Fuel 274 (2020) 117742

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Numerical calculation with detailed chemistry on ammonia co-firing in a T

coal-fired boiler: Effect of ammonia co-firing ratio on NO emissions
Sakiko Ishihara , Juwei Zhang, Takamasa Ito
⁎

Combustion Group, Technology & Integration, IHI Corporation, 1, Shin-nakahara-cho, Isogo-ku, Yokohama 235-8501, Japan

ARTICLE INFO ABSTRACT

Keywords: NH3 co-firing in a commercial 1000 MWe pulverized coal-fired boiler has been considered for reducing CO2
Coal emissions. However, the abundance of fuel-N in NH3 co-firing may cause an increase in NO emissions. The effects
Ammonia of the NH3 co-firing ratio on NO emissions in a commercial boiler are studied through a zero-dimensional
Co-firing numerical calculation with detailed chemistry. A simplified boiler system is composed of a burner zone, an over-
Simulation
fire zone, and two downstream zones. A network of perfectly stirred reactors is used to determine NO emissions
NO
in flue gas. The NH3 co-firing ratio is varied from 0 to 80%. NH3 is injected into the flame zone, which is part of
Boiler
the burner zone. As a result of calculation, amount of CO2 emission decreases as an increase in the NH3 co-firing
ratio. Since the location where NH3 reacts shifts to the downstream side with an increase in the co-firing ratio,
the peak of NO also tends to transfer to the downstream side. Nevertheless, NH3 is almost completely dissociated
in the burner zone and unburned NH3 emissions are approximately zero independent of the co-firing ratio.
Within the range of 20–60%, NO emissions increase monotonically with the co-firing ratio. However, at 80% co-
firing, the NO emission decreases from the value attained at 60% co-firing. With a co-firing ratio higher than
40%, reactions of rich NH3 chemistry, which are characteristic in rich and low-temperature NH3 flame become
effective. Due to these reactions, fuel(NH3)–NO production tends to decrease in the location where NH3 reacts.

1. Introduction
To control global warming, it is of utmost importance to reduce
carbon dioxide (CO2) emissions in various fields globally. In particular,
there is considerable scope for reducing CO2 emissions from coal-fired
boilers in thermal power plants, which generate more CO2 emissions
than any other means of power generation. Various methods have been
proposed to achieve this, such as oxy-fuel combustion [1], carbon
capture and storage [2], and co-firing with carbon-free fuels.
To reduce CO2 emissions during continuing using conventional in-
dustrial facilities, such as pulverized coal-fired boilers, as a partial
substitute fuel for coal, ammonia (NH3) has received more attention
recently. NH3 is expected to act as a hydrogen carrier with high volu-
metric hydrogen density. As NH3 itself is combustible without requiring
a hydrogen extraction process [2–4], NH3 is supposed to have a high
potential as a fuel in thermal power plants where NH3 has already been
used as a fertilizer and a denitrification agent. As the production
technology of NH3 is mature, the initial and operating costs of its usage
are expected to be relatively low compared to those of other hydrogen
carriers and carbon-free fuels. In future, when yield of NH3 much
increases because of its usage as a hydrogen carrier, and some fuel
incentives by the government in order to meet the gap between “supply
price” and “demand price” [5], cost of NH3 decreases further and,
consequently, NH3 will be generally used also as a fuel. Until then,
combustion characteristics of NH3 are required to be investigated.
NH3 co-firing with coal in pulverized coal-fired boilers has been
studied in a national program in Japan, entitled “Cross-ministerial
Strategic Innovation Promotion Program (SIP): Energy carriers” [3,6].
In this project, Yamamoto et al. [7] investigated NH3 co-firing in a coal
combustion facility by using a horizontal test furnace with a single
burner. By performing NH3 injection at various locations in the furnace,
NO emissions were found to be affected by the injection position, and
the values of minimal NO emissions were comparable to those in the
coal-fired case. It was supposed that NH3 acted as both a reducing agent
and a fuel for effective heat release.
Furthermore, in the SIP project, the IHI Corporation successfully
performed coal NH3 co-firing of three-dimensional (3D) numerical si-
mulations [8,9], a zero-dimensional (0D) simulation [10] and experi-
ments using a 10 MWth facility [11,12]. Zhang et al. performed a 3D
computational fluid dynamics (CFD) calculation [8] for the 10 MWth

Abbreviations: MZ, mixing zone; FZ, flame zone; PFZ, post-flame zone; RDZ, reduction zone; OF, zone/OFZ over-fire zone; DZ, Downstream zone
⁎
Corresponding author.
E-mail address: ishihara2302@ihi-g.com (S. Ishihara).

https://doi.org/10.1016/j.fuel.2020.117742
Received 12 December 2019; Received in revised form 26 March 2020; Accepted 28 March 2020
Available online 13 April 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
S. Ishihara, et al.
facility test [12]. The simulation results were found to be in good
agreement with the experimental results. NH3 co-firing resulted in
lower CO2 emissions, flame temperature, and heat flux to the walls, and
higher unburned carbon in ash. However, improvement of NO model
which was used in the calculation was suggested. As for the 10 MWth
facility test [12], NO emissions were suggested to be reduced in com-
parison with the case of coal firing by controlling operating conditions,
such as the air ratio or velocity of NH3 injection. Additionally, as the
unburned NH3 emissions in the experiments were almost zero, the
supplied NH3 could be almost completely consumed. Thus, NH3 co-
firing with pulverized coal in a commercial boiler may be safely con-
ducted.
Furthermore, Zhang et al. studied the effects of NH3 co-firing ratio
by 3D numerical simulation [9]. As a result of varying NH3 co-firing
ratio from 0% to 80%, amount of NO emission was found to become the
largest with 10% co-firing, and with more co-firing ratio it decreased
with an increase of the ratio. Unburned NH3 in emission gas increased
sharply especially with more than 40% of the co-firing ratio. As the co-
firing ratio increases, the high-velocity NH3 jet penetrated the internal
recirculation zone of flame. Consequently, more amounts of unburned
NH3 emission were obtained, and simultaneously NO emissions de-
creased by the DeNOx effect of NH3.
Results of 3D CFD simulations of a furnace in pulverized coal-fired
boilers have also been studied thoroughly [13,14]. Although such si-
mulations are efficient and useful, and can solve thermal and fluid
dynamics problems, they yield a high computational burden, including
long calculation times and high financial costs. Furthermore, as for
chemical reactions, global reactions are typically used for avoiding
heavy computational burden. For this reason, 3D CFD simulations are
not suitable for studying the effects of detailed chemical reactions. 0D
numerical simulation, however, can focus on solving detailed chemical
reactions rather than thermal and fluid dynamics aspects. Computa-
tional burdens are much less than 3D simulations; e.g. calculation time
is about several seconds, and high spec computers are not exactly re-
quired.
The authors studied the effects of NH3 co-firing in a commercial
1000 MWe pulverized coal-fired boiler with 0D numerical simulations
with detailed chemistry [10]. This study can be said to be the first at-
tempt of 0D simulation of a commercial pulverized coal-fired boiler
which uses a reactor network. A commercial coal-fired boiler was
simplified as a reactor network using perfectly stirred reactors (PSRs),
and compositions of emissions with various NH3 injection positions
were studied. As a result, in the case of NH3 injection into flame zone,
amount of NO emission was found to be lower than the case of coal
firing. Since temperature in flame zone is relatively high which is
higher than 2000 K, supplied NH3 is dissociated and converted into NO
prior to char oxidation. Thus, there exists more abundance of NO de-
rived from supplied NH3 and more amount of left char compared to the
case of coal-firing. Generated NO is reduced by char, and effect of re-
duction of NO by char becomes greater. As a result, lower NO emission
compared to the case of coal firing was obtained. Details about the
reactor network and 0D simulation are explained mainly in Section 2.2,
Section 2.3 and Section 2.4. In the present study, using the reactor
network representing a coal-fired boiler, the effects of the NH3 co-firing
ratio are studied with detailed chemical reactions.
2. Numerical simulation
2.1. Detailed chemical reaction model
In this study, the chemical reaction model proposed by Hashemi
et al. [15] was used. This model is originally based on earlier reported
works on reburning with coal [16]. They modified it and developed a
chemical “engineering” model for the simulation of NOx formation and
reduction in the combustion zone during coal combustion. So far, the
modeling studies on NOx have largely been limited to gaseous fuels. As
2
Fuel 274 (2020) 117742
NO is reduced through reactions with hydrocarbon radicals or hetero-
geneous reactions with soot or char, it has been strongly required to
include soot or char in the reaction model. Hashemi et al. improved the
reaction model to involve a detailed description of the gas-phase
chemistry, together with a simplified description of gas–solid reactions
including soot and char. They also developed models in which the
soot + NO or char + NO reaction was disabled, and compared the
calculation results of N conversion ratio among three model types
(original, disabled soot + NO, and disabled char + NO). As a result, the
models without the soot + NO or char + NO effect overestimated the
experimental results as compared to the case with the original model
involving these effects. Thus, heterogeneous reactions, namely reac-
tions of NO with soot and char, were found to be important for the
modeling predictions of NO emissions.
In this reaction model, soot and char are determined to be C166 and
C412N5, respectively. The soot reaction subset of the present model
includes the Nagle and Strickland–Constable oxidation mechanism for
reaction with O2 [17]. The reaction of soot with NO is expressed as
soot + NO 0.9940soot + 0.5N2 + CO (R13)
The oxidation reaction of char is expressed as
char + 208.5O2 412CO + 5NO (R14)
As for these reactions, parameters of the rate coefficient were
maintained the same as those determined by Hashemi et al. Pre-ex-
ponential factor A, index β and activation energy Ea are shown in
Table 1. The NO reduction by char is expressed as
char + NO char + 0.5N2 + 0.5O2 (R15)
Among the parameters of rate coefficient of (R15), the activation
energy and multiplier of temperature were also kept the same as those
determined by Hashemi et al. However, the pre-exponential factor was
adjusted such that the calculation results of NO emissions would reach
the same level as that obtained from the target commercial boiler.
Result of verification is shown in Section 2.5.
2.2. Chemical reactor network of coal-fired boiler
In the present study, 0D calculations are conducted using the che-
mical reaction software ANSYS Chemkin-Pro [18] which can solve
complex chemical kinetics problems. The target boiler is a commercial
1000 MWe pulverized coal-fired boiler. This boiler, used in a com-
mercial thermal power plant, is a very complex facility, comprising tens
of burners and several heat exchangers. Therefore, in this simulation,
the structure of the boiler is simplified and divided into four parts, as
shown in Fig. 1; a burner zone (BZ), an over-fire zone (OF zone), and
downstream zones 1 (DZ1) and 2 (DZ2). Each zone comprises one or
more PSRs in Chemkin-Pro, and thus, the boiler is expressed as a reactor
network. As PSRs are utilized, the time required for mixing in each
reactor is estimated to be zero due to its infinite mixing rate.
Such reactor networks are commonly used to simulate the mixing
and flow characteristics of a gas turbine combustor [19]. Recently, the
DME/air jet diffusion flame for DME-fueled industrial boilers [20] and
pulverized coal jet flames [21] have been studied using chemical re-
actor networks. Nevertheless, the simulation of a commercial pulver-
ized coal-fired boiler using a reactor network has never been conducted.
Thus, this study can be considered to be the first attempt of such a
Table 1
Original reaction parameters in the chemical reaction model. Rate constants are
expressed as k = ATβexp(−Ea/RT) with units of calories, cm3, mole and second.
No. Reaction A β Ea
(R13) soot + NO → 0.9940soot + 0.5 N2 + CO 2.41E+12 0.5 29,808
(R14) char + 208.5O2 → 412CO + 5NO 3.45E+11 0.0 29,800
(R15) char + NO → char + 0.5 N2 + 0.5O2 2.36E+7 0.0 26,690
S. Ishihara, et al. Fuel 274 (2020) 117742

Table 2
Coal analysis.
wt% (air-dried)

Proximate analysis Moisture 1.6

Volatile matter 54.8
Fixed carbon 30.9
Ash 12.6
Ultimate analysis C 87.6
H 5.1
S 0
N 2.9
O 4.4

Table 3
Input data of mass composition of coal (char + vola-
tile).
Mass fraction of coal

Char (C412N5) 0.35

Soot (C166) 0.46
CH4 0.0053
C2H2 0.039
H2 0.043
CO 0.032
CO2 0.013
H2O 0.019
Fig. 1. Reactor network representing a pulverized coal-fired boiler with NH3 HCN 0.027
co-firing. MZ: mixing zone, FZ: flame zone, RCZ: recirculation zone, PFZ: post- NH3 0.0019
flame zone, RDZ: reduction zone, OF Air: over-fire air. Q1-Q4: Local heat ab- N2 0.011
sorption in each zone. Total 1.0

simulation. Because of the large size of the commercial boiler, the re-
sidence time of the particles or gas in the facility is in the order of a few
seconds. As this is several orders longer than the characteristic time of
the chemical reactions, the effects of the chemical reactions can be
independently studied from those of the gas fluid dynamics.
2.3. Initial conditions
In the reactor network, the burner zone, where many burners are
installed and burner flames interact with each other, is simplified si-
milar to a single burner, referred to as an IHI swirl burner [22], illu-
strated in Fig. 2. The burner zone comprises the mixing, recirculation,
flame, post-flame, and reduction zones.
The coal supplied to the mixing zone depicts the integration of
volatile and char. The proximate and ultimate analyses of coal are
shown in Table 2. From this information, input data of volatile and char
for the present study are obtained using the calculation model FLAS-
HCHAIN [23]. FLASHCHAIN is a polymer chemical model for coal
which includes a four-step reaction mechanism, chain statistics, and the
Combustion air
flash distillation analogy to explain the devolatilization of various coal
types. The calculation results of secondary pyrolysis are utilized as the
input data in this study. The input data of the mass composition of coal
(char + volatile) is listed in Table 3.
The air injected into the mixing zone indicates the transportation air
of coal, while the combustion air acts as the oxidant. The combustion
air is preheated to less than 600 K. In the mixing zone, air and coal are
supplied and mixed with 15% of the recirculated gas as shown in Fig. 1.
The mixed gas is ignited, and chemical reactions occur in the flame
zone with 30% combustion air and the remaining recirculated gas. The
rest of the combustion air and 80% of the gas from the flame zone are
mixed in the post-flame zone. The reacted gas enters the reduction zone
and then the over-fire zone. The proportions of gas distribution in the
burner zone are decided based on the results of previous 3D CFD si-
mulations [8,9,13].
In the case of NH3 co-firing, NH3 is supplied into the flame zone in
the burner zone in this simulation. According to our previous study
[10], NH3 injection into the flame zone results in lower NO emissions
compared to the case of coal firing. This indicates that NH3 co-firing in
a zone with high temperature can lead to a relatively low amount of NO
emission.
Similar to conventional pulverized coal-fired boilers, in this study,
staged combustion, i.e., over-fire air, is injected into the over-fire zone
(Fig. 1). The staged air ratio, as defined below, is 0.40.

Staged air ratio = OF air/(Air to mixing zone + Combustion air +OF air)
(1)
In addition, the excess air ratio of the boiler is 1.1. The staged and
excess air ratios are determined from the operating conditions in the
target commercial boiler.
The gas from the over-fire zone flows into downstream zone 1, and
Pulverized coal then into downstream zone 2. The reacted gas in downstream zone 2 is
regarded as the flue gas of the boiler and is the target for the NO
Internal recirculating flow emission evaluation. The residence time of the gas in each zone of this
boiler network is estimated according to the results of the previous CFD
Fig. 2. Schematic image of an IHI swirl burner. simulation [13]. The total residence time, i.e., the time from the burner

3
S. Ishihara, et al.
zone to downstream zone 2, is ~2–3 s.
In the case of NH3 co-firing, the co-firing ratio is determined to be
based on a lower heating value of NH3. The co-firing ratio of NH3 is
varied from 0% to 80% in steps of 20%. Here, 0% indicates the case of
coal firing. The results of NO emissions are compared between the cases
with various co-firing ratios, to study the effects of NH3 co-firing ratio
on NO emissions.
The amount of input calorie in the case of NH3 co-firing is set to be
the same as that in the coal-fired case. The amount of heat absorbed
from each zone in the boiler is accounted by Q1, Q2, Q3, and Q4 (Fig. 1).
In the burner zone, it is assumed that the heat absorption (Q1) occurs
only in the reduction zone, while the other zones are thermally in-
sulated. In the case of coal firing, Q1, Q2, Q3, and Q4 are determined
from the heat fluxes measured at the target commercial boiler. The
walls of the target commercial boiler comprise water-cooled walls,
which are composed of water pipes inside which steam flows. Fur-
thermore, ash is generally attached on the water pipes. Therefore, ra-
diation heat from the burner flame transfers through the ash and the
wall of the water pipe to the steam. At downstream zone 2, the boiler
walls do not face the burner flame. Thermal radiation is much lower
than that in the other zones, so that effect of thermal radiation is ne-
glected, as presented in Table 4.
As for obtaining heat fluxes in the case of NH3 co-firing, the tem-
perature of the steam inside the water pipes and thickness of ash de-
posited on them are assumed to be the same as those in the coal-fired
case in each zone. The heat flux at each zone corresponds to the tem-
perature in each zone. Using the calculation result of the gas tem-
perature, the amount of heat absorption in each zone is obtained in the
case of NH3 co-firing.
2.4. Simulation approach
In this simulation, at first, the case of coal firing is calculated.
Compositions such as those of coal and air, the volume of each zone,
residence time, and amount of heat absorption are used as input data
for the calculation. As a result, the reaction gas composition and tem-
perature at the outlet of each zone are obtained.
Then, the cases of NH3 co-firing are calculated with the same order
of the case of coal firing. As mentioned in Section 2.3, the temperature
of steam inside the water pipes and thickness of ash deposited on the
water pipes are assumed to be the same as those in the coal-fired case.
With an arbitrary amount of heat absorption, gas temperature in the
case of NH3 co-firing in each zone is calculated through a numerical
simulation. The temperature in each zone can be calculated in advance
by using simple equations of thermal conduction and radiation with an
arbitrary amount of heat absorption (heat flux). Thus, when the same
temperature as indicated in the result of the simple calculation is ob-
tained through numerical simulation, the amount of heat absorption in
the case of NH3 co-firing in each zone is determined.
2.5. Verification of the 0D simulation
Calculation results of CO, unburned carbon in ash (UC) and NO
emissions in the 0D simulation are compared to the emissions obtained
from the commercial target boiler for verification. Here, UC is defined
as char/(ash + char) based on the mass flow. As shown in Fig. 3, they
are normalized by those obtained from the target commercial boiler.
Table 4
Effect of radiation in reactor network.
Burner zone Included
Over-fire zone Included
Downstream zone 1 Included
Downstream zone 2 Neglected
4
Fuel 274 (2020) 117742
The unit of CO and NO in the ordinate is ppm, dry and the unit of UC is
wt%. The normalized CO and UC emissions are 0.11 and 0.81, re-
spectively. It is found that the calculation result of CO emission is re-
quired to be adjusted by changing reaction parameters. The calculation
result of UC is in almost good agreement with that obtained from the
target boiler. The normalized calculation result of NO emission is 0.96.
As a result of adjusting as mentioned in Section 2.1, the amount of NO
emission is in good agreement with that obtained from the target boiler.
In order to supplementarily verify the validity and applicability of
the present study, simulation results are compared to the experimental
results obtained by using a small-scale facility. The experimental results
with the 10 MWth facility [12] is utilized for verification of 3D simu-
lation in the reference [9]. The facility is a furnace with the IHI swirl
burner illustrated in Fig. 2. Gas temperature, gas compositions at fur-
nace exit including O2, CO2, CO, NOx and NH3 are measured con-
tinuously and fly ash is sampled to measure the UC content. More de-
tails are seen in the reference [9].
With 20% co-firing ratio, 0.40 of the staged air ratio and 1.1 of the
excess air ratio, experimental results and 0D simulation results of the
gas compositions in the flue gas are shown in Table 5. As a result of the
0D simulation, amount of O2 emission is in good agreement with the
experimental result. Amount of unburned NH3 emission is almost zero
in the flue gas and amount of CO2 emission decreases in 20% by 20%
NH3 co-firing, similar to the experimental results. In addition, amount
of CO emission decreases and amount of UC increases similar to the
experimental results. The amounts of changes are larger in the 0D si-
mulation than those of the experiment. Thus, 0D simulation tends to
overestimate the effects of NH3 co-firing on CO and UC emissions.
As a result of the adjusting, 223 ppm of the simulation result of NO
is different from 101 ppm of the experimental result in the case of coal
firing. The amount of NO emission increases by NH3 co-firing in the
experiment, while it decreases in the 0D simulation. In the case of NH3
co-firing, a flame existing with more distance from the burner throat
was observed in the experiment [12]. Furthermore, as a result of varied
injection velocity of NH3, larger NO emissions were obtained with
higher speed of NH3 injection in the experiments. The 3D simulation
shows that unburned NH3 reaches downstream side of the furnace with
more increase in injection velocity of NH3 [9]. Therefore, it is estimated
that fuel(NH3)–NO produced at the downstream side are discharged as
emissions and NO emission increases more than that in the case of coal
firing in the experiment. However, in the 0D simulation, the effects of
fluid dynamics are neglected. NH3 supplied to the burner zone is con-
sumed instantly prior to char oxidation, since rate of dissociation of
NH3 is larger than that of char oxidation [10]. As a result of NH3
consumption, fuel(NH3)–NO production and NO reduction by char near
the burner, NO concentration at outlet of the burner zone becomes
lower than that in the case of coal firing. NO concentration keeps lower
until the downstream, so that lower NO emission is obtained.
Overall, it can be said that the calculation results of emissions in the
0D simulation are almost in good agreement with emissions obtained
from the target commercial boiler and with the experimental results.
Since distributions of unburned NH3, NO and char in a furnace affect
NO emissions, it is required to be looked precisely their concentrations
in each zone in the reaction network.
3. Results
Fig. 4 depicts the calculation result of NH3 emissions for NH3 co-
firing ratio. The NH3 emissions are shown as lower than 0.005 ppm
independent of the NH3 co-firing ratio. These are sufficiently small and
estimated to be similar order of calculation errors. Thus, it is found that
the NH3 supplied into the boiler is almost completely burned.
The results of the normalized CO2, CO and NO emissions and UC are
depicted in Fig. 5. The ordinates indicate normalized concentrations by
emissions in the case of coal firing. CO2 emissions decrease with an
increase in the co-firing ratio, as expected; for instance, CO2 emissions
S. Ishihara, et al. Fuel 274 (2020) 117742

Fig. 3. Verification of simulation result of CO, UC and NO emission. Unit of CO: ppm, dry. Unit of UC: wt%. Unit of NO: ppm, dry.

Table 5
Comparisons between the experimental results using a small-scale facility and
simulated results at furnace exit. Note that the simulation is for 1000 MWe
commercial boiler.
Coal firing 20% NH3 co-firing
Experiment Simulation Experiment Simulation
O2 (vol%, dry) 2.5 2.8 2.6 2.8
NH3 (ppm, 6%O2) 0 0 0.4 0
CO2 (vol%, 6%O2) 13.2 13.2 10.6 10.8
CO (ppm, 6%O2) 15 28 13 17
UC (wt%) 3.0 2.3 3.6 3.7
NO (ppm, 6%O2) 101 223 136 116

Fig. 4. Effect of the NH3 co-firing ratio on NH3 emissions.

in the case of 20% co-firing decrease by 20% compared to that in the
coal-fired case.
CO emissions also decrease with an increase in the NH3 co-firing
ratio, since the amount of coal is reduced. Furthermore, the water gas
shift reaction, expressed as below, may be affected.
H2 O+ CO H2 + CO2
In the case of NH3 co-firing, H2O concentration increases in the
burned gases. Therefore, CO can react with H2O more easily, and thus,
the amount of CO emissions might be decreased.
As for NO, in the case of 20% co-firing, NO emission becomes less
than that in the case of coal firing. Nevertheless, with an increased
injection of NH3, NO emissions increase compared to the case of coal
firing. For co-firing ratios in the range of 20–60%, NO emissions in-
crease monotonically with an increase in the co-firing ratio. However,
in the case of 80% co-firing, they decrease and reach the same level as
that in the case of 40% co-firing. This trend of NO emissions for the NH3
co-firing ratio is different from the results of 3D simulation [9]. As
mentioned in Section 1 and Section 2.5, injection velocity of NH3 affects
Fig. 5. Effect of the NH3 co-firing ratio on normalized CO2, CO, NO and un-
burned carbon in ash (UC) emissions. The ordinates show concentrations nor-
malized by those in the case of coal-firing. Subscript 0: the case of 0% NH3 co-
firing, i.e. coal firing.
NO emissions. Especially, with more than 40% of the co-firing ratio, the
3D simulation shows that the high-velocity NH3 jet penetrated the in-
(2) ternal recirculation zone of flame. More amounts of unburned NH3
reach the downstream side, so that NO emissions decrease by the
DeNOx effect of NH3. On the other hand, 0D simulation neglects the
effects of fluid dynamics and the effect of injection velocity is not
considered.
The normalized concentration of UC increases with the co-firing
ratio (Fig. 5). Carbon, which is supposed to become CO, can be emitted
as UC. Fig. 6 shows the normalized amount of char residue in each zone.
The ordinate indicates the amount of char normalized by the input
amount of char. Most of supplied char is consumed in the over-fire zone
independent of the co-firing ratio including the coal-fired case. Never-
theless, as an increase in the co-firing ratio, the amount of char residue
at the outlet of the burner zone (in reduction zone) tends to increase;

5
S. Ishihara, et al.
Fig. 6. Effect of the NH3 co-firing ratio on normalized amount of char residue in
each zone. The ordinate shows amount of char normalized by the input amount
of char. MZ mixing zone; FZ flame zone; PFZ post-flame zone; RDZ reduction
zone; OF zone/OFZ over-fire zone; DZ Downstream zone.
Fig. 7. Normalized O2 concentrations in each zone for NH3 co-firing ratio.
Subscript 0: the case of 0% NH3 co-firing, i.e. coal firing. MZ mixing zone; FZ
flame zone; PFZ post-flame zone; RDZ reduction zone; OF zone/OFZ over-fire
zone; DZ Downstream zone.
6
Fuel 274 (2020) 117742
that is, the amount of char consumption in the burner zone tends to
decrease. In the case of coal firing, the amount of char decreases to 55%
in the post-flame zone and is maintained in the reduction zone. On the
other hand, the amount of char residue increases to 71% in 20% co-
firing. With more NH3 injection, the amount of char residue further
increases to 89–93%. Char consumption corresponds to the char oxi-
dation shown in reaction (R14) in this simulation. Fig. 7 shows the
normalized O2 concentrations in each zone. The ordinate indicates
normalized O2 concentration by O2 emission in the case of coal firing.
With NH3 injection, O2 concentrations in the post-flame zone decrease
to less than half of that in the coal-fired case. Therefore, in the case of
NH3 co-firing, more amounts of O2 are consumed despite the decrease
in char consumption and, consequently, O2 is used not only for char
oxidation but also for NH3 reactions in the burner zone. As a result, char
consumption is inhibited because of lack of O2 in the burner zone and
UC emission increases, as shown in Fig. 5.
4. Effects of co-firing ratio on NO concentrations
4.1. Location where NH3 reacts
In the present study, thermal-NO, char-NO, and fuel(NH3)–NO are
investigated as sources of NO produced in the reactor network. NO
derived from volatile compounds is neglected because of its small
amount.
Figure 8 shows changes in NO concentration at different co-firing
ratios in each zone. The ordinate indicates NO concentration normal-
ized by NO emission in the case of coal firing. In the case of coal firing,
the peak of NO concentration is obtained in the flame zone. Since char
is hardly consumed here (Fig. 6), and the temperature is above 2000 K
(Fig. 9), the peak of NO in the case of coal firing is found to be caused
by thermal-NO, and not by char-NO.
With an increase in the co-firing ratio, the peak of NO tends to
Fig. 8. Change of NO concentration in each zone for NH3 co-firing ratio. The
ordinate shows NO concentration normalized by NO emission in the case of coal
firing. Subscript 0: indicates the case of 0% NH3 co-firing, i.e. coal firing. MZ
mixing zone; FZ flame zone; PFZ post-flame zone; RDZ reduction zone; OF
zone/OFZ over-fire zone; DZ Downstream zone.
S. Ishihara, et al. Fuel 274 (2020) 117742

Fig. 9. Temperature in each zone for NH3 co-firing ratio. MZ mixing zone; FZ
flame zone; PFZ post-flame zone; RDZ reduction zone; OF zone/OFZ over-fire
zone; DZ Downstream zone.
Fig. 10. Change of NH3 concentration in each zone for NH3 co-firing ratio.
Values in parentheses indicate ratios of NH3 residue to input amount of NH3.
MZ mixing zone; FZ flame zone; PFZ post-flame zone; RDZ reduction zone; OF
zone/OFZ over-fire zone; DZ Downstream zone.
transfer to the downstream side, as shown in Fig. 8. In the case of 20%
co-firing, the peak of NO concentration is obtained in the flame zone
similar to that in the case of coal firing. However, NO peaks are ob-
served in the post-flame zone in cases of 40% and 60% co-firing. In 80%
co-firing, although a small peak is observed in the post-flame zone, the
maximum concentration is obtained in the over-fire zone. This trend is
caused by a shift of the location where NH3 reactions occur with an
increase in the amount of NH3 injection. In the cases with considerable
NH3 supply, NH3 reactions cannot be completed in the flame zone and
effects of the reactions can be observed in subsequent zones. Therefore,
the zones where the most amount of NH3 is consumed in the reactor
network with each co-firing ratio are focused on.
The change in NH3 concentration in each zone is shown in Fig. 10.
The values in parentheses indicate ratios of NH3 residue to input
amount of NH3. With less than 60% co-firing ratio, most of the supplied
NH3 is reacted in the flame zone. At 20%, 40%, and 60% co-firing ra-
tios, the remaining NH3 amounts are 0.5%, 10% and 33% to input
Fig. 11. Rate of production (ROP) of NH3 where most of supplied NH3 is
amount of NH3, respectively. They decrease further in the post-flame
consumed. (In the cases of 20%, 40%, 60% co-firing: flame zone, in the case of
zone, where NH3 is almost completely consumed. For instance, the
80% co-firing: post-flame zone) FZ flame zone; PFZ post-flame zone.
remaining NH3 becomes 0.03% in 60% co-firing in the post-flame zone.
Nevertheless, at 80% co-firing, NH3 hardly reacts in the flame zone.
As shown in Fig. 10, 99% of the input NH3 remains. The temperature 4.2. NH3 reaction
shown in Fig. 9 is 380 K. In addition, as shown in Fig. 7, the O2 con-
centration in the flame zone is considerably higher than that in the Fig. 11 depicts the results in terms of rate of production (ROP) of
other cases. Therefore, combustion reactions do not occur in the flame NH3 at positions where most of the supplied NH3 is reacted at each co-
zone. In the post-flame zone, the remaining NH3 becomes 0.8% of the firing ratio, as mentioned in Section 4.1. Namely, at 20%, 40%, and
total amount of supplied NH3 (Fig. 10). Most of the supplied NH3 at 60% co-firing, ROP in the flame zone is demonstrated. At 80% co-firing,
80% co-firing is found to be reacted in the post-flame zone. ROP in the post-flame zone is illustrated. A positive ROP suggests
Independent of the co-firing ratio, it is found that most of the sup- production, while a negative ROP indicates consumption.
plied NH3 is consumed in the burner zone, namely until the reduction At 20% and 80% co-firing, reactions (R394) and (R396) are found to
zone. The results of char residue shown in Fig. 6 indicate that the be dominant, and indicate NH3 dissociation. Reaction numbers are
amounts of char consumption decrease in the burner zone due to rapid coincident to the numbers defined in the original reaction model [15].
NH3 reactions with an increase in NH3 co-firing ratio. It can be said that NH3 + H NH2 + H2 (R394)
char oxidation is inhibited by NH3 reactions. As mentioned in Section 3,
this can result in an increase in UC in the case of NH3 co-firing. NH3 + OH NH2 + H2 O (R396)

7
S. Ishihara, et al.
On the other hand, at 40% and 60% co-firing, reaction (R395) be-
comes also effective in addition to reactions (R394) and (R396).
NH3 + O NH2 + OH (R395)
Furthermore, the production of NH3 through reaction (R407) be-
comes effective, although NH3 is hardly produced at 20% and 80% co-
firing.
NH2 + NH2 NH3 + NH (R407)
It is known that in a rich and low-temperature NH3 flame, NH3
becomes stable [3,24]. As shown in Fig. 9, at 20% (in flame zone) and
80% co-firing (in post-flame zone), temperatures are higher than
2000 K. On the other hand, at 40% and 60% co-firing, the temperature
in the flame zone is less than 1800 K. Compared to the case of coal
firing, temperatures decrease by 430 K and 570 K at 40% and 60% co-
firing, respectively. Therefore, in the case of 40% and 60% co-firing,
NH3 production can be observed under NH3-rich and low-temperature
conditions.
Below, each reaction path of NH3 at 20% and 80% co-firing and
40% and 60% co-firing is explained in Section 4.2.1 and Section 4.2.2,
respectively.
4.2.1. Reaction paths of NH3 dissociation to N2 production (20% and 80%
co-firing)
Reaction paths related to NH3 dissociation at 20% and 80% co-firing
are shown in Fig. 12. As products of these reactions, H2, H2O, NO, and
N2 are found to be generated. NH2 produced by reactions (R394) and
(R396) with H/OH becomes NH or HNO by reactions with H/OH again
and O, respectively. NH2 can also directly become N2 through a reac-
tion with N. NH and HNO are converted into N and NO with H/OH. Part
of NH can become HNO through reactions with OH/O2. Furthermore, N
becomes NO through reactions with OH/O2.
At 20% co-firing, the peak of NO concentration is obtained in the
flame zone (Fig. 8). As char is hardly consumed (Fig. 6), the tempera-
ture is above 2000 K (Fig. 9), most of the supplied NH3 is dissociated
(Fig. 10), and considerable NO is obtained in the flame zone. This NO is
fuel(NH3)–NO, derived from NH3 (Fig. 12), and thermal-NO. Because of
the relatively high temperature in the flame zone, the reaction rate of
Fig. 12. Reaction paths relating to NH3 dissociation in flame zone (20% co-
firing) and post-flame zone (80% co-firing). Dashed lines indicate the paths
which are seen in the case of 80% co-firing.
8
Fuel 274 (2020) 117742
NH3 is greater than that of char oxidation. Therefore, the supplied NH3
is dissociated and converted into NO prior to char oxidation. In the
subsequent post-flame zone, the remaining NH3 is dissociated similar to
that in the flame zone. As there exists considerable NO produced in the
flame zone and post-flame zone, and more amounts of char residue
compared to the case of coal firing, the effect of NO reduction by char
increases as compared to the case of coal firing in the post-flame zone.
Consequently, NO concentration becomes lower than that in the case of
coal firing, and maintains this value till the downstream zone 2 (Fig. 8)
[10].
At 80% co-firing, the small peak of NO concentration is obtained in
the post-flame zone (Fig. 8). About 10% of input amount of char is
consumed (Fig. 6). The temperature is above 2000 K (Fig. 9). Fur-
thermore, most of the supplied NH3 is dissociated (Fig. 10). Thus, this
small peak of NO concentration may be caused by production of
thermal-NO, char-NO and fuel(NH3)–NO. However, as shown by the
dashed lines in Fig. 12, the reaction paths of N2 production from N or
NH with NHi (i = 0, 1, 2) are added in comparison with the 20% co-
firing. These reaction paths do not involve NO. Considered that the NO
concentration in the post-flame zone is lower than those at other co-
firing ratios (Fig. 8) in spite of many amount of NH3 consumption
(Fig. 10), it is found that the reaction paths not involving NO become
significantly effective, and many amount of supplied NH3 is dissociated
and converted into N2, not through NO, but through reactions with NHi.
Consequently, NO production in the burner zone is inhibited, so that
relatively low NO emission is obtained at 80% co-firing, although an
increase in NO concentration in the over-fire zone is obtained by char-
NO and fuel(NH3)–NO derived from NH3 residue.
4.2.2. Reaction paths of NH3 dissociation to N2 production (40% and 60%
co-firing)
The reaction paths related to NH3 dissociation in the flame zone at
40% and 60% co-firing are illustrated in Fig. 13. First, NH2 is produced
by reactions (R394), (R396), and (R395) also as shown in Fig. 11. Then,
NH2 becomes NH through reaction with H/OH, N2H2 with NH, NNH
with NO, and directly N2 with N/NO. In addition, NH is converted into
N2H2, N, and N2 through reactions with NH2, H/OH, and N/NH, re-
spectively. N2H2 is transformed into NNH through reaction with H/NH/
NH2. N is converted into N2 through reaction with NO/NH2. NNH is
transformed into N2 with O2 or NNH dissociation. These reaction paths
are different from those in the cases of 20% and 80% co-firing, as shown
Fig. 13. Reaction paths relating to NH3 dissociation in flame zone in 40% and
60% co-firing.
S. Ishihara, et al.
in Fig. 12. Especially, NO is not included in these active reaction paths.
Furthermore, intermediate species N2H2 and NNH become important.
N2H2 and NNH are produced mainly by NHi combination reactions
(reactions of type NHi + NHi). NHi combination reactions are known to
dominate kinetics of the rich NH3 flames and contribute to low NO
production [3,25]. At 80% co-firing, the added reaction paths shown in
Fig. 12 from N and NH to N2 are also NHi combination reactions.
Therefore, at 40% and 60% co-firing, low NO concentration in the
flame zone compared to the cases of coal firing and 20% co-firing
(Fig. 8) is found to be a result of the effects of rich NH3 chemistry.
In the post-flame zone, peaks of NO concentration at 40% and 60%
are obtained (Fig. 8). Char is hardly consumed in this zone (Fig. 6). The
temperature increases to 2100 K (Fig. 9), so that thermal-NO can be
produced more than that in the flame zone. Furthermore, NH3 residues
react and fuel(NH3)–NO is produced (Fig. 10). As the amount of NH3
consumption in the post-flame zone is clearly less than that in the flame
zone, increases of NO concentrations in the post-flame zone are attri-
butable to those in thermal-NO concentration.
5. Conclusions
The partial substitution of NH3 for coal in a pulverized coal-fired
boiler was considered for reducing CO2 emissions. In the present study,
the effects of NH3 co-firing ratio on NO emissions in a commercial
1000 MWe boiler were studied by 0D numerical calculations with de-
tailed chemistry. A pulverized coal-fired boiler was simplified and ex-
pressed as a reactor network, which comprised a burner zone, an over-
fire zone, and two downstream zones using PSRs. The NH3 co-firing
ratio was varied from 0% to 80%, where 0% represents pure coal firing.
NH3 was injected into the flame zone in the burner zone.
As a result of calculation, with an increase in the co-firing ratio, the
location where NH3 reactions occur shifts to the downstream side, since
not all supplied NH3 can be dissociated in the zone where it is injected.
The peak of NO, thus, tends to transfer to the downstream side.
Nevertheless, NH3 was almost completely dissociated in the reactor
network; most of them was consumed in the burner zone. Unburned
NH3 emissions were approximately zero independent of the co-firing
ratio.
The simulations with a co-firing ratio of 20–60% demonstrated that
NO emissions increased monotonically with an increase in the co-firing
ratio. However, at 80% co-firing, NO emissions decreased to the same
level of those at 40% co-firing. With a co-firing ratio higher than 40%,
the reaction paths of NH3 dissociation tended to not involve NO. Such
reactions are known as rich NH3 chemistries, which are characteristic of
rich and low-temperature NH3 flames. When NH3 co-firings are con-
ducted in commercial boilers, NO production derived from supplied
NH3 can be inhibited by using the rich NH3 chemistry, by actively
controlling the combustion conditions, namely, producing locally rich
NH3 flames inside the furnace. Further studies, including flame inter-
actions with multiple burners in the furnace, are required to realize safe
and effective boiler operation with varied NH3 co-firing ratios.
CRediT authorship contribution statement
Sakiko Ishihara: Investigation. Juwei Zhang: Supervision.
Takamasa Ito: Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
Fuel 274 (2020) 117742
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
The present work was supported by the Cross-ministerial Strategic
Innovation Promotion Program (SIP), “Energy Carrier” (Funding
agency: the Japan Science and Technology Agency (JST)).
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