Fuel 275 (2020) 117924

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Fuel
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Full Length Article

Experimental and kinetic study on the transformation of coal nitrogen in the T

preheating stage of preheating-combustion coupling process
⁎
Shuai Wanga, Yanqing Niua, , Tian Lib, Denghui Wanga, Shi'en Huia
a
State Key Laboratory of Multiphase Flow in Power Engineering, Department of Thermal Engineering, School of Energy and Power Engineering, Xi’an Jiaotong University,
Xi’an 710049, PR China
b
Department of Energy and Process Engineering, Faculty of Engineering, NTNU - Norwegian University of Science and Technology, Trondheim, Norway

A R T I C LE I N FO A B S T R A C T

Keywords: Preheating-combustion of pulverized coal has been demonstrated as an effective low NOx combustion tech-
Preheating combustion nology. This method preheats a coal stream to high temperatures before the coal stream is injected into a utility
Preheating temperature boiler for combustion. Considering the complex mechanisms during the preheating, the effects of the preheating
Excess air ratio parameters, including temperature, residence time and excess air ratio are studied in a drop-tube furnace in
Hydrocarbon radical
detail. Meanwhile, a kinetics analysis on the transformation of coal-N in gas phase is also performed by means of
NO
Chemkin-Pro coupled with mature NOx reduction mechanisms. The experimental results show that the yield of
coal-N converted to NO decreases at first and then increases with increasing excess air ratio. The lowest NO yield
after preheating is achieved at excess air ratio of 0.1. To reduce NOx formation effectively, the preheating zone
should be under high temperature and long residence time. Kinetic modeling indicates that NO was reduced into
N2 by both hydrocarbon radical and HCN. Also, the modeling results show that the increasing excess air ratio
weakens the effect of hydrocarbon radical reduction, and the mole ratio of NOHCN/NOHCN+CiHj decreases from
1.99 to 1.17 with the increasing excess air ratio from 0.1 to 0.6.

1. Introduction combustion by using low-NOx combustion strategies, such as air sta-

Currently, coal remains the primary source of energy, especially in
China. Coal-based thermal power generation is still a primary source of
electricity in China, contributing more than 80% of power generation
[1]. However, a large number of pollutants, including NOx, SO2, and
particulate matter, etc. generate during coal combustion [2,3]. NOx is
one of the main substances causing acid rain, extremely harmful to
environment and human being. With an increasing public attention and
demand for pollution reduction, many countries have set a series of
strict standards [4]. NOx emission will have to be lower than
200 mg·Nm−3 (6% O2) in the European Union by 2016 [5]. The allowed
NOx emission had been even confined under 100 mg·Nm−3 (6% O2) for
all of the thermal power plants in China after 2014 [6].
An effective control of the generation of NOx is needed urgently.
Post combustion de-NOx techniques such as Selective Non-Catalytic
Reduction (SNCR) and Selective Catalytic Reduction (SCR) achieve high
NOx reduction efficiencies. However, obvious disadvantages exist, such
as high operation cost, ammonia leakage, easy deactivation of the
catalyst (SCR) [7–9], and a relatively narrow temperature window
(SNCR). Consequently, it is important to reduce NOx formation during
ging, low NOx burner, and exhaust gas recirculation.
Demands for low NOx emissions and high combustion efficiency
have driven the development of combustion technology for decades.
All-Russian Thermal Engineering Institute (VTI) once proposed a novel
technology, namely gas-fired coal preheating (GFCP) method [10]. The
proposed combustion concept aims to greatly improve clean coal
combustion by incorporating a novel modification to conventional or
low-NOx pulverized coal (PC) burning technology using gas-fired coal
preheating to destroy NOx precursors and prevent NOx formation [10].
Prior to coal combustion, a concentrated PC stream is heated by flue gas
from natural gas combustion before enters the burner. This thermal
pretreatment causes the releases of coal volatiles, including fuel-bound
nitrogen compounds into oxygen-deficient atmosphere, as a result fa-
voring N2 formation rather than NO. The main difference between
preheating-combustion and conventional combustion of pulverized coal
is shown in Fig. 1. This concept is subsequently further improved by the
American Gas Technology Institute (GTI) [11]. An advanced PC pre-
heating system was developed with several NOx reduction strategies
combined. For example, air stage is incorporated with a natural gas-
fired PC preheating burner [11,12].

⁎
Corresponding author.
E-mail address: yqniu85@mail.xjtu.edu.cn (Y. Niu).

https://doi.org/10.1016/j.fuel.2020.117924
Received 22 January 2020; Received in revised form 13 March 2020; Accepted 22 April 2020
Available online 29 April 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
S. Wang, et al. Fuel 275 (2020) 117924

Nomenclature xO2 Mole fraction of O2

xCiHj Mole fraction of hydrocarbon
A Cross area of drop tube furnace (m2) yNO NO yield percent of coal-N (%)
b Reaction order τ Residence time (s)
CNO NO concentration in flue gas (μL·L−1)
EAR Excess air ratio Abbreviations
L Reactor length (m)
M Sample mass (g) DTF Drop-tube furnace
Q Volumetric flow rate, (L·min−1) EAR Excess air ratio
t0 Time at which measurement begins (s) GFCP Gas-fired coal preheating
Δt Measurement duration (s) PC Pulverized coal
T Preheating temperature (K) ROC Rate of consumption
w(Nd) Nitrogen content in coal (dry basis, %) SCR Selective Catalytic Reduction
xNO Mole fraction of NO SNCR Selective Non-Catalytic Reduction
xHCN Mole fraction of HCN VTI All-Russian Thermal Engineering Institute

a) Preheating-combustion coupling b) Conventional combustion

Fig. 1. The difference between Preheating-combustion coupling and conventional combustion of pulverized coal.

Recently, by means of a 35 kW drop-tube furnace (DTF) coupled
with the gas-fired coal preheating technology, Liu et al. [13–15] found
that the NO emissions could be reduced by 74% and 67% for high-
volatility bituminous coals with a volatile content of 34.4% and 38.0%
(on a dried ash free basis), while NO only decreased by 48% for low-
volatility coal with a volatile content of 16.75%. In addition, during
coal preheating, a large number of nitrogenous intermediates such as
HCN and NH3 and other nitrogen containing compounds are yielded,
which can effectively improve NOx reduction in subsequent combustion
[16]. However, in oxygen-rich conditions, the nitrogenous compounds
are easily converted to NO, and most soot and hydrocarbons are also
oxidized before reducing the NO to N2. Moreover, the release of ni-
trogenous intermediates and subsequent reactions are affected by
temperatures. Thus, the oxygen content and temperature in the pre-
heating process should be of concern in practice. Niu et al [17] also
investigated the effect of the preheating parameters, including tem-
perature, residence time, excess air ratio, and coal type on NOx removal
efficiency during coal preheating in a laboratory-scale DTF and found
that NOx removal efficiency increases with the increase of both
preheating temperature and preheating residence time.
Raising temperature can cause a remarkable increase of the reaction
rate. When oxygen is deficient, the higher the temperature, the more
NOx can be reduced into N2 and O2. Therefore, to maximize NOx re-
moval efficiency by coal preheating, the preheating temperature should
be raised as much as possible and excess air ratio (EAR) in this region
should be reduced furthest within a reasonable range [5,18]. Up to
now, most investigations have been conducted under the condition of
relatively low temperature (usually below 1173 K). Limited efforts have
been devoted to coal nitrogen conversion under higher temperature for
coal preheating. Therefore, it is important to study the preheating
characteristics of pulverized coals when preheating temperature is
higher than 1173 K. It can provide useful guidelines for improving the
existing low NOx combustion technologies and developing a new low
NOx combustion technology. Therefore, the transformation of coal ni-
trogen and the interaction between NO and hydrocarbon under high
preheating temperature were investigated in this work. Meanwhile, the
effects of various preheating temperatures, excess air ratios, and re-
sidence times on the conversion of main volatiles were analyzed by

2
S. Wang, et al. Fuel 275 (2020) 117924

experiment and kinetic modeling. where τ represents residence time, L and A denotes the reactor length
and cross area respectively, Q is standard gas flow rate and T is pre-
2. Experiments heating temperature.

2.1. Fuel 2.3. Calculation method of coal-N conversion

A typical bituminous coal used in power plants in China, Huangling To quantify the nitrogen conversion at different preheating tem-
(HL) bituminous coal, was used in experiments. The coal properties are peratures, residence times, and excess air ratios, the concentration of
summarized in Table 1. Proximate analysis is performed using Netzsch nitrogen containing products are transferred into the yield percent of
simultaneous thermal analyzer (STA-409PC, Netzsch). Elemental ana- coal-N according to Eq. (2). The measuring result of gas analyzer is
lysis is conducted using elemental analyzer (vario EL cube, Elementar). recorded in ppm (μL·L−1).
It has high volatile content up to 37.69%, favoring the release of vo- t + Δt
latile and the reaction with fuel-bound nitrogen compounds in oxygen- ∫t0 0 Q·CNO·10−6·dt /22.4/60
yNO =
deficient atmosphere during preheating process. The coal sample was M·w (N )/14 (2)
sieved to 75–90 µm and dried at 378 K for 24 h before used. −1
where Q denotes the volumetric flow, L·min ; t0 is the time at which
measurement begins (s); Δt represents the measurement duration (s); M
2.2. Experimental apparatus
is the sample mass (g); w(N) is the nitrogen content in sample as shown
in Table 1 (air-dried base, wt. %); and CNO is the NO concentration in
A schematic of the experimental apparatus is shown in Fig. 2. The
flue gas (μL·L−1). Similarly, the concentration of carbon containing
experimental system is composed of five main parts: the pulverized coal
products are transferred into the yield percent of coal-C according to
feeding system, the gas distribution system, the DTF, the collecting
Eq. (3)
system and the gas analyzing system.
t + Δt
The PC feeding system is placed at the top of the furnace, which ∫t0 0 Q·CCO·10−6·dt /22.4/60
allows to inject the pulverized solid fuel in a continuous and uniform yCO =
M·w (C )/14 (3)
way with a mass flow rate ranging from 0.01 to 2 g·min−1. The pul-
verized coal particles are introduced into the reaction zone by a water- where w(C) is the nitrogen content in sample as shown in Table 1 (air-
cooled feeding tube, in order to avoid partial pyrolysis before the re- dried base, wt. %); and CCO is the CO concentration in flue gas (μL·L−1).
action zone.
During experiments, the gases were provided by gas cylinders and 2.4. Kinetics analysis on NO formation and reduction
controlled by mass flow controllers. The mass flow of O2 was calculated
according the EAR and the feeding rate of pulverized coal (0.64 Study of the formation and destruction processes of NOx is sub-
L·min−1 when EAR is 1). In addition, “Excess air ratio” is defined as stantially aided by computer modeling [19]. Hence, a global chemistry
follow: approach, emphasizing major chemical species and reactions, has been
Amount of oxygen supplied commonly used in the calculation of NO generation and transformation.
EAR = As expressed in R1, the oxidation of HCN can be written in a sim-
Amount of oxygen required for stoichiometry combustion
plified global reaction.
Then, pure N2 was split into two streams. One stream (0.3 L·min−1)
HCN + O2 → NO + ... (R1)
enters the PC feeder to entrain the coal sample into the feeding tube
with a feeding rate of about 0.42 g·min−1, and another stream mixed The reaction rate of above reaction was given by De Soete [20]. The
with O2 enters the reaction zone directly. The N2 flow acting as balance reaction kinetic parameters varied with oxygen concentration and fuel
gas is adjusted to ensure the total mass flow of the gases is the same in air ratio. Under fuel lean conditions, the following expression Eq. (4) is
each run. Total mass flow is 5 L·min−1 at 1573 K. Thus, the ratio of O2 employed.
to N2 goes up when excess air ratio increases.
dxNO 3.37 × 10 4 ⎞
The centerpiece of the DTF system is consisted of two segments. The = 1.0 × 1011xHCN x Ob2 exp ⎛− ⎜ ⎟

dt ⎝ T ⎠ (4)
upper and lower segment are heated with Si-Mo and Si-C heating ele-
ments, respectively. The maximal power and the highest temperature of where xi is the mole fraction of species i. The reaction order b varies
the furnace can be reached are 8 kW and 1873 K, respectively. A cor- according to the oxygen mole fraction, which is fitted according to De
undum tube, 1200 mm in length and 51 mm in inner diameter, is fixed Soete’s work [20], as shown in Eq. (5).
in the center of the furnace. The constant temperature range of the
furnace is approximate 80 cm in length under the tested conditions. The ⎧ 0.0 log x O2 ⩾ −3.00
⎪
reactor could not only achieve high heating rates (approximately 104 b = 233 exp ( 28.0
) − 5.67 < log x O2 < − 3.0
⎨ a + 0.5
K·s−1) [19] but also make coal particle and the atmosphere contact ⎪1.0
⎩ log x O2 ⩽ −5.67 (5)
well. The distance between the outlet of feeding tube and sampling
probe is adjustable to meet the required residence time. On the contrary, the reduction of NO to N2 by HCN can be written in
The PC particle after preheating was collected by a homemade filter. a simplified global reaction R2. And the reaction rate is given by Eq.
The gases after preheating was introduced into the Gasmet DX-4000 (6).
(Temet Instruments Oy, Finland) to analyze the contents of NH3, HCN,
NO, CH4, and CO with an accuracy of ± 2% in volume concentration. Table 1
All experiments were repeated twice. Ultimate and proximate analyses of the Huangling bituminous.a
When particle is smaller than 100 µm, the traction force from gas
C H O N S M A V FC
flow is predominant, and the particle running velocity is approximate to
the gas flow velocity. Thus, based on ideal gas state equation, the re- 65.87 3.96 8.63 0.85 0.54 6.52 13.63 30.34 49.51
sidence time of preheating can be calculated according Eq. (1):
a
The analyses were performed in an air-dried base, and the unit is wt. %. C:
273LA Carbon; H: Hydrogen; O: Oxygen; N: Nitrogen; S: Sulfur; M: Moisture, A: Ash; V:
τ=
Q (T + 273) (1) Volatile, FC: Fixed Carbon

3
S. Wang, et al.
Fig. 2. Schematic of the preheating apparatus.
HCN + NO → N2 + ...
dxNO 3.02 × 10 4 ⎞
= −3.0 × 1012xHCN xNO exp ⎛− ⎜ ⎟
dt ⎝ T ⎠ (6)
The reduction of NO to N2 by hydrocarbons can be written in a
simplified global reaction R3, and the reaction rate is given by Eq. (7).
NO + Ci Hj → HCN + ...
dxNO 9460
= −9.2 × 10 4 exp ⎛− ⎞ xNO x Ci Hj
dt ⎝ T ⎠ (7)
2.5. Kinetics modeling of NO during coal preheating
Gas-phase reactions are dominating nitrogen chemistry during
preheating stage. Modeling of these reactions gives a good approx-
imation on the behavior of the system with respect to NOx formation
and reduction [21]. Therefore, modeling of gas phase nitrogen chem-
istry is also carried out to illustrate the effect on the NO formation and
reduction during preheating process. A detailed kinetic mechanism
developed by Glarborg is used for the calculations [22]. The initial
condition for Chemkin-Pro simulation should change with preheating
temperature because the volatile depend on temperature. However,
concentration is mainly paid to 1573 K. So the initial input condition
for Chemkin-Pro simulation just change with varied excess air ratio. As
listed in Table 2, the yield of main volatile with EAR at 0 is taken as the
initial condition for the kinetic modeling of homogeneous nitrogen
reaction during coal preheating. The plug flow reactor (PFR) in
Chemkin-Pro [23] is used to simulate the preheating stage. The tem-
perature, EAR and residence time of reactants varied with the experi-
mental conditions.
4
Fuel 275 (2020) 117924
3. Results and discussion
3.1. Profiles of main volatile gas products during coal preheating
Fig. 3 shows the instantaneous concentration of main gases (NO,
HCN, CO and CH4) released from the pulverized coal particle at a
preheating temperature of 1573 K and an EAR of 0.1. The major N
species in the gas phase was found to be HCN. The yields of HCN in-
creased with residence time due to the higher releasing rate than the
oxidation consumption. Recently, several works have suggested that
HCN may be the primary nitrogen species during pyrolysis and that
NH3 is partly formed from HCN through hydrogenation [24–29]. The
absence of NH3 from the decomposition products of N containing model
compounds was explained by the lack of hydrogen atoms in these
aromatic compounds [30,31]. This also rationalized the volume frac-
tion of NH3 in gas product is lower than 5 ppm in all experiments,
which is within the measurement error of FTIR DX4000. So, the yield of
NH3 is not shown in Fig. 3 and will not be analyzed in following parts.
NO concentration continues to increase downstream from the nozzle
presumably due to the existence of O2 and the oxidation of N species,
mainly HCN. The NO yield increased continually and reached the
maximum value at L = 150 mm and then decreased. Thus L = 150 mm
can be taken as the position of O2 depletion during preheating zone.
The yields of CO increased with residence time due to the higher
releasing rate than the oxidation consumption. On the other hands, the
CO increase may also be caused by the oxidation of CH4. Because the
last step of CH4 oxidation is oxidation of CO to form CO2, a very slow
process, which promotes CO accumulation [22,32]. The concentration
of CH4 decreased after a moderate increase because of the higher
consumption rate in comparisons with HCN and CO, which will be
analyzed in Section 3.4 in detail.
3.2. Effect of temperature
Fig. 4 shows the effect of preheating temperature on the yields of
NO and HCN under various EARs. It can be observed that the tem-
perature presented different effects on the yields of NO and HCN, de-
pending on EAR. When EAR was zero during preheating stage, the NO
yield went up first and then down with increasing preheating tem-
perature, and when EAR increased to 0.1, the NO yield continuously
decreased with increased temperature. In contrast, high EAR, such as
0.3 and 0.6, resulted in increasing NO yield with the increasing tem-
perature. Under high EARs (such as 0.3 and 0.6), the yield of HCN
slightly increased first and then decreased moderately, while low EARs
(0 and 0.1) resulted in increased HCN rapidly with increased tem-
perature.
During coal combustion, NO emissions mainly come from the oxi-
dation of coal-N and the fixation of atmospheric nitrogen. Compared to
the conversion from fuel-bound nitrogen, the amount of thermal NO
formation is small. Therefore, we focus on the conversion of fuel-N in
this paper. The competition between the NO formation and reduction
caused the changeable NO yield at various temperatures and EARs. The
oxidation of HCN and NH3 released from the fuel-bound nitrogen cause
the formation of NO, while the reduction of NO by HCN and hydro-
carbons happened in the same time. When EAR is low, the oxidation of
Table 2
Input condition for Chemkin-Pro simulation.
species input value (L·min−1)
N2 5; 4.936; 4.808; 4.616 (EAR = 0; 0.1; 0.3; 0.6)
O2 0; 0.064; 0.192; 0.384 (EAR = 0; 0.1; 0.3; 0.6)
HCN 0.00929
NO 0.00293
CO 0.36441
CH4 0.08696
S. Wang, et al. Fuel 275 (2020) 117924

Fig. 5. Effect of temperature on the global reaction rate constant.

Fig. 3. Main gases profiles along the reactor under 1573 K and EAR = 0.
3.3. Effect of EAR

HCN into NO is relatively small, and the increasing temperature im-

Fig. 6 shows the effect of EAR on the yields of NO and HCN under
proves the release of HCN and hydrocarbons as well as the reduction of
various preheating temperatures. It can be observed that yields of NO
NO. Consequently, the yield of NO decreased, while the yield of HCN
and HCN present same trend with EAR varied under different pre-
increased with increased temperature at low EAR at the same time.
heating temperatures. The yield of HCN reduced with increased EAR,
When EAR is high, oxygen tends to react with HCN and hydrocarbon,
while the yield of NO went down first and then up with increased EAR.
resulting in increased NO formation with temperature.
NO yielded the minimum value at EAR of 0.1. When the preheating
Fig. 5 shows the rate constants of HCN oxidation reaction R(1), HCN
temperature was 1573 K, only 4.1 wt% of coal-N converted into NO at
reduction reaction R2, and hydrocarbon reduction reaction R3 at dif-
EAR of 0.1, while it increased to 24.3 wt% at EAR of 0.6.
ferent temperatures. The reaction rate constants increased rapidly with
During coal preheating, the oxidation of coal-N into NO and the
increased temperature, and the difference of the reaction rate constant
reduction of NO into N2 occurred simultaneously. Consequently, the
between HCN oxidation (R1) and reduction (R2) became larger at
competition between the two reaction processes determines the final
higher temperature. The rate constant of NO reduced to N2 by HCN
NO emission. The main oxidation route for HCN oxidation proceeds
(R2) is two orders of magnitude larger than the other two at 1773 K (1/
through NCO [33,34] (which will be analyzed in section 3.4 in detail).
T = 0.00056). That means the reduction of NO by HCN is easier to
The subsequent reactions of NCO determine the fate of the nitrogen
happen, especially under low EAR. Therefore, NO yield dropped down
atom. The increased O-atom concentration also shifts the balance be-
with increased temperature. However, when EAR increased (such as
tween the NCO + O and NCO + NO reactions [22]. Under low EAR,
0.6), HCN was prone to be oxidized into NO, thus the concentration of
the reduction of NO was dominating, resulting in low NO emission;
HCN decreased. Consequently, the role of reduction reaction R2 be-
while under high EAR, the oxidation surpassed the reduction con-
come weak and NO yield increased with temperature.
siderably, resulting in high NO emission. The hydrogenation of HCN to
NH3 is further complicated by the fact that more NH3 has been found in
experiments with relatively high concentrations of oxygen-containing

a) NO yield b) HCN yield

Fig. 4. Both the yield of NO and HCN as a function of temperature under various EARs, residence time = 0.4 s.

5
S. Wang, et al. Fuel 275 (2020) 117924

a) NO yield b) HCN yield

Fig. 6. Both the yield of NO and HCN as a function of EAR at different temperature.

species (O2, O, OH, etc.) [35]. With part of oxygen provided in pre- form NCO, which can react with NO under low O-atom concentration
heating stage will facilitate NH3 formation to reduce NO formed. [22]. Meanwhile hydrocarbon radicals can react with O to form HCCO,
Consequently, the yield of NO decreased first and then increased with which also play a vital role during NO reduction. At low O2 levels,
the increased EAR, and the yield of HCN reduced continuously. minor part of hydrocarbon radical convert to HCCO. The major part of
hydrocarbon will still exist as hydrocarbon radical to react with NO,
3.4. Interactions between hydrocarbon and NO which play an important role in NO reduction. With increased O2 level,
more hydrocarbon radical will contact O radical to form HCCO, and the
Fig. 7 shows the kinetics modeling predictions using Chemkin-Pro effects of NO reduction by hydrocarbon radical becomes weaker gra-
on the NO yield during PC preheating with and without hydrocarbon dually.
radical reduction. The modeling results are evaluated by comparing The main routine of HCN oxidation to form NO follows the sequence
with the experimental data. Meanwhile, the difference prediction re- HCN → NCO → NH → N → NO. It can be clearly seen that during the
sults between taking hydrocarbon radical reduction into consideration initial stages of preheating, HCN will be attacked by O radical to form
(NOHCN+CiHj) and ignoring hydrocarbon radical reduction reaction NCO or by OH radical to form CN. Then NCO is converted to NH and N.
(NOHCN) are also compared to show the importance of hydrocarbon As a key intermediate, N can react with O to form NO or with NO to
radical for NO reduction during PC preheating. The results show that form N2. At low O2 levels, HCN is converted into N2 via an N inter-
the kinetic modeling gives a good approximation on the NO yield when mediate. While high concentration of O radicals changes the N trans-
both HCN reduction and hydrocarbon radical reduction are considered formation routes, and the N radical will be converted into NO rather
simultaneously. Meanwhile, the inflection point with the minimal NO than N2. Consequently, the yield of NO during preheating first rise and
yield also reproduced at EAR of 0.1. When the reduction of hydro- then fall with increased EAR. Similarly, Niksa [36] proposed a “intrinsic
carbon radical is ignored (i.e., only considering the HCN reduction), the reburning” mechanism, where HCN is converted into N2 via an NO
predication value of NO yield deviate from the experimental results,
and the ratio of NOHCN/NOHCN+CiHj decreases with increased EAR. The
mole fraction of NOHCN is 1.99 times as much as NOHCN+CiHj when EAR
is 0.1, while the ratio of NOHCN/NOHCN+CiHj decreases to 1.17 with
increased EAR to 0.6. This means that the reduction effect of hydro-
carbon radical is primary at low EAR, and it becomes weaker with in-
creasing EAR.
Then, normalized rates of consumption (ROC) of NO were computed
to interpret the relative importance of hydrocarbon and nitrogen-con-
tained compounds during NO removal, as shown in Fig. 8. Under low
EAR (Fig. 8a, EAR = 0.1), CH3 + NO < = > HCN + H2O (ROCNO = -
0.243) and CH3 + NO < = > H2CN + OH (ROCNO = -0.243) were
primary NO reduction reactions; with increased EAR to 0.2, the ROCNO
of the two reactions dropped to −0.194, while they both were also the
dominating NO reaction reactions. However,
NH2 + NO < = > NNH + OH will dominate the NO reduction with
ROCNO = -0.198 under EAR = 0.4. These results clearly indicate that
the effects of hydrocarbon radicals on NO reduction become slight
gradually with increased EAR.
Fig. 9 shows a reaction path diagram for the conversion of main
nitrogen compounds. For the reduction of NO, on one hand, the hy-
drocarbon radical can reduce NO directly; on the other hands, oxidation Fig. 7. Comparison of experimental data and modeling prediction on the yield
of HCN produced from the reaction between hydrocarbons and NO can of NO at T = 1573 K.

6
S. Wang, et al.
Fig. 8. Consumption rates of NO during coal preheating under different EAR at
1573 K. ((a) EAR = 0.1, (b) EAR = 0.2, (c) EAR = 0.4).
Fig. 9. Reaction path diagram for formation and reduction of NO during coal
preheating.
intermediate at low O2 levels, while at progressively higher O2 levels
the abundance of OH radial and O2 would react with N and thus pre-
venting the conversion of NO into N2.
4. Conclusion
In order to fully understand the transformation of coal-N and its
interaction with hydrocarbon under high preheating temperature
7
Fuel 275 (2020) 117924
during preheating-combustion coupling process, the effects of residence
time, preheating temperature and EAR on the transformation of coal-N
are investigated by experiments conducted in a DTF. Meanwhile, the
relative importance of HCN and hydrocarbon radical reduction on NO
are compared by kinetic modeling. The general conclusions can be
summarized as follows:
1) Temperature presents different effects on the yields of NO and HCN,
depending on EAR. The NO yield continuously decreases with in-
creased preheating temperature at low EAR. While NO yield in-
creases with the increasing temperature at high EAR.
2) The yield of coal-N converted to NO decreases at first and then in-
creases with increasing EAR, while the yields of HCN goes down
with EAR increases.
3) The kinetic modeling yields a well prediction on the experimental
results when both hydrocarbon radical and HCN reduction reactions
are considered simultaneously. The results show that the hydro-
carbon radical reduction must be taken into consideration for the
modeling of coal-N conversion during coal preheating, which is the
primary path for NO reduction at low EAR. However, with in-
creasing EAR, the hydrocarbon radical reduction on NO becomes
weak, and the effect of HCN reduction gets stronger gradually.
CRediT authorship contribution statement
Shuai Wang: Investigation, Data curation, Formal analysis, Writing
- original draft, Visualization, Validation. Yanqing Niu:
Conceptualization, Methodology, Resources, Writing - review & editing,
Supervision, Funding acquisition. Tian Li: Validation. Denghui Wang:
Investigation. Shi’en Hui: Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The present work was supported by National Natural Science
Foundation of China [Grant Number 51776161], Natural Science Basic
Research Plan in Shaanxi Province of China [Grant Number
2018JQ5010], and Fundamental Research Funds for the Central
Universities. Tian Li would like to acknowledge the financial support by
the Knowledge-Building Project Grate CFD (267957) funded by the
Research Council of Norway and industry partners.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.117924.
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