Fuel 211 (2018) 206–213

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Fuel
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Full Length Article

Characteristics of fine particulate matter formation during combustion of MARK

lignite riched in AAEM (alkali and alkaline earth metals) and sulfur
⁎
Renhui Ruana, Houzhang Tana, , Xuebin Wanga, Yan Lia, shuaishuai Lia, Zhongfa Hua, Bo Weib,
Tao Yanga
a
MOE Key Laboratory of Thermo-Fluid Science and Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China
b
College of Electrical Engineering, Xinjiang University, No. 1230, Yanan Road, Tianshan District, Urumqi 830000, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The high contents of AAEM (alkali and alkaline earth metals) and sulfur in zhundong coal result in more fine
AAEM rich coal particulate matter during coal combustion. In this paper, the emission of fine particulates from zhundong coal
Sulfur rich coal riched in AAEM-sulfur and zhunnan coal riched in aluminum-silicon was investigated in a drop tube furnace. Co-
Iron combustion of zhundong coal and zhunnan coal was further investigated to study the effect of interaction among
Fine particulates
different elements in coal on the PM formation. The size distribution, concentration and composition of the
Co-firing
particulates were analyzed by low pressure impactor (DLPI) and scanning electron microscopy (SEM). The
distribution of sodium, magnesium, calcium, iron and sulfur in fine particulates and their effects on the gen-
eration of fine particulates were obtained. The results show that the fine particulates from AAEM-sulfur rich coal
combustion mainly consist of sulfates and oxides of AAEM. The amount of fine particulates from burning alu-
minum-silicon rich coal decreased significantly. The composition of PM0.4 and PM0.4+ are significantly different.
Co-firing of AAEM-sulfur rich coal with aluminum-silicon rich coal has an obviously synergetic effect of reducing
the fine particulates emission. The capture of AAEM and iron by aluminum-silicon compounds plays an im-
portant role in PM10 reduction during blended coal combustion. The change of sulfur content in PM0.4 is con-
sistent with the change of AAEM content.

1. Introduction to be related to the gasification of inorganic elements in coal [6–10].

Coal will still be the main energy resource in china for a long time.
Recently a large integrated coalfield was found in Xinjiang with a
forecast reservation of 390 billion tons [1,2]. It can be used for more
than 100 years at the current coal consumption rate of china and will be
the main energy base in the future of china. Zhundong coal is char-
acterized by high volatile, low ash content, good combustion char-
acteristics and low mining costs [2]. It is considered a good thermal
coal.
However, the extensive usage of coal has caused serious air pollu-
tion [3], especially the current removal efficiency of fine particles in
coal-fired power plant is still low [4,5]. The combustion of zhundong
coal will generate more fine particulates due to the high content of
AAEM (alkali and alkaline earth metals) in raw coal [6]. It is important
to study the characteristics of fine particles and control the PM emission
during the clean utilization of zhundong coal. There have been many
researches on the formation mechanisms of fine particulate matter from
coal combustion and the formation of submicron particles is considered
Most of the alkali metal in coal was water-soluble especially sodium
[11]. The alkali metal is easy to vaporize during coal combustion and
will condensate to be fine particulate matter as the flue gas is cooling
[8,11]. The formation of larger particles (PM1+) is usually related to
the evolution of refractory minerals in coal [10,12,13]. Zeng [14] stu-
died the characteristics of fine particulates from coal firing in air at the
combustion temperature of 1173 K, 1273 K, 1373 K and 1573 K. He
found an increase of magnesium and calcium with a decrease of sodium
and sulfur in the fine particulate matter when increasing the combus-
tion temperature. The reason of PM1 reduction is considered to be the
absorption of sodium by fly ash. Li [6] investigated the fine particles
formation during combustion of zhundong coal in a 25 KW down-fired
furnace. It was found that the PM0.4 is mainly composed of sodium
sulfate. With the increase of particle size, aluminosilicates become the
main component of fine particulates. Gao [7] collected the ultra-fine
particles generated from zhundong coal combustion by the thermo-
phoresis micro-probe from the Hencken burner. The analysis results of
TEM show that the amount of sodium and silicon is highest in the ultra-

⁎
Corresponding author.
E-mail address: tanhz@mail.xjtu.edu.cn (H. Tan).

http://dx.doi.org/10.1016/j.fuel.2017.08.114
Received 25 April 2017; Received in revised form 10 July 2017; Accepted 30 August 2017
0016-2361/ © 2017 Published by Elsevier Ltd.
R. Ruan et al. Fuel 211 (2018) 206–213

fine particulates. The Na2O·nSiO2 is thought to be the precursor of ultra- from the flue gas. The PM10 particles were collected by DLPI (Dekati
fine particles. In the process of coal combustion, the refractory oxides low pressure impactor) into 13 fractions. The combustion temperature
(magnesium oxide, calcium oxide, silicon oxide, iron oxide) can be for experiment was 1573 K and the flue gas temperature at the fly ash
reduced to more volatile sub-oxides (silicon monoxide) or simple sub- sampling position was 873 K. Each case was repeated three times to
stances (magnesium, calcium, silica, iron) [6,8]. The volatilization of ensure the reliability of the experimental data.
these refractory oxides also lead to the formation of fine particulates Aluminum foil coated with Apiezon L resin was used to sampling
and precursor of PM. So far, the researches on fine particulate matter PM10 for analysis. The mass of particulate matter on the foil was ob-
from coal combustion are mainly focused on alkali metal, especially the tained by a precision electronic balance (Sartorius M2P, 0.001 mg). The
contribution of sodium in fine particulate formation [11,15,16]. In the particulates on the foil was analysed by scanning electron microscopy
previous researches of our group [1,17], the ash deposited on the equipped with an energy dispersive spectrometer (SEM-eds, JSM-
heating surface of a 350 MW coal-fired power plant showed a layered- 6390A). The main considered elements included sodium, magnesium,
structure and were rich in calcium sulfate. The reaction between cal- potassium, calcium, aluminum, silicon, sulfur and iron.
cium oxide and sulfur promotes the formation of the initial layer during
the ash deposition process. However, the role of alkaline earth metal on 3. Results and discussion
the formation of PM has not been fully studied [18].
In this work, a zhundong lignite riched in AAEM and sulfur were 3.1. Mass-particle size distribution of PM10
burned in a drop tube furnace to study the formation of PM. The co-
firing of zhundong lignite and high content aluminum-silicon zhunnan The mass-particle size distributions of ZD, 9:1, 7:3, ZN are presented
coal was further carried out to study the characteristics of PM reduction in Fig. 2. The y axis represents the ability of fine particulate matter
during co-combustion. Through the analysis of the main elements in PM generated from coal combustion and is scaled by ‘mg/g coal’. The x axis
among different combustion condition, the effect of sodium, magne- represents the aerodynamic diameter of particulate matter and is in the
sium, calcium, sulfur and iron on the PM formation was discussed in form of logarithmic coordinate.
detail. All of the four curves present a bimodal distribution with the peak of
fine model locates at around 0.16 μm and the peak of coarse model
2. Experimental locates at around 2.5 μm. The fine model of ZN is not clear because the
amount of fine particulates generated from ZN is little. There is a
2.1. Coal properties transition point locates at around 0.4 μm between the fine and coarse
model. When ZD coal is burned separately, the amount of PM10 is
The two coals used in this work were sampled from a coal-fired highest and the submicron particles were significantly higher than that
power plant in Xinjiang province. Both the two coal were dried first and from ZN coal combustion. The submicron particle formation is mainly
then ground to less than 100 μm in size. The coal properties are pre- relates to the nucleation and condensation process of gasified species.
sented in Table 1. The zhundong coal is rich in alkali and alkaline earth Alkali and alkaline earth metals are thought to be the main components
metals, especially sodium and calcium. The amount of silicon and of submicron particles [6,11,19]. When burning ZD coal, the alkali
aluminum in zhunnan coal is high, which is 44.90% and 17.33%, re- metals which are easy to gasify in coal particles will volatilize into the
spectively. gas phase. The alkaline earth metals (calcium and magnesium) can be
reduced to more volatile matter under the reducing atmosphere of char
combustion [8]. Meanwhile, a small part of the refractory metals such
2.2. The drop tube furnace, sampling systems and analysis method as iron and silicon will also gasify under the reducing atmosphere of
char particles [6,8]. These mineral vapors will react with oxygen when
The experiment was carried out in a drop tube furnace which is diffusing to the ambient environment from char. The decrease of
shown in Fig. 1. The blending ratio of zhundong coal and zhunnan coal oxygen partial pressure results in the increase of mineral vapor partial
is selected as 10:0, 9:1, 7:3, 0:10 which are expressed as ZD, 9:1, 7:3 pressure, which leads to the ultrafine particulates formation. These
and 0:10 later in this paper. The drop tube furnace is 1.2 m high with an aerosols are the precursors of submicron particles. In the process of
isothermal zone of 0.6 m heated by a three-stage silicon carbide rods. devolatilization, volatile combustion and char burnout, the char parti-
The primary air and the secondary air are mixing gas of oxygen and cles can be expanded and broken to generate particles much larger than
nitrogen at a ratio of 2:8. A self-designed micro powder feeder was used that from the process of gasification-nucleation/condensation [10,20].
to feed the coal. The residence time is about 3 s with an excess air The components of these particles are consistent with the mineral
coefficient of 2.5. The fine particulates in flue gas were sampled by a matter in coal particles [10]. In addition, the mineral matter melting in
water-cooled sampling tube. A flow of nitrogen was injected into the high temperature of coal combustion can grow up to form particles
sampling tube to quench and dilute the flue gas, preventing the sub- larger than 1 μm by coalescence [20]. Some researchers think the salt
sequent reactions. A PM10 cyclone after the sampling tube was used to (sulfate and chloride) and oxide of alkali metal are the main component
separate the particulates with aerodynamic diameter larger than 10 μm of fine particulates from coal combustion, especially for coal in zhun-
dong coalfield riched in alkali and alkaline earth metals [1,6]. The
Table 1 content of sodium in ZD coal is 3.83 mg/g coal, which is more than
Typical properties of coal and ash used in this study (wt%).
twice as much as it in ZN coal for 1.75 mg/g coal. However, the sub-
Coal Proximate analysis Ultimate analysis micron particles from ZD coal combustion are much more than that
from ZN coal combustion. This indicates that there are some other
Mad Ad Vdaf FCdaf Car Har Oar Nar St,ar factors affecting the formation of fine particulate matter. The content of
zhundong 14.36 8.50 30.86 69.14 53.83 2.38 10.61 0.47 0.33
silicon and aluminum in ZN coal is 6 times of that in ZD coal. The
zhunnan 8.88 17.58 36.79 63.21 56.52 3.21 10.60 0.69 0.44
silicon-aluminum species in coal generally form PM10+ during coal
Ash compositions combustion. The high content silicon-aluminum mineral in ZN coal has
an obvious absorption of alkali metal aerosol, resulting in significantly
Fe2O3 Al2O3 CaO MgO TiO2 SiO2 SO3 K2O Na2O
less submicron particles of ZN coal [21].
zhundong 8.02 7.68 40.69 6.6 0.65 17.38 11.32 0.55 6.07
zhunnan 9.01 17.33 13.36 5.04 0.71 44.90 6.47 1.26 1.34 In order to investigate the effect of co-combustion on the formation
of PM0.4 and PM10, the calculated value (particles concentration is
M: moisture, A: ash, V: volatile, FC: fixed carbon. calculated assuming that there are no interactions among the mineral

207
R. Ruan et al. Fuel 211 (2018) 206–213

5
6
7

8
9
4

2
1

10 11 12 13 14 15 16 17 18 19

1. Oxygen cylinder 2. Nitrogen cylinder 3. Micro powder feeder 4. Mass flow meter 5. Feed tube 6. Feed tube
Cooling water inlet 7. Feed tube Cooling water outlet 8. Silicon carbide heating rod 9. Thermocouple 10. Power
11. Sample probe cooling water inlet 12. Sample probe cooling water outlet 13. Sample probe 14. Dilution
nitrogen inlet 15. thermocouple 16. Thermometer 17. PM10 cyclone 18. DLPI Dekati low pressure impactor
19. Vacuum pump
Fig. 1. System schematic diagram of the drop tube furnace.

25 18 70
PM0.4 and PM10 mass concentration

Percentage of PM reduction %
ZD
16
9:1 60
20 7:3 14 51.7
50
dm/dlog Dp Pg/g FoDl

ZN 12
15 10 40
mg/g coal

32.7 33.2
8 27.0 30
10 6
20
4
10
5 2
0 0
ZD 9:1 7:3 ZN
0 coal blending ratio
PM10 experiment PM0.4 experiment PM0.4 reduction percentage
0.01 0.1 0.4 1 10
PM10 calculation PM0.4 calculation
Dp ȝP) PM0.4-10 reduction percentage

Fig. 2. Particle size distribution of PM10 from combustion of different blending coals. Fig. 3. Experimental and calculated amount of PM from combustion of different blending
coals.

matters in ZD and ZN coal) and the experimental value of PM0.4 and

PM10 for all of the four blending coals are compared as presented in PM concentration. PMZD and PMZN represent the concentration of PM
Fig. 3. The calculated formula of PM from co-firing is as follow: from ZD and ZN coal combustion. The calculation of PM reducing
percentage is expressed as follow:
PMΘ cal = x PMΘ ZD + yPMΘ ZN
PMΘ cal −PMΘ exp
In the formula above, x, y corresponds to the ratio of ZD and ZN in Percentage of PMΘ Reduction = × 100%
PMΘ cal
co-combustion. In this work, x: y were taken as 90%:10%, 70%:30%. Θ
represents the range of particles size and it represents 0.4 μm or According to Fig. 3, the mass concentration of PM10 from ZD coal
0.4–10 μm in this work. For example, PMcal represents the calculated combustion is 16.8 mg/g coal and the mass concentration of PM10 from
value of PM concentration; PMexp represents the experimental value of ZN coal combustion is 6 mg/g coal. Combining with the coal properties

208
R. Ruan et al. Fuel 211 (2018) 206–213

from Table 1, the PM10 from ZD coal combustion is 25% of the total ash
while the PM10 from ZN coal combustion is only 4% of the total ash. It
is clear that the ratio of PM10 in total ash is very high for ZD coal
combustion and the PM10+ is the main product for ZN coal combustion.
The PM0.4 mass concentration for ZD coal and ZN coal combustion is
4.1 mg/g coal and 0.6 mg/g coal. Both the experimental value of PM0.4
and PM10 for the two blending coal combustion is lower than the cor-
responding calculated value. The percentage of PM0.4 reduction for 9:1
and 7:3 blending is 32.7% and 51.7%, a little higher than the PM0.4–10
reduction percentage as 27% and 33.2%, respectively. It is obvious that
the 7:3 blending combustion is more advantageous for PM reduction
than 9:1 blending combustion. Later in this article, the characteristics of
fine particulates from high AAEM-sulfur coal and the PM reduction
during co-combustion will be discussed through the particles compo-
nents based on scanning electronic microscopy analysis.
3.2. The composition of PM10
To illustrate the fine particles formation mechanisms of high AAEM-
sulfur coal and clarify the reason of PM reduction during co-firing, the
compositions of PM10 are drawn in the form of particle size distribution
bar graph as shown in Fig. 4. The x axis represents the aerodynamic
diameter of DLPI stages.
The PM10 from ZD coal combustion is mainly consists of calcium,
magnesium, iron, sulfur, silicon and aluminum. The main components
of PM0.4 are calcium, magnesium, iron, sulfur and the mass fraction of
these elements change little with the particle size. The content of cal-
cium, silicon, aluminum in the larger particles is more than that in
PM0.4 and it is opposite for magnesium, iron and sulfur. The particle
size between 0.3 and 0.4 μm is supposed to be the boundary region of
different particle formation mechanism for ZD coal. The fine particles
from ZN coal combustion are mainly consists of calcium, magnesium,
iron and silicon. With increasing the particle size, the mass fraction of
calcium, silicon and aluminum increase significantly while iron and
magnesium decrease obviously. The mass fraction of iron in particles
smaller than 0.1 μm from ZN coal combustion is close to 50%. It is
widely believed that iron containing minerals in coal can be reduced or
decomposed to more volatile form and gasify in the strong reducing
atmosphere [22,23]. These iron vapor can condense and nuclear to be
the precursor and is one source of the ultrafine particles. The elemental
components of 9:1 blending coal combustion are similar to that of ZD
coal, indicating weak interaction between mineral matters in ZD and
ZN coal. When adding 30% ZN coal, the relationship between the
particle composition and particle size is much more different from that
of ZD and ZN coal. The mass fraction of main elements such as calcium,
magnesium, iron and silicon change little with the particle size. The
components of different size particles are close to each other. A large
number of studies have presented that the combustion products of
different coals can react with each other, which can change the char-
acteristic of the fine particulates from single coal combustion
[21,24,25]. The elemental mass fraction distribution of 7:3 blending
coal combustion in Fig. 4 (d) changes greatly compared to that of the
pure coal, indicating obvious interaction between mineral matters in ZD
and ZN coal.
During coal combustion, ultrafine particles usually generate from
the condensation and nucleation of the gasified minerals. The alkali and

100 100

80 80
Mass fraction %

Mass fraction %

60 60

40 40

20 20

0 0
53 155 382 946 2378 6642 53 155 382 946 2378 6642
91 262 613 1592 3972 91 262 613 1592 3972
(a) ZD Dp (nm) (b) ZN Dp (nm)
100 100

80 80
Mass fraction %
Mass fraction %

60 60

40 40

20 20

0 0
53 155 382 946 2378 6642 53 155 382 946 2378 6642
91 262 613 1592 3972 91 262 613 1592 3972
(c) 9:1 Dp (nm) (d) 7:3 Dp (nm)

Fe Ca K Cl S P Si Al Mg Na
Fig. 4. Element components of particulate matter on DLPI stages.

209
R. Ruan et al. Fuel 211 (2018) 206–213

27 According to the ash composition in Table 1, the content of sulfur is

ZD transition point locates
24 much less than the content of calcium, magnesium, sodium and po-
9:1 at around 0.4 ȝm
(2Ca+2Mg+Na+K)/(2S+Cl)

tassium for both ZD and ZN coal. The AAEM in ZD and ZN coal could
21 7:3
not be sulfated completely. The sulfur content in ZD is 11.32% which is
ZN
18 nearly twice of the sulfur content in ZN coal as 6.47%. Correspondingly,
Li[6]
molar ratio

15
12
9
molar ratio = 6
6 3.3. Distribution of main elements in coal combustion products
molar ratio = 3
3
molar ratio = 1
0 content regardless of the ash content. When considering the ash con-
0.1 0.4 1 10
Dp (ȝm)
Fig. 5. Size distribution of the (2Ca+2Mg+Na+K)/(2S+Cl) molar ratio.
alkaline earth metals in coal are easy to vaporize and can react with
sulfur and chlorine to form sulfate and chloride [19,26]. The size dis-
tribution of the (2Ca+2Mg+Na+K)/(2S+Cl) molar ratio in particles
for all the four blending coals are shown in Fig. 5. Comparing the dif-
ference between the molar ratio and 1, the ratio of alkali and alkaline
earth metals in the form of sulfate and chloride in particulate matter
can be inferred during combustion of different blending coals.
The variation trends of the four curves are basically same. At the
range of aerodynamic diameter smaller than 0.3–0.4 μm, the molar
ratio changes little. However, when particle size is bigger than
0.3–0.4 μm, the molar ratio begin to increase. Li [6] analysed the
composition of fine particulates generated from the combustion of a
kind of zhundong coal through SEM-eds. He found that 0.4 μm is the
transition point of (2Ca+2Mg+Na+K)/(2S+Cl) molar ratio as pre-
sented in Fig. 5. Similar to Li’s results, the molar ratio in this work also
begin to increase at around 0.4 μm, but when particle size is smaller
than 0.4 μm, the molar ratio located between 3 and 6 while the value in
Li’ research is 1. It could be inferred that there are one third to one sixth
of AAEMs in PM0.4 exists as the form of sulfate or chloride in this ex-
periment. The differences between the molar ratio from Li and this
work could be attributed to the different amount of AAEM and sulfur in
coal. The zhundong coal used in Li’s research has more sulfur than the
ZD coal used in this work as presented in Fig. 6 while the amount of
AAEM in Li’s zhundong coal is less than that in this work. The sulfation
ratio of AAEM in PM0.4 from Li’s zhundong coal is more than this work.
80
SO3 Na2O K2O MgO CaO
70
60
Ash composition %
the molar ratio of ZD coal when particle size is smaller than 0.4 μm is
approximately equal to 3, which is nearly half of that for ZN coal. Apart
from the sulfate or chloride in PM0.4, the other mineral elements mainly
exist in the form of oxide.
The ash composition data we usually used in Table 1 is the relative
tent, the net contents of mineral elements in coal are shown in Fig. 7.
Except for sodium and calcium, the net content of magnesium, iron and
sulfur in ZN coal are more than that in ZD coal by 57%, 132% and 13%,
respectively. The elements presented in Fig. 7 are all the main com-
positions of PM0.4 and there are no obvious differences in the total net
content. Fig. 7 also presents the distribution of each element in the
combustion products. For ZD coal, the proportion of elements in PM0.4
are much larger than that of ZN coal, especially for sodium, magnesium,
calcium, sulfur and iron. As for PM0.4–10, the proportion of magnesium,
calcium, sulfur and iron are obviously lager than that of ZN coal. In
conclusion, the volatile elements in ZD coal are more easier to transfer
into PM0.4 than ZN coal. Considering the net content of silicon and
aluminum in ZN coal are more than that in ZD coal by 367% and 434%
respectively, the absorption of AAEM and iron by the silicon-aluminum
species could significantly reduce the fine particles generated during ZN
coal combustion [27–30]. This can be confirmed from the mass-particle
size distribution curves in Fig. 2 or the sector region of PM0.4 and
PM0.4–10 in Fig. 7.
3.4. Effect of co-combustion on PM formation
It has been proved by many scholars that co-combustion can in-
crease the ratio of liquid phase in fly ash in case that the mixed coal has
enough AAEM, iron and aluminum-silicon compounds [21,31,32]. The
differences between the experimental value and the calculated value for
elements content in PM are presented in Fig. 8. The x axis represents
PM0.4 and PM0.4–10. The y axis represents elements in particulates. The
z axis represents the reducing percentage of the experimental contents
relative to the calculated contents in PM0.4 or PM0.4–10.
When blending ratio is 7:3, the content of sodium, magnesium,
sulfur, calcium, iron in PM0.4 are reduced to a great extent, with the
decline ratio of sodium, magnesium, sulfur and iron are more than 50%.
When the blending ratio is 9:1, the reduction of the above five elements
are all lower than that of 7:3 blending. The reaction between vaporized
elements and aluminum-silicon compounds is the main reason for the
decrease of sodium, magnesium, sulfur, calcium and iron in PM0.4
[6,18,28]. Under the 7:3 blending condition, the fuel contains more ZN
coal which is rich in aluminum-silicon compounds. This would help

50
capturing the volatile elements during coal combustion, resulting in a
more obvious PM0.4 reduction under 7:3 blending ratio. Table 2 shows
40
the experimental and calculated contents of silicon and aluminum in
30 PM0.4 and PM0.4–10. It is noted that the experimental content of silicon
and aluminum in PM0.4 and PM0.4–10 is close to the calculated value,
20 except for the PM0.4 of 7:3 blending. It indicates a more important role
of PM10+ in reducing fine particulates during the mixed coal combus-
10 tion.
Wang [24] burned two different coals in a drop tube furnace to
0 investigate the effect of coal blending on the reduction of PM10. He
this work Li[6] found that calcium, iron could form a liquid substance with silicon-
Zhundong coal aluminum compounds and the liquid phase form in co-firing can pro-
mote the transformation of calcium, iron to PM10+. According the
Fig. 6. Comparison of AAEM and sulfur content in two kinds of zhundong coal.
above discussion, the formation mechanisms of fine particulates

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R. Ruan et al. Fuel 211 (2018) 206–213

1.4% 2.86% 0.21% 5.06% 12.64% 1.15% 2.08%

Fig. 7. Elements distribution in combustion
19.99% products.

Na : 3.83mg/g ZD coal Na : 1.75mg/g ZN coal Mg : 3.37mg/g ZD coal Mg : 5.32mg/g ZN coal

95.74% 94.73% 67.37% 96.76%

3.26% 0.44% 4.92% 9.66% 1.42% 5.01%

19.55% 10.26%

Ca : 24.70mg/g ZD coal Ca : 16.77mg/g ZN coal Fe : 4.77mg/g ZD coal Fe : 11.09mg/g ZN coal

77.19% 94.64% 80.08% 93.57%

8.59% 0.52% 1.08%

8.54%

S : 4.47mg/g ZD coal S : 5.07mg/g ZN coal PM0.4

PM0.4 -10
PM10+
Flue gas & PM10+
82.87% 98.4%

generated from high AAEM-sulfur coal are presented in Fig. 9. Table 2

Sodium [11,26], magnesium [18], calcium [18,33], iron [22,23] The calculated and experimental amount of Al and Si in PM0.4 and PM0.4–10 under 7:3 and
will vaporize in different degree and then nucleate or condensate to 9:1 coal blends.

form fine particles during coal combustion which are the main com- (μg/g coal)
ponents of PM0.4. Most of the silicon-aluminum species and the mi-
nerals (included or excluded) will decompose or fragment into PM1+ or Coal blend Elements PM0.4cal PM0.4exp PM0.4–10cal PM0.4–10exp
PM10+ [10,12]. When the content of sulfur in coal is high such as the
7:3 Al 56 21 752 624
ZD coal used in this work, a large number of the alkali and alkaline Si 103 145 1042 1025
earth metals will be sulfated [6,34], leading to the increase of PM0.4. In 9:1 Al 62 59 802 647
the case of co-combustion with high aluminum-silicon coal such as the Si 82 67 1041 933
ZN coal in this work, the aluminum-silicon compounds in PM10+ can
form liquid phase [18,35] or eutectic compounds [31,32] with iron and cal: calculated value, exp: experimental value.

Fig. 8. Reduction ratio of main elements content in PM at 7:3 and 9:1 coal blends.

211
R. Ruan et al. Fuel 211 (2018) 206–213

Si-Al-Fe-Ca-Na-Mg
(l,s)
Decomposition PM 10+ (s)
Fragmentation Si-Al (g,s)

Gasification Fe (g,s)
Decomposition PM 0.4-10 (s)
Condensation
Nucleation
SO 2 (g) SO 2 (g) SO 2 (g)
CaSO4
Coal particles Coagulation
Ca (g,s) Sulfation Na2SO 4 (g,s)
Aggregation
MgSO4 PM 0.4 (s)

Na, Mg (g,s)

PM formation
Fig. 9. PM formation mechanisms during coal combustion of high content AAEM-sulfur coal.

AAEM to capture PM0.4 and PM0.4–10, resulting in the decrease of fine
particulates in co-combustion. The decease of AAEM in PM0.4 will re-
duce the amount of sulfur in fine particles due to the reduction of
sulfation site [6,34].
4. Conclusions
1) The ZD lignite is rich in AAEM (alkali and alkaline earth metals) and
sulfur. The sulfate and oxide of AAEM are the main component of
PM0.4 generated from ZD coal combustion. The mass fraction of
calcium and magnesium are highest in PM0.4. With the increase of
particle size, the mass fractions of magnesium and sulfur decrease
significantly while the contents of aluminum and silicon increase
obviously. ZN coal is rich in aluminum and silicon. The amount of
PM0.4 from ZN coal combustion is less than that from ZD coal. The
contents of silicon and iron in PM0.4 from ZN coal are more than that
from ZD coal.
2) The co-combustion of high AAEM-sulfur coal and high aluminum-
silicon coal can reduce PM0.4 significantly. The capture of AAEM
from ZD coal by aluminum-silicon compounds from ZN coal plays an
important role in PM0.4 reduction. The low melting point eutectic
compounds formation in the presence of AAEM, iron, and alu-
minum-silicon compounds promotes the transformation of PM0.4
and PM0.4–10 to PM10+.
3) 0.4 μm is the transition point of particle composition. PM0.4 is rich
in sulfate while PM0.4–10 is rich in aluminum-silicon compounds.
During co-combustion of ZD coal and ZN coal, the change of sulfur
content in PM0.4 is consistent with the change of AAEM content in
PM0.4.
Acknowledgement
This study was supported by the National Natural Science
Foundation of China (No. 91544108, No. 51376147, No. 51676157).
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