5, a large amount of NO will be generated leading to increased NOx
concentrations downstream the OFA port. Under higher NH3 cofiring
ratios, the amount of NO generation by the residual NH3 with overfire
air would surpass the reduction of NO in the main combustion zone (as
will be shown in Fig. 10). This is why the NOx emission begins to in­
crease with the NH3 cofiring ratio under 30% OFA rate when RNH3 in­
creases beyond 10%, as seen in Fig. 9(a).
This mechanism can be further reinforced by the results shown in
Fig. 9(b). It is seen that when NH3 is injected into the furnace through
the downstream port 3, the combustion of NH3 will take place in an even
Y. Xie et al.
Fig. 9. Variations of NOx emissions (@6% O2) with NH3 cofiring ratio under different OFA rates (SM).
Fig. 10. Variations of NOx concentrations (@6% O2) along furnace under 20%
and 25% NH3 cofiring ratios (SM-P3, OFA = 20%).
more O2-deficient environment in comparison to the SM-P1 case
because the combustion of coal would consume more O2 before NH3 is
injected into the furnace. Under 10% OFA rate, the O2 in the upper
furnace is sufficient for the fuels to achieve complete combustion and
there is little residual NH3 to form NO with the overfire air. Thus, the
NOx emission still exhibits monotonical decrease with the increase of
NH3 cofiring ratio and is considerably lower than those of the SM-P1
case. However, under higher OFA rates because of the increased resid­
ual NH3 in the main combustion zone resulted from the late injection of
NH3, more NO tends to be generated by the overfire air in comparison to
the SM-P1 case. Consequently, the variation of NOx emission with NH3
cofiring ratio begins to exhibit the decrease-then-increase trend under a
lower 20% OFA rate.
Fig. 10 compares the NOx concentrations of SM-P3 case along the
furnace under 20% and 25% NH3 cofiring ratios and 20% OFA rate.
When NH3 is injected through port 3, the NOx before port 3 are only
generated by the combustion of coal. Note that the coal flow rate de­
creases with the increase of NH3 cofiring ratio. Thus, the combustion of
coal before port 3 under RNH3 = 25% takes place in a relatively more O2-
rich environment than that of RNH3 = 20% case, which promotes the
formation of fuel NOx of coal. Therefore, the initial NOx concentration at
port 1 under RNH3 = 25% appears higher than that ofRNH3 = 20%.
However, the greater amount of NH3 injection under RNH3 = 25% also
results in more rapid reduction of NO downstream of port 3, and
8
Fuel 363 (2024) 130996
consequently, the NOx concentration at port 4 is lower than that of RNH3
= 20%. However, the late injection of NH3 from port 3 under RNH3 =
25% also results in more residual NH3 from the main combustion zone
which subsequently leads to greater increase of NOx concentrations after
mixing with the overfire air. As a result, the NOx emission at the furnace
outlet under RNH3 = 25% becomes higher than that of RNH3 = 20%, as
shown in Fig. 10 and Fig. 9 as well. The differences between RNH3 = 20%
and 25% cases in the distribution of NOx concentrations along furnace
clearly demonstrate that the NOx emissions of NH3/coal cofiring are
determined by the combined effects of the NO-formation and NO-
reduction reaction pathways of NH3 along the entire furnace.
3.4. NOx control of NH3 cofiring in full-scale coal-fired boilers
The above results showed a variety of trends of NOx emissions under
different NH3 injection modes and OFA rates, and that by modulating
the combustion environment of NH3, the NOx emissions of NH3 cofiring
could be substantially lower than those of the coal combustion cases.
This basically addresses one of the largest concerns of NH3 cofiring –
high NOx emissions. Based on the findings from these results, the
following measures can be implemented in the design and operation of
NH3 cofiring system in coal-fired boilers to realize effective NOx control.
1) Air-staging combustion. Air-staging technology can readily modulate
the overall combustion environment of the main combustion zone. It
has been widely used in coal-fired boilers to reduce the NOx emis­
sions. Under the top mixing mode of NH3/coal cofiring, it was shown
that air-staging is still an effective measure of NOx control. Under the
side mixing mode, however, it was shown that air-staging could lead
to higher NOx emissions under high NH3 cofiring ratios, and hence, is
not always effective in NOx reduction. For this reason, the OFA rates
under the side mixing mode need to coordinate with the NH3 injec­
tion locations and cofiring ratios to ensure the effectivity of air-
staging combustion in NOx reduction.
2) Fuel-staging combustion. Cofiring two fuels provides us with addi­
tional flexibility to modulate the combustion environment of NH3.
We can utilize the combustion consumption of O2 by one fuel to
modulate the combustion environment of the other fuel. For
example, NH3 can be fed through separate ports into the furnace
regions (e.g. between the coal burners and OFA ports) where the
combustion of coal has consumed a significant portion of O2. Under
the basis of air-staging, fuel-staging can provide a more flexible O2-
deficient environment for the combustion of NH3, and thereby, can
Y. Xie et al.
further suppress the formation of NO. However, as stressed above,
extra caution needs to be exercised when applying fuel-staging along
with air-staging. Specifically, the NH3 cofiring ratios need to be co­
ordinated with the NH3 injection locations and OFA rates to avoid
excessive formation of NO by the residual NH3 with the overfire air.
4. Conclusion
Systematic experimental studies were conducted to investigate the
NOx emission characteristics of NH3/coal cofiring under different NH3
cofiring ratios and NH3 injection modes. A test furnace was designed to
allow for flexible control of the combustion environment of NH3 and
measurements of species concentrations along the furnace.
The results show a variety of trends of NOx emissions with the in­
crease of NH3 cofiring ratio under different NH3 injection modes and
OFA rates. Specifically, Under the top mixing mode, the NOx emissions
increase and then decrease with the increase of NH3 cofiring ratio under
all OFA rates. This is due to the reduction of NO by the residual NH3
during the later stage of combustion in the main combustion zone that
gradually surpasses the NO generation of NH3 under higher RNH3 . Under
the side mixing mode, the NOx emissions exhibit distinct trends under
different OFA rates. Under lower OFA rates, the NOx emissions show
monotonical decrease with the increase of cofiring ratio, while under
higher OFA rates the NOx emissions tend to first decrease and then in­
crease with increase of NH3 cofiring ratio. Consequently, higher OFA
rates could produce higher NOx emissions than those of lower OFA rates.
This is due to the generation of NO by the large amount of residual NH3
with the overfire air under high NH3 cofiring ratios. These results
demonstrate that that air-staging is not always an effective measure for
the NOx reduction of NH3 cofiring under the side mixing mode. Thus,
extra caution is needed to accommodate the OFA rates with NH3 cofiring
ratio to avoid excessive NO generation by the residual NH3 with the
overfire air.
The results of this study show that although different trends of NOx
emissions are observed under different experimental conditions, these
trends are all governed by the same mechanism − the NOx emissions are
determined by the competition between the NO-formation and NO-
reduction reactions of NH3 in the varying O2 environment in the
entire furnace space. Different experimental conditions (NH3 cofiring
ratios, injection modes and OFA rates etc.) create different O2 environ­
ment in the furnace space. Thus, the relative role of the two competing
reaction pathways could vary significantly in the furnace space, leading
to distinct NOx emission behavior. This may also explain the divergent
trends observed in previous studies.
CRediT authorship contribution statement
Yan Xie: Writing – original draft, Methodology, Investigation,
Formal analysis, Data curation. Jingwen Yan: Writing – review &
editing. Jun Li: Writing – review & editing, Conceptualization. Chao­
qun Zhang: Resources, Project administration. Xin Liu: Validation,
Software, Resources. Wenzhen Zhang: Validation, Software, Resources.
Heyang Wang: Writing – review & editing, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The authors do not have permission to share data.
Fuel 363 (2024) 130996
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