i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7

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Effects of nitrogen dilution on the NOx formation

characteristics of CH4/CO/H2 syngas counterflow
non-premixed flames

Sangwoon Park, Yongmo Kim*

Department of Mechanical Engineering, Hanyang University, Haengdang-Dong, Sungdong-Ku, Seoul 133-791,
Republic of Korea

article info abstract

Article history: In the present study, the effects of the composition and nitrogen dilution level on the
Received 24 December 2016 precise structure and NOx formation characteristics were numerically investigated for
Received in revised form ternary syngas composed of H2, CO, and CH4 in laminar counterflow non-premixed
10 February 2017 flames. Prior to the parametric study, in order to evaluate the prediction capability for
Accepted 10 February 2017 the NOx formation characteristics of syngas/air counterflow non-premixed flames, the
Available online xxx GRI 3.0 mechanism was validated against measurements. Numerical results indicate
that the GRI 3.0 mechanism yields good overall agreement with the measured peak level
Keywords: and distribution of the NO mole fraction over a relatively wide range of H2/CO compo-
Syngas sitions and strain rates. Computations were carried out for wide ranges of ternary
CH4/CO/H2 composition syngas composition and nitrogen dilution level. Based on the numerical results, the
Counterflow diffusion flames detailed discussions are made for the essential features and precise structure of the
NO formation non-diluted and nitrogen-diluted CH4/CO/H2 syngas counterflow diffusion flames
Fuel-side nitrogen dilution including the temperature, species mole fractions, and NO production rate and its in-
tegral. Special emphasis was given to the effects of the fuel-side nitrogen dilution on the
NOx formation characteristics of the CH4-rich, CO-rich, and H2-rich syngas diffusion
flames for the different ternary syngas compositions. The dominant physical processes
and chemical paths to influence the precise flame structure and NO generation
encountered under the actual syngas combustion conditions were systematically
analyzed and identified.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

contains methane, carbon dioxide, water vapor, and nitrogen

Introduction [1e3]. Due to the lack of petrochemical energy sources and
strict emission regulations, syngas has been recognized as a
Synthesis gas or syngas produced in various gasification pro- promising alternative energy source. Syngas produced
cesses is a mixture of carbon monoxide and hydrogen and also through the coal gasification process is a useful byproduct of

* Corresponding author. Department of Mechanical Engineering, Hanyang University, 17 Haengdang-Dong, Sungdong-Gu, Seoul 133-791,
Republic of Korea. Fax: þ82 2 2297 3432.
E-mail address: ymkim@hanyang.ac.kr (Y. Kim).
http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7
clean coal combustion technologies applied in power gener-
ation. In particular, improvements of the gas turbine effi-
ciency and reliability have made syngas a viable fuel for
electric power generation using the integrated gasification
combined cycle (IGCC) [4]. In particular, IGCC systems can
improve the thermal efficiency and dramatically lower envi-
ronmental impacts compared to traditional coal-fired power
plants. Moreover, syngas can be blended with hydrocarbon
fuels to extend the utilization of the syngas mixture in prac-
tical combustion systems.
Syngas can be obtained from fossil fuels, biomass, coal, and
even organic waste and refinery residual. Because of the vari-
ability of the sources and processing techniques, the compo-
sition of syngas fuels is widely varied and this variability
substantially impacts steady state and dynamic combustion.
Variation in composition significantly affects the kinetics in
terms of ignition delay [5e7], extinction limit [8,9], and flame
speeds [10e13]. However, syngas combustion and emission
characteristics are not yet well understood. In particular, to
comply with current and future emission regulations, NOx
emission control in high-performance syngas combustion
systems is a challenging task due to the widely variable fuel
composition and physically complex reaction processes. Thus,
research efforts to investigate syngas combustion aim to gain
better understanding of the syngas combustion and NO for-
mation characteristics as well as to identify the optimum
design and operating conditions of combustion devices with
higher efficiencies and lower pollutant emissions.
There have been many research activities to investigate
the combustion and emission characteristics of premixed and
non-premixed flames. Giles et al. [14] investigated the effects
of air stream dilution on the NOx emissions of syngas and
revealed that H2O and CO2 are more effective in reducing NO
emissions than is N2 diluent. Shih and Hsu [15] studied the
effects of composition, pressure, and dilution on the NOx
emission characteristics of an opposed-jet syngas diffusion
flame. They demonstrated that, due to a higher flame tem-
perature, a H2-rich composition syngas flame produces more
NO through the thermal NO route compared to NNH and N2O
intermediate routes. Som et al. [16] numerically and experi-
mentally studied counterflow syngas flames at different
pressures. Their numerical studies utilizing three syngas re-
action kinetics (Davis et al. [17], Muller et al. [18], GRI 3.0 [19])
indicated that a reburn route involving the consumption of NO
due to third-body reactions becomes increasingly important
at high pressures. Drake and Blint [20] numerically investi-
gated the effect of stretch on thermal NO in laminar, coun-
terflow syngas diffusion flames and observed that the NO
concentration decreases dramatically as the flame stretch is
increased. Park et al. [21] numerically studied the addition
effects of CO/CO2 in H2/Ar fuel on the flame structure and NO
emission in counterflow diffusion flames. Park et al. [22]
clarified the preferential diffusion effects of H2 and H on the
flame characteristics of H2-enriched and CO-enriched syngas
flames with CO2 dilution. It was found that, in a H2/CO diffu-
sion flame, the preferential diffusion of H2 impacts the flame
characteristics much more significantly than the results ob-
tained by Guo and Neill [23], who numerically investigated the
effect of reformate gas (syngas) addition on NO formation in
strained methane/air diffusion flames. They showed that the
Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
addition of a small amount of reformate gas has a minor effect
on NO formation at low strain rates, but a small increase in NO
formation at moderate or high strain rates. However, addition
of a large amount of reformate gas resulted in a decrease of NO
formation due to reduction in nitrogen consumption rate by
the prompt route. Sahu et al. [8] numerically investigated NOx
chemical kinetics in low-calorific value H2/CO syngas flames
and identified key reactions. They also highlighted the need
for experimental data in syngas diffusion flames in order to
assess and optimize the H2/CO and nitrogen chemistry. Lee
et al. [24] numerically investigated the effects of fuel-side ni-
trogen dilution on the precise structure and NOx formation
characteristics of turbulent syngas non-premixed jet flames.
The numerical results indicate that, for the highly nitrogen-
diluted case with a higher scalar dissipate rate and shorter
flight time, the flame structure is dominantly influenced by
the turbulenceechemistry interaction and marginally modi-
fied by the radiation effect. On the other hand, the flame
structure for the non-dilution case with a longer flight time
and relatively intermediate scalar dissipate rate is strongly
influenced by radiative cooling and moderately affected by
turbulenceechemistry interactions. Safer et al. [25] numeri-
cally investigated the structure and NO reaction pathways of
the syngas counterflow nonpremixed flames over a wide
range of operating pressure 1e10 atm. It was found that the
contribution of thermal route to the NO production continu-
ally increases with the hydrogen level and pressure.
Charlston-Goch et al. [26] experimentally and numerically
studied the NO formation characteristics in premixed CO/H2/
CH4/air flames over a wide range of pressures. Specifically,
quantitative measurements of NO were obtained for various
equivalence ratios and flow rates. In a recent study, NO for-
mation in model syngas and biogas blends/air premixed
flames was evaluated by Watson et al. using a PLIF technique
[27]. Their numerical results indicate that the syngas kinetic
mechanisms have shortcomings to predict both the burning
velocities and NO emissions for all syngas compositions. To
investigate the effect of composition on NO formation, Wang
et al. [28] carried out quantitative laser saturated fluorescence
measurements of NO in H2/CO/CO2/N2/O2 adiabatic premixed
flat flames. They obtained accurate quantitative in-situ NO
measurements, which can be used to assess and validate
existing or new kinetic mechanisms. On the other hand,
measurements of NO concentration data are quite limited for
non-premixed syngas flames. It is important to study the NOx
kinetics and formation pathways in diffusion flames, espe-
cially for fuels comprised of species with large differences in
diffusivity and reactivity such as syngas. Additionally, since
all practical flames are either positively or negatively
stretched, the effect of stretch rate on NO kinetics in syn-
gaseair non-premixed flames is also a very important aspect.
Li [29] investigated a series of laminar diffusion flames of CH4/
air and syngas/air using in-situ measurements with varying
levels of NH3 to understand the dominant mechanisms of NO
formation. Quantitative measurement of NO concentration
was compared with numerical results in terms of NH3 con-
centrations in CH4/air and syngas/air flames. Very recently,
Sahu and Ravikrishna [30] carried out quantitative measure-
ments of the NO concentration in syngas/air counterflow
diffusion flames. Their measurements were performed over a
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7 3

wide range of strain rates and three H2/CO compositions to

provide validation cases for the syngas kinetics. In terms of
NO mole fraction, they assessed the prediction capability of
the existing syngas chemical kinetics (Davis et al. [17], GRI 3.0
[19], Li et al. [31], Ranzi et al. [32] and Konnov [33]). For clarity,
the previous numerical works for syngas counterflow diffu-
sion flame are summarized in Table 1.
Considerable efforts have been made to investigate the
combustion and NOx emission characteristics of syngas
flames for wide ranges of composition, pressure, stretch, and
dilution. However, most previous experimental and numeri-
cal studies have been performed mainly for individual com-
ponents such as methane or hydrogen fuels or for hydrogen/
carbon monoxide syngas compositions rather than for ternary
CH4/CO/H2 syngas compositions, which are encountered in
practical combustion systems. It is well known that most
syngas used in practical combustors contains a certain frac-
tion of methane. Giles et al. [14] simulated syngas counterflow
diffusion flames for two representative syngas mixtures con-
taining CO, H2, and CH4, one containing 50% H2 and 50% CO by
volume and the other containing 45% H2, 45% CO, and 10% CH4
by volume. According to Giles et al. [14], the presence of
methane in syngas considerably influences the peak temper-
ature, NOx formation characteristics, and the effectiveness of
diluents. Even if the methane fraction in syngas can sub-
stantially modify the precise flame structure and NO emission
characteristics, extensive studies have not been conducted for
a wide range of ternary CH4/CO/H2 syngas compositions.
Therefore, the present study was motivated to numerically
investigate the combustion and NOx formation characteristics
of CH4/CO/H2 syngas counterflow diffusion flames. Moreover,
special emphasis was given to the nitrogen dilution effects on
the precise flame structure and NOx formation characteristics
for a wide range of ternary syngas compositions. Based on the
numerical results, the essential features and precise structure
of the non-diluted and nitrogen-diluted CH4/CO/H2 syngas
counterflow diffusion flames were evaluated considering the
temperature, species mole fractions, and the NO production
rate and integral.
Modeling of the counterflow syngas diffusion
flame
In a counterflow, axisymmetric laminar syngas diffusion
flame, jets of fuel and oxidizer impinge on one another,
forming a stagnation plane whose location depends on the
momentum ratio of fuel and oxidizer. In the counterflow
burner configuration, the flat diffusion flame established near
the plane of stoichiometric composition can be analyzed by a
one-dimensional model. The mathematical description of the
combustion field along a stagnation streamline is one-
dimensional, and this OPPDIF code [34,35] was developed by
Kee et al. [36] and extended by Lutz et al. [34]. The reaction
rate, transport, and thermodynamic properties are evaluated
by the CHEMKIN library of subroutines. The governing equa-
tions for mass, momentum, chemical species, and energy in
addition to the solution technique were presented by Lutz
et al. [34]. The optically thin approximation employed to ac-
count for radiative heat loss is mainly impacted by CO2, H2O,
CO, and CH4, as follows:

X
V$qrad ðT; Yk Þ ¼ 4sB T4  T4b Pk $aP;k (1)
where sB is the StefaneBoltzmann constant, Pk is the partial
pressure of species k, T and Tb are the local and ambient
temperatures, respectively, and aP,k is the Plank mean ab-
sorption coefficient. The Plank mean absorption coefficient is
approximated as a polynomial function of temperature.
The velocities of the fuel and oxidizer streams are imposed
to conform to the global strain rate expressed below.
 pffiffiffiffiffi 
2jVO j jVF j rF
as ¼ 1þ pffiffiffiffiffi (2)
L jVO j rO
Here, V and r represent the velocity and density, respec-
tively, with the subscripts ‘O’ and ‘F’ denoting the oxidizer
and fuel streams. In this study, L is the separation distance
between the two nozzles, which is 2 cm. The ambient pres-
sure is 1 atm, and the temperatures of both the nitrogen-

Table 1 e Summary of researches on numerical simulation of syngas combustion in OPPDIF configuration.

Composition (%) Strain rate (/s) Dilution (%) Reaction mechanism Flame type
H2 CO CH4
Sahu and Ravikrishna [8] 5e20 20e35 2 448e2500 Fuel-side Li, Davis, GRI 3.0, Ranzi Nonpremixed
58% N2
Giles et al. [14] 45e50 45e50 0e10 100 Air-side GRI 3.0 Nonpremixed
10% CO2, N2, H2O
Shih and Hsu [15] 20e80 20e80 0 10 Non-dilution GRI 3.0 Nonpremixed
0
Som et al. [16] 10e100 0e90 0 35e100 Non-dilution Davis, Muller, GRI 3.0 Nonpremixed
Partially premixed
Park [21] 50 10e40 0 5.6e5555.3 Fuel-side GRI 2.11 Nonpremixed
CO2 10%e40%
Ar 10%e25%
Park [22] 20e80 20e80 0 15 Fuel-side GRI 3.0 Nonpremixed
CO2 30%
Safer et al. [25] 29e71 33e71 0 5 Non-dilution GRI 3.0 Nonpremixed
Sahu [30] 8e32 8e32 0 35e750 Fuel-side Li, Davis, GRI 3.0, Ranzi, Konnov Nonpremixed
N2 60%

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7
diluted syngas and oxidizer streams are 300 K. Using the
momentum balance, the fuel and air stream velocities can be
computed for a given strain rate. Plug flow boundary condi-
tions are used to specify the fuel and air stream velocities at
the boundaries. The mole fractions of all participating spe-
cies are also imposed at the fuel-side and air-side
boundaries.
In order to analyze the precise flame structure and NO
emission characteristics for the wide range of the ternary CH4/
CO/H2 syngas compositions, the present study adopted the
GRI 3.0 mechanism, which involves 40 reactions related to
NOx formation. In order to precisely analyze the NOx forma-
tion characteristics, the NOx formation reactions are repre-
sented by thermal, prompt, N2O, NO2, and NNH mechanisms.
The contribution of the respective NO formation mechanism
on total NO production was evaluated in the following way,
where the numbers in parenthesis correspond to those in the
GRI 3.0 mechanism.
a) Thermal NO (Zeldovich) is obtained by the following three
mechanisms.
O þ N2 4NO þ N ðR178Þ
N þ O2 4NO þ O ðR179Þ
N þ OH4NO þ H ðR180Þ
b) The N2O mechanism is the summation of production by
the following three reactions in the full mechanism
calculation.
N2 O þ O42NO ðR182Þ
N2 O þ H4NH þ NO ðR199Þ
N2 O þ CO4NCO þ NO ðR228Þ
c) The NO2 mechanism is the summation of production by
the following five reactions in the full mechanism
calculation.
NO2 þ OH4HO2 þ NO ðR186Þ
NO2 þ M4O þ M þ NO ðR187Þ
NO2 þ O4O2 þ NO ðR188Þ
NO2 þ H4OH þ NO ðR189Þ
NO2 þ CN4NCO þ NO ðR281Þ
d) The NNH mechanism consists of only the following one
reaction in the full mechanism calculation.
NNH þ O4NH þ NO ðR208Þ
In addition, the contributions of the prompt NO mecha-
nism and reburn chemistry are also considered in the present
study. The prompt mechanism contains 20 elementary re-
actions and the reburn mechanism consists of 8 elementary
reactions. Using these classifications, the contribution of each
mechanism can be evaluated in numerical calculations.
Several important reactions involving the prompt and reburn
NO routes are listed in Table 2.
Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
Results and discussions
In the present study, to evaluate the prediction capability of
the GRI 3.0 mechanism for the NOx formation characteristics
of syngas/air counterflow non-premixed flames, measure-
ments made by Sahu and Ravikrishna [30] were utilized as
validation cases. Sahu and Ravikrishna [30] quantitatively
measured the NO concentration in syngas/air counterflow
diffusion flames. Their measurements were performed over a
wide range of strain rates for three H2/CO compositions. The
local strain rate of the flames was varied from 35 s1 to 750 s1
for three syngas compositions (8:32, 20:20, and 32:8 H2/CO
ratio). In the remaining 60% of these syngas mixtures, all three
compositions contain 58% N2 and 2% CH4 by volume. Com-
putations were made over wide ranges of H2/CO composition
and strain rate. Fig. 1 presents the predicted and measured NO
profiles for the three H2/CO compositions (8:32, 20:20, and 32:8)
and three strain rates including low, intermediate, and high
levels. The peak NO levels predicted by the GRI 3.0 mechanism
agree reasonably well with experimental data for all test cases
even if noticeable deviations exist for certain conditions.
However, for these test cases, the predicted peak locations are
marginally different from the measured locations. These dis-
(3) crepancies are mainly caused by multidimensional effects [37]
of the counterflow flames.
At the low strain rate (45 s1) for three syngas composi-
tions, the GRI 3.0 mechanism yields good agreement with the
measured peak NO level. However, the GRI 3.0 mechanism
underestimates the NO peak level approximately 6 ppm for
the higher H2 concentration case. At the intermediate strain
rate (100 s1), the GRI mechanism overestimates the peak NO
level about 4 ppm for the low H2 composition and roughly
(4)
6 ppm for the intermediate H2 level while it underestimates
the peak NO level about 8 ppm for the high H2 composition. At
high strain rates (450 s1 and 460 s1), the GRI 3.0 mechanism
produces the favorable agreement for the high H2 composi-
tion. On the other hand, the GRI 3.0 mechanism yields the
underestimation about 4 ppm for the low H2 composition and
the overestimation roughly 3 ppm for the intermediate H2
composition. These numerical results indicate that the GRI 3.0
mechanism yields reasonably good agreement with the
measured peak level and distribution of the NO mole fraction
(5) over relatively wide ranges of the H2/CO composition and
strain rate. Thus, the present approach employed the GRI 3.0
mechanism to numerically investigate the precise structure
Table 2 e The important reaction steps involved in the
prompt/reburn mechanism.
(6) Reaction number Reaction step
R212 H þ NO þ M4HNO þ M
R214 HNO þ H4H2 þ NO
R215 HNO þ OH4NO þ H2 O
R245 C þ NO4CO þ N
R246 CH þ NO4HCN þ O
R249 CH2 þ NO4H þ HNCO
R255 CH3 þ NO4HCN þ H2 O
R274 HCCO þ NO4HCNO þ CO
R283 N þ CO2 4NO þ CO
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7 5

Fig. 1 e Predicted and measured NO profiles for three H2/CO compositions (8:32, 20:20, and 32:8) and three strain rates of
low, intermediate, and high levels.

and NOx formation characteristics of CH4/CO/H2 syngas
counterflow diffusion flames.
In order to systematically investigate the NO formation
characteristics for real syngas flames, a parametric study was
performed for the ternary syngas compositions shown in
Fig. 2. The ternary syngas compositions consist of hydrogen,
carbon monoxide, and methane.
To estimate the strength of the NO emission characteris-
tics, Takeno and Nishioka [38] suggested the emission index of
NO (EINO), which is defined in terms of the NO production
rate, u_ NO , and the fuel consumption rate, u_ F , as expressed in
Eq. (7).
Z acceptable results. However, this EINO estimation procedure is
L
u_ NO MWNO dx
L
EINO ¼ Z L
 u_ F MWF dx
L
Here, MWNO and MWF are the molecular weights of nitric
oxide and fuel, respectively. However, the emission index of
NO is not applicable to general situations. According to Giles
et al. [14], if methane is added to syngas (H2/CO), CO and H2 are
generated from the reaction process of methane, and the de-
nominator in Eq. (7) is increased due to the increased fuel
consumption rates corresponding to the elevated H2 and CO
concentrations. Consequently, EINO is actually under-
estimated for these ternary (CH4/CO/H2) compositions. In their
study, in order to circumvent this shortcoming, EINO was
calculated for the CO/H2/CH4 fuel composition as well as the
CO/H2 fuel composition, and the real emission index of NO was
obtained by averaging these two EINO values. Their analysis
[14] based on only 10% CH4 in the fuel composition yielded
not suitable for the present parametric study, which covers a
(7) wide range of methane compositions from 0% to 100%. Thus,
in this study, the strength of the NO emission characteristics
for ternary (CH4/CO/H2) compositions was estimated in terms
of the integrated NO production/consumption rate, similar
to the procedure employed by Shih and Hsu [15].

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7

monoxide situation. As presented in Fig. 3, the total NO pro-

duction rate integral is increased by elevating the hydrogen
12.5 87.5 content and by reducing the amount of carbon monoxide in
the fuel. Since the flame temperature is higher for the richer
25.0 75.0 hydrogen composition, the NO production rate integrals ob-
tained from the thermal, N2O, and NNH routes are enhanced
CH4 37.5 62.5
H2 by increasing the hydrogen percentage. However, the thermal
CH4 37.5 %
NO route has the most dominant contribution to the total NO
50.0 50.0 production rate integral, followed by the NNH and N2O routes.
H2 37.5% The peak level of the thermal NO production rate integral is on
62.5 37.5 the order of 1  106 while those of the NO production rate
integral through N2O and NNH mechanisms are on the order
75.0 25.0 of 1  107. In particular, for the richer hydrogen composition,
the distribution of the total NO production rate integrals quite
CO 25.0 %
87.5 12.5 similar to that of the thermal NO production rate integral
because the thermal NO production rate integrals an order of
magnitude higher than the NO production rates through N2O
12.5 25.0 37.5 50.0 62.5 75.0 87.5 and NNH routes. In terms of the prompt and reburn mecha-
nisms, the distributions are quite different from the other
CO mechanisms. As the methane is increased in the fuel
composition, the prompt and reburn mechanisms show high
Fig. 2 e The domains of the ternary syngas fuel
reactivates where the prompt mechanism generates NO, but
compositions consisting of CH4, CO, and H2.
the reburn mechanism consumes NO. In the prompt mecha-
nism, NO is formed at all compositions except the syngas
In the present study, computations were performed for the composition that lies in the H2eCO line in the ternary syngas
ternary syngas compositions with a stretch rate of 50 s1, an composition table. Consumption of NO occurred in the
inflow temperature of 300 K, and atmospheric pressure. Fig. 3 prompt mechanism in these compositions because the
shows the predicted contours of the total NO production rate contribution of R212, which is a third-body reaction, is sud-
integral and NO production rate integral through each NO denly increased relative to other reactions. A large quantity of
formation route for the ternary syngas compositions. It is also NO consumption was obtained in the reburn mechanism,
necessary to set the NO production rate integral value to zero especially in the CH4-rich region. According to Xue and
for the 100% CO composition as stable combustion and nu- Aggawal [39], the reburn mechanism is mainly controlled by
merical convergence are nearly impossible for the pure carbon the following chemical path: CHi þ NO4products. As the

Fig. 3 e Total NO production rate integrals and NO production rates for each constituent NO mechanism at 1 atm without
dilution: (a) total, (b) thermal mechanism, (c) N2O mechanism, (d) prompt mechanism, (e) NNH mechanism, and (f) reburn
mechanism.

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7 7

reactions progress, methane breaks down to CH3, CH2, and
CH, and these radicals enhance the reburn mechanism. As a
result, enhanced reaction of the reburn mechanism is ob-
tained in the CH4-rich region.
As shown in Fig. 4, to precisely analyze the NO character-
istics in ternary syngas non-premixed flames, the predicted
profiles of the temperature and mole fractions of key species
are displayed for three representative compositions of CH4-
rich (CH4 75%/CO 12.5%/H2 12.5%), CO-rich (CH4 12.5%/CO 75%/
H2 12.5%), and H2-rich (CH4 12.5%/CO 12.5%/H2 75%) fuels. In
terms of the peak flame temperature, the H2-rich syngas
composition yields the highest temperature of 2,321 K, fol-
lowed by the CO-rich and CH4-rich compositions. The pre-
dicted peak temperatures for the CH4-rich and CO-rich cases
are 2,068 K and 2,078 K, respectively. Compared to CO-rich and
CH4-rich flames, the location of the peak temperature in the
H2-rich flame further leans to the oxidizer side because the
inflow fuel velocity for the H2-rich case is much faster to
satisfy the momentum balance. In terms of the CH, HCN, and
C2H2 profiles associated with the prompt NO and reburn
routes located in the fuel-rich side, the CH4-rich case produces
the highest level. The H2-rich case generates the highest peak
OH level as well as the lowest C2H2 and CH levels. Around the
fuel-rich side (x ¼ 0.7 cm), the H2-rich syngas flame creates a
noticeably high peak CO level due to the fast consumption of
hydrogen resulting from the high reactivity and differential
diffusion of hydrogen.
Fig. 5 presents the predicted profiles of NO mole fraction,
total NO production rate, and NO production rate through
various NO formation routes for the three syngas composition
flames. In terms of the NO mole fraction, the H2-rich syngas
flame produces the highest peak level, and the CO-rich flame
yields the lowest level. In terms of the NO production rates,
the total NO production rate is mainly influenced by the
thermal, prompt, and reburn routes and is marginally affected
by the N2O, NO2, and NNH mechanisms for all compositions.
As illustrated in Fig. 5, the highest NO production rate was
obtained for the CH4-rich flame, and the widest NO reaction
zone was obtained for the H2-rich flame. In the CH4-rich flame,
the peak NO production mainly contributed by the thermal
and prompt routes occurs at the near-stoichiometric rich re-
gion, while the peak NO consumption rate mainly contributed
to by the reburn route takes place at the slightly fuel-rich side.
On the other hand, the CO-rich flame yields much lower peak
production and consumption rates, while the peak reaction
rates for all NO routes occur at the further fuel-rich side.
However, the H2-rich flame produces distinctly different dis-
tributions of the NO production rate, which is characterized by
double peaks. The first peak production rate slightly leans
toward the fuel-rich side and is contributed to by the thermal
and prompt routes, while the second peak production rate
near the near-stoichiometric lean side is mainly contributed
to by the thermal mechanism.
Fig. 6 shows the distribution of NO reaction rates associ-
ated with the important elementary reactions in the thermal,
prompt, and reburn paths under the non-diluted condition.
For CH4-rich and CO-rich flames, the thermal NO reaction
rates are dominantly influenced by R180. The CH4-rich and
CO-rich flames yield a similar distribution trend for the ther-
mal NO production rates associated with R180, but the CO-rich
flame generates a much lower peak reaction rate at the further
fuel-rich side. On the other hand, for the H2-rich syngas flame,

Fig. 4 e One-dimensional flame structures, main species, and minor species of the representative fuel compositions at 1 atm
without dilution.

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7

(a) (b) CH4-rich

0.0003

CH4-rich Total

NO production rate [mole/cm3s]

CO-rich 4E-06 THERMAL
0.00025 H2-rich N2O
NO2
PROMPT
NO mole fraction

NNH
0.0002 REBURN

0.00015 0

0.0001

5E-05

-4E-06

0
0.6 0.8 1 1.2 1.4 0.8 1 1.2 1.4
X [cm] X(cm)

(c) CO-rich (d) H2-rich

NO production rate [mole/cm3s]

NO production rate [mole/cm3s]

4E-06 4E-06

0 0

-4E-06 -4E-06

0.8 1 1.2 1.4 0.8 1 1.2 1.4

X(cm) X(cm)

Fig. 5 e NO mole fraction distributions and NO production rate distributions for three representative fuel compositions at
1 atm without dilution.

the distribution of the thermal NO production rate is
controlled mainly by R178 and R180. The predicted profile of
the thermal NO production rate clearly indicates that there
exist double peaks mainly caused by R178 and R180. At the
fuel-rich flame zone for the three syngas compositions, the
NO consumption rates are dominantly influenced by the
reburn path especially associated with R249 and R255. On the
other hand, at the near-stoichiometric and fuel-lean flame
zones, the NO reaction rates are basically controlled by ther-
mal routes (R178 and R180) and prompt paths (R214 and R215).
In actual IGCC gas turbine combustors, the NOx emission is
effectively controlled by injecting dilution gases such as N2,
H2O, and CO2 at the fuel side or oxidizer side. In this study, the
effects of fuel-side nitrogen dilution on the flame structure and
NO formation were numerically investigated for the ternary
syngas compositions. First, calculations were made for the
100% nitrogen dilution condition. In this dilution condition,
based on fuel volume, 100% nitrogen was added to the fuel side
nozzle, and all other all conditions are identical to those given
above. Fig. 7 shows the predicted contours of the total NO
production rate integral and NO production rate integral
through each NO formation route for the nitrogen-diluted
ternary syngas compositions. As presented in Fig. 7, the total
NO production rate was increased by elevating the H2 and CH4
percentages and by reducing the carbon monoxide percentage
in the fuel composition. In this fuel-side nitrogen case, the
peak level of the total NO production rate integral appeared
along the H2eCH4 line of the ternary syngas composition. The
predicted contours reveal that the thermal NO route has the
most dominant contribution to the total NO production rate
integral, followed by the prompt, NNH, and N2O routes. On the
other hand, in the reburn route, the NO production rate in-
tegrals are negative, and NO is partly converted to N2. The NO2
route also converted NO to N2 and NO2 even though the related
results are not included in Fig. 7. With the non-diluted condi-
tions, this implies that NO2 and the reburn mechanism play
roles in consuming NO. In the ternary syngas composition with
fuel-side nitrogen dilution, the thermal and prompt routes are
still the most dominant mechanisms to produce NO. The
highest total NO production rate integral through the thermal
route occurs near a composition of 37.5% CH4/62.5% H2 rather
than the pure hydrogen case. In this study, the strain rate is

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7 9

(a) CH4-rich (b) CO-rich (c) H2-rich

2E-06 2E-06
Thermal Thermal Thermal
NO production rate [mole/cm3s]

NO production rate [mole/cm s]

NO production rate [mole/cm s]

R178 R178 R178

3
R179 R179 R179
4E-06
R180 R180 R180

1E-06 1E-06

2E-06

0 0

Thermal NO Thermal NO Thermal NO

-1E-06 -1E-06
0.9 1 1.1 1.2 1.3 1.4 0.9 1 1.1 1.2 1.3 1.4 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
X [cm] X [cm] X [cm]

(d) CH4-rich (e) CO-rich (f) H2-rich

Prompt Prompt Prompt
NO production rate [mole/cm s]

NO production rate [mole/cm s]

NO production rate [mole/cm s]

4E-06 R214 4E-06 -R212 4E-06 -R212
3

3
R215 R214 R214
R215 R215
R283

0 0 0

-4E-06 -4E-06 -4E-06

0.8 1 1.2 1.4 0.8 1 1.2 1.4 0.8 1 1.2 1.4

X(cm) X(cm) X(cm)

(g) CH4-rich (h) CO-rich (i) H2-rich

Reburn Reburn Reburn
NO production rate [mole/cm s]

NO production rate [mole/cm s]

NO production rate [mole/cm s]

4E-06 -R249 4E-06 -R244 4E-06 -R249
3

3
-R255 -R245 -R255
-R274 -R249
-R255

0 0 0

-4E-06 -4E-06 -4E-06

0.8 1 1.2 1.4 0.8 1 1.2 1.4 0.8 1 1.2 1.4

X(cm) X(cm) X(cm)

Fig. 6 e NO production rates for the thermal and prompt mechanisms with each constituent elementary reaction rate at
1 atm without dilution.

fixed for all composition cases. Thus, the different composition compositions. In terms of the peak flame temperature, the H2-
case has the different inflow velocity corresponding to the rich syngas composition yields the highest temperature of
different volumetric flow rate. Since the percentage of nitrogen 2016 K, followed by the CH4-rich and CO-rich compositions.
dilution is based on the fuel volume flow rate, the N2 volume The predicted peak temperatures for the CH4-rich and CO-rich
flow rate increases with the fuel volume flow rate. For instance, cases are 1913 K and 1776 K, respectively. Thus, at the 100%
at the 100% N2 dilution condition, the pure H2 case has about nitrogen dilution, a temperature reduction of roughly 300 K
20% higher N2 volume flow rate, compared to the pure CH4 was achieved for the H2-rich and CO-rich flames, while a
case. This different N2 volume flow rate directly influences the reduction of 155 K was obtained for the CH4-rich flame. These
flame temperature and the NO formation through thermal numerical results suggest that, in terms of the flame tem-
route. Thus, in the nitrogen-diluted conditions, the peak level perature, the CH4-rich flame is less sensitive to the fuel-side
of thermal NO is not appeared at the pure H2 composition case. nitrogen dilution compared to the H2-rich and CO-rich
Fig. 8 shows the predicted profiles of the temperature and flames. Compared to the non-diluted fuel conditions, the
mole fractions of key species for three representative peak levels of minor species (OH, H, O, C2H2, and HCN) at all
nitrogen-diluted compositions of CH4-rich (CH4 37.5%/CO fuel compositions are substantially decreased. In terms of the
6.25%/H2 6.25%/N2 50%), CO-rich (CH4 6.25%/CO 37.5%/H2 CH, HCN, and C2H2 profiles associated with the prompt and
6.25%/N2 50%), and H2-rich (CH4 6.25%/CO 6.25%/H2 37.5%/N2 reburn routes, the CH4-rich case maintains a much higher
50%) fuels. As expected, the fuel-side nitrogen dilution level than the two other fuel compositions, but its peak level is
considerably reduces the flame temperature for the three fuel greatly reduced due to the fuel-side nitrogen dilution. The H2-

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
10 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7

Fig. 7 e Total NO production rate integral and NO production rate for each constituent NO mechanism at 1 atm with 100%
nitrogen dilution: (a) total, (b) thermal mechanism, (c) N2O mechanism, (d) prompt mechanism, (e) NNH mechanism, and (f)
reburn mechanism.

rich flame generates the highest peak OH level and the lowest side (x ¼ 0.7 cm) due to suppression of the differential diffu-
C2H2 and CH levels. Unlike the non-diluted H2-rich fuel sion effects through nitrogen dilution.
composition, this nitrogen-diluted H2-rich flame does not Fig. 9 shows the predicted profiles of NO mole fraction,
yield a noticeably high peak CO level around at the fuel-rich total NO production rate, and NO production rates obtained

Fig. 8 e One-dimensional flame structures, main species, and minor species for representative fuel compositions at 1 atm
with 100% nitrogen dilution.

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7 11

through various NO routes for three syngas flames with fuel-
side nitrogen dilution. As depicted in Figs. 7 and 9, the nu-
merical results indicate that the fuel-side nitrogen dilution
considerably suppresses the NO peak levels for all syngas
compositions, and the CH4-rich fuel composition yields the
highest peak NO level, followed by the H2-rich and CO-rich
compositions. In the non-diluted syngas flame characteris-
tics discussed above, the H2-rich syngas flame produces a
much higher peak NO level than the CH4-rich flame. Thus, in
terms of NO emission characteristics, these numerical results
imply that the nitrogen-diluted syngas flames are distinctly
different from the non-diluted syngas flames. Compared to
the non-diluted flames, the peak NO level in the 100%
nitrogen-diluted syngas flames was decreased by roughly 65%
for the H2-rich and CO-rich flames and 35% for the CH4-rich
flame. Thus, the NO emission characteristics of the CH4-rich
fuel composition are less sensitive to the fuel-side nitrogen
dilution compared to the H2-rich and CO-rich fuel composi-
tions. These results suggest that, for a given condition, by
increasing the methane percentage in the fuel composition,
the dilution effects on the reduction of NO emissions are less
effective than for the other syngas compositions. In terms of
the NO production rates depicted in Fig. 9, the total NO pro-
duction rates are mainly influenced by thermal and prompt
routes and are marginally affected by the N2O, NO2, and NNH
mechanisms. For the three syngas compositions, the total NO
consumption rate at the further fuel-rich side was primarily
influenced by the reburn path, while the total NO production
rate at the fuel-rich side leaning to stoichiometry was mainly
controlled by the thermal and prompt mechanisms. It can be
clearly seen that the NO production rates for the three syngas
compositions are substantially decreased by the fuel-side ni-
trogen dilution. The highly nitrogen-diluted flames have
uniquely different NO formation characteristics especially for
CH4-rich and H2-rich syngas compositions.
Fig. 10 shows the distribution of the NO reaction rates
associated with important elementary reactions through the
thermal, prompt, and reburn paths at the 100% nitrogen-
diluted condition. For the three representative syngas com-
positions, the numerical results reveal that R180 is the most
dominant elementary reaction step in the thermal NO
mechanism. In the CH4-rich and CO-rich compositions, it is
found that the distribution trends of the thermal NO produc-
tion rates associated with R180 are similar for the non-diluted

(a) (b) CH4-rich

0.0002

CH4-rich Total
NO production rate [mole/cm3s]

CO-rich 4E-06 THERMAL

H2-rich N2O
NO2
0.00015 PROMPT
NO mole fraction

NNH
REBURN

0.0001 0

5E-05

-4E-06

0
0.6 0.8 1 1.2 1.4 0.8 1 1.2 1.4
X [cm] X(cm)

(c) CO-rich (d) H2-rich

NO production rate [mole/cm3s]

NO production rate [mole/cm3s]

4E-06 4E-06

0 0

-4E-06 -4E-06

0.8 1 1.2 1.4 0.8 1 1.2 1.4

X(cm) X(cm)

Fig. 9 e NO mole fraction distributions and NO production rate distributions for three representative fuel compositions at
1 atm with 100% dilution.

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
12 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7

(a) CH4-rich (b) CO-rich (c) H2-rich

2E-06 2E-06 2E-06
Thermal Thermal Thermal
NO production rate [mole/cm3s]

NO production rate [mole/cm s]

NO production rate [mole/cm3s]

R178 R178 R178

3
R179 R179 R179
R180 R180 R180

1E-06 1E-06

0 0 0

Thermal NO Thermal NO Thermal NO

-1E-06 -1E-06
0.9 1 1.1 1.2 1.3 1.4 0.9 1 1.1 1.2 1.3 1.4 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
X [cm] X [cm] X [cm]

CH4-rich (e) CO-rich H2-rich

3E-06 3E-06 3E-06
Prompt Prompt Prompt
NO production rate [mole/cm s]

NO production rate [mole/cm s]

NO production rate [mole/cm s]

R214 -R212 -R212
3

3
R215 R214 R214
R283
2E-06 2E-06 2E-06

1E-06 1E-06 1E-06

0 0 0

-1E-06 -1E-06 -1E-06

0.8 1 1.2 1.4 0.8 1 1.2 1.4 0.8 1 1.2 1.4
X(cm) X(cm) X(cm)

CH4-rich CO-rich CO-rich

1E-06 1E-06 1E-06
Reburn Reburn Reburn
NO production rate [mole/cm s]

NO production rate [mole/cm s]

NO production rate [mole/cm s]

-R246 -R244 -R244
3

-R245 3 -R245
-R249
-R274 -R246 -R246
-R249 -R249
0 0 0

-1E-06 -1E-06 -1E-06

-2E-06 -2E-06 -2E-06

Reburn Reburn Reburn

-3E-06 -3E-06 -3E-06
0.8 1 1.2 1.4 0.8 1 1.2 1.4 0.8 1 1.2 1.4
X(cm) X(cm) X(cm)

Fig. 10 e NO production rates of the thermal and prompt mechanisms for each constituent elementary reaction rate at 1 atm
with 100% nitrogen dilution.

and nitrogen-diluted flames. On the other hand, in the H2-rich NO reaction paths, the CH4-rich flame yields the highest peak
syngas flame, the thermal NO production rate for the 100% NO reaction rate, while the H2-rich flame leads to the widest
nitrogen-diluted flame is controlled dominantly by R180, reaction zone.
while the thermal NO production rate for the non-diluted In order to precisely analyze the effect of fuel-side nitrogen
flame is influenced mainly by R178 and R180. Thus, in the dilution on the structure and NO emission characteristics in
profile of the thermal NO production rate, double peaks do not theCH4/CO/H2 counterflow diffusion flames, computations
exist for the highly nitrogen-diluted H2-rich flame. In the were made for 10 different nitrogen-dilution levels ranging
prompt NO route, R214 is the most important elementary re- from 10% to 100%. Fig. 11 shows the predicted contours of the
action step for all representative fuel compositions. Although total NO production rate integral for 6 dilution levels (0, 20, 40,
the NO production rate from the prompt route has a positive 60, 80, and 100%). In the non-dilution case, the NO production
value, the elementary reaction R212 consumes NO. At the rate integral increased by elevating the H2 level, while it
fuel-rich flame zone for the three syngas compositions, the decreased by enhancing the CO level. Thus, the pure hydrogen
NO consumption rates are dominantly contributed to by the composition case yields the highest NO production rate inte-
reburn path associated with R249 and R246. On the other gral. It is also observed that this distribution trend is roughly
hand, at the near-stoichiometric fuel-rich zone, the NO reac- maintained up to the nitrogen dilution level of 50%. However,
tion rates are basically controlled by the thermal route (R180) when the nitrogen dilution level reaches 60%, the peak levels
and prompt path (R214). In the thermal, prompt, and reburn of the NO production rate integral region are distributed over a

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7 13

Fig. 11 e Total NO production rate integral distributions for the various fuel-side nitrogen dilution levels.

much broader region along with the low-CO concentration moderate H2/moderate CH4 concentrations. This trend pro-
region with high H2/moderate CH4 concentrations. On the gressively appeared for the 100% nitrogen dilution case.
other hand, by increasing the nitrogen dilution level above Fig. 12 depicts the NO production rate integrals for the total
80%, the peak values of the NO production rate integral are not reaction path contribution versus the nitrogen dilution level
observed for the pure hydrogen composition case, and they for the three representative syngas compositions. Among the
are distributed in the low-CO concentration region with three fuel compositions, with a relatively low nitrogen

CH4-rich CO-rich H2-rich

8E-06 8E-06 8E-06
THERMAL
N2O
NO production rate integral [g/cm s]

NO production rate integral [g/cm s]

NO production rate integral [g/cm s]

6E-06 NO2 6E-06 6E-06

PROMPT
NNH
4E-06 REBURN 4E-06 4E-06
TOTAL

2E-06 2E-06 2E-06

0 0 0

-2E-06 -2E-06 -2E-06

-4E-06 -4E-06 -4E-06

-6E-06 -6E-06 -6E-06

0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
N2 dilution [%] N2 dilution [%] N2 dilution [%]

CH4-rich CO-rich H2-rich

200

400 400
NO production rate integral [g/cm s]

150
NO production rate integral %

NO production rate integral %

100
200 200

50

0 0
0

-200 -200 -50

-100
-400 -400
-150

-600 -600 -200

0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
N2 dilution [%] N2 dilution [%] N2 dilution [%]

Fig. 12 e NO production rate integral profiles for each representative fuel composition flame as a function of the fuel-side
nitrogen dilution level.

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
14 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7

dilution, the H2-rich composition yields the most sensitive
variation of the NO production rate integrals. However, in the
H2-rich flame with a relatively high dilution, the NO produc-
tion rate integrals less sensitively decrease with nitrogen
dilution compared to the low nitrogen dilution condition. The
H2-rich composition yields the highest value of the total NO
production rate integral with nitrogen dilutions below 80%
while the CH4-rich composition generates the highest rate
with nitrogen dilutions higher than 80%. In terms of the NO
production rate integral percentage for the three fuel com-
positions, the thermal route and prompt route result in NO
productions above 100% for all conditions. These percentages
are offset by the NO consumption contribution from the
reburn route. It can also be seen that the total NO production
rate integral is dominantly influenced by the thermal, prompt,
and reburn mechanisms and marginally affected by the other
mechanisms. In addition, by increasing the nitrogen dilution,
the NO percentage contribution of the thermal route is line-
arly decreased for all fuel compositions. In terms of the
prompt and reburn routes, except for the H2-rich composition,
the influence decreased by increasing the dilution level; in
contrast, for the H2-rich composition, the contributions
increased with increasing dilution level. In the H2-rich
composition with the low dilution condition, the thermal
route was found to be the most dominant NO production
mechanism. However, when the dilution level exceeds 60%,
the thermal route and the prompt route have nearly the same
contributions to generate NO.
Fig. 13 shows the effects of fuel-side nitrogen dilution on
the flame structures for the three representative fuel compo-
sitions. In terms of temperature and the O radical and NO
mole fractions, a higher nitrogen dilution level leads to a sig-
nificant decrease in peak levels, noticeable movement of the
peak locations to the fuel-rich side, and gradual reduction of
the distribution zone. The H2-rich composition yields the most
sensitive variation versus the nitrogen dilution level, followed
by the CO-rich and CH4-rich compositions. By increasing the
nitrogen dilution level up to 100%, the peak temperature
decreased from 2313 K to 2015 K for the H2-rich case, from
2031 K to 1776 K for the CO-rich case, and from 2048 K to
1914 K for the CH4-rich case. The corresponding peak NO level
decreased by roughly 70% for the H2-rich case, 50% for the CO-
rich case, and 30% for the CH4-rich case. On the other hand, in
terms of the CH radical mole fraction, by increasing the

Fig. 13 e Temperature, NO, and minor species distribution variations within the flame with increasing fuel-side dilution
level for each representative fuel composition.

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7 15

Fig. 14 e Variations of the total and related route NO formation routes according to the increase of the fuel-side nitrogen
dilution level for each representative fuel composition flame.

nitrogen dilution, the peak levels are slightly elevated for the
H2-rich composition, while they are noticeably decreased for
the two other fuel compositions.
Fig. 14 presents the effects of fuel-side nitrogen dilution on
the total NO production rate and specific NO production rates
for the three representative fuel compositions. The numerical
results indicate that the total NO production rate profiles of all
syngas compositions are influenced mainly by the thermal,
prompt, and reburn routes. In addition, the total NO produc-
tion rates are marginally affected by other NO mechanisms
through the N2O, NO2, and NNH paths. For the CH4-rich and
CO-rich compositions, the NO production rates are influenced
by the thermal, prompt, and reburn mechanisms. On the
other hand, for the H2-rich composition, the NO production
rates are mainly controlled by the thermal mechanism. For
the three fuel compositions, the NO consumption rates in the
fuel-rich side are primarily controlled by the reburn route. By
increasing the nitrogen dilution, the NO production and con-
sumption zones become progressively thinner for all fuel
compositions, and the H2-rich composition yields the most
sensitive decrease in the NO reaction zone. The increase in
dilution level leads to a significant decrease in peak NO
production rates for the CH4-rich and CO-rich compositions as
well as the peak NO consumption rates for all compositions.
However, for the H2-rich composition, with increasing nitro-
gen dilution, the NO production rates do not sensitively
decrease, especially at high dilution levels. The H2-rich flame
has a double-peak distribution of the total and thermal NO
production rates at low nitrogen dilution levels. However, this
double-peak structure disappeared with nitrogen dilution
levels above 60%.
Conclusions
The effects of composition and nitrogen dilution level on the
precise structure and NOx formation characteristics were
numerically investigated for various ternary syngas compo-
sitions composed of H2, CO, and CH4 in laminar counterflow
diffusion flames. Based on the numerical results obtained in
this study, the following conclusions were made.
1) To evaluate the prediction capability for the NOx formation
characteristics of syngas/air counterflow non-premixed

Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
16 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 7
flames, the GRI 3.0 mechanism was validated against
measurements. Numerical results indicate that the GRI 3.0
mechanism yields good overall agreement with the
measured peak level and distribution of the NO mole
fraction over a relatively wide range of H2/CO compositions
and strain rates.
2) In the ternary syngas counterflow non-diluted diffusion
flames, the NO production rate integral obtained through
thermal, N2O, and NNH routes is enhanced by increasing
the hydrogen percentage. The thermal, prompt, and reburn
routes were the most dominant mechanisms to produce or
consume NO. In terms of the NO mole fraction, the H2-rich
syngas flame produces the highest peak level and the CO-
rich flame yields the lowest level.
3) In the non-diluted flames, compared to the CH4-rich and
CO-rich flames, the H2-rich flame produces a distinctly
different distribution of the NO production rate, which is
characterized by double peaks. On the other hand, the
thermal NO production rate for the highly nitrogen-
diluted H2-rich flame is controlled dominantly by R180,
while the thermal NO production rate for the non-
diluted flame is influenced mainly by R178 and R180.
Thus, in the thermal NO production rate profile, double
peaks do not exist for the highly nitrogen-diluted H2-rich
flame.
4) In the highly nitrogen-diluted ternary syngas composi-
tions, the total NO production rate is increased by elevating
the H2 and CH4 contents and by reducing the carbon
monoxide content in the fuel. The peak level of the total NO
production rate integral appeared along the H2eCH4 line of
the ternary syngas composition. In terms of the flame
temperature, the CH4-rich fuel flame is less sensitive to
fuel-side nitrogen dilution compared to the H2-rich and
CO-rich flames.
5) By increasing the methane content in the syngas, the ef-
fects of dilution on the reduction of NO emissions are less
effective than at the other syngas compositions. In terms of
the NO production rate, the prompt and reburn paths are
more dominant for the nitrogen-diluted CH4-rich flame,
while the thermal, prompt, and reburn paths crucially
contribute to the non-diluted CH4-rich flame. These trends
can be tied to the reduced sensitivity to the fuel-side ni-
trogen dilution in the NO emission characteristics of the
CH4-rich flame.
6) In the non-dilution case, the NO production rate integral
increased by elevating the H2 level, while it decreased by
enhancing the CO level. However, by increasing the nitro-
gen dilution level above 80%, the peak values of the NO
production rate integral were not observed for the pure
hydrogen composition case and were distributed at the
low-CO concentration region with moderate H2/moderate
CH4 concentrations.
7) The H2-rich composition yields the highest value of the
total NO production rate integral for nitrogen dilutions
below 80%, while the CH4-rich composition generates the
highest rate for nitrogen dilutions higher than 80%. It was
also found that, by increasing the nitrogen dilution, the NO
percentage contributions of the prompt and reburn routes
decreased for the CH4-rich and CO-rich compositions and
increased for the H2-rich composition.
Please cite this article in press as: Park S, Kim Y, Effects of nitrogen dilution on the NOx formation characteristics of CH4/CO/H2 syngas
counterflow non-premixed flames, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.080
8) In terms of temperature and O radical and NO mole frac-
tions for all fuel compositions, the increased level of ni-
trogen dilution led to a significant decrease in peak levels,
noticeable movement of the peak locations to the fuel-rich
side, and a gradual reduction of the distribution zone. The
H2-rich composition yields the most sensitive variation
versus the nitrogen dilution level, followed by the CO-rich
and CH4-rich compositions. By increasing the nitrogen
dilution level to 100%, the peak NO level decreased by
roughly 70% for the H2-rich case, 50% for the CO-rich case,
and 30% for the CH4-rich case.
Acknowledgment
This project is supported by the “R&D Center for reduction of
Non-CO2 Greenhouse gases (2013001690013)” funded by Korea
Ministry of Environment (MOE) as “Global Top Environment
R&D Program”.
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