Fuel Processing Technology 211 (2021) 106618

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Fuel Processing Technology

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Research article

A comparative experimental study on characteristics of ultra-low NOx T

emission and fly ash between Fugu bituminous and its semi-coke with post-
combustion
Guoliang Songa,b,c, , Yuan Xiaoa,b, Zhao Yanga,b, Xueting Yanga,b, Qinggang Lyua,b,c
⁎

a
Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China
b
University of Chinese Academy of Sciences, Beijing 100049, China
c
Dalian National Laboratory for Clean Energy, Dalian 116023, China

ARTICLE INFO ABSTRACT

Keywords: The ultra-low emission standard will be enforced on circulating fluidized bed (CFB) boilers in the near future in
CFB China. The coordinated control of NOx and CO emission was realized on a 0.5 MWth CFB test platform by new
Post-combustion post-combustion technology with low NOx emission. When NOx reached ultra-low emission standard (≤50 mg/
NOx emission m3, at 6% O2), CO emissions of Fugu bituminous and its semi-coke were only 101.1 and 91.8 ppm, respectively.
Fly ash
Moreover, the influence of coal variety on NOx emission and fly ash characteristics during the post-combustion
Coordinated control
was investigated. The experimental results indicated that the post-combustion technology had a better de-NOx
effect on volatile-N. The speciation of residual nitrogen in fly ash was investigated by XPS, but it could not be
linked to NOx emission by the present study. The post-combustion technology had various influences on the
morphology of fly ash from different fuels. In addition, the fly ash of semi-coke had a more developed pore
structure, which probably led to a more intense NOx reduction reaction in the post-combustion chamber.

1. Introduction
Nitrogen oxides (NOx) is one of the most important air pollutants
because it is hazardous to the environment and human health, and can
induce photochemical smog or acid rain [1,2]. With increasing con-
cerns regarding NOx emissions over the last decades, the thermal power
plants as the main source of NOx emission are subjected to increasingly
strict environmental regulation. Circulating fluidized bed (CFB) tech-
nology develops rapidly in China, due to its attractive features of low
NOx emission and fuel flexibility [3–7]. Many studies had tried to cut
down the NOx emission by adjusting operating parameters, such as
combustion temperature [8–12], combustion atmosphere [13–17] and
the secondary air (SA) arrangement [18–21]. Without Selective Cata-
lytic Reduction (SCR) and/or Selective Non-Catalytic Reduction
(SNCR), the original NOx emission from existing CFB boilers was be-
tween 200–300 mg/m3 when burning high-volatile coal, and can reach
200 mg/m3 when burning low-volatile coal [22]. Unfortunately, the
ultra-low emission limit (≤50 mg/m3) will be enforced in the near
future in china [23]. However, conventional CFB combustion could not
meet the ultra-low emission standard without Selective Catalytic Re-
duction (SCR) and/or Selective Non-Catalytic Reduction (SNCR) [24].
However, the operating cost of CFB will be increased due to the use of
denitrification systems, thereby reducing its market competitiveness.
Thus, it is crucial to explore the potential of NOx emission reduction
during the combustion for CFB technology.
Currently, the post-combustion technology is being investigated by
the Institute of Engineering Thermophysics, Chinese Academy of
Science. It is one of the most promising technologies because of its
superiority with respect to the retrofit of CFB thermal power plants
[25–28]. Post-combustion technology could be concluded as furnace
lean oxygen combustion followed by a post-combustion chamber (PCC)
for burnout. In conventional CFB combustion, the furnace maintains an
oxidation atmosphere, and this promotes the generation of NOx.
Nevertheless, for post-combustion technology, the furnace maintained a
weak reduction atmosphere. Therefore, the NOx generation would be
inhibited in the whole furnace [29]. Unburned gas and char particles
will burn out with the injection of post-combustion air (PCA) in the
PCC.
As is known to all, char and CO were two kinds of the most im-
portant NOx reduction agent [30–36]. On the one hand, a large amount
of char and CO would significantly reduce the NOx emission con-
centration. On the other hand, char and CO directly affect the

⁎
Corresponding author at: Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China.
E-mail address: songgl@iet.cn (G. Song).

https://doi.org/10.1016/j.fuproc.2020.106618
Received 28 April 2020; Received in revised form 5 August 2020; Accepted 16 September 2020
Available online 05 October 2020
0378-3820/ © 2020 Elsevier B.V. All rights reserved.
G. Song, et al. Fuel Processing Technology 211 (2021) 106618

combustion efficiency, which in turn affected the operating economy. Table 2

In the present studies, most of the results could merely control the NOx Compositions and fusibility of fly ash.
emission below 100 mg/m3. Even though a few studies could meet the Items Unit FG SC
ultra-low NOx emission standard, it is at the expense of combustion
efficiency [27,28,37], but this violates the original intention of the SiO2 w/% 19.77 33.78
Al2O3 12.2 13.74
design.
Fe2O3 11.41 10.16
Therefore, the present study focused on the cooperative control of CaO 32.61 21.35
NOx and CO emission, that is, based on ensuring NOx ultra-low emis- MgO 1.24 1.74
sion standard, burning out CO as much as possible. The original NOx K2O 0.26 0.68
emission of Fugu bituminous and its semi-coke were 38.4 and 48.7 mg/ Na2O 1.53 0.82
SO2 9.74 6.65
m3, with CO concentration of 101.1 and 91.8 ppm, respectively.
Deformation temperature (DT) °C 1190 1100
Besides, the effect of coal variety on characteristics of NOx emission and Softening temperature (ST) 1210 1120
fly ash during conventional CFB combustion and post-combustion was Hemispherical temperature (HT) 1230 1130
identified in this study. Fluid temperature (FT) 1260 1160

2. Methodology of the experiment 30

Volume fraction 100
2.1. Fuels Cumulative volume fraction

Cumulative volume fraction (%)

80
The combustion fuel was Fugu bituminous (FG) and Fugu semi-coke

Volume fraction (%)

20
(SC). SC was a product from the slow pyrolysis of FG at a relatively low
temperature, about 500 °C. Proximate and ultimate analyses of FG and 60
SC were listed in Table 1.
In comparison to the FG, the ash and fixed carbon of SC increased, 40
10
and the volatile matter of SC decreased. In other words, SC was more
difficult to burn out than FG. Besides, the compositions and fusibility of
20
fly ash for FG and SC were also analyzed, and the results were shown in
Table 2.
For guaranteeing fluidization and stable combustion, the fuel was 0 0
sieved between 0 and 2 mm. About 5 g samples were used to carry out
0.0001 0.001 0.01 0.1 0.5 2
the particle size analysis every time. In addition, the results were the (a)
average value of three times of measurement, the repeatability of par- Particle size (mm)
ticle size analysis was guaranteed. The results of particle size analysis
were shown in Fig. 1. In Fig. 1, the pic (a) and (b) represented the FG 30
and SC, respectively. Volume fraction 100
The bed material was 40–70 mesh coarse screening quartz sand. Cumulative volume fraction

Cumulative volume fraction (%)

95.64% of the quartz sand composition was SiO2, and the compositions
of the quartz sand were listed in Table 3. The results of particle size 80
Volume fraction (%)

20
analysis for bed material were shown in Fig. 2.
60
2.2. Test platform
10 40
The experiments were carried out on a 0.5MWth pilot-scale CFB Test
platform, which was schematically drawn in Fig. 3. The test platform 20
was composed of a circulating fluidized bed (CFB), a post-combustion
chamber (PCC), and auxiliary system. The main components of the test 0 0
platform (such as furnace, cyclone, and PCC) were made of thermal
insulation materials. The furnace had a total height of 14,000 mm and 0.0001 0.001 0.01 0.1 0.5 2
an inner diameter of 480 mm. In addition, the diameter of the insula- (b) Particle size (mm)
tion material outside the furnace was 1230 mm. The post-combustion
chamber had an inner diameter of 700 mm and a total height of Fig. 1. Particle size analysis results of FG and SC.
9500 mm. The thickness of the refractory insulation structure outside
the PCC was 400 mm. A water-cooled pipe of 8 m was arranged on the The combustion air was divided into primary air (PA), secondary air
top of the furnace. The test platform had two screw feeders, the first one (SA), and post-combustion air (PCA). PA and SA provided by two dif-
(S1) was arranged at the bottom of the furnace, and another (S2) was ferent frequency conversion roots blowers were injected into furnace.
set at the outlet of the loop seal.

Table 1
Analysis of coal slime and its raw coal.
Items Proximate analysis w/% Ultimate analysis w/% Low heat value

Mad Aad Vad FCad Cad Had Oad Nad Sad Qad,net (MJ/kg)

FG 3.36 5.02 33.40 58.22 73.86 4.37 12.09 0.98 0.32 28.65
SC 2.77 12.76 11.13 73.34 76.56 1.74 4.94 0.89 0.34 25.13

2
G. Song, et al. Fuel Processing Technology 211 (2021) 106618

Table 3 Table 4
Compositions of bed material. Operational conditions of the experiments.
Composition SiO2 Al2O3 Fe2O3 CaO K2O Na2O Others Case 1 2 3 4

Quality fraction (%) 95.64 1.74 0.13 0.02 0.53 0.22 1.72 Fuel Fugu bituminous (FG) Fugu semi-coke (SC)
Furnace temperature (°C) 901 967 957 945
PCC temperature (°C) 740 952 779 915
Primary air (m3/h) 449 438 424 452
25 Volume fraction 100 Primary air temperature (°C) 103 124 103 120
Secondary air (m3/h) 416 358 338 292

Cumulative volume fraction (%)

Cumulative volume fraction
Secondary air temperature (°C) 106 134 142 149
20 80 First stage post-combustion air \ 70 \ 68
Volume fraction (%)

(m3/h)
Second stage post-combustion air \ 59 \ 58
15 60 (m3/h)
Post-combustion air temperature \ 310 \ 326
(°C)
10 40
Screw feeder S1 S2
Coal-feeding rate (kg/h) 114 122 105 123
5 20 λCFB 1.10 0.98 1.12 0.97
λPCC \ 0.14 \ 0.13
λ 1.10 1.12 1.12 1.10
0 0

0.1 0.5 1 2 ash, there was a sampling port, which was set next to the zirconia
Partivle size (mm)
oxygen analyzers.
Fig. 2. The particle size distribution of quartz sand.

2.3. Experimental conditions

The secondary air nozzle was arranged at the height of 800 mm above
the furnace bottom. An induced draft fan was arranged at tail flue to
After checking the air tightness, about 80 kg quartz sand was fed
control the micro-negative pressure in the furnace during the experi-
into the furnace as bed material. At first, the oil ignition burner was
ment. A separate PCA blower provided PCA. As shown in Fig. 3, PCA
used to warm up the furnace. When the temperature at furnace bottom
was divided into two paths. The first level of PCA was injected into the
reached 500 °C, the fuel was fed into the furnace and the oil ignition
inlet of the horizontal flue pipe, and the second level of PCA was in-
burner was stopped. Furthermore, the circulation was established when
jected into the inlet of the PCC. An air compressor provided loose air,
the temperature of the furnace bottom was 800 °C. Then, the experi-
fluidized air and coal-spreading air.
mental conditions were realized by adjusting the coal-feeding rate and
The flue gas cooler, PCA preheater, PA preheater, and SA preheater
air flow.
were arranged in the tail flue in turn. The flue gas was finally dis-
The operational conditions were listed in Table 4. The operation
charged from the chimney after passing through the bag filter. The
parameters and emission data were the actual operation data, which
oxygen content in the flue gas was monitored online by a CY-IS-G zir-
represented the average value during the stable experiment time (about
conia oxygen analyzer at the tail flue duct. For sampling flue gas and fly
2 h). The temperatures of furnace and PCC were the highest

Fig. 3. The schematic diagram of 0.5MWth pilot

platform.
(1) furnace; (2) cyclone; (3) loop seal; (4) screw
feeder (S1, 5) screw feeder (S2); (6) water-cooled
pipe; (7) post-combustion chamber; (8) flue gas
cooler; (9) post-combustion air preheater; (10) pri-
mary air preheater; (11) secondary air preheater;
(12) zirconia oxygen analyzers; (13) bag filter; (14,
15, 16) roots fan and (17) induced draft fan.

3
G. Song, et al. Fuel Processing Technology 211 (2021) 106618

temperature in the furnace and PCC. The fuel of the first two cases was 14000
FG, and the fuel of the last two cases was SC. A previous study had
found that feeding coal into the outlet of the loop seal was conducive to 12000 FG,CFB
burnout [28]. Therefore, S2 was used in the semi-coke cases, because FG,Post-combustion
semi-coke was difficult to ignite and burn out. 10000

Furnace Heigh (mm)

SC,CFB
λ was the total excess air ratio, and it was calculated by oxygen SC,Post-combustion
concentration in the tail flue duct. λCFB and λPCC represented the excess 8000
air ratio in the CFB furnace and the post-combustion chamber, re-
spectively. λCFB and λPCC were calculated as follows: 6000
PAf + SAf
CFB = × 4000
PAf + SAf + PCAf (1)

PCAf 2000
PCC = ×
PAf + SAf + PCAf (2)
0
3 3
The above-mentioned PAf (m /h) and SAf (m /h) represented the 0 2 4 6 8 10 12 14
primary air flow rate and secondary air flow rate, respectively. Absolute Pressure (kPa)
Moreover, PCAf (m3/h) was post-combustion air flow rate. In this
paper, the NOx was the sum of NO and NO2. Moreover, all of the NOx Fig. 4. Pressure profiles along the furnace.
concentrations had been converted to flue gas with a dry and oxygen
concentration of 6%. 15 50
The standard deviation was calculated by the following equation to

Water cooled pipe flow (m3/h)

analyze the stability of operation. The Xi in the following equation re-

Temperature of water (℃)

14 45
presented the measurement value, such as operation data and gas
concentration.
13 40
n
1
X = (Xi µ) 2
n i=1 (3) 12 35

According to the above formula, the standard deviation of major

Water cooled pipe flow
operational data was obtained and exhibited in Table 5. It could be seen 11 30
Outlet temperature
that the operation parameters remained stable during the operation Inlet temperature
condition. 10 25
1 2 3 4
3. Results and discussion
Case
Fig. 5. Operation parameters of the water-cooled pipe.
3.1. Pressure and temperature distribution characteristic
In Eq. (4), Q was the water flow (m3/h), c was the specific heat
The absolute pressure along the furnace could reflect the particle
capacity of water (kJ/(kg·°C)), Tinlet and Toutlet were the water tem-
concentration in the furnace, and the particle concentration influenced
perature in inlet and outlet of the water-cooled pipe. In addition, the R
the heat transfer. Fig. 4 showed the pressure profiles along the furnace.
was the coal-feeding rate (kg/h). Qad.net was the Low calorific value of
There was an obvious dense zone and a dilute zone in the furnace. By
coal (MJ/kg). After calculation, it was found the ratios of the heat ab-
calculation, the average pressure drops in the dilute zone (from 4.5 m to
sorption of the water cooling tube to the heat release of the fuel in four
13.5 m) in four cases were 57.27, 76.71, 110.79 and 92.47 Pa/m, re-
cases were 18.08%, 22.88%, 21.20%, and 20.13%, respectively. They
spectively. The average pressure drop for semi-coke was higher than
had no relationship with CFB combustion or post-combustion, neither.
coal due to higher ash content. Nevertheless, the average pressure drop
Thus, the temperature distribution discussed following was mainly in-
had no relationship with CFB combustion or post-combustion.
fluence by combustion reaction progress rather than operation para-
As above-mentioned, there was a water-cooled pipe in the furnace.
meters.
The operation parameters of the water-cooled pipe had an obvious in-
As shown in Fig. 5, the parameters of the water-cooled pipe were
fluence on the temperature distribution along the furnace. Fig. 5 ex-
almost unchanged during the experiment. Thus, the water-cooled pipe
hibited the operation parameters with standard deviation.
had little effect on the temperature distribution along the furnace.
The ratio of the heat absorption of the water cooling tube to the heat
Temperature distribution could reflect the combustion character-
release of the fuel was calculated by the following equation.
istic. Fig. 6 showed the temperature profiles of furnace and PCC in FG
Q c (Toutlet Tinlet ) cases. The FG was fed into the bottom of the furnace by S1 in both
r= 100%
R Qad, net (4) conventional CFB combustion and post-combustion cases. The green
curve represented the conventional CFB combustion case, and the post-
Table 5 combustion case was exhibited with a red one. The blue error bar was
The standard deviation of major operational data. the standard deviation of specific temperature points. The highest
temperature of the two curves was both appeared in the middle of the
Case 1 2 3 4
furnace, which was above the secondary air nozzle. The temperature in
Furnace temperature (°C) 2.68 2.16 1.56 2.49 the upper dilute phase region was low because of the presence of a
PCC temperature (°C) 4.09 2.82 1.33 10.82 water-cooled pipe in the upper furnace. Moreover, the addition of cold
Primary air (m3/h) 2.38 6.23 1.54 1.30 fuel and the return of the circulating materials resulted in relatively low
Secondary air (m3/h) 2.18 4.54 1.46 1.06
temperature at the bottom of the furnace.
First stage post-combustion air (m3/h) \ 0.17 \ 0.19
Second stage post-combustion air (m3/h) \ 0.17 \ 0.16 The temperature distribution of the dense phase region at the
bottom in the above two cases was similar, while the temperature

4
G. Song, et al.
14000
Height above the distribution plate(mm)
12000
10000
8000
6000
4000
2000
0
800 850 900 950 1000
Temperature(
Fig. 6. Temperature profiles of CFB and PCC in Fugu bituminous cases.
distribution of the dilute phase region was different. It was caused by a
different atmosphere in the furnace. In post-combustion case, the λCFB
was 0.98, and a weak reducing atmosphere appeared in the furnace.
However, the reduction atmosphere was not strong, the share of char
participating in endothermic gasification reaction (R1 and R2) was
small. Most of the char participated in exothermic combustion reaction
or incomplete combustion reaction (R3 and R4). Low oxygen con-
centration slowed down the combustion rate, thus coal needed more
time to burn out. It meant that more combustion share transformed
from dense zone to dilute zone, which made the temperature of the
dilute phase region increased.
C + CO2 = 2 CO
C + H2 O = CO + H2
C + O2 = CO2
2C + O2 = 2CO
Another difference was the temperature distribution of PCC. In the
conventional CFB combustion case, the PCC temperature decreased
along the height. Because there was almost no combustion reaction
along PCC, but only heat loss. Nevertheless, the temperature distribu-
tion of PCC in the post-combustion case showed a different trend. There
was a distinct temperature peak in the middle of PCC instead of de-
creasing along the height. When the furnace contained a weak reducing
atmosphere, the gasification combustion reactions would happen,
which were listed below:
C + CO2 = 2 CO
C + H2 O = CO + H2
Besides, the carbon particle could not burn thoroughly when the
λCFB was less than1.0. Therefore, there were amounts of combustible
components, such as carbon particle and CO in the flue gas. With the
injection of PCA, the combustible components burned rapidly, the
temperature also rose.
The temperature profiles along the furnace and PCC in SC cases
were exhibited in Fig. 7. Although the different fuel was used, the
furnace temperature profiles for FG and SC were similar. Generally, the
temperature of the middle furnace was higher than the upper and
bottom of the furnace. Moreover, the furnace temperature profile in the
dilute phase region for post-combustion was slightly ascended instead
Fuel Processing Technology 211 (2021) 106618
Distance from top of PCC(mm)
0
2000
4000
6000
8000
600 700 900 1000
Temperature( )
CFB
PC
)
of decline.
The main difference was the PCC temperature profiles had no ap-
parent peak in the post-combustion case with semi-coke. As above-
mentioned, the semi-coke was the product of coal pyrolysis. The vola-
tile content in SC was obviously lower than FG. The lower the volatile
content was, the lower the calorific value of gas was. This was the
reason why there was no distinct temperature peak in the PCC tem-
perature profile.
3.2. NOx emission characteristics
(R1)
The NOx (dry, at 6% O2) and CO emission concentrations were
(R2) shown in Fig. 8. A dotted line separated the FG and SC. The combustion
temperature was lower than 1000 °C in both conventional CFB case and
(R3)
post-combustion case, much lower than the formation temperature of
(R4) thermal NOx. It was evident that the NOx emission of FG and SC were
below 50 mg/m3 in the post-combustion cases. In addition, the CO
emission concentrations also reached about 100 ppm, a level of con-
ventional CFB combustion. The coordinated control of NOx and CO
emissions concentrations was achieved.
In the conventional CFB combustion case of FG, the original NOx
and CO emission concentrations were 119.9 mg/m3 and 256.3 ppm,
respectively. Relatively low combustion temperature and λ resulted in a
relatively high CO emission concentration. In the post-combustion case
of FG, the NOx emission decreased to 38.4 mg/m3, meeting the ultra-
low NOx emission standard (≤50 mg/m3). As the combustion tem-
(R5) perature increased to 968 °C, the CO concentration also decreased, only
101.1 ppm.
(R6)
Under almost the same λ, the original NOx emission for conven-
tional CFB combustion of SC was 206.1 mg/m3 when the combustion
temperature was 957 °C. Simultaneously, the CO concentration was
50.6 ppm. After using post-combustion technology, the NOx emission
decreased to 48.7 mg/m3. However, the CO concentration increased to
91.8 ppm due to using of post-combustion technology. In conventional
CFB combustion of SC, sufficient residence time in the oxidation at-
mosphere made the SC burn out. However, in post-combustion condi-
tions, incomplete combustion would happen instead of complete com-
bustion in the furnace. Although the combustible compounds in flue gas
would burn rapidly with a reasonable arrangement of PCA. The re-
sidence time in the oxidation atmosphere was shortened and not
5
G. Song, et al. Fuel Processing Technology 211 (2021) 106618

14000

Distance from top of PCC(mm)

0

Height above the distribution plate(mm)

12000 2000

10000 4000

8000 6000

6000 8000
700 750 900 950
4000 Temperature( )

CFB
2000
PC

0
850 900 950 1000
Temperature( )
Fig. 7. Temperature profiles of CFB and PC in Fugu semi-coke cases.

250 350 For the above reasons, the NOx emission was able to be greatly re-
Fugu Bituminous Fugu Semi-coke
duced. The combustible components could burn out as much as possible
NOx 300 with a reasonable PCA arrangement. Therefore, the coordinated control
200 CO of NOx and CO emissions concentrations was realized through the post-
CO Concentration (ppm)
NOx Emission (mg/m3)

250 combustion technology.

Noteworthy, the post-combustion cases of FG and SC had almost the
150 same operation parameters, but the NOx emission was different. On the
200
one hand, the volatile content in FG was higher. The volatile-N would
150 be easier to release low oxygen concentration. In contrast, the char-N
100
would not release unless the char participated in the combustion.
100 Furthermore, released nitrogen would convert to N2 in a reduction at-
mosphere.
50
50 On the other hand, many studies had proved that the release of NH3
from low-rank coals was greater than the higher-rank coals, and the
0 0 ratio of NH3 to HCN for low-rank coal was usually higher than high-
CFB PC CFB PC rank coals [30]. NH3 was not only one kind of precursor of NOx, but
also a reducing agent involved in the NOx reduction reaction. In post-
Fig. 8. NOx and CO emission concentration of FG and SC.
combustion cases, the oxygen concentration in the furnace was low, the
conversion from NH3 to NO (R12) was inhibited. Simultaneously, the
enough for CO to burn out. following reaction (R13–R15) would occur [30–36].
In conventional CFB combustion, the NOx emission of SC was re-
5 3
lative higher due to high temperature, oxygen concentration, and the NH3 + O2 NO + H2 O
4 2 (R12)
ratio of primary air flow and secondary air flow. When the post-com-
bustion was used, the oxygen concentration in the furnace decreased. 3 1 3
NH3 + O2 N2 + H2 O
The generation reactions of NOx (R7) were inhibited by a weak re- 4 2 2 (R13)
duction atmosphere. Moreover, the low oxygen concentration in the
furnace increased the CO and char particle concentrations. High con- 1 3
NH3 + NO + O2 N2 + H2 O
centration CO and char particle enhanced the homogeneous reactions 4 2 (R14)
(R8) and heterogeneous reactions (R9–R11) for the reduction of NOx 2 5
[30–36]. NH3 + NO N2 + H2 O
(R15)
3 6
fuel N + O2 NO (R7)
Therefore, the NOx emission of FG was lower than SC under the
1 same condition. In conclusion, the post-combustion technology had a
NO + CO CO2 + N2
2 (R8) better de-NOx effect on volatile-N rather than char-N.
Besides, the Ca/S molar ratio might be another factor, which made
1
NO + Cf C (O ) + N2 the NOx emission of FG lower than SC. The Ca/S molar ratio was cal-
2 (R9)
culated by the following:
2NO + C N2 + CO2 (R10) Ca A × w (CaO ) Ar (S )
= ad ×
1 S Sad Ar (Ca) (5)
NO + C N2 + CO
2 (R11)
The Aad and Sad represented the ash content and sulfur content in

6
G. Song, et al.
Carbon Nitrogen
0.20
15
Nitrogen Content (%)
Carbon Content (%)
12
0.15
9 Oxidized nitrogen
0.10
6 represented SC fly ash of conventional CFB combustion and post-com-
0.05
3
0 0.00
1 2 3 4
Cases
Fig. 9. Carbon content and nitrogen content in fly ash.
fuel (%). w(CaO) was the ratio of CaO in ash. Moreover, the Ar was the
relative atomic mass.
After calculation, the Ca/S molar ratios of FG and SC were 4.3 and
7.1, respectively. NOx emissions increased with the Ca/S molar ratio
had been proved [38–40]. Hence, this was another reason that made
the NOx emission of SC was higher in post-combustion.
3.3. Fly ash characteristics
3.3.1. Carbon and nitrogen residual in fly ash
As above-mentioned, there was a sample point next to the zirconia
oxygen analyzers. The fly ash would be continuously sampled for about
2 h in every case. Residual carbon and nitrogen content analysis of fly
ash was carried out, and the results were shown in Fig. 9. The left slash
pattern in red meant carbon residual content of fly ash, and residual
nitrogen content was represented by the right slash pattern with green
color.
As shown in Fig. 9, the carbon content in fly ash in the post-com-
bustion cases was relatively higher than the conventional CFB com-
bustion, no matter FG or SC was used. In post-combustion cases, the
furnace atmosphere was a weak reducing atmosphere, and the O2
concentration was lower than the conventional CFB combustion. Lower
O2 concentration resulted in ignition delay and longer overall com-
bustion time [41–43]. Besides, the reducing atmosphere in the furnace
led to incomplete combustion. The above two reasons were harmful to
burning out of char in fuel. Char particles, unlike CO and other com-
bustible gas, could not burn out quickly in the PCC. Therefore, the
carbon content in fly ash would increase in post-combustion cases. The
content of nitrogen compounds in fly ash had the same trend with
carbon content. This was because the nitrogen in coal existed in the
organic forms, such as pyrrole, pyridine and so on [44,45]. In other
words, the nitrogen atoms and the carbon atoms usually bounded to a
cyclic structure in coal. Char-N was released gradually when the char
was being burnt. Therefore, the content of carbon and nitrogen had the
same trend.
To confirm which kind of residual nitrogen speciation was more
easily enriched in fly ash emission during the post-combustion, the
nitrogen speciation of fly ash was investigated by XPS (THERMO,
250XI). According to existing studies, there were usually four kinds of
nitrogen speciation in coal classified by binding energy [44,45]. Detail
classification was listed in Table 6.
The curve fitting results of XPS-N1s spectra for fly ash were shown
in Fig. 10. In Fig. 10, the ordinate and the abscissa represented the
signal strength of the deducted background and the binding energy,
respectively. Fig. 10(a) and (b) were FG fly ash of conventional CFB
combustion and post-combustion, respectively. Fig. 10(c) and (d)
7
Fuel Processing Technology 211 (2021) 106618
Table 6
The binding energy of nitrogen speciation.
Nitrogen morphology Symbol Binding energy/eV
Pyridine N-6 398.7 ± 0.4
Pyrrole N-5 400.5 ± 0.3
Quaternary nitrogen N-Q 401.5 ± 0.3
N-X 403.5 ± 0.3
bustion. The black line was the measured signal value of the deducted
background, and the red line was the fitting curve.
For the quantitative comparison, the relative content of nitrogen
speciation was obtained from the area under the curve and then ex-
hibited in Fig. 11. The same kind of nitrogen speciation was indicated
by the same color as in Fig. 10.
The relative content of nitrogen speciation in fly ash illustrated that
the N-5 would enrich in fly ash during post-combustion, and more
amounts of N-5 and N-Q were detected in fly ash of conventional CFB
combustion. Whether it was FG or SC, the above trend existed.
Nevertheless, for N-X, the different trends were observed in FG and SC.
The relative contents of N-X in fly ash were 15.3% and 29.2%, re-
spectively, in case 1 and case 2. Nevertheless, for SC, when the con-
ventional CFB combustion transformed to post-combustion, the relative
content of N-X decreased from 23.2% to 13.4%. At present, there was
also no definite evidence from the study of nitrogen functionality, in
either coals or carbons as models for coal chars, for a direct link be-
tween nitrogen functionality in coal and the formation of NOx during
combustion [46–48]. Therefore, no evidence could prove the relation-
ship between the residual nitrogen speciation in fly ash and NOx
emission either.
3.3.2. Morphological characteristics of fly ash
Besides the element content of fly ash was analyzed, the morpho-
logical characteristics of fuels and fly ash were also carried out. The
results were listed in Table 7.
The results demonstrated fly ash had a more developed pore
structure than original fuel, no matter for FG or SC. Similarly, the fly
ash of SC had a more developed pore structure than FG in post-com-
bustion. This might promote the NOx reduction reaction in the PCC.
The specific surface area and pore volume of FG fly ash both de-
creased from conventional CFB combustion to post-combustion.
However, for SC, the specific surface area of fly ash decreased, while
the pore volume increased.
In order to further confirm the variation of pore structure, the pore-
size distributions of fly ash were shown in Fig. 12. The classic BJH
model was used for the calculation of pore-size distribution [49].
Pores with diameters smaller than 2 nm were called micropores,
those between 2 and 50 nm were called mesopores, and those greater
than 50 nm were called macropores. The specific surface area mainly
depended on the number of micropores [50]. According to Fig. 12,
when combustion mode transformed from the conventional CFB com-
bustion to the post-combustion, there were fewer micropores in fly ash,
no matter FG or SC was used.
During the combustion, the process such as evolution and com-
bustion of volatile would promote the micropores formed in the original
structure, then both the specific surface area and the pore volume in-
creased. At the same time, the combustion of char could make the
carbon skeleton in coal collapse, which would cause the macropores
and mesopores to collapse and turn into the micropores. In this process,
the specific surface area increased, but the pore volume decreased.
During the combustion of FG, the former formation mechanism of
micropores dominated, in that the content of volatile in FG was higher.
But for SC with the low volatile matter, the latter formation mechanism
of micropores would happen. According to the carbon content of fly
G. Song, et al. Fuel Processing Technology 211 (2021) 106618

500 500
Measured Value Measured Value
Fitted Value Fitted Value
N-6 N-Q N-6 N-Q
400 400
N-5 N-X N-5 N-X
Intensity (cps)

Intensity (cps)
300 300

200 200

100 100

0 0
394 396 398 400 402 404 406 408 394 396 398 400 402 404 406 408
B.E.(eV) B.E.(eV)

(a) FG, CFB (b) FG, PC

500 500
Measured Value Measured Value
Fitted Value Fitted Value
N-6 N-Q N-6 N-Q
400 400
N-5 N-X N-5 N-X
Intensity (cps)

Intensity (cps)
300 300

200 200

100 100

0 0
394 396 398 400 402 404 406 408 394 396 398 400 402 404 406 408
B.E.(eV) B.E.(eV)

(c) SC, CFB (d) SC, PC

Fig. 10. XPS (N1s) analyses of fly ash.

50 Table 7
Relative content of nitrogen speciation (凘)

N-6 N-5 Pore structure characteristics of fuel and fly ash.

N-Q N-X
Fuel Combustion mode Specific surface Pore volume
40 area (m2/g) (mm3/g)

Fugu bituminous (FG) None 3.4680 9.757

CFB combustion 12.8932 20.893
30 Post-combustion 6.1805 17.051
Fugu semi-coke (SC) None 14.0323 17.649
CFB combustion 20.2223 19.460
Post-combustion 15.3713 24.636
20

4. Conclusions
10
The experimental studies were performed on a 0.5 MWth CFB test
platform, which was consist of a CFB and a PCC. The characteristics of
0 NOx emission and fly ash of two types of fuel (Fugu bituminous and its
1 2 3 4 semi-coke) during conventional CFB combustion and post-combustion
Cases were investigated. The main conclusions were as follows:
Fig. 11. The relative content of nitrogen speciation.
1) Based on post-combustion new technology, the NOx emission of FG
and SC were reduced to only 38.4 and 48.7 mg/m3, respectively,
ash, coal could combust more thoroughly in conventional CFB com- while there was no significant increase in CO concentration, the
bustion, which led to the differences in the morphological character- coordinated control of NOx and CO emissions concentrations was
istics of fly ash. realized.

8
G. Song, et al. Fuel Processing Technology 211 (2021) 106618

fluidised bed combustion of semi-dried municipal sewage sludge, Fuel 80 (2) (2001)
0.004 FG, CFB combustion 167–177.
dV/dD Pore Volume (cm³/g·nm)

FG, Post-combustion
SC, CFB combustion
SC, Post-combustion
0.003
0.002
0.001
0.000
1 5 10 25 50
Pore Diameter (nm)
Fig. 12. Pore-size distribution of fuel and fly ash.
2) Volatile-N was more likely to release and convert to N2 in a re-
duction atmosphere, and the post-combustion technology had a
better de-NOx effect on volatile-N.
3) The carbon and nitrogen content in fly ash generated from post-
combustion was higher than the conventional CFB combustion. N-6
would enrich in fly ash for the post-combustion, but the content of
N-5 and N-Q decreased. In addition, the content of N-X in FG and SC
fly ash increased and decreased, respectively. However, there was
limited evidence to prove that residual nitrogen speciation in fly ash
had a relationship with NOx emission.
4) When the combustion mode transformed from the conventional CFB
combustion to post-combustion, the specific surface area and pore
volume of FG fly ash both decreased. However, the specific surface
area of SC fly ash decreased after using post-combustion, while the
pore volume increased. The characteristics of the fuel itself de-
termined this difference.
CRediT authorship contribution statement
Guoliang Song: Conceptualization, Validation, Resources, Writing -
review & editing, Project administration, Funding acquisition.
Yuan Xiao: Validation, Formal analysis, Investigation, Writing -
original draft, Visualization.
Zhao Yang: Validation, Investigation.
Xueting Yang: Validation, Investigation.
Qinggang Lyu: Resources, Writing - review & editing, 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
This work was financially supported by the National Key Research
and Development Program of China, Grant No. 2018YFB0605002 and
Strategic Priority Research Program of the Chinese Academy of
Sciences, Grant No. XDA21040100.
References
[1] Y. Hu, S. Naito, N. Kobayashi, et al., CO2, NOx and SO2 emissions from the com-
bustion of coal with high oxygen concentration gases, Fuel 79 (15) (2000)
1925–1932.
[2] M. Sänger, J. Werther, T. Ogada, NOx and N2O emission characteristics from
[3] L. Lafanechere, P. Basu, L. Jestin, The effects of fuel parameters on the size and
configuration of circulating fluidized-bed boilers, J. Inst. Energy 68 (477) (1995)
184–192.
[4] H. Wu, M. Zhang, Y. Sun, et al., Research on the heat transfer model of platen
heating surface of 300 MW circulating fluidized bed boilers, Powder Technol. 226
(2012) 83–90.
[5] J. Lu, J. Zhang, H. Zhang, et al., Performance evaluation of a 220t/h CFB boiler with
water-cooled square cyclones, Fuel Process. Technol. 88 (2) (2007) 129–135.
[6] Z. Gong, Z. Liu, T. Zhou, et al., Combustion and NO emission of Shenmu char in a 2
MW circulating fluidized bed, Energy Fuel 29 (2) (2015) 1219–1226.
[7] P. Basu, Combustion of coal in circulating fluidized-bed boilers: a review, Chem.
Eng. Sci. 54 (22) (1999) 5547–5557.
[8] A. Gungor, Simulation of NOx emission in circulating fluidized beds burning low-
grade fuels, Energy Fuel 23 (5) (2009) 2475–2481.
[9] W. Zhou, C. Zhao, L. Duan, et al., Two-dimensional computational fluid dynamics
simulation of nitrogen and sulfur oxides emissions in a circulating fluidized bed
combustor, Chem. Eng. J. 173 (2) (2011) 564–573.
75 [10] L. Diego, C. Londono, X. Wang, et al., Influence of operating parameters on NOx,
and N2O axial profiles in a circulating fluidized bed combustor, Fuel 75 (8) (1996)
971–978.
[11] A. Tourunen, J. Saastamoinen, H. Nevalainen, Experimental trends of NO in cir-
culating fluidized bed combustion, Fuel 88 (7) (2009) 1333–1341.
[12] Z. Gong, L. Wang, Z. Wang, et al., Experimental study on combustion and pollutants
emissions of oil sludge blended with microalgae residue, J. Energy Inst. 91 (2018)
877–886.
[13] J. Li, M. Zhang, H. Yang, et al., The theory and practice of NOx emission control for
circulating fluidized bed boilers based on the re-specification of the fluidization
state, Fuel Process. Technol. 150 (2016) 88–93.
[14] Y. Yao, J. Zhu, Q. Lu, Experimental study on nitrogen transformation in combustion
of pulverized semi-coke preheated in a circulating fluidized bed, Energy Fuel 29 (6)
(2015) 3985–3991.
[15] Z. Ouyang, J. Zhu, Q. Lu, Experimental study on preheating and combustion
characteristics of pulverized anthracite coal, Fuel 113 (2013) 122–127.
[16] S. Zhu, Q. Lyu, J. Zhu, et al., Effect of air distribution on NOx emissions of pul-
verized coal and char combustion preheated by a circulating fluidized bed, Energy
Fuel 32 (7) (2018) 7909–7915.
[17] P. Wang, C. Wang, M. Yuan, et al., Experimental evaluation on co-combustion
characteristics of semi-coke and coal under enhanced high-temperature and strong-
reducing atmosphere, Appl. Energy 260 (2020) 114203.
[18] A. Lyngfelt, L. Åmand, B. Leckner, Reversed air staging-a method for reduction of
N2O emissions from fluidized bed combustion of coal, Fuel 77 (9) (1998) 953–959.
[19] Y. Yao, J. Zhu, Q. Lu, et al., Experimental study on preheated combustion of pul-
verized semi-coke, J. Therm. Sci. 4 (2015) 370–377.
[20] J. Mereb, J. Wendt, Air staging and reburning mechanisms for NOx abatement in a
laboratory coal combustor, Fuel 73 (7) (1994) 1020–1026.
[21] J. Yan, X. Lu, Q. Wang, et al., Study on the influence of secondary air on the dis-
tributions of flue gas composition at the lower part of a 600 MW supercritical CFB
boiler, Fuel Process. Technol. 196 (2019) 106035.
[22] G. Yue, J. Lu, P. Xu, et al., The up-to-date development and future of circulating
fluidized bed combustion technology, Electric Power 49 (01) (2016) 1–13.
[23] F. Lin, Z. Wang, Z. Zhang, et al., Flue gas treatment with ozone oxidation: an
overview on NOx, organic pollutants, and mercury, Chem. Eng. J. 382 (2020)
123030.
[24] L. Gasnot, D. Dao, J. Pauwels, Experimental and kinetic study of the effect of ad-
ditives on the ammonia based SNCR process in low temperature conditions, Energy
Fuel 26 (5) (2012) 2837–2849.
[25] T. Zhou, Z. Gong, Q. Lu, et al., Experimental study on enhanced control of NOx
emission from circulating fluidized bed combustion, Energy Fuel 29 (6) (2015)
3634–3639.
[26] Z. Gong, T. Zhou, Q. Lu, et al., Combustion and NOx emission characteristics of
Shenmu char in a circulating fluidized bed with post-combustion, Energy Fuel 30
(1) (2016) 31–38.
[27] T Zhou, Q Lu, Y Cao, et al. Study on the combustion and NOx emission character-
istics of low rank coal in a circulating fluidized bed with post-combustion. Canadian
Journal of Chemical Engineering, 2017, 95 (12).
[28] Y. Xiao, G. Song, W. Song, et al., Influence of feeding position and post-combustion
air arrangement on NOx emission from circulating fluidized bed combustion, Fuel
269 (2020) 117394.
[29] A. Hayhurst, A. Lawrence, The amounts of NOx and N2O formed in a fluidized bed
combustor during the burning of coal volatiles and also of char, Combust. Flame
105 (3) (1996) 341–357.
[30] J. Johnsson, Formation and reduction of nitrogen oxides in fluidized-bed combus-
tion, Fuel 73 (1994) 1398–1415.
[31] T. Furusawa, M. Tsunoda, M. Tsujimura, et al., Nitric oxide reduction by char and
carbon monoxide: fundamental kinetics of nitric oxide reduction in fluidized bed
combustion of coal, Fuel 64 (9) (1985) 1306–1309.
[32] C. SchöNenbeck, R. Gadiou, D. Schwartz, A kinetic study of the high temperature
NO–char reaction, Fuel 83 (4–5) (2004) 443–450.
[33] M. Xu, S. Li, Y. Wu, et al., Reduction of recycled NO over char during oxy-fuel
fluidized bed combustion: effects of operating parameters, Appl. Energy 199 (2017)
310–322.
[34] M. Xu, S. Li, Y. Wu, et al., The characteristics of recycled NO reduction over char
during oxy-fuel fluidized bed combustion, Appl. Energy 190 (2017) 553–562.
[35] J Krzywanski, T Czakiert, W Muskala, et al. Modeling of solid fuels combustion in

9
G. Song, et al.
oxygen-enriched atmosphere in circulating fluidized bed boiler: part 1. The math-
ematical model of fuel combustion in oxygen-enriched CFB environment. Fuel
Processing Technology, 2010, 91(3):290–295.
[36] J Krzywanski, T Czakiert, W Muskala, et al. Modeling of solid fuel combustion in
oxygen-enriched atmosphere in circulating fluidized bed boiler: part 2. Numerical
simulations of heat transfer and gaseous pollutant emissions associated with coal
combustion in O2/CO2 and O2/N2 atmospheres enriched with oxygen under cir-
culating fluidized bed conditions. Fuel Processing Technology, 2010,
91(3):364–368.
[37] X. Ke, R. Cai, M. Zhang, et al., Application of ultra-low NOx emission control for
CFB boilers based on theoretical analysis and industrial practices, Fuel Process.
Technol. 181 (2018) 252–258.
[38] F. Miccio, G. Löffler, V.J. Wargadalam, et al., The influence of SO2 level and op-
erating conditions on NOx and N2O emissions during fluidised bed combustion of
coals, Fuel 80 (11) (2001) 1555–1566.
[39] J. Krzywanski, W. Nowak, Artificial intelligence treatment of SO2 emissions from
CFBC in air and oxygen-enriched conditions, J. Energy Eng. 142 (1) (2016)
04015017.
[40] J. Krzywanski, T. Czakiert, T. Shimizu, et al., NOx emissions from regenerator of
calcium looping process, Energy Fuel 32 (5) (2018) 6355–6362.
[41] Y. Tan, E. Croiset, M. Douglas, et al., Combustion characteristics of coal in a mixture
of oxygen and recycled flue gas, Fuel 85 (4) (2006) 507–512.
10
Fuel Processing Technology 211 (2021) 106618
[42] B. Arias, C. Pevida, F. Rubiera, et al., Effect of biomass blending on coal ignition and
burnout during oxy-fuel combustion, Fuel 87 (12) (2008) 2753–2759.
[43] L. Duan, H. Sun, C. Zhao, et al., Coal combustion characteristics on an oxy-fuel
circulating fluidized bed combustor with warm flue gas recycle, Fuel 127 (2014)
47–51.
[44] M. Wojtowicz, J. Pels, J. Moulijn, The fate of nitrogen functionalities in coal during
pyrolysis and combustion, Fuel 74 (4) (1995) 507–516.
[45] Y. Zhang, J. Zhang, C. Sheng, et al., X-ray photoelectron spectroscopy (XPS) in-
vestigation of nitrogen functionalities during coal char combustion in O2/CO2 and
O2/Ar atmospheres, Energy Fuel 25 (1) (2011) 240–245.
[46] K. Thomas, The release of nitrogen oxides during char combustion, Fuel 76 (6)
(1997) 457–473.
[47] K. Stanczyk, Nitrogen oxide evolution from nitrogen-containing model chars com-
bustion, Energy Fuel 13 (1) (1999) 82–87.
[48] P. Li, C. Chyang, H. Ni, An experimental study of the effect of nitrogen origin on the
formation and reduction of NOx in fluidized-bed combustion, Energy 154 (2018)
319–327.
[49] J Groen, L Peffer, J Pérez-Ramírez. Pore size determination in modified micro- and
mesoporous materials. Pitfalls and limitations in gas adsorption data analysis. mi-
croporous and mesoporous materials, 2003, 60(1–3):1–17.
[50] G. Simons, The role of pore structure in coal pyrolysis and gasification, Prog. Energy
Combust. Sci. 9 (4) (1983) 269–290.