Combustion and Flame 211 (2020) 406–416

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Combustion and Flame

journal homepage: www.elsevier.com/locate/combustflame

Control of NOx and other emissions in micro gas turbine combustors

fuelled with mixtures of methane and ammonia
Ekenechukwu C. Okafor a,∗, K.D. Kunkuma A. Somarathne b,
Rattanasupapornsak Ratthanan b, Akihiro Hayakawa b, Taku Kudo b, Osamu Kurata c,
Norihiko Iki c, Taku Tsujimura a, Hirohide Furutani a, Hideaki Kobayashi b
a
Fukushima Renewable Energy Institute, National Institute of Advanced Industrial Science and Technology (AIST), 2-2-9 Machiikedai, Koriyama, Fukushima
963-0298, Japan
b
Institute of Fluid Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
c
Research Institute for Energy Conservation, National Institute of Advanced Industrial Science and Technology (AIST), Namiki 1-2, Tsukuba 305-8564,
Ibaraki, Japan

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

Article history: Methane–ammonia mixtures have potentials as low-carbon fuels for gas turbines, however significantly
Received 3 June 2019 high fuel NOx production in their flames present challenges to their application. This study aims to pro-
Revised 31 July 2019
vide deep insight into the physical and chemical processes involved in the formation and control of emis-
Accepted 5 October 2019
sions from the combustion of CH4 –NH3 –air with up to 30% ammonia by heat fraction in gas turbine com-
bustors. Hence, laser diagnostics techniques such as Particle Image Velocimetry (PIV), and Planar Laser
Keywords: Induced Fluorescence (PLIF) imaging, in addition to Fourier Transform Infrared (FTIR) gas analysis were
Micro gas turbine employed to study the flow field, flame structure and emissions characteristics of a micro gas turbine
Ammonia swirl combustor fuelled with CH4 –NH3 –air mixtures. The control of emissions from the flames was fur-
Fuel NOx
ther studied using Large Eddy Simulation (LES) of a model swirl combustor. The results show that NOx
Rich-lean combustion
emissions from premixed CH4 –NH3 –air in single-stage combustion were more than 50 0 0 ppmv at equiv-
Emissions control
alence ratios,  = 0.8–1.1, which is about twice more than the values already reported for NH3 –air. Trends
in NOx emissions correspond with the trends in OH radicals concentration in the combustor owing to the
relevance of OH radicals in fuel NOx production. Emissions control leading to significantly low emissions
such as 49 ppmv of NOx, 2 ppmv of CO and approximately zero N2 O, HCN and NH3 emissions with a
99.8% combustion efficiency was achieved using rich-lean combustion. An optimum  of the primary
combustion zone for low NOx emission was identified, which varied from 1.30 to 1.35 depending on the
ammonia fraction. For  richer (leaner) than the optimum Φ , NOx emission increased due to an increase
in NOx production in the secondary (primary) combustion zone. Rich-lean combustion of CH4 –NH3 –air
emitted less NOx than that of NH3 -air because the higher flame speed of CH4 –NH3 –air mixtures ensured
lower NOx production in the secondary combustion zone.
© 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

1. Introduction tion as an alternative fuel in thermal power generation may ensure

Ammonia (NH3 ), with a well-established global production and
transportation infrastructure, a high hydrogen density, and boiling
and condensation temperatures similar to propane, has recently at-
tracted interest as an option for hydrogen transport and storage.
On the other hand, there has been a rekindled interest in ammonia
as a fuel for combustion systems, especially micro gas turbines and
industrial furnaces [1,2]. Being a carbon-free fuel, its wide applica-
∗
Corresponding author.
E-mail address: ekenechukwu.okafor@aist.go.jp (E.C. Okafor).
a substantial reduction in global CO2 emissions. Furthermore, the
introduction of ammonia as a gas turbine fuel may not demand
huge extra costs on infrastructures for ammonia transportation and
storage because ammonia is already being used in most large-scale
thermal power plants for selective catalytic reduction of NOx [2].
Until recently however, ammonia combustion applications had
been discouraged mainly by the relatively low flame speeds of
ammonia–air mixtures and the high fuel NOx production in the
flames. A stoichiometric NH3 –air mixture has a laminar burning
velocity that is one-fifth that of CH4 –air mixture at 298 K and
0.10 MPa [3]. Previous studies by Pratt [4] reported that the low
burning velocity of NH3 –air mixtures required the use of low inlet

https://doi.org/10.1016/j.combustflame.2019.10.012
0010-2180/© 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
velocities in ammonia gas turbine combustors to ensure sufficient
fluid residence time for ammonia consumption. However, low inlet
velocities inhibited turbulent mixing and flame stabilization. Thus,
unacceptably low combustion efficiencies were recorded in the gas
turbine combustor. Given that ammonia is a toxic substance [1],
unburned ammonia emission from gas turbines is undesirable. On
the other hand, NO emissions from ammonia combustion could be
several thousand ppmv owing to high NO production from the N
atom in ammonia molecule [5,6].
Recent numerical and experimental studies [2,5–11] have how-
ever shown that NH3 -air flames can be stabilized over a wide
range of conditions by employing swirling flows in combustors.
Three-dimensional Large Eddy Simulations (LES) by Somarathne et
al. [8–10] using detailed chemistry indicate that stable NH3 –air
flames can be achieved using swirl combustors even for high in-
let velocities of 39.1 m/s. The flow field of combustors with strong
swirls are characterized by regions of recirculating fluid motion
which circulates hot products and active radicals from downstream
to upstream of the combustor. Consequently, mixing and preheat-
ing of the fresh unburned mixture is enhanced thereby enhanc-
ing the stability of the flame [12–14]. In addition, the recirculating
motion increases the fluid residence time, allowing more time for
consumption of the fuel. [15].
Kurata et al. [5] employed a high-swirl non-premixed combus-
tor (swirl number = 0.88) in which the fuel was injected parallel
to the combustor central axis, and reported successful generation
of power from a 50 kWe-class regenerative cycle micro gas turbine
fuelled with NH3 –air mixtures. They reported combustion efficien-
cies of up to 96% for Combustor Inlet Temperatures (CIT) above
700 K. Lower CIT however was characterized by high level of un-
burned NH3 emissions. A more recent study by Okafor et al. [6] us-
ing a similar combustor in a laboratory combustor test rig showed
that the combustion efficiency of non-premixed NH3 –air flames
could be improved by the use of inclined fuel injection as opposed
to fuel injection parallel to the combustor central axis. This has
been demonstrated to improve the combustion efficiency of non-
premixed NH3 –air mixtures in a micro gas turbine even at low CIT
[11].
Furthermore, two-stage rich-lean combustion has been demon-
strated to control NOx emissions from combustors fuelled with
NH3 –air mixtures [2,6,9,10]. Rich-lean combustion takes advantage
of the low NOx production from the oxidation of ammonia at fuel-
rich conditions. The primary combustion zone is maintained at a
fuel-rich condition to ensure low NOx production while air is in-
jected in the secondary combustion zone to burn off the unburned
NH3 and H2 from the fuel-rich primary combustion zone. Okafor
et al. [6] showed that NOx emission from two-stage combustors
fuelled with NH3 –air mixtures varied non-monotonically with the
equivalence ratio of the primary combustion zone, Φ pri , and had
a minimum value at Φ pri = 1.10. At this optimum low NOx equiv-
alence ratio and an ambient pressure of 0.30 MPa, they reported
NOx emission from premixed NH3 –air combustion of 42 ppmv at
16% O2 concentration with a combustion efficiency of 99.5%.
On the other hand, there is growing interest in the combus-
tion applications of blends of ammonia and other fuels such as
hydrogen [16–21], diesel [22,23], methane [5,24–30] and pulver-
ized coal [2]. The present study focuses on mixtures of methane
and ammonia. An important advantage of ammonia blending in
hydrocarbon combustion is the reduction in CO2 emission due
to the replacement of some part of the hydrocarbon by ammo-
nia. On the other hand, such blending offers potentials for an
improvement of the combustion characteristics of ammonia mix-
tures. It has already been reported that mixtures of CH4 –NH3 –
air with up to 30% of ammonia by heat fraction (52% by volume
fraction) in the fuel have burning velocities twice more than that
of NH3 –air mixtures at the same conditions [25,26]. Studies in a
407
micro gas turbine demonstrated that CH4 –NH3 –air mixtures re-
sult in higher combustion and thermal efficiencies than NH3 –air
mixtures [5].
However, CH4 –NH3 –air flames may produce significantly higher
NOx emissions than NH3 –air flames [5,26,28]. NOx production
from ammonia containing flames increases with an increase in the
concentration of O, H and OH radicals in the flames because these
O/H radicals promote the oxidation of NH2 and NH to form NO
via a HNO intermediate route [31]. The combustion of hydrocar-
bon species in ammonia-containing flames generates high amounts
of O/H radicals leading to high NO production [32]. 1D numerical
simulation of adiabatic and unstretched CH4 –NH3 –air flames indi-
cated that CH4 –NH3 –air flames with more than 10% of NH3 in the
fuel by volume may produce more NO than NH3 –air flames [26].
Furthermore, studies on the oxidation of mixtures of ammonia
and carbon-containing species in staged combustion indicate
that HCN and consequently, N2 O production may be important
in hydrocarbon–ammonia–air combustion [33,34,35]. Kristensen
et al. [35] studied the nitrogen chemistry in the burnout zone of
staged combustion containing a mixture of CO, NO, HCN, NH3 and
O2 . They found that HCN oxidation leads to high N2 O production
and recorded up to 100 ppmv of N2 O emission at lean burn out
conditions. Wargadalam et al. [32] investigated the homogenous
formation of NO and N2 O from the combustion of HCN and NH3 at
873–1273 K and noted that HCN oxidation promotes NO and N2 O
formation. Takagi et al. [33] suggests that HCN contributes to
the higher NOx production from hydrocarbon-ammonia flames in
comparison to ammonia-containing flames with no hydrocarbon
content. This is because HCN has a higher tendency than NH3 to
be oxidized to NO, being consumed at leaner combustion zones
with higher OH concentrations. Note that HCN is a very toxic gas
and 1 min exposure to ca. 300 ppmv of HCN is lethal [36]. On
the other hand, N2 O is a greenhouse gas whose Global Warming
Potential (GWP) is 298 times larger than that of CO2 [5]. Therefore,
it is desirable to achieve a complete consumption of these species
in the combustor.
Most of the previous experimental studies on the control of
emissions from ammonia-blended hydrocarbon combustion con-
sidered only small quantities of ammonia in the order of few
thousand ppmv in the fuel. Because ammonia was seldom consid-
ered a fuel until recently, the characteristics and control of emis-
sions from combustors fuelled with hydrocarbon-ammonia mix-
tures with high ammonia concentration in the fuel has seldom
been investigated. Jójka and Ślefarski [37] studied the combustion
of CH4 –NH3 –air mixtures with up to 5% volume fraction of am-
monia in the fuel in a nozzle burner and found that NOx emis-
sion, which was in the order of 20 0 0–30 0 0 ppmv increased with
the ammonia content in the fuel. Valera-Medina et al. [38] stud-
ied the stability and emissions characteristics of CH4 –NH3 –air mix-
tures with 69% ammonia volume fraction in the fuel using a single-
stage tangential swirl combustor and showed that NOx emissions
at fuel-lean conditions ( = 0.8) was more than 30 0 0 ppmv. They
concluded that a stratified injection of methane and ammonia
as opposed to fully premixed injection is required to encourage
the production of active radicals for NOx reduction. Ramos et al.
[29] measured emissions from premixed CH4 –NH3 –air flames with
up to 70% NH3 by mole fraction stabilized on a laminar flame
burner. They reported that NOx emission increased as NH3 mole
fraction increased up to 50% and then decreased afterwards. Li et
al. [28] numerically analysed the combustion of methane-ammonia
mixtures in a model combustor consisting of perfectly stirred reac-
tors and plug flow reactors at 2.3 MPa. The 1D calculations indicate
the potential of two-stage combustion in controlling NOx emis-
sions from the combustion of CH4 –NH3 –air mixtures with 40% am-
monia volume fraction when the equivalence ratio of the primary
combustion zone is 1.5. However, there is yet no experimental
408 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
Fig. 1. The swirl combustor and liners. The model liner shown in (c) has similar dimensions as the original gas turbine liner shown in (a).
evidence of control of NOx and other emissions from CH4 –NH3 –
air flames with high ammonia contents.
In this study, experiments and 3D computations which comple-
ment each other were employed to study the control of NOx, in-
cluding NO2 and N2 O, and other emissions such as HCN and CO
from combustors fuelled with mixtures of methane and ammo-
nia with up to 30% of ammonia by heat fraction (52% by volume).
In the experiments, laser diagnostics techniques such as PIV, OH-
PLIF and simultaneous OH/NO-PLIF imaging were first employed to
characterize the flow field and the flame structure in the com-
bustor. Then the emission characteristics of CH4 –NH3 –air flames
in single stage and two-stage combustion were investigated, em-
ploying Fourier Transform Infrared (FTIR) gas analysis. The effects
of ammonia fraction, equivalence ratio, mixture homogeneity, and
ambient pressure on emissions were examined. On the other hand,
the computational approach involved the application of Large Eddy
Simulation (LES), which provides a compromise between cost and
accuracy, to study the process of emissions formation and control
in a two-stage combustor in order to advance the understanding of
the experimental observations.
The objective of this study is thus to provide deep insight into
the physical and chemical processes involved in emissions forma-
tion and control in the combustion of mixtures of methane and
ammonia with high ammonia concentration, as well as demon-
strate the potential of achievement of low levels of NOx and other
emissions in the application of such mixtures as gas turbine fuels.
2. Experimental and numerical methods
2.1. The combustor
The combustor, shown schematically in Fig. 1a, was that of a
50 kWe type micro gas turbine employed by Kurata et al. [5,11].
The combustor had a swirler, shown in Fig. 1b, with a swirl num-
ber of 0.88 surrounding a 12-hole fuel injector. The injection an-
gle of each hole was 45° to the combustor central axis. In this
study, premixed and non-premixed combustion were investigated.
In non-premixed combustion, the fuel was introduced through the
injector while the swirler was used for air. To ensure comparable
fluid residence times in both non-premixed and premixed com-
bustion cases, about equal flow rates were allowed through the
injector and swirler in both cases at any given condition. In the
premixed case, the mixture flow rate was divided between the
swirler and injector in a proportion approximately equivalent to
the swirler/injector flow ratio in the corresponding non-premixed
case.
Two combustor liners with similar dimensions were employed,
namely; the real gas turbine combustor liner shown in Fig. 1a, and
a model liner shown in Fig. 1c. The real gas turbine liner had six
holes in the secondary combustion zone with diameter of 23 mm,
which allowed for secondary air injection. On the other hand, the
model liner had no holes for secondary air injection, instead the
cylindrical sections were made of quartz glass to allow for optical
measurements. The regions enclosed by the dash lines in Fig. 1c
indicate the measurement areas for PIV and PLIF. The methodology
and results of the PIV measurement are provided as supplementary
materials to this article.
The combustor was installed inside a laboratory combustor test
rig described in our previous studies [6] and in the present supple-
mentary material. Gaseous ammonia (> 99.9% purity) and methane
(99.0% purity) were supplied from their respective pressurized
cylinders, and mixed at a point 5 m upstream of the combustor in-
let ports. The concentration of ammonia in the fuel was expressed
in terms of the heat fraction, ENH3 , and was varied from 0 to 0.30.
xNH 3 LHVNH 3
ENH3 = (1)
xNH 3 LHVNH 3 + xCH 4 LHVCH 4
Here, xNH3 and xCH4 are mole fractions of NH3 and CH4 in the bi-
nary fuel and LHV stands for the lower heating value (LHVCH 4 =
802.30 kJ/mol, LHVNH 3 = 316.84 kJ/mol).
The air flowrate was measured with Brooks mass flow con-
trollers with an accuracy of ±0.9% of the set point. On the other
hand, the flowrates of ammonia and methane were measured with
Kofloc mass flow meters with accuracies ranging from ± 1% to
± 1.5% of full scale (F.S.) depending on the value of F.S. The esti-
mated absolute uncertainties in measuring the equivalence ratio
and fuel fraction increased with ENH3 and the maximum values
were ± 0.04 and ± 0.015, respectively. The primary combustion air
was separately measured and supplied directly to the swirler while
the secondary combustion air, whose flowrate was also separately
controlled, was supplied to the base of the combustor test rig and
made to flow through the holes on the combustor liner. The com-
bustor inlet temperature (CIT) was kept at 298 K at all measure-
ments in the present study. The chamber pressure was manually
controlled using valves mounted on the exhaust pipe. Three K-type
thermocouples were placed at the liner exit to measure the com-
bustor outlet temperature, (COT).
 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
Fig. 2. Setup for simultaneous OH/NO-PLIF imaging.
2.2. Planar laser induced fluorescence (PLIF) imaging
The OH-PLIF and simultaneous OH/NO-PLIF imaging were con-
ducted in the flames at 0.10 MPa. The OH-PLIF system consisted
of a frequency doubled dye laser (Lumonics, 13 mJ/pulse at
282.929 nm after SHG) pumped by an Nd:YAG laser (Spectral
physics, 300 mJ/pulse at 532 nm), a digital delay generator (Stan-
ford Research Systems Inc.), photomultiplier and an ICCD camera
(Andor technology). The dye laser was tuned to 282.929 nm to ex-
cite the (1, 0) band of the OH (X2  ← A2  + ) system. The OH flu-
orescence was detected at around 310 nm using the ICCD camera
mounted with a combination of a Schott UG11 optical filter cen-
tered at 325 nm (FWHM = 110 nm) and LX0313 filter centered at
313 nm (FWHM =10 nm). All OH-PLIF images in the present study
were taken with the same laser excitation power and image acqui-
sition settings of the ICCD camera.
The setup for simultaneous OH/NO-PLIF imaging is as shown
schematically in Fig. 2. For NO excitation, an Nd:YAG laser was
used to pump a wavelength tunable dye laser with a frequency
doubler (Sirah Precision Scan). The laser wavelength was tuned to
226.298 nm in order to excite the Q1(29.5) transition for NO with
a power of 5 mJ/pulse. The OH-PLIF and NO-PLIF were separately
detected with two intensified CCD (ICCD) cameras (Andor technol-
ogy) mounted with the appropriate optical filters. A band pass fil-
ter centered at 236 nm was employed in the case of NO-PLIF.
2.3. Exhaust gas analysis
The exhaust gases from the exit of the combustor were ana-
lyzed using a Fourier Transform Infrared (FTIR) gas analyzer (BOB-
20 0 0FT) containing O2 and H2 analyzers with a scanning frequency
of 5 Hz. The temperature of the sampling line was maintained at
464 K to avoid condensation of water vapor along the line. Before
each series of measurements, the gas analyzer was calibrated using
span gases, while for each measurement, the species concentration
in the exhaust gases were allowed to attain approximately steady
values before data was logged for about 60 sec. The emission val-
ues reported here are the mean. The standard deviation from the
mean at all conditions and the repeatability of the measurements
are less than 5% of the mean values. Because the accuracy of the
measurements was dependent on the range of the measuring scale,
409
multiple scales were employed in analyzing species such as NO,
NH3 , and CO, whose mole fractions may vary from several thou-
sand ppmv to few ppmv. On the other hand, single scales were
employed for species such as NO2 , N2 O, and HCN. The maximum
uncertainty was less than ±8 ppmv for most measurements. How-
ever, for NO and NH3 mole fractions more than 500 ppmv the un-
certainties were about ±15 ppmv and ±30 ppmv, respectively. For
all experiments on emission measurement, the swirler mean inlet
velocity was kept at ∼2.70 m/s in order to ensure an approximately
constant fluid residence time in the combustor at all conditions.
2.4. Large eddy simulation (LES)
Two-stage combustion of CH4 –NH3 –air mixtures in a gas
turbine-like combustor was modeled using OpenFOAM [39]. De-
tails of the computational domain and the numerical methods are
as described in the previous modeling studies on NH3 –air com-
bustion by Somarathne et al. [10] and also provided in the present
Supplementary materials. Few relevant points are mentioned here.
The unstructured 3D computational domain was a cylindrical non-
premixed combustor with two annulus swirlers and eight square-
shaped secondary combustion air injection ducts.
The LES model employed spatially filtered mass, momentum,
energy and species equations [40], in which scales smaller than
the grid size were not resolved but were accounted for through
the sub-grid scale tensor modeled based on an eddy-viscosity as-
sumption. The wall adaptive local eddy-viscosity (WALE) model
[41] was employed for modeling the sub-grid scale viscosity. Un-
resolved fluxes of species and sensible enthalpy in the spatially fil-
tered mass fraction and sensible enthalpy equations were adopted
as gradient assumptions. Furthermore, turbulence was modeled
by solving a model transport equation for the turbulent kinetic
energy [42]. The filtered reaction rate terms were modeled us-
ing partially stirred reactor (PaSR) model [43], which is a multi-
scale model accounting for the turbulent–chemistry interaction.
The LES-PaSR model has been extensively used and validated for
modeling turbulent–chemistry interactions [44]. The walls of the
combustor were non-slip and adiabatic, and the outlet was speci-
fied by the continuity boundary condition. An in-situ adaptive tab-
ulation algorithm library [45] was combined with the main com-
putational program in order to speed up the calculations. A con-
stant total air flow rate of 0.022 m3 /s was maintained for all
computations to ensure an approximately constant fluid residence
time, while the ratio of the primary to the total air flow rates was
constant at 0.306. The computations were performed at an ambi-
ent pressure of 0.50 MPa, air inlet temperature of 500 K and fuel
inlet temperature of 300 K.
In the previous numerical work by Somarathne et al. [10] on
NH3 –air combustion, the chemical reaction mechanism by Miller
et al. [46] was employed. The present LES however employed a
reduced reaction mechanism by Okafor et al. [26] with 42 species
and 130 reactions. The mechanism was developed and optimized
with measured values of the unstretched laminar burning velocity
of CH4 –NH3 –air, and NH3 –air flames and species concentrations in
the flames over a wide range of conditions including equivalence
ratios = 0.7–1.3, ENH3 = 0–1.0, and mixture pressure = 0.10 MPa–
0.50 MPa. On the other hand, a detailed mechanism by Okafor et al.
[25] validated for modeling the burning velocity and speciation
in CH4 –NH3 –air flames [25,26,47] was used in 1D analysis of the
chemistry of pollutants formation in the unstretched and adiabatic
flames using ANSYS Chemkin-PRO software [48]
We recognize that the equivalence ratio of the non-premixed
flames varies locally in the combustor. Therefore, the term “global
equivalence ratio, Φ ” is henceforth used to refer to the average
equivalence ratio. To avoid confusion that may arise due to the use
of numerous symbols for equivalence ratios, Φ is used for both
410 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
Fig. 3. (a) Single shot OH-PLIF images and (b) time-average OH-PLIF images of 200
single shots in premixed CH4 –NH3 –air flames with ENH3 = 0.30.
non-premixed and premixed flames in this study. Where staged
combustion (such as rich-lean) strategy is employed, Φ overall is
used to refer to the equivalence ratio obtained based on the to-
tal air and fuel supplied to the combustor while Φ pri is used to
refer to the equivalence ratio of the primary combustion zone.
3. Results and discussion
3.1. Flame structure
Figure 3a shows single shot OH-PLIF images of premixed
CH4 –NH3 –air flames of ENH3 = 0.3 at different equivalence ratios.
Note that the laser sheet passed from right to left hence the de-
crease in OH-PLIF intensity from right to left on the images is
due to laser absorption. A time-averaged image of 200 single shots
shown in Fig. 3b highlights the mean flame shape and may also
represent a probability density map of OH-PLIF intensity in the
combustor. Across the reaction zone, the concentration of OH rad-
icals rises sharply from zero (in the unburned mixture) to super
equilibrium concentrations, represented by the brightest regions in
Fig. 3a. Note that OH-PLIF intensity is proportional to the concen-
tration of OH radicals in a flame [51,52]. Therefore, the approxi-
mate location of the reaction zone can be identified as the position
of relatively steep gradients of the OH-PLIF intensity [49,50,53].
The intensity of the OH-PLIF was found to be highest around
equivalence ratio of 0.9, which corresponds to the equivalence ra-
tio where the OH concentration in 1D unstretched and adiabatic
CH4 –NH3 –air flames peaks. As the flame became richer, the inten-
sity of the OH-PLIF decreased. The OH-PLIF intensity at Φ = 1.2 can
be seen to be relatively low. At Φ = 1.4, the OH-PLIF intensity was
too low to allow identification of the flame structure (not shown
in this manuscript).
Fig. 4. (a) Single shot OH-PLIF images and (b) time-average OH-PLIF images of 200
single shots in non- premixed CH4 –NH3 –air flames with ENH3 = 0.30.
Figure 4 shows the single shot and the time-averaged OH-PLIF
images for the non-premixed flames. Two important differences
can be observed between the OH-PLIF images of the premixed
flames and those of the non-premixed flames. As the equivalence
ratio increased, the reaction zone tended to move closer to the
combustor walls in the non-premixed flames. The regions close to
the combustor wall may be leaner than regions around the center
of the combustor because the air swirler surrounded the fuel in-
jector in this study. In addition, unlike in the premixed case, the
OH-PLIF intensity did not decrease appreciably with an increase
in equivalence ratio. The OH-PLIF intensity was high enough even
at Φ = 1.4 for the flame structure to be clearly observed in non-
premixed combustion.
The plane-integrated time-averaged OH-PLIF intensities of the
premixed and the non-premixed flames at various equivalence ra-
tios are shown in Fig. 5. The premixed flame had a significantly
higher OH-PLIF intensity close to stoichiometric equivalence ra-
tios and clearly showed a peak at  = 0.9. On the other hand,
the non-premixed flame had higher OH-PLIF intensities in fuel-lean
(Φ ≤ 0.7) and fuel-rich (Φ ≥ 1.2) conditions. It is considered that
in the fuel-lean and the fuel-rich non-premixed flames there may
exit local regions with equivalence ratios close to unity where the
OH radical concentrations are relatively high. Consequently, the
OH-PLIF intensity for the non-premixed flame at Φ = 1.4 was com-
parable to that at Φ = 1.0.
The qualitative trends in OH-PLIF intensities shown in
Fig. 5 may represent the trends in the concentration of OH radi-
cals in the combustor since all the measurements were completed
using the same laser excitation power and image acquisition set-
tings. It is worth noting here that these trends in Fig. 5 corre-
spond with the trends in NO emission from the flames discussed in
Section 3.3 (See Fig. 7) because NO production from CH4 –NH3 –air
flames is promoted by the production of OH radicals. Simultane-
 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
Fig. 5. Variation of the plane-integrated time-averaged OH-PLIF intensities with
equivalence ratio for CH4 –NH3 –air flames with ENH3 = 0.30. The error bars repre-
sent the standard deviation from the mean of plane-integrated intensities of 400
single shots.
Fig. 6. Pairs of simultaneously captured instantaneous OH-PLIF and NO-PLIF images
in fuel-rich ( = 1.4) non-premixed CH4 –NH3 –air flames with ENH3 = 0.20. The top
and bottom pairs are separated only by time.
ous imaging of OH-PLIF and NO-PLIF performed in the fuel-rich
(Φ = 1.4) non-premixed flame indicates, as shown in Fig. 6, that
the local regions of relatively high OH-PLIF intensity in the fuel-
rich flame correspond with regions of relatively high NO-PLIF in-
tensity. This observation, which is important in NOx control using
two-stage combustion, suggests that the fuel-rich non-premixed
flames with Φ > 1.2 may produce more NO in the primary com-
bustion zone than the fuel-rich premixed flames as discussed in
Section 3.4 (see also Fig. 12).
411
Fig. 7. Measured emissions of (a) NO, (b) NO2 and (c) N2 O from single-stage com-
bustion of CH4 –air and CH4 –NH3 –air mixtures.
3.2. Measured emissions from single stage combustion
An understanding of the emission characteristics of single stage
combustion is relevant to the control of emissions using two stage
combustion because the concentration of species from the primary
combustion zone of two-stage combustors is related to the emis-
sions from single-stage combustion. In addition, the optimum Φ pri
for low NOx emission in two-stage combustion may correspond to
the equivalence ratio in single stage combustion where the sum of
NO and unburned NH3 emissions have a minimum value, as dis-
cussed in Section 3.4.
Figure 7 shows that CH4 –NH3 –air premixed flames emitted
several times more NO than CH4 –air flames. For Φ = 0.8–1.0,
the emissions were larger than 50 0 0 ppmv which is the maxi-
mum measurable range of NO in this study. It can be seen that
NO emissions decreased as the equivalence ratio became leaner
(richer) than 0.7 (1.1). However even at Φ 0.6, NO emission from
CH4 –NH3 –air combustion was more than 20 0 0 ppmv. The leaner
conditions also had high N2 O emission of up to 120 ppmv for
ENH3 = 0.3 at Φ = 0.6. Note that these measured values of NOx
emissions from CH4 –NH3 –air flames are about twice more than
the already reported values of NOx emissions from NH3 -air flames
at similar conditions by Okafor et al. [6].
NO formation/reduction in ammonia containing flames is
mainly through the fuel NOx route, which is strongly dependent on
the concentration of O, H and OH radicals in the flame. N2 O is pro-
duced mainly through the reactions of NO with NH and with HO2 .
It is then rapidly consumed mainly through reaction with H rad-
icals and through thermal dissociation. Hence, low temperatures
and low concentration of H radicals, which are typical conditions
in far-lean equivalence ratios, may hinder N2 O consumption and
consequently lead to significant emissions of N2 O as observed in
the experiment.
Because of the dependence of NO production on OH concentra-
tion, NO emissions in Fig. 7 has a similar trend with the OH-PLIF
intensities in Fig. 5. It can be seen that the high OH-PLIF intensity
in the fuel-lean premixed flames conditions corresponds with the
high NO emissions at this condition. Furthermore, the difference
between the measured NO emissions from the premixed flames
and the non-premixed flames corresponds with the disparity in the
OH-PLIF intensities of the two modes of combustion. The produc-
412 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
Fig. 8. Measured emissions for (a) NH3 , (b) HCN and (c) H2 from single-stage com-
bustion of CH4 –air and CH4 –NH3 –air mixtures.
tion of OH and NO in the non-premixed flame may be lower than
that in the premixed flame due to less efficient combustion owing
to insufficient mixing. This conclusion is supported by the signifi-
cantly higher emissions of unburned fuels from the non-premixed
flame (see Fig. 8).
Observe however that even though Figs. 5 and 6 suggest that
the fuel-rich non-premixed flames of Φ > 1.2 may produce higher
NO due to the high OH concentration from the local lean regions
in the combustor, Fig. 7 shows that NO emissions from the non-
premixed flames was not higher than that of premixed flames at
Φ > 1.2. This is because the NO produced in single-stage com-
bustion at fuel-rich conditions has sufficient residence time to be
reduced by the large concentration of unburned NH3 in the com-
bustor. However, in two-stage rich-lean combustion where the un-
burned NH3 is consumed completely in the secondary combustion
zone, NO produced in the primary combustion zone may not be
sufficiently reduced due to the shorter residence time for its reduc-
tion. Consequently, this NO contributes to the higher NO emission
from the non-premixed flames in two stage rich-lean combustion
when the equivalence ratio of the primary zone is larger than 1.20
as discussed in Section 3.4 (see Fig. 12.)
Figure 8 shows the emissions of NH3 , HCN and H2 from the
flames. The emissions increased rapidly with equivalence ratio in
the fuel-rich conditions, with values exceeding the measurable
range for the species in this study at some conditions (as indi-
cated by the arrows). HCN emissions of more than 500 ppmv was
recorded in the non-premixed CH4 –NH3 –air flame at Φ ≥ 1.25.
HCN is formed in CH4 –NH3 –air flames through reaction of NO or N
with CH3 , CH2 and CH. The production of HCN from the reaction of
NO with hydrocarbon radicals is dominant in fuel-lean conditions
while its production from the reaction of N atom with the hy-
drocarbon radicals is dominant in fuel-rich conditions. The formed
HCN is then oxidized mainly through reactions with O and OH rad-
icals in the postreaction zone. The abundance O and OH radicals in
fuel-lean conditions facilitate rapid consumption of HCN to even-
tually produce NHi radicals and, then, NO. However, in fuel-rich
conditions HCN oxidation tends to be hindered by the relatively
low concentration of O and OH radicals, consequently leading to
the high HCN emissions as observed in the experiments.
Figure 8 shows that H2 emissions was insensitive to the fuel
composition at a constant Φ . H2 production from the NH3 oxida-
tion at fuel-rich conditions is predominantly through the reaction
of NHi (i = 1,2,3) with H radicals [2]. On the other hand, H2 pro-
duction from the methane oxidation chemistry at fuel-rich condi-
tion is predominantly through the reaction of CH4 and CH2 O with
H radicals. As the ammonia content in the CH4 –NH3 –air flames in-
creases, a decrease in H2 production from the methane chemistry
tends to be compensated by an increase in production from the
ammonia chemistry. Contrary to the trend in Fig. 8, the equilibrium
mole fraction of H2 in rich CH4 –NH3 –air combustion may increase
with an increase in ENH3 owing to increased H2 production from
the NH3 chemistry. However, an increase in residence time is re-
quired for an increase in the production of H2 when ENH3 increases
because the reactivity of the mixture decreases. Therefore, the con-
stant finite residence time in the present combustor may limit the
production of H2 as ENH3 increases leading to the observed trend
in H2 emission.
The COT and the emissions of CO2 , H2 O, CO and CH4 are pro-
vided as supplementary materials to this article.
3.3. LES of two-stage combustion
The primary target of NOx control in combustors fuelled with
ammonia mixtures is to control the oxidation of NH2 and NH by
the O/H radicals. To this effect, a control of the equivalence ra-
tio is critical because it ensures a control of the distribution of
the radicals. Unlike in thermal NOx control, temperature tends to
play a secondary role in promoting fuel NOx formation through
its influence on the production rate of the O/H radicals. Figure 9
shows the profiles of temperature and NO in the modeled two-
stage combustor for four different conditions. The temperature in
the primary combustion zone is lowest for the fuel-lean case of
Φ pri = 0.8, however the NO emission is highest for that condition.
Observe also that the cases with stoichiometric and fuel-rich pri-
mary combustion zones show relatively higher NO production near
the combustor wall because the near-wall regions are leaner than
the central regions of the combustor.
A comparison of the space time average NO concentration at
75 mm from the base of the combustor and at the combustor
exit indicates that NO concentration decreased after the injection
of secondary combustion air. This apparent decrease is primar-
ily due to the dilution effect of the injected air rather than a
chemical reduction of NO. It is reasonable to expect a selective
non-catalytic reduction (SNCR) of NO in the secondary combustion
zone, as suggested by Kurata et al. [5], given that the temperature
is largely within the thermal DeNOx temperature window (1100–
1400 K) [54]. However, Fig. 10 shows that for Φ pri < 1.2, HCN and
unburned NH3 concentration from the primary combustion zone
were too low to support any significant NO reduction. On the other
hand, the relatively high concentration of HCN and unburned NH3
from the primary combustion zone of the richer flames favors NO
formation more than its reduction in the secondary combustion
zone due to the high concentration of O2 , CO and H2 as discussed
in the next paragraph.
Figure 11 shows that the high concentration of H2 , CO, OH,
and HCN from the fuel-rich primary combustion zone are effec-
tively consumed in the secondary combustion zone with the injec-
tion of fresh air. An inspection of the species profiles shows that
H2 and CO consumption leads to the production of OH radicals.
H2 and CO are consumed mainly via chain-propagating reactions
H2 +OH=H + H2 O and CO+OH=CO2 +H, respectively, which pro-
mote O and OH radicals production through the chain-branching
reaction H + O2 =OH+O. This contributes to an increase in O/H rad-
ical concentration in the secondary combustion zone thereby en-
abling the oxidation of HCN and the unburned fuels. Owing to the
high concentration of O/H radicals, HCN and NH3 are converted
predominantly to NO in the secondary combustion zone.
 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
Fig. 9. Computed 2D profiles of temperature and mole fraction of NO in the two-stage non-premixed combustion of CH4 –NH3 –air mixtures with ENH3 = 0.20. The space-
time-average NO mole fractions at the exit and at 75 mm downstream of the combustor are indicated. (xNO represents the mole fraction of NO).
Fig. 10. Computed space-time-average mole fractions of NH3 , HCN, H2 , and CO at
75 mm from the base of the combustor which gives an estimate of the mole fraction
of the species from the primary combustion zone.
It can be deduced from the above discussion that even though
that with an increase in Φ pri , NO production in the fuel-rich pri-
mary combustion zone decreases, the corresponding increase in
H2 , CO, HCN and unburned NH3 concentrations from the primary
combustion zone leads to an increase in NO production in the sec-
ondary combustion zone.
3.4. Measured emissions from two-stage combustion
Figure 12 shows the dependence of the COT, and emissions
of CO2 and NO on Φ pri for a constant Φ pri = 0.38 in two-stage
413
combustion. The average temperature at the combustor exit de-
creased with the injection of fresh air into the secondary zone. The
COT was however around 10 0 0 K for the conditions with Φ pri ≥
1.3. Figure 12b shows that the CO2 emissions at 16% O2 concen-
tration decreased with an increase in ENH3 and did not vary with
Φ pri . On the other hand, NO emissions varied non-monotonically
with Φ pri as shown in Fig. 12c. For the premixed flames, the
optimum low-NOx Φ pri , i.e. Φ opt , was found to be around 1.30
for ENH3 = 0.20 and 0.30, and 1.35 for ENH3 = 0.10. Φ opt tends to
decrease with an increase in ENH3 and has been reported to be
around 1.10 for NH3 -air flames [6]. For Φ pri > Φ opt , NO emission
increased with Φ pri due to an increase in NO production in the
secondary zone as explained in Section 3.3.
NO emissions from the non-premixed combustion was less
sensitive to Φ pri and had Φ opt = 1.2. Non-premixed combustion
resulted in lower NO emissions than the premixed combustion
for Φ pri ≤ 1.25. However, higher NO emissions were recorded
from non-premixed combustion for Φ pri > 1.25. Notice also
that at the respective Φ opt for the two modes of combustions,
non-premixed combustion emitted more than three times more
NO than premixed combustion. These higher NO emissions from
non-premixed combustion is partly due to higher NO formation
from the higher concentration of HCN and unburned NH3 in the
secondary combustion zone, as suggested by Fig. 8. In addition,
the non-premixed combustion may have higher NO production
in the primary combustion zone than the premixed combustion
when Φ pri > 1.25 due to the presence of local relatively lean
regions with high NO production.
On the other hand, Fig. 13 shows that NO emission from pre-
mixed CH4 –NH3 –air combustion was insensitive to Φ overall for a
range of Φ overall from about 0.3 to 0.9 at a constant Φ pri = Φ opt .
414 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416

Fig. 11. Computed 2D profiles of the mole fractions of H2 , CO, OH and HCN in rich-lean non-premixed combustion of CH4 –NH3 –air mixtures with ENH3 = 0.20 for Φ pri = 1.4.
The space-time-average concentration of H2 , CO and HCN at the exit of the combustor are indicated.

Fig. 12. Measured values of (a) combustor outlet temperature, COT (b) CO2 emis- Fig. 13. Measured variation of emissions from two-stage premixed combustion of
sions, and (c) NO emissions from two-stage combustion of CH4 –NH3 –air mixtures CH4 –NH3 –air and NH3 –air mixtures with Φ overall at Φ opt . The data for NH3 –air mix-
at a constant overall equivalence ratio of Φ overall = 0.38. tures were adopted from [6].

The figure also shows that unburned NH3 and HCN emissions were
approximately zero, while N2 O emission was less than 2 ppmv.
CO emission was less than 100 ppmv for Φ overall = 0.3 to 0.6 but
was about 20 0 0 ppmv at Φ overall = 0.9 for the flame of ENH3 = 0.10.
The figure also shows the corresponding emissions from NH3 –air
flames [6] in the combustor recorded at similar conditions as the
present study. It can be seen that at Φ opt for CH4 –NH3 –air and
NH3 –air combustion, NO emission from CH4 –NH3 –air combustion
was lower than that from NH3 –air flames in rich-lean combus-
tion. Since in rich-lean combustion, efficient consumption of the
fuel in the primary combustion zone ensures low NO production
in the secondary combustion zone, fuels with high flame speeds
may produce lower fuel NO emissions than slower burning fuels
when Φ pri = Φ opt .
Figure 14 shows the dependence of the COT, the combustion
efficiency, NOx and CO emissions on ambient pressure. The com-
bustion efficiency was obtained based on the heating values of the
fuels, considering CH4 , NH3, CO and H2 as the unburned fuels in
the exhaust gases. The figure shows that the COT and the com- Fig. 14. Dependence of the combustor outlet temperature (COT), the combustion
bustion efficiency increased with ambient pressure. The maximum efficiency(ƞcombust ), NOx and CO emissions on ambient pressure for CH4 –NH3 –air
combustion efficiency recorded in the present study was 99.8% at mixtures (ENH3 = 0.20) at constant Φ overall = 0.56 and Φ pri = 1.30.

0.25 MPa. On the other hand, CO and NOx emissions decreased

 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
with an increase in ambient pressure with values of 2 ppmv and
49 ppmv at 0.25 MPa, respectively. N2 O and HCN emissions at
0.25 MPa were 0.5 ppmv and 0.1 ppmv, respectively, at 16% O2
concentration. It has been reported that fuel NO production may
decrease with pressure as a result of a decrease in O/H radical
pool, and an increase in the combination reaction of NHi radi-
cals [2,6,10,26]. Furthermore, the increase in combustion efficiency
with pressure suggests an increase in the rate of consumption of
H2 , CO, HCN and unburned NH3 in the primary combustion re-
sulting to lower concentrations of these species in the secondary
combustion zone. Consequently, NO production in the secondary
combustion zone and the overall NO emission may decrease with
an increase pressure [6].
The lowest NOx emission level recorded in this study is well
below the 70 ppmv regulatory limit imposed by the Japanese gov-
ernment for gas turbines, however it is still well above the more
stringent limits of about 10 ppmv enforced by various prefectural
governments in Japan [2]. Therefore, it may still be necessary to
employ exhaust gas aftertreatments for NOx reduction. Low NOx
emission from the combustor such as demonstrated in this work
would encourage a significant reduction in the cost and size of SCR
systems needed to achieve below-regulatory-limits NOx values.
4. Conclusions
This work demonstrates the application of rich-lean combustion
strategy in the control of NOx and other emissions from CH4 –NH3 –
air combustion in a micro gas turbine combustor with up to 30%
of ammonia in the fuel in terms of heat fraction. The following is
a summary of major findings in this study.
• OH-PLIF and simultaneous OH/NO-PLIF measurements showed
that local lean regions with high OH and NO concentrations
in the fuel-rich primary combustion zone of the rich-lean non-
premixed combustor may contribute to the higher NOx emis-
sions from the combustor in comparison to the rich-lean pre-
mixed combustor.
• LES of two stage combustion of CH4 –NH3 –air mixtures shows
that a fuel-rich primary combustion zone ensures low NO pro-
duction but with relatively high H2 , CO, HCN and unburned
fuels concentration. The combustion of CO and H2 in the sec-
ondary combustion zone produces high concentration of O/H
radicals that facilitate the conversion of HCN and NH3 mainly
to NO.
• Although single stage combustion of CH4 –NH3 –air resulted in
about twice more NOx emissions than that of NH3 -air, rich-lean
combustion of CH4 –NH3 –air emitted less NOx than NH3 –air be-
cause the higher flame speed of CH4 –NH3 –air mixtures ensured
lower NOx production in the secondary combustion zone.
• The optimum low NOx primary zone equivalence ratio for
CH4 –NH3 –air combustion was found to vary from 1.30 to 1.35
as ammonia heat fraction in the fuel decreased from 0.30 to
0.10.
• Significantly low emissions such as 49 ppmv of NOx, 2 ppmv of
CO and approximately zero N2 O, HCN and NH3 emissions with
a combustion efficiency of 99.8% were achieved using rich-lean
premixed combustion at 0.25 MPa.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
415
Acknowledgment
Part of this research was supported by the Council for Science,
Technology and Innovation (CSTI), the Cross-ministerial Strategic
Innovation Promotion Program (SIP), “Energy Carriers” (Funding
Agency: The Japan Science and Technology Agency (JST)). We also
acknowledge the support from the collaborative research project,
Institute of Fluid Science, Tohoku University.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.combustflame.2019.10.
012.
References
[1] A. Valera-Medina, H. Xiao, M. Owen-Jones, W.I.F. David, P.J. Bowen, Ammonia
for power, Prog. Energy Combust. Sci. 69 (2018) 63–102.
[2] H. Kobayashi, A. Hayakawa, K.D.K.A Somarathne, E.C. Okafor, Science and tech-
nology of ammonia combustion, Proc. Combust. Inst. 37 (2019) 109–133.
[3] A. Hayakawa, T. Goto, R. Mimoto, Y. Arakawa, T. Kudo, H. Kobayashi, Laminar
burning velocity and Markstein length of ammonia/air premixed flames at var-
ious pressures, Fuel 159 (2015) 98–106.
[4] D.T. Pratt, Performance of Ammonia-Fired Gas- Turbine Combustors, Technical
Report No.9, DA- 04-200-AMC-791(x), Berkley University of California, 1967,
available at http://www.dtic.mil/dtic/tr/fulltext/u2/657585.pdf.
[5] O. Kurata, N. Iki, T. Matsunuma, T. Inoue, T. Tsujimura, H. Furutani,
H. Kobayashi, A. Hayakawa, Performances and emission characteristics of
NH3 -air and NH3 -CH4 -air combustion gas-turbine power generations, Proc.
Combust. Inst. 36 (2017) 3351–3359.
[6] E.C. Okafor, K.D.K.A Somarathne, A. Hayakawa, T. Kudo, O. Kurata, N. Iki,
H. Kobayashi, Towards the development of an efficient low-NOx ammonia
combustor for a micro gas turbine, Proc. Combust. Inst. 37 (2019) 4597–4606.
[7] A. Hayakawa, Y. Arakawa, R. Mimoto, K.D.K.A. Somarathne, T. Kudo,
H. Kobayashi, Int. J. Hydrogen Energy 42 (2017) 14010–14018.
[8] K.D.K.A. Somarathne, A. Hayakawa, H. Kobayashi, Numerical investigation on
the combustion characteristics of turbulent premixed ammonia/air flames sta-
bilized by a swirl burner, J. Fluid Sci. Technol. 11 (2016) JFST0026.
[9] K.D.K.A. Somarathne, S. Hatakeyama, A. Hayakawa, H. Kobayashi, Numerical
study of a low emission gas turbine like combustor for turbulent ammonia/air
premixed swirl flames with a secondary air injection at high pressure, Int. J.
Hydrogen Energy 42 (2017) 27388–27399.
[10] K.D.K.A. Somarathne, S. Colson, A. Hayakawa, H. Kobayashi, Modelling of am-
monia/air non-premixed turbulent swirling flames in a gas turbine-like com-
bustor at various pressures, Combust. Theory Model. 22 (2018) 973–997.
[11] O. Kurata, N. Iki, T. Inoue, T. Matsunuma, T. Tsujimura, H. Furutani, M. Kawano,
K. Arai, E.C. Okafor, A. Hayakawa, H. Kobayashi, Development of a wide range–
operable, rich-lean low-NOx combustor for NH3 fuel gas-turbine power gener-
ation, Proc. Combust. Inst. 37 (2019) 4587–4595.
[12] T. Terasaki, S. Hayashi, The effects of fuel-air mixing on NOx formation in
non-premixed swirl burners, Proc. Combust. Inst. 26 (1996) 2733–2739.
[13] N. Syred, A review of oscillation mechanisms and the role of the precessing
vortex core (PVC) in swirl combustion systems, Prog. Energy Combust. Syst. 32
(2) (2006) 93–161.
[14] A. Valera-Medina, N. Syred, A. Griffiths, Visualization of isothermal large co-
herent structures in a swirl burner, Combust. Flame 156 (2009) 1723–1734.
[15] V.M. Reddy, A. Katoch, W.L. Roberts, S. Kumar, Experimental and numerical
analysis for high intensity swirl based ultra-low emission flameless combustor
operating with liquid fuels, Proc. Combust. Inst. 35 (2015) 3581–3589.
[16] P. Kumar, T.R. Meyer, Experimental and modeling study of chemical-kinetics
mechanisms for H2-NH3-air mixtures in laminar premixed jet flames, Fuel 108
(2013) 166–176.
[17] J. Li, H. Huang, N. Kobayashi, Z. He, Y. Nagai, Study on using hydrogen and
ammonia as fuels: combustion characteristics and NOx formation, Int. J. Energy
Res. 38 (2014) 1214–1223.
[18] A. Ichikawa, A. Hayakawa, Y. Kitagawa, K.D.K.A. Somarathne, T. Kudo,
H. Kobayashi, Laminar burning velocity and Markstein length of ammo-
nia/hydrogen/air premixed flames at elevated pressures, Int. J. Hydrogen En-
ergy 40 (2015) 9570–9578.
[19] D. Pugh, P. Bowen, A. Valera-Medina, A. Giles, J. Runyon, R. Marsh, Influence of
steam addition and elevated ambient conditions on NOx reduction in a staged
premixed swirling NH3 /H2 flame, Proc. Combust. Inst. 37 (2019) 5401–5409.
[20] R.C. Rocha, M. Costa, X.-.S. Bai, Chemical kinetic modelling of ammo-
nia/hydrogen/air ignition, premixed flame propagation and NO emission, Fuel
246 (2019) 24–33.
[21] X. He, B. Shu, D. Nascimento, K. Moshammer, M. Costa, R.X. Fernandes, Au-
to-ignition kinetics of ammonia and ammonia/hydrogen mixtures at interme-
diate temperatures and high pressures, Combust. Flame 206 (2019) 189–200.
[22] A.J. Reiter, S.C. Kong, Combustion and emissions characteristics of compres-
sion-ignition engine using dual ammonia-diesel fuel, Fuel 90 (2011) 87–97.
416 E.C. Okafor, K.D. .A. Somarathne and R. Ratthanan et al. / Combustion and Flame 211 (2020) 406–416
[23] A.J. Reiter, S.C. Kong, Demonstration of compression-ignition engine combus-
tion using ammonia in reducing greenhouse gas emissions, Energy Fuels 22
(2008) 2963–2971.
[24] A. Valera-Medina, S. Morris, J. Runyon, D.G. Pugh, R. Marsh, P. Beasley,
T. Hughes, Ammonia, methane and hydrogen for gas turbines, Energy Proce-
dia 75 (2015) 118–123.
[25] E.C. Okafor, Y. Naito, S. Colson, A. Ichikawa, T. Kudo, A. Hayakawa, H. Kobayashi,
Experimental and numerical study of the laminar burning velocity of
CH4 –NH3 –air premixed flames, Combust. Flame 187 (2018) 185–198.
[26] E.C. Okafor, Y. Naito, S. Colson, A. Ichikawa, T. Kudo, A. Hayakawa, H. Kobayashi,
Measurement and modelling of the laminar burning velocity of methane-am-
monia-air flames at high pressures using a reduced reaction mechanism, Com-
bust. Flame 204 (2019) 162–175.
[27] A. Ichikawa, Y. Naito, A. Hayakawa, T. Kudo, H. Kobayashi, Burning velocity and
flame structure of CH4 /NH3 /air turbulent premixed flames at high pressure,
Int. J. Hydrogen Energy 44 (2019) 6991–6999.
[28] S. Li, S. Zhang, H. Zhou, Z. Ren, Analysis of air-staged combustion of NH3 /CH4
mixture with low NOx emission at gas turbine conditions in model combus-
tors, Fuel 237 (2019) 50–59.
[29] C.F. Ramos, R.C. Rocha, P.M.R. Oliveira, M. Costa, X.-.S. Bai, Experimental and ki-
netic modelling investigation on NO, CO and NH3 emissions from NH3 /CH4 /air
premixed flames, Fuel 254 (2019) 115693.
[30] H. Xinlu, W. Zhihua, M. Costa, S. Zhiwei, H. Yong, C. Kefa, Experimental and
kinetic modeling study of laminar burning velocities of NH3 /air, NH3 /H2 /air,
NH3 /CO/air and NH3 /CH4 /air premixed flames, Combust. Flame 206 (2019)
214–226.
[31] P. Glarborg, J.A. Miller, B. Ruscic, S.J. Klippenstein, Modelling nitrogen chem-
istry in combustion, Prog. Energy Combust. Sci. 67 (2018) 31–68.
[32] V.J. Wargadalam, G. Loffler, F. Winter, H. Hofbauer, Homogenous formation of
NO and N2 O from the oxidation of HCN and NH3 at 60 0-10 0 0 °C, Combust.
Flame 120 (20 0 0) 465–475.
[33] T. Takagi, T. Tatsumi, M. Ogasawara, Nitric oxide formation from fuel nitrogen
in staged combustion: roles of HCN and NHi, Combust. Flame 35 (1979) 17–25.
[34] J.B. Mereb, J.O.L. Wendt, Reburning mechanisms in a pulverized coal combus-
tor, Proc. Combust. Inst. 23 (1990) 1273–1279.
[35] P.G. Kristensen, P. Glarborg, K. Dam-Johansen, Nitrogen chemistry during
burnout in fuel-staged combustion, Combust. Flame 107 (1996) 211–222.
[36] P. Dagaut, P. Glarborg, M.U. Alzueta, The oxidation of hydrogen cyanide and
related chemistry, Prog. Energy Combust. Sci. 34 (2008) 1–46.
[37] J. Jójka, R. Ślefarski, Dimensionally reduced modeling of nitric oxide forma-
tion for premixed methane-air flames with ammonia content, Fuel 217 (2018)
98–105.
[38] A. Valera-Medina, R. Marsh, J. Runyon, D. Pugh, P. Beasley, T. Hughes, P. Bowen,
Ammonia-methane combustion in tangential swirl burners for gas turbine
power generation, Appl. Energy 185 (2017) 1362–1371.
[39] OpenFOAM 1.7.1 (2010) Available at:http://openfoam.org/version/1- 7- 1/.
[40] T. Poinsot, D. Veynante, Theoretical and Numerical Combustion, 2nd ed., R.T.
Edwards, Inc., Pennsylvania, USA, 2005, pp. 164–169.
[41] F. Nicoud, F. Ducros, Subgrid-Scale stress modelling based on the square of the
velocity gradient tensor, Flow Turbul. Combust. 62 (1999) 183–200.
[42] S. Menon, P.-.K. Yeung, W.-.W. Kim, Effect of subgrid models on the computed
interscale energy transfer in isotropic turbulence, Comput. Fluids 25 (1996)
165–180.
[43] S.M. Correa, Turbulence-chemistry interactions in the intermediate regime of
premixed combustion, Combust. Flame 93 (1993) 41–60.
[44] G. Bulat, E. Fedina, C. Fureby, W. Meier, U. Stopper, Reacting flow in an indus-
trial gas turbine combustor: les and experimental analysis, Proc. Combust. Inst.
35 (2015) 3175–3183.
[45] T. Lucchini, F. Contino, G.D. Errico, Coupling of in situ adaptive tabulation and
dynamic adaptive chemistry: an effective method for solving combustion in
engine simulations, Proc. Comb. Inst. 33 (2011) 3057–3064.
[46] J.A. Miller, M.D. Smooke, R.M. Green, R.J. Kee, Kinetic modelling of the oxida-
tion of ammonia in flames, Combust. Sci. Technol. 34 (1983) 149–176.
[47] X. Han, Z. Wang, M. Costa, Z. Sun, Y. He, K. Cen, Experimental and kinetic mod-
elling study of laminar burning velocities of NH3 /air, NH3 /H2 /air, NH3 /CO/air
and NH3 /CH4 /air premixed flames, Combust. Flame 206 (2019) 214–226.
[48] CHEMKIN-PRO 17.2, ANSYS, Inc., San Diego (2016)
[49] M. Stöhr, I. Boxx, C.D. Carter, W. Meier, Experimental study of vortex-flame in-
teraction in a gas turbine model combustor, Combust. Flame 159 (2012) 2649.
[50] U. Stopper, W. Meier, R. Sadanandan, M. Stöhr, M. Aigner G. Bulat, Experimen-
tal study of industrial gas turbine flames including quantification of pressure
influence on flow field, fuel/air premixing and flame shape, Combust. Flame
160 (2013) 2103–2118.
[51] J.W. Daily, Laser induced fluorescence spectroscopy in flames, Prog. Energy
Combust. Sci. 23 (1997) 133–199.
[52] Y. Fan, W. Lin, S. Wan, Y. Suzuki, Investigation of wall chemical effect using
PLIF measurement of OH radical generated by pulsed electric discharge, Com-
bust. Flame 196 (2018) 255–264.
[53] R. Sadanandan, M. Stöhr, W. Meier, Simultaneous OH-PLIF and PIV measure-
ments in a gas turbine model combustor, Appl. Phys. B 90 (2008) 609–618.
[54] S.J. Klippenstein, L.B. Harding, P. Glarborg, J.A. Miller, The role of NNH in NO
formation and control, Combust. Flame 158 (2011) 774–789.