Mechanism of NOx Formation from Nitrogen

in the Combustion of the Coals Used in Sintering

Process
LEONARDO TOMAS DA ROCHA, HYOJUNG KIM, CHANGMIN LEE,
and SUNG-MO JUNG

The released NOx during fuel combustion is one of the major air pollutants, directly related to
acid rain and photochemical smog. At present, there is not an economical and effective method
of inhibiting NOx emission from sintering flue gas. Therefore, controlling the conditions of fuel
combustion is extremely required for the reduction in NOx. The current research investigated
the effects of different combustion parameters on the formation of NOx for three type of coals.
The formation of NOx decreased with increasing temperature and heating rate while it increased
when oxygen content in an atmosphere increased. Anthracite coal replacement with coke up to
100 pct promoted a decrease in the formed NOx amount and XNO by 21 and 53 pct,
respectively. The addition of CaO and FeO enhanced the conversion of nitrogen to NOx,
especially at temperatures below 1273 K (1000 C). Taking both the oxidation reaction to form
NOx and reduction reaction of NOx to form N2 into account, the activation energy (EA) values
of anthracite and coke were evaluated to be 2.2 and 3.6 kJ/mol, respectively. The combustion of
semi-anthracite coal emitted the largest amount of NOx, but the anthracite coal containing less
fuel-N than other coals showed the highest value of XNO, which indicates that nitrogen content
in coal is not the major factor affecting the formation of NOx. The change in nitrogen
functionality after combustion process might be the reason for the unpredicted results in the
XNO. The pyrrolic-N in anthracite coal might be considered to be the major functional form that
directly affects the conversion of nitrogen to NO.

https://doi.org/10.1007/s11663-020-01923-8
 The Minerals, Metals & Materials Society and ASM International 2020

I. INTRODUCTION burning fuel-N present in coal/coke. In addition, there

IRON ore sinter is considered the main iron-bearing
burden of the blast furnace (BF) ironmaking, which
accounts for more than 75 pct of all the raw materials in
BF.[1–3] Iron ore sintering process consumes about
10 pct of the total energy in an integrated steel plant
of which 75-80 pct is supplied by the combustion of
solid fuels, such as coke breeze and anthracite.[4,5] After
the ignition of the sintering process, coal/coke particles
are exposed to a combustion atmosphere, where N
present in the fuel reacts with O2 to form NOx (98 pct
represented by NO).[6] NOx formed in the sintering
process is called fuel-NOx since it is generated from the
LEONARDO TOMAS DA ROCHA and SUNG-MO JUNG are
with the Graduate Institute of Ferrous Technology (GIFT), Pohang
University of Science and Technology (POSTECH), Pohang 790-784,
Korea. Contact e-mail: smjung@postech.ac.kr HYOJUNG KIM is
with the POSCO, Pohang, Korea. CHANGMIN LEE is with the
POSCO, Kwangyang, Korea.
Manuscript submitted February 23, 2020.
Article published online August 10, 2020.
are two possible ways to form NOx: thermal-NOx by the
reaction between N2 and O2 gases present in the air and
prompt NOx in terms of the decomposition of nitrogen
compounds in the combustion zone.[3,7,8] Among them,
fuel-NOx represents the majority of total NOx formed in
the sintering process.[8–15] Furthermore, the combustion
of solid fuels in sintering bed materials is also the main
source of CO2 and SOx.
Nitrogen oxides (NOx) are one of the major air
pollutants in the world, and very harmful to human
health, directly related to photochemical smog and acid
rain.[9,10,13,16] Iron ore sintering process represents more
than 40 pct of the total NOx emissions from steel
industries, which accounts for more than 10 pct of the
total NOx emission among all kinds of indus-
try.[3,6,12,14,17–21] Nowadays, steelmaking companies are
facing bigger challenges for environmental protection
due to change in gas emission regulation, especially in
NOx case.[7,13,18,19] As an example, South Korea and
China determined to reduce NOx emission by national
law. This global concern about NOx emission is the
driving force for the reduction of NOx in the sintering

2068—VOLUME 51B, OCTOBER 2020 METALLURGICAL AND MATERIALS TRANSACTIONS B

process. In addition, the shortage in the supply of
anthracite containing low nitrogen will lead to the use of
the coals containing high nitrogen, which results in the
emission of more NOx.[10–12,14]
The previous studies have shown that sintering
parameters such as temperature, oxygen content, heat-
ing rate, fuel type and additional materials had a
notable influence on the nitrogen conversion ratio to
NOx which decreased with increasing temperature—
NOx reduction by CO (g) and C (s) were predominant at
high temperatures,[22,23] but the opposite trend was
verified by other studies.[6,24] NOx increased when
oxygen content increased—more O2 was available to
react with fuel-N.[23,25] Some studies showed that CaO
could enhance the conversion ratio of nitrogen provid-
ing a non-desirable effect.[6,26–30] Wu et al.[31] found that
FeO played a significant role in decreasing NO concen-
tration formed during coal combustion at 1273 K
(1000 C). His research also showed that FeO ability
to reduce NO gas increases with experiment tempera-
ture. Kasai et al.[32] investigated the effect of metallic
iron addition to coke on NOx formation during com-
bustion at 1273 K (1000 C) and found that as Fe
content increased, NOx formation was decreased.
The current research aims to investigate the effect of
nitrogen content, sintering parameters and additional
materials on the formation of NOx behavior, with the
special purpose of understanding NOx formation mech-
anism and then, finding the proper way to reduce the
formation of NOx in the sintering process.
II. EXPERIMENTAL
A. Materials Preparation
The current study used three type of coals (anthracite,
coke, and semi-anthracite) whose proximate and ulti-
mate analyses are shown in Table I. Two different
particle sizes were prepared: powder (< 250 lm) and
granule (1 to 2.8 mm).
As shown in Table I, the three coals were ranked by
volatile matter and fixed carbon amount, and anthracite
and coke are compared with semi-anthracite in view of
volatile matter, ash and fixed carbon. Also from Table I,
with reference to anthracite, coke contains two times
more nitrogen, while the nitrogen in semi-anthracite is
three times greater.
Analytical grade reagents of CaO (96 pct purity,
SAMCHUN Chemical) and FeO (over 60 pct purity,
JUNSEI Chemical) samples were used in this study. In
the case of FeO, the sample was also submitted to
Table I. Chemical Analysis of Coals
Proximate Analysis (wt pct, db)
Sample Moisture Volatile Matter Ash
Anthracite 1.95 7.44 15.75
Coke 0.00 5.64 13.48
Semi-anthracite 0.36 17.51 24.06
METALLURGICAL AND MATERIALS TRANSACTIONS B
chemical analysis to evaluate the exact amount of FeO,
which was found to be 99 pct. Both materials were
crushed and screened to obtain a particle size smaller
than 250 lm.
B. Experimental Apparatus and Procedure
Laboratory-scale equipment was set up to investigate
the effects of several sintering parameters, such as
temperature, oxygen content, and heating rate, on the
conversion of nitrogen to NOx in the absence and
presence of additive materials. Figure 1 shows the
schematic diagram of the experimental apparatus
employed for coal combustion.
The experimental system mainly consists of a hori-
zontal gold-image furnace, gas supply system and in situ
gas analyzer. An alumina crucible was located in the
middle of the reactor. A thermocouple was installed
above the crucible to accurately control the experimen-
tal temperature. The total gas flow rate was adjusted to
be 600 mL/min and was controlled by Mass Flow
Controller (MFC). The compositional change in outlet
gases was analyzed by Quadrupole Mass Spectroscopy
(QMS) during the experiment. Two different heating
patterns were applied in this study: First, a non-isother-
mal heating at 30 K/min up to 1623 K (1350 C) in an
atmosphere of 79 vol pct Ar and 21 vol pct O2.
Secondly, isothermal heating at a rate of 80 K/min up
to a target temperature in an Ar atmosphere was
employed and when target temperature was reached, a
gas mixture comprised of 79 vol pct Ar and 21 vol pct
O2 was blown into the furnace while the sample was held
for 90 minutes.
Three type of coals (anthracite, coke and semi-an-
thracite) were exposed to different combustion condi-
tions such as temperature, particle size, oxygen content,
and heating rate, to clarify their influence on the
formation of NOx. Two grams of sample were placed
inside alumina crucible (65 mm length 9 20 mm
width 9 10 mm height), and then the crucible was
charged into the gold-image furnace to which
non-isothermal and isothermal heating were performed.
To find a countermeasure for the formation of NOx,
different type of materials were added to coal to examine
their effect on the reduction in NOx. As previously
mentioned, CaO and FeO were used as prospective
catalysts. Each compound was uniformly mixed with the
coals at different ratios for 30 minutes employing the
Turbula Mixer (T2F Nr. 120942 Switzerland) at 34
revolutions per minute. Table II summarizes the mixing
ratios of each compound to coal. The samples were
Ultimate Analysis (wt pct, db)
Fixed Carbon C H N S
74.85 84.6 0.04 0.691 0.481
80.88 86.8 0.00 1.191 0.791
58.07 65.6 2.94 1.955 0.254
VOLUME 51B, OCTOBER 2020—2069
Fig. 1—Schematic diagram of the experimental apparatus.

Table II. Mixing Amount of Each Compound to Coal Table III. List of Rate Expressions of Reaction Models Used
in this Study.[21]
CaO (wt pct) FeO (wt pct)
Model Integrate Form G(X) = kt
1, 5, 10 1, 5, 10
Shrinking core model [1  (1  X)]1/m
m = 1/2 (R1/2) [1  (1  X)]2
non-isothermally heated at 30 K/min to 1623 K m = 1/3 (R1/3) [1  (1  X)]3
(1350 C) in an atmosphere consisting of 79 vol pct Ar m = 1/4 (R1/4) [1  (1  X)]4
and 21 vol pct O2 to compare the fractional conversion m = 2 (R2) [1  (1  X)]1/2
of nitrogen with single coal combustion baseline. m = 3 (R3) [1  (1  X)]1/3
The adding amount showed in Table II was with Diffusion model
reference to coal weight of 2 g. Therefore, the final addition 1D diffusion (D1) X2
of CaO and FeO was 0.02, 0.1 and 0.2 g, respectively. 2D diffusion (D2) X + [(1  X)ln(1  X)]
3D diffusion (D3) [1  (1  X)1/3]2

C. Evaluation of the Fractional Conversion of Nitrogen

to NO (XNO)
To evaluate the amount of nitrogen in coal that has
been converted to NOx during the experiment, a
D. Kinetic Analysis: Mechanism Model
fractional conversion of N into NOx (XNO) was evalu-
ated according to the NO concentration determined by In the isothermal experiments, XNO is expected to
Quadrupole Mass Spectroscopy (QMS) in terms of show different values for each coal and temperature.
Eqs. [1] and [2]: One important measurement to understand the NOx
Z   formation mechanism is to determine what is the
ðvol pct NOÞ rate-controlling step involved in the experiment. For
½Ngas ¼  Qtotal  pAr
ðvol pct ArÞ this study, the existence of two main reaction controls
1 mol were assumed: Interfacial Chemical Reaction (ICR) and
 ; ½1
22; 400 mL Mass Transfer (MT).
Table III lists different model functions, presented by
Zhou et al.,[21] for both reaction control mechanism—
½Ngas chemical reaction (represented as the shrinking core
XNO ¼ ; ½2 model) and diffusion model. For the evaluation of
½wt pct N 1 mol appropriate model—G(X), x was represented by con-
Wsample ðgÞ  100  14 gN version of nitrogen to NO-XNO.
where [N]gas is the moles of nitrogen in the outlet gas The proper mechanism function for each coal could
(moles), Qtotal is the total flowrate of inlet gas at stan- be selected through the comparison of correlation
dard state (mL/min), pAr is the partial pressure of Ar coefficients (R2). This value was obtained by plotting
gas in the inlet gas, XNO is the fractional conversion of G(X) against time and then, checking the similarity
nitrogen in the coal and Wsample is the weight of sam- between this study data and linear fitting by Origin 9.0
ple used (grams). software.

2070—VOLUME 51B, OCTOBER 2020 METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 2—Effect of temperature and coal particle size on the
conversion of nitrogen to NOx.
III. RESULTS
A. Effect of Sintering Parameters on the Conversion
of Nitrogen to NO
Anthracite coal (granule type) was submitted to
isothermal tests at different temperatures of 1273 K,
1373 K, and 1473 K (1000 C, 1100 C, and 1200 C) to
clarify the effect of temperature on the fractional
conversion of nitrogen into NO (XNO). As previously
mentioned, the sample was heated from room to target
temperature at 80 K/min in an Ar atmosphere. After the
target temperature was reached, Ar-21 vol pct O2 was
blown into the furnace for 90 minutes. As shown in
Figure 2, the fractional conversion of nitrogen in coal to
NO (XNO) decreased with increasing temperature, which
is in good agreement with the previous studies.[22,23] This
trend might be directly related to the reduction potential
of NOx which is favored at high temperatures. It is
believed that solid carbon (C) and carbon monoxide
(CO) acted as reducing agents of NOx according to the
following Reactions [3] and [5][33]:
1 Four different oxygen amounts were tested for 10, 21, 35
NO ðgÞ þ C ðsÞ ¼ N2 ðgÞ þ CO ðgÞ; ½3
2 and 50 vol pct in Ar. A non-isothermal heating pattern
DG0 ¼ 203; 300  73:8TðJ=molÞð298 K to 2273 KÞ;
½4
1 with fuel-N. As more oxygen is supplied, the probability
NO ðgÞ þ CO ðgÞ ¼ N2 ðgÞ þ CO2 ðgÞ; ½5
2 of forming NOx increases as shown by the following
DG0 ¼ 372; 300  98:36 TðJ=molÞð298 K to 2273 KÞ:
½6
The effect of coal particle size was evaluated by
applying the same experimental procedure as one for
checking the effect of temperature, but the current study
used anthracite powder in place of granule. Figure 2
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 3—Effect of oxygen content on the conversion of nitrogen to
NOx.
shows that the formation of NOx in coal granules
(1-2.8 mm) was higher than that seen in the case of
powder particles (< 250 lm). The obtained result is the
opposite of the expected ones in the beginning since the
powdered coal has a higher surface area, which will
enhance its reactivity to form more NOx. Therefore, the
coal was placed into an alumina crucible and piled up,
which suggests that the diffusion of O2 through the
space among coal particles greatly contributes to the
formation of NOx. However, for complete understand-
ing, the sample left in each experiment was submitted to
further chemical analyses to estimate the remaining
amount of nitrogen in coal, which confirmed that
granule samples contained more nitrogen than powder.
This indicates that the powder was more reactive.
Hence, to explain the difference in the conversion of
nitrogen, it was suggested that coal powder reacted
more to form NOx, but simultaneously more CO was
produced, which can reduce NOx at high temperatures,
as shown by Reaction [5].
Anthracite coal was also used to check the influence
of oxygen content present in gas composition on XNO.
was applied for this experiment at a heating rate of
30 K/min. Figure 3 shows the oxygen content effect on
the fractional conversion of nitrogen in coal. The
formation of NOx increased with increasing oxygen
content, which is in agreement with the previous
research results.[23,25] This result can be explained by
the availability of O2 inside the reactor that can react
chemical reaction:
NðsÞ þ O2 ðgÞ ¼ NOx ðgÞ: ½7
The effect of the heating rate on XNO was evaluated
by applying five different heating rates (20, 30, 40, 50
and 80 K/min) at constant oxygen content (21 vol pct)
and flow rate (600 mL/min). The tests were performed
non-isothermally. Figure 4 provides the relationship
between XNO and heating rate. The formation of NOx
VOLUME 51B, OCTOBER 2020—2071
Fig. 4—Effect of heating rate on the conversion of nitrogen to NOx.
Fig. 5—The formation of NOx for anthracite coal, coke and
semi-anthracite coal.
decreased with increasing the heating rate, which is in
agreement with the previous study.[23] It is believed that
the higher heating rates reduce the oxygen potential,
which leads to a decrease in interaction time between O2
and fuel-N.
B. Effect of Coal Type Containing Various Nitrogen
Content on the Conversion of Nitrogen
Based on the understanding of the effect of different
sintering parameters on the nitrogen conversion ratio, it
is required to figure out the formation mechanism of
NOx formation for three different types of coal for
explaining how fuel-N converts into NOx. Anthracite,
coke and semi-anthracite coals were non-isothermally
heated up to 1623 K (1350 C) at 30 K/min in an
atmosphere Ar-21 vol pct O2. The amount of NOx
formation and pattern for the three types of coals are
represented in Figure 5. According to the results
obtained from the combustion experiments of each type
of coal, the formation of NOx (ppm) was higher for
semi-anthracite coal containing 1.955 wt pct of nitrogen.
2072—VOLUME 51B, OCTOBER 2020
Fig. 6—Fractional conversion of nitrogen to NOx according to three
different type of coals: (a) Non-isothermal heating up to 1623 K
(1350 C) and (b) Isothermal tests at three different temperatures.
Anthracite containing 0.691 wt pct N produced a total
of NOx emission higher than that of coke containing
1.191 wt pct N. According to Thomas[34] who reported
the effect of coal rank on the absolute formation of NO
during pulverized fuel combustion, it was verified that
the formation of NO increases with nitrogen content
present in coal. The current results are in partial
agreement with that by Thomas,[34] where semi-an-
thracite coal containing more nitrogen than anthracite
and coke produced more NO. However, as compared
with coke, the coal containing less nitrogen (anthracite)
formed more NOx. Thomas[34] studied the relationship
between the formation of NOx and nitrogen amount in
coal without considering that coke is a mixture of coals
previously submitted to pyrolysis conditions.
However, when analyzing the data in terms of the
nitrogen conversion ratio (XNO) instead of the formed
amount of NOx, the results showed a completely
different trend. Figure 6 summarized the nitrogen con-
version ratios of the three coals in non-isothermal and
isothermal heating patterns.
As shown in Figure 6, there is no trend that the coal
containing a higher amount of nitrogen proportionally
resulted in the higher fractional conversion of nitrogen
to NOx, which is in agreement with the previous
METALLURGICAL AND MATERIALS TRANSACTIONS B
studies.[34–36] Thomas[34] compared the formation of NO
for two lignite coals containing similar nitrogen content,
and found that the total emitted amount was different
by almost 60 pct. This indicates that XNO did not follow
a relationship with nitrogen content in coal. Wang
et al.[35] also found that the conversion of N into NO has
no direct relation with the nitrogen content present in
char. Furthermore, according to the study about the
effect of coal rank on XNO by Johnsson,[36] the conver-
sion of nitrogen to NOx might be related to the type of
coal rather than the nitrogen content present in the coals
of different ranks. In this study, anthracite coal con-
taining less fuel-N than coke and semi-anthracite
produced the highest N-conversion to NOx.

C. Effect of Anthracite Replacement with Coke

on the Conversion of Nitrogen
Anthracite coal and coke are the most frequently used
carbonaceous fuels in the sintering process of iron ores.
By changing the mixing ratio between them, the effect of
fuel composition on XNO can be considered to suggest
the optimal coal mixing for the minimum formation of
NOx in the sintering plant. Coke replaced anthracite
with 30, 50, 70 and 100 wt pct of which effects on XNO
are shown in Figure 7.
Replacement of anthracite with coke resulted in the
decrease in the conversion of nitrogen to NO (XNO) as
shown in Figure 6 where coke showed a lower conver-
sion ratio of nitrogen than anthracite. In case that coke
replaced anthracite by 70 and 100 pct, XNO was reduced
by 45 and 53 pct, respectively. However, to find the
proper coal mixing which reduces the emission of NOx
in the sintering plant, it is necessary to compare the
formed amount of NOx. Table IV provided the initial
amount of nitrogen (in grams) and total NO produced
(in grams) to examine the effect of anthracite replace-
ment with coke.
With reference to the anthracite only, all the other
samples (coke addition) promoted a decrease in NOx
formation. In the case of 70 pct replacement, NOx was
reduced by about 18 pct. In the case of complete
replacement of anthracite with coke, the formation of
NOx was reduced by 21 pct. As shown in Tables I and
IV, although coke contains higher nitrogen content than
anthracite, its total formation of NOx was lower. These
results suggest that nitrogen content is not the dominant
factor that determines the formation of NOx. Therefore,
it might be better to charge more coke to the sintering
plant for controlling the emission of NOx than
anthracite even though coke contains more nitrogen.
However, Wang et al.[37] showed that the addition of
coke to coal increases NOx formation, which is in
contrast to the current results.
D. Effect of the Addition of CaO and FeO to Coal
on XNO
To figure out a countermeasure mechanism for the
formation of NOx, CaO and FeO were added to coal
combustion as prospective catalysts for the reduction in
NOx. Firstly, CaO and FeO were uniformly mixed with
Fig. 7—Effect of anthracite replacement with coke on the conversion
of nitrogen to NOx: (a) Non-isothermal heating up to 1623 K
(1350 C) and (b) isothermal tests at three different temperatures.
2 g of anthracite coal in three different mixing ratios as
shown in Table II. Then the samples were exposed to
the same experimental conditions as single anthracite
combustion to examine the effect of CaO and FeO on
the conversion of nitrogen to NO as shown in Figure 8.
The addition of CaO and FeO promoted the increase
in NOx formation with respect to the coal baseline. CaO
acted as a catalyst for the formation of NOx at
temperatures below 1273 K (1000 C).[26–30] Since the
experiments were non-isothermally conducted, the cat-
alytic effect of CaO in low temperature region could not
be avoided. When the NOx formation pattern was
analyzed at temperatures above 1473 K (1200 C), NOx
formation was decreased when compared to anthracite
combustion, which is in agreement with previous
results.[38] Lee et al.[38] found that lime addition to coke
combustion promoted an increase in XNO up to 1373 K
(1100 C), and then XNO decreased at higher tempera-
tures. In addition, several researchers have figured out
that lime (CaO) has a catalytic effect on the reduction in
NO by carbon monoxide.[39,40]
FeO was selected as a prospective catalyst due to its
ability to be oxidized at low temperatures, which could
catch oxygen from NOx to form N2, as shown by
Reaction [8]:[33]

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 51B, OCTOBER 2020—2073

 Table IV. Effect of Anthracite Replacement with Coke on the Formation of NOx
Sample Anthracite (wt pct) Coke (wt pct)
1 100 0 0.01382
2 70 30
3 50 50
4 30 70
5 0 100
Fig. 8—Effect of the addition of CaO and FeO to anthracite coal on
the conversion of nitrogen to NOx.
1 (g), and WN is the initial amount of nitrogen con-
NO ðgÞ þ 3FeO ðsÞ ¼ N2 ðgÞ þ Fe3 O4 ðsÞ;
2 value used to get G(X) was XNO + XN2 . Table V pro-
DG0 ¼  401; 500 þ 126:3TðJ=molÞð298 K to 1653 KÞ:
However, the sample was heated from room to target
temperature in an oxidizing atmosphere (21 vol pct O2),
which promoted the oxidation of FeO before it could
reduce NOx by Reaction [8]. This phenomenon limited
the catalytic effect of FeO on the reduction in NOx. As is
similar to that shown by CaO at temperatures above
1473 K (1200 C), the formation of NOx was also
decreased in the presence of FeO. There are two possible
mechanisms for this reduction at high temperatures. The
oxidized FeO (Fe3O4/Fe2O3) was reduced by carbon
monoxide (CO) or solid carbon (C) and then FeO
reduced NOx. On the other hand, oxidized FeO acted as
a catalyst for NO-CO reduction reaction (Reaction [5]),
which was previously reported by Illan-Gomez et al.[41]
The difference in the catalytic effect of CaO and FeO
on XNO can be explained by the mechanism that CaO
and FeO promoted. As the amount of catalyst
increased, CaO acted to promote nitrogen conversion
into NOx more and more while FeO was oxidized in the
presence of oxygen up to a certain amount, and then
non-oxidized FeO could act to decrease the formation of
NOx.
2074—VOLUME 51B, OCTOBER 2020
Initial Nitrogen (g) Produced NO (g) Reduction (pct)
0.003739 —
0.01682 0.003512 6.07
0.01882 0.003531 5.56
0.02082 0.003066 17.99
0.02382 0.002949 21.13
IV. DISCUSSION
A. Evaluation of Activation Energy (EA)
for the Conversion of Nitrogen in Anthracite and Coke
to NO
The isothermal results shown in Figure 6(b) were used
to evaluate the activation energy (EA) for the conversion
of nitrogen in anthracite and coke based on the models
summarized in Table III. Since the oxidation reaction of
forming NOx and reduction reaction of producing N2
are combined in actual experiments, it might be difficult
to use XNO for x value in the models for evaluating EA
by plotting the reaction rate constant against tempera-
ture. Therefore, the conversion of NOx to N2 (XN2 ) was
assumed to be estimated by Eq. [10]:
RN
XN2 ¼ 1  XNO  ; ½10
WN
where XNO represents the nitrogen conversion to NO,
RN represents the nitrogen left after the experiment
½8 tained in coal (g). Therefore, after considering XN2 , X
vided the correlation coefficients for anthracite and
coke according to different mechanism models.
From the above results, the proper mechanism
½9 function for each coal was selected by the correlation
coefficients (R2) between G(X) and time. In the case of
anthracite and coke using x as XNO, the model R3
showed the best fitting while the models D2 and D3 are
found to be applied to anthracite and coke, respectively,
when the value, x*, was used. Using these values, it was
possible to evaluate the apparent reaction rates (k) by
plotting G(X) against experimental time. The k values
are shown in Table VI.
To obtain the activation energy (EA) value for each
coal, Arrhenius equation was employed. By plotting the
natural logarithm of k values obtained from Table VI
against the reciprocal of temperature, it was possible to
evaluate the activation energy (EA) from the slope,
represented by ( EA/R), where R is the universal gas
constant. EA was evaluated to be 2.2 and 3.6 kJ/mol for
anthracite and coke, respectively. This suggests that it is
more difficult to convert nitrogen in coke to NO than
anthracite requiring less energy, which confirmed the
formation amount of NOx in Figure 5, and the conver-
sion of nitrogen to NO (XNO) showing a higher value for
anthracite as shown in Figure 6. Similar kinetic analyses
have not been performed by previous researchers who
basically evaluated X based on the weight change in
METALLURGICAL AND MATERIALS TRANSACTIONS B
 Table V. Correlation Coefficients of Anthracite and Coke Samples at Different Temperatures According to Different Mechanism
Models

Correlation Coefficients of Different Mechanism Models

Sample Temperature R1/2 R1/3 R1/4 R2 R3 D1 D2 D3

Anthracite 1273 K (1000 C) 0.993 0.987 0.983 0.998 0.999 0.959 0.955 0.951
1373 K (1100 C) 0.994 0.990 0.986 0.998 0.999 0.959 0.955 0.952
1473 K (1200 C) 0.993 0.990 0.986 0.997 0.997 0.965 0.962 0.960

Anthracitea 1273 K (1000 C) 0.990 0.979 0.964 0.999 0.999 0.999 0.999 0.998
1373 K (1100 C) 0.990 0.978 0.961 0.999 0.999 0.999 0.999 0.999
1473 K (1200 C) 0.988 0.976 0.961 0.998 0.998 0.998 0.999 0.999

Coke 1273 K (1000 C) 0.996 0.995 0.993 0.998 0.998 0.956 0.955 0.953
1373 K (1100 C) 0.993 0.991 0.990 0.995 0.995 0.970 0.969 0.968
1473 K (1200 C) 0.992 0.991 0.990 0.994 0.994 0.970 0.969 0.968

Cokea 1273 K (1000 C) 0.991 0.981 0.968 0.999 0.999 0.999 0.999 0.999
1373 K (1100 C) 0.985 0.972 0.956 0.997 0.998 0.996 0.998 0.999
1473 K (1200 C) 0.985 0.972 0.957 0.997 0.998 0.995 0.997 0.999
Bold values indicate the proper reaction mechanism for each sample, based on R2 value.
X = XNO.
Xa = XNO + XN2 .

Table VI. Apparent Reaction Rate Constants of Anthracite
and Coke Samples (3 1025)
Temperature Anthracite Anthracitea Coke
1273 K (1000 C) 1.83 3.50 0.82
1373 K (1100 C) 1.63 3.97 0.63
1473 K (1200 C) 1.29 3.58 0.53
X = XNO.
Xa = XNO + XN2 .
sample during the experiment. In the current study, X
was considered to be the conversion of fuel-nitrogen to
NO. Therefore, it might not be possible to directly
compare the activation energy values of anthracite and
coke for confirming their relative easiness of forming
NO.
B. Effect of Functional Form of Nitrogen in Coal on Its
Conversion to NO
The network structure of coal with a special focus on
the functional form of nitrogen can be investigated by
two different approaches. The first one involves the
degradation of the macromolecular network into
numerous small molecules, and then the initial struc-
tures are inferred by identifying the fragments. How-
ever, the main problem of using this technique is that
secondary reactions such as rearrangement, cracking
and polymerization can simultaneously occur along with
the degradation of coal into small fragments. The
second method is to characterize the nitrogen function-
ality in coal which applies non-destructive spectroscopic
methods such as X-ray photoelectron spectroscopy
(XPS), X-ray absorption near-edge structure (XANES)
and nuclear magnetic resonance (NMR) spec-
troscopy.[42] In the case of XPS, the irradiation of a
surface with monochromatic X-rays ejects electrons with
kinetic energies characteristics of both the element and
its bonding state. This technique has been used to
Cokea compare surface and bulk atomic concentrations for
nitrogen in coal, kerogen and pitch. In addition, it was
1.52
previously used to investigate the nitrogen functionality
1.59
1.59 in coals and char.[43]
As shown in Figure 5, the formation pattern of NOx
in each coal was different, which suggests that coal
structure might influence how nitrogen is converted into
NOx. Hence, it is important to study how nitrogen is
present in the carbon structure in each coal. Several
researchers studied about the functional forms of
nitrogen in coal and concluded that nitrogen can be
found in three major forms: quaternary-N, pyrrolic-N
and pyridinic-N. X-ray photoelectron spectroscopy
(XPS) results indicated that their binding energies are
401.4 ± 0.3, 400.3 ± 0.3 and 398.7 ± 0.3 eV, respec-
tively.[44–46] The distribution of nitrogen functional
forms analyzed in this study before combustion is
shown in Figure 9.
As shown in Figure 9, the way that nitrogen is
attached in each coal is completely different. In the case
of anthracite and semi-anthracite coals before combus-
tion, pyrrolic-N was found to be the major structure
while quaternary-N was the dominant one for coke.
In order to clarify the effect of combustion experiment
on nitrogen structure, the change promoted by oxidizing
atmosphere on each nitrogen functionality in the coal
left behind combustion was also evaluated by XPS
analysis as also shown in Figure 9. It can be seen that
combustion environment promoted a notable change in
nitrogen functionality for each coal. Quaternary-N was
found to be the major functionality for all the coals in
this study. Table VII summarized the composition of
nitrogen functionality for each coal before and after
combustion. No relation was found between XNO and

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 51B, OCTOBER 2020—2075

Fig. 9—Change in nitrogen functional forms of different coals after combustion: (a) anthracite, (b) coke and (c) semi-anthracite.

Table VII. Distribution of Nitrogen Functionality Before and After Combustion for Three Type of Coals

Before Combustion (pct) After Combustion (pct)

Coals Quaternary-N Pyrrolic-N Pyridinic-N Quaternary-N Pyrrolic-N Pyridinic-N

Anthracite 32.6 43.1 24.3 39.4 31.2 29.4
Coke 48.8 28.8 22.4 47.7 36.7 15.6
Semi-anthracite 15.3 49.3 35.4 39.0 36.9 24.1

nitrogen functional forms before combustion, which is structure was related to the conversion of nitrogen to
in agreement with the results by Wojtowicz et al.[47] who NOx, it was attempted to evaluate the difference in each
found that XNO has no direct relation with the amount structure before and after combustion as shown in
of pyridinic-N in coal. To understand which change in Table VIII.

2076—VOLUME 51B, OCTOBER 2020 METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table VIII. Change in Nitrogen Functional Forms After Combustion Process
Samples Quaternary-N (pct)
Anthracite 6.8
Coke  1.2
Semi-anthracite 23.7
Chara ~  39.0
a
Char 50 pct burn-off from Zhang et al.[48]
The combustion process promoted the decrease in the
relative amounts of pyrrolic-N for anthracite, of pyrid-
inc-N for coke and of pyrrolic-N/pyridinic-N for
semi-anthracite. According to Zhang et al.[48] who
studied the effect of char combustion on the change in
nitrogen functionality, in the case of char combustion
which is similar to coke, the combustion experiments
induced the increase in the relative amount of pyrro-
lic-N, which is in agreement with the result for coke in
the current research. However, in the case of quater-
nary-N and pyridinic-N, coke and char showed a
different trend, as summarized in Table VIII. The
difference shown in the combustion of anthracite and
coke might be ascribed to the previous exposition of
coke to heating treatment during cokemaking process,
which might have promoted the significant release of
pyrrolic-N. Therefore, when coke was exposed to
combustion atmosphere, pyridinic-N was the major
functionality released, which could be related to the
formation of NOx. The change in nitrogen functional
forms summarized in Table VIII might be one possible
explanation for the results shown in Figure 6 where
smaller conversion of nitrogen in semi-anthracite to NO
has resulted than that in anthracite although semi-an-
thracite contains more nitrogen. A preliminary conclu-
sion might be that the conversion of nitrogen to NOx
could be highly affected by the change in nitrogen
functionality after and before combustion. The coal
rank influences how the nitrogen functionality can be
modified after the combustion process. The pyrrolic-N
in anthracite coal might be considered to be the major
functional form that directly affects the conversion of
nitrogen to NO while both pyrrolic-N and pyridinic-N
in semi-anthracite were mostly converted into quater-
nary-N of higher binding energy where it is is more
difficult to release nitrogen in the form of NO. This
might be the reason why semi-anthracite resulted in
lower values of XNO compared with anthracite coal. It is
required to further investigate this relationship for
clarifying the mechanism of nitrogen conversion to
NOx.
V. CONCLUSIONS
1. The conversion of nitrogen to NOx (XNO) was highly
affected by sintering conditions. XNO decreased with
increasing temperature and heating rate, and in-
creased when oxygen content in an atmosphere also
increased.
2. It was attempted to add CaO and FeO as prospective
catalysts for the reduction of NOx in the sintering
METALLURGICAL AND MATERIALS TRANSACTIONS B
Pyrrolic-N (pct) Pyridinic-N (pct)
 11.9 5.1
8.0  6.8
 12.4  11.3
~35.0 ~5.0
process. The addition of CaO and FeO enhanced the
conversion of nitrogen to NOx, especially at tem-
peratures below 1273 K (1000 C). CaO acted as a
catalyst for the formation of NOx, and FeO was
oxidized before it could reduce the formed NOx.
3. Taking both the oxidation reaction to form NOx and
reduction reaction of NOx to form N2 into account,
the activation energy (EA) values of anthracite and
coke were evaluated to be 2.2 and 3.6 kJ/mol,
respectively. This indicates that it is more difficult to
convert nitrogen in coke to NO than anthracite
requiring less energy, which confirmed that the
formed amount of NOx and the conversion of
nitrogen to NO (XNO) showed higher values for an-
thracite.
4. The combustion of semi-anthracite coal emitted the
largest amount of NOx, but the anthracite coal con-
taining less fuel-N than other coals showed the
highest value of XNO, which indicates that nitrogen
content in coal is not the major factor affecting the
formation of NOx. The XPS results suggested that
the three coals have completely different distribution
of nitrogen functionality, which might influence the
conversion ratio of nitrogen to NOx (XNO).
5. The pyrrolic-N in anthracite coal might be consid-
ered to be the major functional form that directly
affects the conversion of nitrogen to NO while both
pyrrolic-N and pyridinic-N in semi-anthracite were
mostly converted into quaternary-N of higher bind-
ing energy where it is more difficult to release nitro-
gen in the form of NO. This might be the reason why
semi-anthracite resulted in lower values of XNO
compared with anthracite coal.
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