Fuel Processing Technology 174 (2018) 95–103

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Fuel Processing Technology

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Research article

Effect of HCl and CO on sulfur trioxide formation mechanisms during oxy-

fuel combustion
⁎ ⁎
Junzhe Guo, Xiaowei Liu , Hao Wang, Penghui Zhang, Yishu Xu, Zhenguo Chen, Minghou Xu
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China

AR T IC L E I N F O AB S T R AC T

Keywords: The concentration of SOX, HCl, CO, NOX etc. in the flue gas during oxy-fuel combustion is all relatively higher
SO3 compared with air combustion. Higher SO3 concentration increases the risk of low-temperature corrosion. The
HCl higher concentration of HCl and CO can also cause corrosion, and they may play roles on SO3 formation. Thus
CO
homogeneous experiment and pulverized coal experiment were done on different furnace system to clarify the
Oxy-fuel combustion
effects of HCl and CO on SO 3 formation during oxy-fuel combustion. Different inlet concentration of HCl, CO,
SO2, H2O, O2 and CO2 were used to simulate the flue gas of the combustion. The results indicated that HCl
inhibited SO3 formation but CO promoted SO3 formation at the experimental temperature. HCl richens the
radical pool and might generate HO2 radical which was negative to SO3 formation. CO could react with O2 to
generate more O radical which was vital to SO3 formation and consume HO2 radical when steam existed. The
pulverized coal experiment presented a different SO3 concentration at the same input sulfur and steam level,
meaning the fly ash and other gas phase components in the flue gas could also influence SO3 formation.

1. Introduction the corrosion now is to heat the wall to keep the flue gas temperature
above the dew point of sulfuric acid vapor, which will cost extra power
The hydrogen chloride compound has the HCl formula. At room
and reduce the efficiency of the power plant. So it matters to study the
temperature, HCl is a colorless gas that forms a white mist of hydrochlori
formation of SO3 during oxy-fuel combustion to give the guiding opi-
cacid when in contact with air humidity. Hydrogenchloride and hydrochloric
gases are important compounds in thefield sof technology and industry. HCl is nions on reducing the concentration of SO3 in the flue gas.
a polar covalent compound so that when dissolved in waterit can conduct an The formation has been widely studied in recent years, and the
electriccurrent. In general, many parameters can affect SO3 formation and researchers found that temperature, sulfur dioxide (SO2), oxygen (O2),
the flue gas temperature of sulfuric. steam, fly ash and many other parameters could all influence SO3 for-
mation:
Oxy-fuel combustion has higher pollutant concentration in the flue
gas due to the recirculation of flue gas and the enrichment of the
components. The concentration of sulfur oxides (SOX) [1–4], hydrogen • Temperature: In a pilot-scale experiment, Ahna et al. [10] found
that the temperature has a strong impact on the formation of SO3,
chloride (HCl) [5–7], carbon monoxide (CO) [8,9], nitrogen oxides
too high or too low can both reduce SO3 concentration. Fleig et al.
(NOX) [1,3] etc. in the flue gas are all relatively higher. According to
[13] conducted experiments in a drop tube furnace during air
the researches [10,11], sulfur trioxide (SO3) concentration in the flue
combustion and suggested that SO3 concentration increased as the
gas can be 4–6 times higher during oxy-fuel combustion (reaching
experimental temperature increased. The previous study of our
160 ppm) than that during air combustion. SO3 can cause damage to the
group [14] in a laboratory scale also indicated that with the growth
boiler system, especially the low-temperature corrosion. In the low-
of the temperature, SO3 concentration will increase first and then
temperature section of the flue, SO3 and steam will generate sulfuric
decrease, reaching the peak at around 950 °C.
acid vapor and then condense on the flue wall to corrode the low-
temperature heating surface such as the air preheater. During oxy-fuel • SO2 concentration: Belo et al. [15] found that the increasing input of
SO2 could promote the concentration of SO3 in the homogenous and
combustion, the higher concentration of SO3 and steam will raise the
heterogeneous experiments. After performing the modeling and
dew point of sulfuric acid vapor [12], thus the acid vapor will condense
experimental study, Choudhury [16] put it that outlet SO3 con-
at a relatively higher temperature to make the low-temperature cor-
centration would increase as inlet SO2 increased.
rosion worse. This will put the system a greater risk. The way to weaken

⁎
Corresponding authors.
E-mail addresses: xwliu@hust.edu.cn (X. Liu), mhxu@hust.edu.cn (M. Xu).

https://doi.org/10.1016/j.fuproc.2018.02.016
Received 1 December 2017; Received in revised form 31 January 2018; Accepted 12 February 2018
0378-3820/ © 2018 Elsevier B.V. All rights reserved.
J. Guo et al.
•O 2 concentration: By using a detailed gas-phase model, Fleig et al.
[17] simulated the impact of different combustion parameters and
atmosphere on the formation of SO3 during oxy-fuel combustion and
the results showed that O2 can strongly enhance the SO3 formation
as they increase. Another experiment [13] during air combustion
showed the same results. Lawrence P. Belo et al. [15] also found the
stimulative behavior of O2 in their experiments.
• Steam: Fleig et al. [18] found that the SO3 concentration is lower
under wet flue gas recirculation (FGR) than dry FGR at similar
temperature conditions for a lab test unit. By conducting the
homogeneous and the pulverized coal experiments separately in
laboratory scale, the previous study of our group [14] found that
steam can strongly inhibit the formation of SO3 in all tested cases.
• Fly ash: Lawrence P. Belo et al. [15] found the addition of iron oxide
in the fly ash could all promote the concentration of SO3. Duan et al.
[11] designed homogeneous and heterogeneous experiments and
then examined the results in a pilot-scale test and drew the con-
clusion that the fly ash could influence SO3 formation, but whether
promote or restrain the formation depends on the composition of the
fly ash.
• Other parameters: Spörl et al. [19] carried out experiments at a
20 kW once-through combustion rig and found that the SO3 con-
centration could be affected greatly by the coal type as the sulfur
and metal element contents varied. The experiments of Fleig et al.
[13] during air combustion suggested that SO3 concentration in-
creased when nitric oxide (NO) or methane was introduced. The
simulated gas-phase model of Fleig et al. [17] indicated that resident
time can strongly enhance the SO3 formation as it increased. After
introducing NO, SO3 concentration increased but as NO increasing,
SO3 would decrease. Choudhury [16] also found that SO3 con-
centration would increase first and then decrease as the introduced
NO increasing, reaching the peak at 500 ppm NO.
In general, many parameters can affect SO3 formation, making it
very complicated, and all components in the flue gas may play roles in
the formation of SO3. So far, the components in the flue gas such as
steam, SO2 and O2 have been widely studied. These parameters are the
relatively higher parameters in the flue gas. However, SO3 formation
may also be affected by the trace components in the flue gas such as HCl
and CO. Their concentrations are all relatively higher during oxy-fuel
combustion. Up to now, few works give a systematic study on the effect
of HCl and CO on SO3 formation during oxy-fuel combustion. Does SO3
formation change when the concentration of HCl and CO increases
during oxy-fuel combustion? If it changes, how does HCl and CO affect
it, promote or suppress? And what are the mechanisms that they affect
the formation? The answers to these questions remain unclear.
To explore the effect and reveal the mechanisms of the interactions
between SO3 and HCl or CO, homogeneous experiment and pulverized
coal experiment were designed and carried out separately on a hor-
izontal tube furnace system and a drop tube furnace system. Different
concentration of HCl and CO with SO2, H2O, O2 and CO2 were used to
simulate the flue gas. The mechanism of how HCl and CO affect SO3
formation by the elementary reactions during oxy-fuel combustion was
analyzed based on the results of the experiments.
2. Experimental
2.1. Homogeneous experiment test facility
The experiment was done on an electrical heating horizontal tube
furnace (shown in Fig. 1). This facility was described at length in the
previous literature of our team [14]. The temperature of the furnace
was set to 950 °C. SO3 formation rate reaches the peak around this
temperature according to our previous study [14], and thus this tem-
perature was chosen in this research to maximize the presentation of
the experimental results. There was a quartz glass tube acting as the
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Fuel Processing Technology 174 (2018) 95–103
reactor in it with a length of 500 mm and an inner diameter of 34 mm.
HCl, CO, SO2, O2, CO2 and steam were used as the simulated flue gas
and the total flow rate was 1 L/min. In the simulated flue gas, 0.03%
steam was set to facilitate the well collection of SO3. SO3 and SO2 in the
outlet flue gas would be collected separately for 30 min using a
common and standard method named controlled condensation method
(CCM) according to the German standard method VDI2462, sheet 7. A
glass spiral tube was placed into a water bath set to 80 °C. The tube was
made of glass, with an inner diameter of 6.6 mm and an outer diameter
of 9 mm. The entire tube was plated into a spiral, the height of the spiral
under water bath was 180 mm and the outer diameter was 65 mm. The
spiral consisted of 8 loops, and the vertical distance between the ad-
jacent loops was about 9.5 mm. The temperature measurement point
was 20 mm from the point receiving water bath. The inlet gas tem-
perature was kept above 220 °C and the outlet temperature was mea-
sured to be about 62 °C, thus the temperature of the spiral tube was kept
above the water dew point temperature but below the acid dew point
temperature. In this way, SO3 and sulfuric acid vapor would condense
onto the surface of the spiral tube but SO2 and steam would not. SO2
was oxidized to H2SO4 by H2O2 and then dissolved.
The operating conditions of the experiment were listed in detail in
Table 1. The pressure was 1 atm. Before SO2 was introduced, all the
other gases had been fed into the whole system to make sure that there
was no sulfide. Similarly, when an individual experiment was over, SO2
gas cylinder was closed first and the other gases would still be fed for
minutes to ensure all sulfides had been collected. Each condition was
done at least three times to ensure repeatability.
2.2. Pulverized coal experiment test facility
The experiment was carried out on an electrical heating drop tube
furnace (shown in Fig. 2), which was also described at length previously
[14]. The temperature of the furnace was set to 950 °C. The size of the
quartz glass tube in the furnace was changed to a length of 1500 mm
and an inner diameter of 60 mm. There was a disc vibration coal feeder
above the furnace. A water-cooled quartz injector was placed between
the feeder and the tube. At the outlet of the tube, a glass fiber filter was
used to capture the fly ash in the flue gas. And at the end of the
scrubbing bottles, another bottle filled with silica gel, a mass flow
controller and a vacuum pump were set to guarantee a smooth flow.
The inlet gas components of the experiment were listed in detail in
Table 2. A Ping Ding Shan bituminous coal (PDS coal) was chosen for
the experiment and has a size distribution ranging from 45–90 μm. The
proximate and elemental analyses of the coal were listed in Table 3. The
total flow rate of the simulated gas was 4 L/min. Before each individual
experiment, the coal feeder was calibrated with a feeding rate of 0.2 g/
min. The pressure was 1 atm and the resident time of the pulverized
coal was 1.8 s.
2.3. Sampling and measurement methods
After each individual experiment, SO3 and sulfuric acid in the spiral
tube were washed and diluted the volume in a volumetric flask with
deionized water. Three scrubbing bottles with H2O2 and H2SO4 were
also diluted the volume in another volumetric flask. Samplings from the
volumetric flasks were measured by the ion chromatograph system
(ICS-1100, Thermo Scientific). The data of the sulfate ion from ICS-
1100 were calibrated with GSB 04-1773-2004 sulfate ion standard so-
lution.
In pulverized coal experiment, the microwave digestion method was
used to deal with the fly ash captured by the glass fiber filter. The di-
gestion solution was also diluted and sampled to measure the sulfate ion
by ICS-1100.
J. Guo et al. Fuel Processing Technology 174 (2018) 95–103

Fig. 1. Schematic diagram of the homogeneous experiment system.

Table 1 provided by the software, and the data which were not included in the
Inlet gas compositions of the homogeneous experiment. file were added according to the mechanism data adopted by Giménez-
López et al. [21]. The mechanism used for the modeling was well or-
(a)
ganized and provided as Supplementary material, which was taken
Case SO2 (ppm) H2O (%) O2 (%) from Giménez-López et al. [22] and Yang et al. [23].
Sensitivity analysis was carried out to determine the rate dom-
S1H0 1000 0.03 5 inating reactions for SO3 formation in the presence of HCl or CO in
S3H0 3000 0.03 5
S1H15 1000 15.03 5
homogenous experiment. For this purpose, the sensitivity function in
S3H15 3000 15.03 5 CHEMKIN-PRO was used, and the data were analyzed based on nor-
malized coefficients.

(b) 3. Results and discussion

Test HCl (ppm) CO (ppm) Case CO 2 (%)
3.1. Sulfur mass balance
1 0 – S1H0 94.87
2 20 – 94.87 The sulfur mass balance was calculated to ensure the accuracy of the
3 60 – 94.86 experiment. The input sulfur was based on the injected SO2
4 100 – 94.86
5 0 – S3H0 94.67
(SO2add) and the elemental analyses of the coal (Scoal). The output
6 20 – 94.67 sulfur was based on the data measured by ICS-1100, as the sulfur was
7 60 – 94.66 almost in- cluded in the flue gas (SO3 + SO2out), condensed water
8 100 – 94.66 and fly ash (Sash), while the sulfur in the condensed water was
9 – 100 S1H0 94.86
negligible.
10 – 500 94.82
11 – 1000 94.77 Balance = (SO3 + SO2out + Sash)/(SO2add + Scoal )
12 – 2000 94.67
13 – 100 S3H0 94.66 Table 4 shows the sulfur mass balance of all tests. The balance
14 – 500 94.62 ranged from 0.904 to 1.060, and the deviation between the measured
15 – 1000 94.57
16 – 2000 94.47
and theoretical value was less than 10%, which is within the acceptable
17 0 – S1H15 79.87 range in the calculation of sulfur balance. This indicated that all ex-
18 20 – 79.87 perimental results were credible.
19 60 – 79.86
20 100 – 79.86
3.2. Influence of HCl on SO3 formation in homogenous system
21 0 – S3H15 79.67
22 20 – 79.67 Fig. 3 shows the measured generated SO3 concentrations at different
23 60 – 79.66 HCl concentrations in the homogeneous experiment. Fig. 3(a) shows the
24 100 – 79.66
simulated low steam concentration FGR at two different initial SO2
25 – 100 S1H15 79.86
26 – 500 79.82 concentrations (1000 ppm, 3000 ppm). As is shown in the figure, SO3
27 – 1000 79.77 concentrations were 38 ppm and 82 ppm when there was no HCl in the
28 – 2000 79.67 flue gas. When 20 ppm HCl was introduced, SO3 concentrations
dropped sharply to 32 ppm (decreased by 17.6%) and 68 ppm (de-
creased by 16.2%) respectively. However, while the inlet concentration
2.4. Kinetic simulation
of HCl increased to 100 ppm, the generated SO 3 decreased gently, and
the decline rate were 3.8% and 8.6% correspondingly.
The kinetic simulation was conducted using the software CHEMKIN-
Fig. 3(b) shows the simulated high steam concentration FGR (with
PRO [20] to investigate the effect of HCl and CO on SO3 formation. A
15.03% steam in the flue gas) at two different initial SO2 concentrations
plug flow reactor (PFR) model under the actual experimental tem-
(1000 ppm, 3000 ppm). It presents the same tendency as that of
perature was used as the reaction system to simulate the homogenous
Fig. 3(a), which means that HCl inhibits the formation of SO3 indeed.
experimental system. The thermodynamic data consisted of the file
By comparing Fig. 3(a) and (b), a sharp decrease of SO3 concentration

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J. Guo et al. Fuel Processing Technology 174 (2018) 95–103

Fig. 2. Schematic diagram of the pulverized coal experiment system.

Table 2 Table 4
Inlet gas compositions of the pulverized coal experiment. Sulfur mass balance of the all tests.

Test HCl (ppm) CO (ppm) O2 (%) CO 2 (%) Test Balance Test Balance Test Balance

29 0 – 27 73.00 1 0.934 13 0.931 25 0.984

30 20 – 27 73.00 2 1.011 14 0.998 26 0.975
21 60 – 27 72.99 3 0.911 15 0.981 27 0.959
32 100 – 27 72.99 4 0.922 16 0.999 28 0.946
33 – 500 27 72.95 5 1.021 17 0.956 29 1.060
34 – 1000 27 72.90 6 0.947 18 0.999 30 1.047
35 – 2000 27 72.80 7 0.916 19 0.917 31 0.983
8 0.947 20 0.942 32 1.018
9 0.911 21 0.943 33 0.959
10 0.912 22 0.904 34 0.972
Table 3
11 0.943 23 0.908 35 0.985
The proximate and elemental analyses of PDS coal (wt%, ad basis).
12 0.981 24 0.918 – –
Moisture Ash Volatiles Fixed C H O N S Cl
carbon

0.73 27.33 22.54 49.40 59.68 3.68 4.04 0.92 3.62 0.017

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J. Guo et al. Fuel Processing Technology 174 (2018) 95–103

SO3 + HO2 ⇌ HOSO2 + O2 (R-3)

Fig. 3. SO3 concentration at different HCl concentrations in the homogeneous experiment
(a) Low steam concentration FGR (b) High steam concentration FGR.
can be seen when 15.03% steam existed. Even if the initial SO2 con-
centration in the high steam concentration FGR was 3000 ppm, SO3
concentration (18 ppm) was still lower than that (38 ppm) in the low
steam concentration FGR when the initial SO2 concentration was
1000 ppm. This phenomenon meant that steam had a strong inhibition
on SO3 formation, which was well coincident with the previous study of
our group [14].
The SO3 formation and decomposition mechanism includes a large
number of interactions of sulfur and other components in the radical
pool [22,23]. And different combustion parameters will influence the
radical pool to affect SO3 formation indirectly. SO3 was formed mainly
through two pathways. The primary pathway was SO2 react with O
atom through (R1). The secondary pathway was SO2 react with OH
radical through (R2)–(R3). The O radical came mainly through (R4).
SO3 was consumed by reacting with H, HO2, O and OH radicals through
(R-3), (R5)–(R7). Here (R-3) means the inverse reaction of (R3).
SO2 + O (+M) ⇌ SO3 (+M)
SO2 + OH (+M) ⇌ HOSO2 (+M)
SO3 + O ⇌ SO2 + O2 (R6)
SO3 + OH ⇌ SO2 + HO2 (R7)
Most of SO3 was formed through (R1) at the experimental tem-
perature, while just a little bit was formed through the secondary
pathway, as the stability of the intermediate product HOSO2 was very
poor and it would decompose back to SO2 and OH as soon as it was
generated, and only 1%would form SO3 through (R3) [24]. It was
concluded that (R5), (R-3) and (R6) were major to the consumption of
SO3. However, the influence of (R7) was very limited and could be
ignored [14]. These formation pathways were well coincident with the
model.
There was a little steam in the flue gas, resulting in the introduction
of H and OH radicals through (R8). And H radical could react with O2
through (R9)–(R10).
H2 O ⇌ H + OH (R8)
O2 + H ⇌ HO2 (R9)
O2 + H ⇌ O + OH (R10)
The rate constants of (R9), (R10) and (R5) were calculated based on
the coefficients taken from NIST Database [25] using Arrhenius equa-
tion and were listed in Table 5. What can be drawn from the table was
that almost all the resultants were HO2 radicals when O2 reacted with H
radicals. What more can be seen was that the rate constant and the
reactant concentration of (R9) were higher than (R5), resulting in a
greater reaction rate, and the consumption of H radical happened
through (R9) mainly. So the consumption of SO3 through (R5) was
suppressed, and SO3 might react with HO2 through (R-3) mainly.
With HCl introduction, sensitivity analysis was performed in the
presence of 20 ppm HCl in the reactor. Except for those reactions
without the presence of HCl, reactions influencing SO3 generation at
varied extents has been listed below (in the decreasing order), and the
sensitivity coefficients have been presented in Fig. 4(a).
HCl + O2 ⇌ HO2 + Cl (R-11)
HCl + OH ⇌ H2 O + Cl (R12)
Negative sensitivity for SO3 generation was shown by (R-11) and
(R12). HO2 radical was generated through (R-11). OH radical was
consumed through (R12) but H2O was produced. HO 2 radical and H 2O
had negative effects on SO3 formation, while OH radical had a positive
effect.
To explain in detail, when HCl was injected, the radical pool was
richened. Before the injection, there were only C/H/O/S related radi-
cals in the radical pool, and the main interactions in the pool concerned
to SO3 formation mechanisms have been mentioned above. After the
injection, HCl appeared in the radical pool, and the interactions become
more complicated. In the pool, HCl could react with O2 to generate Cl
and HO2 radicals through (R-11). This reaction would increase HO2
concentration. It has been discussed that HO2 had a negative effect on
SO3 formation through (R-3). In this way, the amount of SO 3 was re-
duced.
Table 5
Rate constants of (R9), (R10) and (R5).
(R1)
Temperature (°C) (R9): O 2 + H ⇌ (R10): O 2 + H ⇌ (R5): SO 3 + H ⇌
HO2 O + OH SO2 + OH
(R2) (cm6 mol−2 s −1) (cm3 mol−1 s −1) (cm3 mol−1 s −1)

HOSO2 + O2 ⇌ SO3 + HO2 (R3) 750 3.84 × 1015 1.87 × 10−2 6.72 × 1012
850 3.46 × 1015 4.07 × 100 8.69 × 1012
O2 ⇌ O + O (R4) 950 3.15 × 10 15 5.36 × 10 1 1.09 × 10 12
1050 2.89 × 1015 4.77 × 102 1.32 × 1013
15 3 13
SO3 + H ⇌ SO2 + OH (R5) 1150 2.67 × 10 3.13 × 10 1.58 × 10

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Fig. 4. Sensitivity coefficients (HCl/CO-related) for SO3 formation in the presence of HCl/CO (a) In the presence of HCl (b) In the presence of CO.

Besides, HCl could also react with OH radical to generate H2O and
Cl radicals through (R12). This reaction would consume OH radical,
leading to a reduction of SO3 formed through the secondary pathway of
SO3 formation. But because this pathway contributed little to SO3 for-
mation, this reduction could be ignored.
However, H2O was formed. It has been mentioned in Section 1 that
H2O could inhibit the formation of SO3. The mechanism was explained
in detail in the previously published literature [14] of our group. The
main reason was that H2O could react with O radical through (R13).
The rate constant of (R13) was higher than that of (R1) at the same
temperature, and the concentration of H2O was also higher than SO2,
thus H2O would compete O radical with SO2 to suppress it from being
oxidized.

H2 O + O ⇌ OH + OH (R13)

To sum up, HCl inhibits SO3 formation mainly by generating those

bad for SO3 formation and consuming SO3 directly. It should be stressed
that due to the lack of some relevant thermodynamic data, a kinetic
modeling was still difficult to be done to be compared with the ex-
perimental work. Fig. 5. SO3 concentration at different CO concentrations in the homogeneous experiment.

recirculation. Similarly, SO3 concentrations were lower than that in the

3.3. Influence of CO on SO3 formation in homogenous system
Case-S1H0, indicating the inhibition of high steam concentration on
SO3 formation.
Fig. 5 gives the measured generated SO3 concentration at different
With CO introduction, sensitivity analysis was performed in the
CO concentrations in the homogeneous experiment. Case-S1H0 and
presence of 100 ppm CO in the reactor. Except for those reactions
Case-S3H0 show the simulated low steam concentration FGR at two
without the presence of CO, reactions in fluencing SO3 generation at
different initial SO2 concentrations (1000 ppm, 3000 ppm). It can be
varied extents has been listed below (in the decreasing order), and the
concluded that SO3 was significantly increased from 38 ppm and
sensitivity coefficients have been presented in Fig. 4(b).
81 ppm to 48 ppm (increased by 24.6%) and 91 ppm (increased by
11.2%) when 100 ppm CO was introduced. While the concentration of CO + O2 ⇌ CO2 + O (R14)
CO increased to 2000 ppm, the generated SO3 also increased, but very
gently. The increasing rates were 16.1% and 20.7% respectively. CO + HO2 ⇌ CO2 + OH (R15)
Besides, while the initial SO2 concentration was increased (from
1000 ppm to 3000 ppm), more SO3 was formed. But the conversion rate CO + O + M ⇌ CO2 + M (R16)
of SO2 to SO3 decreased (from 3.85% in Test 1 to 2.72% in Test 5) when
CO + OH ⇌ CO2 + H (R-17)
the initial SO2 increased. This trend was the same as that in the HCl
experiment. Positive sensitivity for SO3 generation was shown by (R14) and
Case-S1H15 shows the generated SO3 concentration when 15% (R15). O radical was generated through (R14). HO2 radical was con-
steam was added to simulate the high steam concentration FGR. There sumed through (R15) but OH radical was generated. O and OH radicals
was no obvious difference in the tendency between the two kinds of had positive effect on SO3 formation, while HO2 radical had a negative

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Table 6 Table 7
Rate constants of (R14) and (R4). The percentage of sulfur-related components to total sulfur in the flue gas.

Temperature (°C) (R14): CO + O2 ⇌ CO2 + O (R4): O2 ⇌ O + O Test SO3 (ppm) SO3 SO2 (ppm) SO2 Sulfur Ash
(cm3 mol−1 s−1) (cm3 mol−1 s−1) percentage percentage in ash percentage
(%) (%) (%) (%)
750 1.56 × 102 1.06 × 10−10
850 1.26 × 103 1.71 × 10−8 29 37 2.95 1020 81.40 2.05 15.65
950 7.27 × 103 1.18 × 10−6 30 34 2.70 1029 81.79 2.04 15.51
1050 3.21 × 104 4.30 × 10−5 31 32 2.52 1054 83.08 1.91 14.40
1150 1.15 × 105 9.38 × 10−4 32 31 2.52 1023 83.11 1.85 14.38
33 46 3.68 1017 81.33 1.96 14.99
34 49 3.94 1016 81.62 1.88 14.45
effect. Negative sensitivity was shown by (R16) and (R-17). O radical 35 48 3.80 1057 83.70 1.65 12.50

was consumed through (R16). OH radical was consumed through (R-

17) but H radical was generated. H radicals had a negative effect.
However, the sensitivity of (R14) and (R15) were all greater than that
of (R16) and (R-17), and the positive effect of CO on SO3 formation was
bigger than the negative effect.
To explain in detail, when CO was injected, no more elements were
brought into the radical pool. However, it increased CO concentration
in the radical pool. Before the injection, CO in the radical pool came
from (R-17) mainly. After the injection, the progress of (R-17) would be
inhibited.
Meanwhile, the increased CO could affect a series of interactions.
CO was oxidized and O radical was formed through (R14) at the same
time. The rate constants of (R14) and (R4) were listed in Table 6. It can
be seen that the rate constant of (R14) is far greater than that of (R4) at
the experimental temperature. Considering about the concentrations of
CO and O2, the reaction rate of (R14) was still greater, thus more O
radical was generated in the same time, and more SO3 would be gen-
erated through (R1).
CO could also react with HO2 through (R15). On the one hand, the
HO2 was consumed. After the injection, this consumption would be
greater, and the consumption of SO3 through (R-3) would be weakened
to some extent. On the other hand, OH radical was generated through
(R15), resulting in a minor enhancement of SO3 formed through the
secondary pathway.
Nevertheless, CO also played a negative role. One is another
pathway to the oxidation of CO. Except for the oxidation by O2 through
(R14), CO could also be oxidized by O radical through (R16). So CO
could also compete for O radical with SO2. Besides, the inhibition of (R-
17) would make it reverse to some extent, thus more H radical would
exist.
Although CO could be negative to SO3 formation, the influence is
not that great as the positive effect because of the huge gap between the
oxidizing agents in the reactants of (R14), (R16) and (R-17). As a
whole, CO would promote the formation of SO3 from the macro point of
view.
To sum up, the formation of SO3 was strengthened and the con-
sumption was inhibited when CO was injected. Thus showing an in-
crease in the formation of SO3. And SO3 formation was promoted
mainly by generating O radical through (R14) and consuming HO2
radical through (R15). Fig. 6. SO3 concentration in pulverized coal experiment (a) Different HCl concentrations
(b) Different CO concentrations.

3.4. Influence of HCl and CO on SO3 formation in pulverized coal

combustion
In the pulverized coal experiment, sulfur was present not only in the
gaseous SO2 and SO3, but also in solid fly ash. The percentage of sulfur-
related components to total sulfur in the flue gas was listed in Table 7. It
could be seen that SO2 accounted for the largest proportion, but sulfur
in the fly ash accounted for only a dozen percentage points. Pulverized
coal cannot be burned out due to the insufficient temperature so that
the sulfur in the ash could not be released completely. Meanwhile, some
of the gaseous sulfur oxides were also trapped in the fly ash.
The results of the pulverized coal experiment were shown in Fig. 6.
Fig. 6(a) gives the measured generated SO3 concentration at different
HCl concentrations, showing the same trend as that in the homogenous
experiment. SO3 concentration decreased from 37 ppm to 34 ppm by
9.9% when 20 ppm HCl concentration was introduced. When the initial
HCl concentration increased to 100 ppm, the generated SO3 decreased
gently, and the decline rate was 5.9%.
Fig. 6(b) gives the measured generated SO3 concentration at dif-
ferent CO concentrations, also showing the same trend as that in the
homogenous experiment. SO3 concentration increased from 37 ppm to
46 ppm by 10.0% when 500 ppm HCl concentration was introduced.
When the initial CO concentration increased to 2000 ppm, the gener-
ated SO3 increased gently, and the increasing rate was 7.4%.

101
J. Guo et al.
It can be seen from Table 7 that released sulfur (about 1000 ppm)
was almost the same as that in the homogenous experiment
(1000 ppm). However, by comparing Fig. 6(a) with Fig. 3(a) Case-S1H0
and Fig. 6(b) with Fig. 5 case-S1H0, it was found that the generated SO3
concentration was different in the two experiments at the same HCl or
CO concentration.
For one thing, the chlorine element originally contained in the
pulverized coal would release a small amount of HCl during the com-
bustion process. And at the same time, CO could also be generated
because the temperature was not high enough to burn the pulverized
coal out. So the concentration of HCl or CO in the flue gas was different
from the initial concentration that was introduced. And HCl and CO
could influence the migration and transformation of the minerals and
the formation of the ultrafine particulate matter during the coal com-
bustion [26–29]. Besides, H element in the coal was converted to H2O
concentration in the flue gas, and there was a difference between it
(about 2.06%) and the low steam concentration FGR in the homo-
genous experiment (0.03%). H2O had a negative effect on SO3 forma-
tion, thus the generated SO3 concentration would be different from that
in the homogenous experiment.
For another, the other components in the flue gas could also affect
SO3 formation. One is the fly ash. Some of the SOX could be captured by
alkaline elements in the fly ash. In these alkaline elements, calcium
played a dominate role in sulfur retention [30,31]. Besides, as has been
mentioned in Section 1, SO3 could be generated by catalytic oxidation
of the fly ash. It was found that Fe2O3 in the fly ash contributed the
most to the catalytic oxidation of SO2 [15,32]. Another one is NOX.
During the pulverized coal combustion, the nitrogen element in the coal
was released. About 95% of the total NOx was NO, and NO2 occupied
the most of the remaining NOx [6]. NO and NO2 could react with SO2 or
with other radicals that could affect SO3 formation [16,17].
Through the above analysis, it can be seen that many other factors
such as the fly ash and NOX could also affect SO3 formation during
pulverized coal combustion. But these factors did not change the effect
of HCl and CO on SO3 formation as the trend of SO3 concentration were
the same. And the mechanism of how HCl and CO influence the for-
mation of SO3 in the homogenous system was still suitable in the pul-
verized coal combustion.
4. Conclusions
In this study, the formation of SO3 with the presence of HCl and CO
during oxy-fuel combustion was investigated under laboratory condi-
tions. The homogenous experiment was done on a horizontal tube
furnace system and the pulverized coal experiment was carried out on a
drop tube furnace test facility at 950 °C. Different concentrations of HCl
and CO with SO2 were introduced separately in a single experiment.
The results of the experiments given the following conclusions:
1. HCl could inhibit SO3 formation. SO3 concentration decreased
sharply when HCl was introduced at the experimental temperature.
With the initial HCl concentration increased, SO3 concentration
decreased gently. HCl might influence the radical pool and affect
SO3 formation indirectly by generating HO2 radical which was ne-
gative to SO3 formation.
2. CO had a positive effect on SO3 formation. And with the initial CO
concentration increased, SO3 concentration increased gradually and
tended to be stable. CO might promote SO3 formation also by af-
fecting the radical pool to create more O radical and consume HO2
radical.
Acknowledgements
This work was supported by National Key R&D Program of China
(2017YFB0603204). We also appreciate the support given by the
Analytical and Testing Center at Huazhong University of Science and
102
Fuel Processing Technology 174 (2018) 95–103
Technology.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuproc.2018.02.016.
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