Energy Conversion and Management 77 (2014) 349–355

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Energy Conversion and Management

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NO emission characteristics of superfine pulverized coal combustion

in the O2/CO2 atmosphere
Jiaxun Liu a, Shan Gao b, Xiumin Jiang a,⇑, Jun Shen a, Hai Zhang a
a
School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, PR China
a
Opto-Electronic Engineering college, Zaozhuang University, Zaozhuang 277160, PR China

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

Article history: The combination of O2/CO2 combustion and superfine pulverized coal combustion technology can make
Received 17 June 2013 full use of their respective merits, and solve certain inherent disadvantages of each technology. The tech-
Accepted 26 September 2013 nology of superfine pulverized coal combustion in the O2/CO2 atmosphere is easy and feasible to be ret-
rofitted with few reconstructions on the existing devices. It will become a useful and promising method
in the future. In this paper, a one-dimensional drop-tube furnace system was adopted to study the NO
Keywords: emission characteristics of superfine pulverized coal combustion in the O2/CO2 atmosphere. The effects
Superfine pulverized coal
of coal particle size, coal quality, furnace temperature, stoichiometric ratio, etc. were analyzed. It is
NO emission characteristics
O2/CO2 combustion
important to note that coal particle sizes have significant influence on NO emissions in the O2/CO2 com-
Fuel-N conversion bustion. For the homogeneous NO reduction, smaller coal particles can inhibit the homogeneous NO for-
Homogeneous and heterogeneous reduction mations under fuel-rich combustion conditions, while it becomes disadvantageous for fuel-lean
combustion. However, under any conditions, heterogeneous reduction is always more significant for
smaller coal particle sizes, which have smoother pore surfaces and simpler pore structures. The results
from this fundamental research will provide technical support for better understanding and developing
this new combustion process.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Anthropogenic greenhouse gases emissions from fossil fuel
combustion, which causes serious global warming and climate
changing problems, has gained attention and credibility in recent
years [1]. Many technologies for controlling CO2 emissions have
been developed [2–4], among which the O2/CO2 combustion meth-
od is a high cost-effective and promising clean combustion tech-
nology [5–7]. The concept of oxy-fuel combustion was proposed
almost simultaneously by Horn and Steinberg [8] and Abraham
et al. [9] in the early eighties. There are many high quality papers
reviewing the development of this technology from a technical
point of view [10–12]. Oxy-fuel combustion technology has many
advantages for controlling CO2 emissions. The exhaust flue gas
consists of high concentration of CO2 (normally >90% on a dry ba-
sis) ready for sequestration, which can reduce the CO2 capture
costs a lot. The volume of flue gas emitted from power plant is re-
duced by about 80%, because of the flue gas recycling, which is use-
ful for increasing the thermal efficiencies. It also has the potential
to reduce the cost of pollutant control, especially on NOx emissions.
Additionally, oxy-fuel combustion technology is technically and
economically feasible for retrofitting existing power plants.
⇑ Corresponding author. Tel.: +86 21 3420 5681.
E-mail address: xiuminjiang@sjtu.edu.cn (X. Jiang).
However, there are still some barriers for its wide application in
coal-fired power plants. Besides the significant capital and opera-
tion costs of the air separation unit (ASU) [13], the replacement
of N2 by CO2 in the reacting atmosphere may also result in worse
combustion performances and more serious corrosion and deposit-
ing problems. Bejarano and Levendis [14] conducted single-coal-
particle combustion experiments and found that coal particles
burned at higher mean temperatures and shorter combustion time
in O2/N2 than in O2/CO2 environments. The volatile flame temper-
atures are reduced by 250 K, while coal char surface temperatures
decrease by 200 K. Zhang et al. [15] studied the coal burning tran-
sient phenomena and observed that substitution of CO2 for N2 de-
layed the coal ignition significantly. Molina and Shaddix [16]
pointed out that the presence of CO2 retards coal particle ignition
but demonstrates no measurable effect on the duration of volatile
combustion. Borrego and Alvarez [17] compared the char charac-
teristics obtained under oxy-fuel combustion and air combustion.
The results showed that the main difference between two series
of chars were the surface areas. The burnout levels were lower in
CO2 than in N2 when O2 were kept the same amount. Suda et al.
[18] studied the flame propagation in the O2/CO2 combustion
and suggested that flame propagation velocity decreased to about
1/3–1/5 in O2/CO2 mixtures than in O2/N2 mixture under the same
oxygen concentration. Kiga et al. [19] also drew similar conclusions
that the flame propagation speed in the O2/CO2 atmosphere was

0196-8904/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.enconman.2013.09.048
350 J. Liu et al. / Energy Conversion and Management 77 (2014) 349–355
markedly low, compared with that in O2/N2. Liu et al. [20] experi-
mentally investigated the coal combustion characteristics in O2/
CO2 mixtures and found that simply replacing N2 with CO2 de-
creases the gas temperatures and char burnouts significantly,
which may destabilize the coal flame. Maier et al. [21] detected
that increased corrosion happens if the atmosphere at the furnace
walls is reductive. Therefore, the corrosion and depositing prob-
lems will be more serious in the O2/CO2 combustion where in-
creased concentrations of CO are created.
The proposal of superfine pulverized coal particle combustion
provided a new way to understand the particle size effect on com-
bustion [22]. Through our previous research, we found that super-
fine pulverized coal can solve these inherent disadvantages in
normal O2/CO2 combustion to a certain extent. The coal particles
with sizes below 20 lm have little differences on ignition temper-
atures in the O2/CO2 atmosphere, compared with O2/N2 mixtures.
The gently released volatile matter makes the ignition processes
less violent [23]. The influences of particle sizes on coal ignition
and burnout characteristics were also investigated through ther-
mal gravimetric (TG)/differential thermal gravimetric (DTG) and
the results showed that the ignition and burnout temperatures de-
crease slightly as the mean particle sizes decrease [24]. It is found
that after ultrafine grinding of coal particles, the fusion points of
coal ashes increase significantly and the situations of ash and slag
buildup in boilers are relieved to some degree [25].
Therefore, the O2/CO2 combustion of superfine pulverized coal
technology is proposed in this paper, which introduces superfine
pulverized coal to the traditional O2/CO2 combustion technology.
The combination of the superfine pulverized coal and O2/CO2 com-
bustion technology makes full use of their respective merits and
solves the inherent disadvantages of each technology, which can
accomplish the NOx removing and CO2 capturing simultaneously.
It is a new technology which is feasible and easy to be retrofitted
with few reconstructing on the existing devices. Therefore, super-
fine pulverized coal combustion in the O2/CO2 atmosphere tech-
nology will become a useful and promising method in the future.
The primary objective for oxy-fuel combustion is sequestration of
CO2. It implies that the technique is also a new option for the con-
trol of NOx [26,1]. It has been widely accepted by researchers that
there is a large decrease of NOx emissions in oxy-fuel combustion
compared with conventional air combustion, though the detailed
mechanisms are under extensive research. In this paper, we focus
on the NO emission characteristics and detailed de-NO mecha-
nisms of this new technology.
There are few reports of superfine pulverized coal combustion in
the O2/CO2 atmosphere. Flue-gas recirculation is beyond the scope
of this work, although important in oxy-coal combustion. In this pa-
per, the one-dimensional drop-tube furnace system (once-through
system) was adopted to study the NO emission characteristics of
superfine pulverized coal combustion in the O2/CO2 atmosphere.
The effects of coal particle size, coal quality, furnace temperature,
stoichiometric ratio, etc. were analyzed. The results from this
fundamental research will provide technical support for better
understanding and developing this new combustion process.
2. Experimental section
2.1. Materials
Two typical Chinese coals with obvious differences in the extent
of coalification were chosen for the experiments. Shenhua (SH) and
Neimongol (NMG) coal samples were pulverized into superfine pul-
verized coal, with the particle sizes between 10 lm and 55 lm. The
specific equivalent mean particle sizes of SH samples are 14.7, 17.4,
21.3 and 44.2 lm while NMG samples are 12.5, 14.9, 25.8 and
52.7 lm. The properties of the coals are listed in Table 1.
2.2. Apparatus and procedure
The schematic diagram of the coal combustion experimental
system is depicted in Fig. 1. The one-dimensional droptube furnace
system was adopted in this work. A cylindrical quartz glass tube
with an inner diameter of 60 mm serves as the combustion cham-
ber, the electrically heated part of which is 2000 mm long in the
furnace. Globar heating components are used in the system and
the highest wall temperature can reach 1300 °C. The electric heat-
ing power is about 12 kW. Multipath inlets for oxidizer are ar-
ranged along the combustion chamber to simulate the staged
combustion situations in future experiments. Temperature profiles
along the furnace axis were measured using a movable thermocou-
ple before experiments when the reactor was heated up to 1100 °C,
which was shown in Fig. S1 in Supplementary material. It can be
seen that temperatures in the main reaction zone are basically sta-
ble. A micro-screw feeder was applied in the coal feeding system.
The feeding system can regulate the powder flow rate continu-
ously, steadily and precisely (0–1 g/min), with the help of the
vibration devices, pressure balance system and injecting system
on the storage bin. The feeder was pre-calibrated before each
experimental operation. Pulverized coal samples, flowing down-
ward, were brought into the combustion chamber by the primary
oxidizer. The flue gas was simulated by a mixture of high purity
O2 (99.999%) and CO2 (99.999%), which were supplied by gas cylin-
ders and regulated by mass flow controllers. The amount of theo-
retical air can be calculated on the basis of the ultimate analysis
of each coal sample. Then the amount of the oxygen was concluded
according to the operating conditions (given the oxygen concentra-
tion or the stoichiometric ratio) and the total flow rates can be
confirmed (2.46–10.16 L/min). A portable FTIR (Fourier transform
infrared) gas analyzer Gasmet DX-4000 (Finland) which is an
on-line real-time detecting system, was used to monitor the
compositions of outlet gases at the exit of the furnace. The Gasmet
DX-Series enables identification and quantification of multiple
gaseous compounds simultaneously and accurately, with results
available in seconds. The sample cell was a gold-coated aluminum
White cell with the maximum optical path length of 9.8 m, which
is heated up to 180 °C to rule out the condensation problems.
Beer’s law is applied for the quantitative analysis of FTIR spectra.
The law shows the concentration of the sample gas is related to
the measured absorbance of the sample spectrum. The Gasmet
needs calibrations using single component calibration gases. The
reference spectra, which are stored in the computer, are loaded
during the analysis. In our case, the compositions of outlet gases
including CO2, CO, CH4, SO2, H2O, HCl, HF, NO, N2O, NO2, HCN
and NH3 can be measured quantitatively by Gasmet. The lowest
detectable concentrations are 0.1–2 ppm and the accuracy is 2%,
depending on the application.
Table 1
Ultimate and proximate analysis of tested coal samples.
Proximate analysis (mass%) (ad) Ultimate analysis (mass%) (ad)
SH
Moisture 11.5 C 63.13
Volatile 24.22 H 3.62
Ash 10.7 O 9.94
Fixed carbon 53.58 N 0.70
S 0.41
NMG
Moisture 14.72 C 54.82
Volatile 35.69 H 4.39
Ash 10.64 O 14.58
Fixed carbon 38.95 N 0.63
S 0.22
 J. Liu et al. / Energy Conversion and Management 77 (2014) 349–355 351

Entrained
flow

Coal
feeder

Mass Program Furnace

flowmeter temperature
controller controller

Air
preheater
Pressure
gauge
Pressure
gauge
Pressure Mass
gauge flowmeter Gas
mixer

O2 N2 Program
CO2
gas gas temperature
gas
controller

Bottom
ash
pot Gas
analyzer

Thermostatic
water bath

Fig. 1. Schematic diagram of coal combustion experimental system.

2.3. Small-angle X-ray scattering (SAXS) analysis at the Shanghai
Synchrotron Radiation Facility
Coal is a complex polymeric material with extremely heteroge-
neous porous structures that are difficult to classify. The pore net-
work serves as a path by which reagents gain access to and leave
the interior of coal structure. The porous structure is a crucial fac-
tor for the coal combustion process because of its influences on
heat transfer rate and reaction surface. Therefore the knowledge
of the porous structure in coal will help us better understand the
de-NO mechanisms of the superfine pulverized coal combustion
technique. The small angle scattering of X-rays (SAXS) technique
was adopted to analyze the porous structures of superfine pulver-
ized coal particles.
The SAXS experiment was performed using synchrotron radia-
tion as the X-ray source with a long-slit collimation system at
the Shanghai Synchrotron Radiation Facility (SSRF). The wave-
length of X-ray is 1.24 Å, which is focused to 0.5 (vertical)  0.5
(horizontal) mm2 at the detector, with a camera length of
5417 mm. The absorption of the sample and the background scat-
tering were corrected. All the intensities of the samples are nor-
malized by the data recorded from ionization chambers.
3. Results and discussions
3.1. Influence of temperature and coal quality
It is widely accepted that the replacement of N2 by CO2 in the
reacting atmosphere may result in worse combustion perfor-
mances. To attain a similar temperature profile, heat flux and com-
bustion performances as the conventional air combustion, the inlet
oxygen concentrations should be raised to 30–42% [27,28]. How-
ever, increasing oxygen will raise the operation costs and bring
some new issues in practical operation. Plus, NOx emissions will
also increase. Zhang et al. [15] investigated the coal burning tran-
sient phenomena of brown coals in O2/N2 and O2/CO2 mixtures. Re-
sults show that similar temperatures of volatile flame and burning
char particles can be achieved in 27% oxygen concentrations. In
this paper, the main operating conditions of the atmosphere were
set as for 30% O2 and 70% for CO2.
Fig. 2 reveals the influence of temperatures on the emissions of
NO in the O2/CO2 atmosphere (O2 30%, CO2 70%). The stoichiome-
tric ratio (SR) was kept steadily as k = 1.2. The NO concentration
was converted into a 6% O2 basis, both here and infra. To evaluate
the conversion degree of fuel-N to NO, the conversion ratio (CR)
was calculated by dividing the amount of input coal-N with the
amount of total nitrogen of NO in the exhaust gas, which is ex-
pressed in formula (1) [29]:
CR ¼ F NO =F N ð1Þ
where FN is N-atom number of fuel-N and FNO is N-atom number of
total NO formed from fuel-N.
From Fig. 2 it can be observed that with increase of the temper-
atures, the amounts of exhausted NO increase, especially for SH
coal. In the O2/CO2 atmosphere, the formation of fuel NO plays
the leading role. With the temperatures increasing, more fuel-N
is oxidized to NO and the nitrogen conversion ratio increases, that
can be confirmed from pyrolysis experiments. Influence of temper-
atures on evolutions of nitrogen-containing gases during pyrolysis
in CO2 atmosphere is shown in Fig. S2. With the increase of the
352 J. Liu et al. / Energy Conversion and Management 77 (2014) 349–355

2000 28 NO þ HCN=NH3 ! N2 þ . . . ð4Þ

NMG_12.5 NO x 26
1800 24
SH_14.7 NO x
22 NO þ Char ! N2 þ . . . ð5Þ
1600 NMG_12.5 CR

Conversion Ration (%)

20
NO (mg/m ) @ 6% O2

1400 SH_14.7 CR 18
16
1200 14
12
3.2. Influence of stoichiometric ratio
1000
3

800
600
400
200
0
800 900 1000
Temperature ( ) The influence of stoichiometric ratio on NO emissions is re-
Fig. 2. Influence of the temperature on NO emissions in the O2/CO2 atmosphere (O2
30%, CO2 70%, the stoichiometric ratio 1.2).
temperatures, the yields of HCN and NH3 are raising. The amounts
of NH3 reach the maximum around 750 °C, while there are two
releasing peaks at about 600 °C and 950 °C. These released NOx
precursors are oxidized during combustion, which causes the in-
crease of NO at higher temperatures. When the temperatures reach
800–1000 °C, the combustion of volatile matter is nearly complete
and the combustion of char-N begins. The release of NO reaches
the maximum at 800–1000 °C. The increasing trend of NO emission
for the NMG coal is not significant within the uncertainty of mea-
surements. This is probably due to the higher volatile contents in
them. During combustion of the NMG sample, more CO and NOx
precursors are released. The yields of CO and NH3 during pyrolysis
of SH and NMG coal in CO2 atmosphere are depicted in Figs. S3 and
S4. It shows that the yields of these reductive components from
NMG coal are much higher than SH coal. Then the exhausted NO
can be reduced to a certain extent, which may cause the decrease
of NO in NMG coal combustion. If the temperatures keep rising, the
reduction reaction of NO will be enhanced in the O2/CO2 atmo-
sphere because of the gasification effects. The reduction rates could
probably exceed the formation rates of NO when the temperature
is over 1200 °C, and the concentrations of NO may become lower.
However, this is not involved in this paper because the limits of
the combustion chamber (quartz glass tube cannot run for a long
time above 1200 °C). The speculation will be verified in the high
temperature combustion platform in the future.
Furthermore, all NO emissions of SH coal are higher than NMG
coal under the same situations. From the ultimate analysis in Ta-
ble 1, it is known the fuel-N in SH coal are higher than NMG coal.
The concentration of nitrogen in parent coal is an important factor
that influences the NO emissions. Additionally, the volatile matter
in NMG coal is higher, compared with SH coal. During the volatile
compound’s releasing phase, more CO, light hydrocarbon, and NOx
precursors are released. The releasing processes are more prompt
10
8 The NOx precursors such as HCN and NHi released during com-
6
4 bustion can be oxidized to NOx by reacting with O2 or free radicals
2 such as O and OH. Meanwhile, reductive reactions between NOx
0
and the precursors also exist, where the NOx is reduced to N2.
-2
-4 Therefore, the stoichiometric ratio (SR) is a crucial parameter to
control NOx emissions.
flected in Fig. 3, under the operation conditions of 30% O2/70%
CO2 and 1000 °C. With increasing SR from 0.6 to 1.4, both NMG
and SH coal show the same trend that NO emissions increase ini-
tially before k = 1.2 and reduces afterward around k = 1.4. Under
the fuel-rich combustion conditions, the oxygen concentrations
are inadequate and large amounts of reductive gases such as CO
and CH4 are produced (see Fig. S5), which suppress the conversion
from fuel-N to NO, and thus the nitrogen conversion ratio is low.
With the increase of SR, there are more chances for the precursors
to be oxidized, and NO emissions increase. In the fuel-lean com-
bustion, when SR exceeds 1.2, the low ratio of coal to inlet gas
led to low NO content in the flue gas [30,31]. On the other hand,
NO conversion ratios increase monotonically with SRs under both
fuel-lean and fuel-rich combustion, due to the increasing amounts
of oxygen.
3.3. Influence of inlet oxygen concentration
The oxygen concentrations have significant influence on NO
emissions, which is revealed in Fig. 4. SRs were kept k = 1.2 and
the temperatures were all 1000 °C. In all cases, NO contents in flue
gases increase initially with inlet oxygen concentrations and then
decline slightly as oxygen concentrations exceed 30%. With the
increase of oxygen concentrations, the flame temperatures
increase, promoting the formations of NO. Moreover, with oxygen
concentrations increasing, in order to keep the same SRs, the flow
rates of CO2 are reduced and the total flue gases decrease. There-
fore, NO emissions also increase due to lower NO dilution effects
[28]. The decreasing CO2 concentrations cause the drops of CO
formed in flue gas, which is disadvantageous for the NO reductions.
The NOx precursors and certain reductive radical groups such as
CHi are prone to be oxidized in higher oxygen concentrations. On
2400 30
NMG_12.5 NO
2200
2000 SH_14.7 NO 25
1800
Conversion Ration (%)

NMG_12.561 CR 20
NO (mg/m ) @ 6% O2

for NMG coal than SH coal. This can also be observed from 1600 SH_14.705 CR
Figs. S3 and S4. The maximum releasing rates of CO appear around 1400 15
768 °C and 765 °C for SH and NMG coal. It is more significant for 1200
10
the maximum releasing rates of NH3, which show up at about
3

1000
758 °C and 738 °C for SH and NMG coal separately. Therefore, there 800 5
are more chances for the NO, which are formed during the combus- 600
400 0
tion phase to be reduced, and thus NO emissions are lower for
NMG coal. It is concluded that CO2 atmosphere is more advanta- 200
-5
0
geous for higher volatile coal on NO reductions. The simplified
-200 -10
mechanism is shown as follows: 0.6 0.8 1.0 1.2 1.4

NO þ CO ! 1=2N2 þ CO2 ð2Þ Stoichiometric Ratio

Fig. 3. Influence of the stoichiometric ratio on NO emissions in the O2/CO2

2NO þ CHi ! N2 þ CO þ OH þ . . . ð3Þ atmosphere (O2 30%, CO2 70%, temperature 1000 °C).
 J. Liu et al. / Energy Conversion and Management 77 (2014) 349–355 353

2400 27 emissions have positive relationships with the nitrogen contents

2200 24 in raw coals.
2000 21

Conversion Ration (%)

NO (mg/m ) @ 6% O2

1800 NMG_12.5 NO 18 3.4.1. Influence of coal particle size on homogeneous reaction

1600 SH_14.7 NO
15 Research indicates that NOx emissions from homogeneous reac-
1400
NMG_12.5 CR 12
tions show a linear correlation with the nitrogen contents in raw
3

1200
SH_14.7 CR coals [32]. Meanwhile, with the decrease of coal particle sizes,
1000 9
the flame temperatures increase, promoting the formations of
800 6
NO. Furthermore, with the decrease of coal particle sizes, yield
600 3 temperatures of the volatile matter move forward, and the
400
0 amounts of these pyrolysis gases such as CH4, NH3 and HCN in-
200
-3 crease significantly. Fig. S6 reflects the relationship between coal
15 20 25 30 35 40 particle sizes and the yields of NH3. Basically, the amounts of
Inlet O2 Concentration (%) NH3 increase with the decrease of particle sizes. The volatile matter
is prone to be oxidized by the oxygen under fuel-lean combustion
Fig. 4. Influence of the inlet O2 concentration on NO emissions in the O2/CO2 conditions, converting more precursors into NO. In other words,
atmosphere (the stoichiometric ratio 1.2, temperature 1000 °C).
the smaller the particle size is, the higher the possibility becomes
that the species released from the char are oxidized. As the sample
the other hand, the reactions between oxygen and char-N also in- size increases, the atmosphere becomes more reductive, because of
crease the NO contents. the slow combustion rate, and delayed ignition point. This will be
However, when oxygen concentrations exceeded 30%, both NO helpful for the reduction of NOx [33]. We can draw the conclusion
emissions and CRs are declined, especially for CRs. The existence of that decreasing coal particle sizes is disadvantageous for the
NO and O2 will promote the formations of N2O and the simplified homogeneous NO reduction under fuel-lean combustion condi-
mechanism is shown as follows: tions. However, the influence of coal particle sizes will be com-
pletely different under fuel-rich combustion conditions. This is
NCO þ NO ! N2 O þ CO ð6Þ because when the oxygen is insufficient, the earlier the volatile
matter is released, the more resident time there will be to reduce
NH þ NO ! N2 O þ H ð7Þ the existing NO. Additionally, the more pyrolysis gases there are,
the easier it will be to remove the existing NO in the reductive
HCN þ O ! NCO þ H ð8Þ atmosphere.

NO þ ðNÞ ! N2 O
NO þ ðCNOÞ ! N2 O þ ðCOÞ
N2O can be homogeneously reduced to N2 by CO and it can also
be disposed through some other homogeneous and heterogeneous
reactions:
N2 O þ H ! N2 þ OH
N2 O þ OH ! N2 þ HO2
N2 O þ ðCÞsolid ! N2 þ CO
2N2 O þ ðCOÞsolid ! 2N2 þ 2CO
There are significant decreasing trends for CRs, because of the
possibilities that parts of the fuel-N are converted to N2 through
above reaction channels when the oxygen concentrations exceed
30%. Fig. 4 shows that the CRs of 40% oxygen concentrations are
even lower than that of 15% for both coal samples. However, all
NO emissions decline slightly as oxygen concentrations exceeded
30%, due to the lower dilution effects mentioned before.
3.4. Influence of coal particle size
NOx can be generated from homogeneous combustion of vola-
tiles and heterogeneous combustion of chars. The coal particle
sizes have significant influence on NOx emissions under different
conditions. Fig. 5 reflects the influence of particle sizes on NO emis-
sions in the O2/CO2 combustion, under the operation conditions of
k = 1.2, 30% O2/70% CO2, 21% O2/79% CO2 and 1000 °C. There are
similar trends for different inlet oxygen concentrations that NO
emissions increase with the decrease of coal particle sizes. Chem-
ical composition analysis of coal samples with different sizes is
summarized in Table 2, from which it can be observed that NO
ð9Þ
3.4.2. Influence of coal particle size on heterogeneous reaction
ð10Þ On the other hand, NO emissions from heterogeneous reactions
must be considered, and the influence of different coal particle
sizes on the char-N conversion paths will be discussed in detail.
First, with the decrease of coal particle sizes, the release of vol-
atile matter gets much more intense. Thus the surfaces become
ð11Þ more uneven and rougher, which makes the specific surface areas
of chars much larger. The higher reactivity of char surfaces is
ð12Þ advantageous for the heterogeneous reduction of NO. To test this
speculation, the pore structures of superfine pulverized coal were
ð13Þ investigated. N2 adsorption experiments were carried out to study
the textural characteristics of coal chars, presented in Fig. S7. Both
ð14Þ the specific surface areas and pore volumes increase significantly
with the increase of pyrolysis temperatures. Pores of coal chars
from CO2 atmosphere are more abundant than from N2 atmo-
sphere because of the gasification effects. Therefore, the heteroge-
neous reduction of NO becomes more important in the O2/CO2
combustion technique.
Second, the prompt releasing of volatile-N from small coal par-
ticles will be oxidized to NO, which makes the concentrations of
NO around the coal surfaces appear higher than larger coal parti-
cles. This can be tested from the yields of NO during pyrolysis of
superfine coal in CO2 atmosphere, which is shown in Fig. S8. It is
obvious that with the decrease of the particle sizes, the amounts
of NO increase significantly from 67 ppm to 76 ppm. Visona and
Stanmore [34] predicted that the conversion of char-N to NO de-
creased linearly with increasing external NO, expressed as NO par-
tial pressure in the single particle model. Spinti and Pershing [35]
also discovered similar results that as the initial NOx rises, appar-
ent conversion of char-N to NOx decreased dramatically, because
large quantities of NOx are reduced to N2. Therefore, with the de-
crease of coal particle sizes, NO partial pressure and the initial
NO concentrations around the coal particle surfaces increase, pro-
viding advantages in reducing NO.
354 J. Liu et al. / Energy Conversion and Management 77 (2014) 349–355

2400 32 1200 12
SH 30% 2ONO NMG 30% 2O CR 30 1150
2200 1100 10

NO (mg/m3) @ 6% O2
NO (mg/m3) @ 6% O2
28

Conversion Ration (%)

SH 21% 2ONO NMG 21% 2O CR

Conversion Ration (%)

2000 26 1050
24 1000 8
1800 22 950
900 NMG 30% 2ONO NMG 30%2O CR 6
1600 20 850
18 800 NMG 21% 2ONO NMG 21%2O CR 4
1400 16 750
14 700 2
1200 12 650
1000 10 600 0
8 550
800 6 500 -2
4 450
600 400
2 -4
400 0
350
10 15 20 25 30 35 40 45 10 20 30 40 50 60

Particle size ( µm) Particle size ( µm)

(a) SH coal samples (b) NMG coal samples

Fig. 5. Influence of the particle size on NO emissions in the O2/CO2 atmosphere (30% O2/70% CO2, 21% O2/79% CO2, the stoichiometric ratio 1.2, temperature 1000 °C).

Table 2 Table 3
Chemical composition analysis of coal samples with different sizes. Parameters and fractal dimensions of pore structures in coal chars.
Samples Fixed carbon (%, daf) Volatile content (%, daf) N content (%) Samples Temperature Particle SBET Pore DSAXS DPSD
SH_14.7 65.501 34.498 0.825 (°C) sizes (m2/g) volume
SH_17.4 66.888 33.110 0.828 (lm) (m3/g)
SH_21.3 63.813 36.185 0.774 NMG 400 12.5 5.5379 0.02920 2.429 2.300
SH_44.2 62.240 37.757 0.798 600 12.5 21.791 0.04556 2.497 2.352
NMG_12.5 53.503 46.495 0.779 800 12.5 89.360 0.08058 2.661 2.455
NMG_14.9 54.198 45.799 0.795
NMG_25.8 53.071 46.928 0.742 NMG 600 12.5 21.791 0.04556 2.497 2.352
NMG_52.7 53.508 46.489 0.790 600 14.9 6.1231 0.02848 2.517 2.747
600 25.8 8.7006 0.02604 2.550 2.750
600 52.7 12.872 0.03105 2.582 2.880

Third, during the releasing process of char-N, some of the re-

leased nitrogen encounters with the oxygen, which diffused into volatile-N converts into NO, which makes CRs increase. Although
the particles, and then NO are released. Part of the generated NO smaller coal particles have better abilities of heterogeneous reduc-
will escape from the particle while others will continue to diffuse tion for NO, the fraction of volatile-N conversion to NO may be
into the particle. The heterogeneous reduction of NO is closely re- higher than the reducing fraction of char-N in superfine pulverized
lated with the pore structures and pore surfaces of char particles. coal combustion. Therefore, the total CRs and NO emissions still in-
Therefore, we further extended the experiments to learn more crease with the decrease of coal particle sizes under fuel-lean com-
about the porous information. bustion, where volatile-N conversion dominates the final NO
Pore surface fractal dimensions calculated from small-angle X- emission processes. However, this is still controversial, and needs
ray scattering (SAXS) experiments (DSAXS) were applied to analyze further investigations.
the pore surfaces of superfine pulverized coal particles. The pore In conclusion, under fuel-lean combustion conditions, with the
structure fractal dimensions obtained from pore size distribution decrease of coal particle sizes, volatile NO increases, resulting in
(DPSD) were utilized to analyze the pore structures. The specific the larger nitrogen CR and higher final NO emissions. However, un-
experimental procedures were described in detail in the previous der fuel-rich combustion, more abatement of volatile NO and bet-
work [36]. Influence of particle sizes on fractal dimensions of NMG ter abilities of heterogeneous reduction of char NO can be obtained
samples is revealed in Fig. S9 in Supplementary material and the fi- from smaller pulverized coal, which is advantageous for NO con-
nal results are summarized in Table 3. Conventional textural charac- trol. We can draw the conclusion that superfine pulverized coal
teristics of coal chars analyzed from N2 adsorption data are also has no obvious advantages in reducing NO emissions under normal
shown there. Physically, the pore surface fractal dimension is a mea- combustion conditions. However, once combined with certain low
sure of surface roughness. The larger the fractal dimension is, the NO combustion technologies, such as staged combustion, fuel
rougher the pore surfaces are. Meanwhile, the pore structure fractal reburning and flue gas recirculation, superfine pulverized coal will
dimension represents the pore structure irregularity: the larger the show significant advantages, not only in combustion performances
value of the pore fractal dimension, the more inhomogeneous pores but also in NO emissions control.
there are. Table 3 suggests that with the decrease of the coal particle
sizes, the channels for reactant gas transportation become smoother 4. Conclusions
(smaller pore surface fractal dimensions) and simpler (smaller pore
structure fractal dimensions). The mass transfer resistance dimin- Based upon the investigations on superfine pulverized coal
ishes, which is easier for the gas transportation. Additionally, with combustion in the O2/CO2 atmosphere, the following conclusions
the decrease of particle sizes, both the pore volumes and pore spe- can be drawn:
cific surface areas increase significantly, providing more active sites
and reaction areas, which will promote char/NO reduction reac- 1. With the increase of temperatures, both NO emissions and NO
tions. Therefore, heterogeneous reduction is more significant for conversion ratios increase. The higher the nitrogen contents
smaller coal particle sizes, which is advantageous for NO reducing, are in parent coal, the more NO will be released from the coal.
under any conditions (fuel-lean or fuel-rich combustion). 2. With the increase of stoichiometric ratios, NO emissions
Fig. 5 shows that under fuel-lean combustion, there is a increase initially before k = 1.2 and reduce afterward around
decreasing trend for CRs with the increase of coal particle sizes. k = 1.4. NO conversion ratios increase monotonically with stoi-
This is because under fuel-lean combustion conditions, with the chiometric ratios under both fuel-lean and fuel-rich combustion
decrease of particle sizes, a larger proportion of prompt released conditions.
 J. Liu et al. / Energy Conversion and Management 77 (2014) 349–355
3. The oxygen concentrations have significant influence on NO
emissions. NO contents in flue gases increase initially with inlet
oxygen concentrations, and then decline slightly as oxygen con-
centrations exceeded 30%.
4. With the decrease of the coal particle sizes, the channels for
reactant gas transportation become smoother (smaller pore
surface fractal dimensions) and simpler (smaller pore structure
fractal dimensions).
5. Decreasing coal particle sizes is disadvantageous for homoge-
neous NO reduction under fuel-lean combustion conditions,
while superfine pulverized coal can inhibit the homogeneous
NO formations under fuel-rich combustion conditions. Hetero-
geneous reduction is more significant for smaller coal particle
sizes, which is advantageous for NO reducing, under both
fuel-lean and fuel-rich conditions.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (Grant Nos. 51306116 and 51376131) and China
Postdoctoral Science Foundation funded Project (2012M511091).
We are grateful for the help from Prof. Weidong Fan (SME, SJTU)
with the experimental platform. The authors also thank beamline
BL16B1 (Shanghai Synchrotron Radiation Facility) for providing
the beam time.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.enconman.2013.
09.048.
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