Effects of coal blending on the reduction of PM

10
during high-temperature
combustion 1. Mineral transformations
Qunying Wang
a
, Lian Zhang
b
, Atsushi Sato
a
, Yoshihiko Ninomiya
a,
*
, Toru Yamashita
c
a
Department of Applied Chemistry, Chubu University, 1200 Matsumoto-cho, Kasugai, Aichi 487-8501, Japan
b
Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8569, Japan
c
Coal and Environment Research Laboratory, Industrial Energy Department, Idemitsu Kosan Co. Ltd., Chiba 299-0267, Japan
a r t i c l e i n f o
Article history:
Received 22 August 2007
Received in revised form 26 December 2007
Accepted 21 April 2008
Available online 16 May 2008
Keywords:
Coal blending
Coal combustion
PM
10
Mineral transformation
a b s t r a c t
Two coals with comparable mineral particle distributions, but different contents of Ca were blended and
combusted. Mineral transformations and their effects on particulate matter smaller than 10 lm (PM
10
)
emissions were investigated during the combustion of single and blended coals. Combustion experiments
were carried out at 1450 C in air atmosphere using a lab-scale drop tube furnace (DTF). The particle size
distributions (PSD), morphologies, elemental compositions, and chemical composition of minerals in coal
and PM were analyzed. The results indicate that emissions of PM smaller than 1 lm (PM
1
) and particulate
matter sized between 1 and 10 lm (PM
110
) are reduced compared to their calculated linear results dur-
ing combustion. The transformation of P, S, Al, and Si from submicron particles to PM larger than 1 lm
(PM
1+
) reduces PM
1
emissions. The transformation of Ca, Fe, Al, and Si from PM
10
to particles larger than
10 lm (PM
10+
) reduce PM
110
emissions. The high concentration of Ca in coal blends enhances the liquid
phase percentage produced during combustion, and as a result, improves both the adhesion of volatilized
P, S, Al, and Si on the sticky surface of large particles to be transformed to PM
1+
, and the probability of
collision and coalescence of particles to form larger particles of CaFeAlSi, CaAlSi, or FeAlSi. Thus,
as Ca, Fe, Al, and Si are transformed into PM
10+
. PM
1
and PM
110
emissions are reduced accordingly.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
PM
10
released fromcoal combustion causes serious air pollution
problems and adverse heath effects [1-3]. Adverse health effects
are a function of particle size, chemical compositions, and PM con-
centrations [4-6].
In order to reduce PM
10
emissions from coal-red plants, mech-
anisms governing PM formation during coal combustion have been
studied extensively. The literature suggests that PM formed during
coal combustion be classied into three typical fractions according
to its size [2,3,7]. The smallest fraction is termed PM
1
, which is
formed from vaporization and the subsequent nucleation and
accumulation of material. The concentration of PM
1
is approxi-
mately 1 wt.% of the total coal mineral. The main factors that deter-
mine PM
1
emission are coal rank, coal type, coal particle size,
oxygen content, and the coal mineral content. Despite signicant
variance in the elemental composition of coal, the main constitu-
ents in PM
1
are S, Si, P, and Na [5,7-8]. The second fraction is
termed PM
12.5
, for particles sized from 1.0 to 2.5 lm. PM
12.5
is
formed from the liberation of ne minerals during fragmentation
and burnout [9]. The third fraction is termed PM
2.510
, for particles
sized from 2.5 to 10 lm, and is formed from the collision and coa-
lescence of coarse minerals present in the solid or liquid phase
throughout combustion. Previous studies suggest that PM
12.5
and PM
2.510
have similar compositions of Ca, Fe, Al, and Si, which
indicate the same formation mechanisms, and therefore are to-
gether referred to as PM
110
[10,11]. In addition, interactions of
Ca-species, Fe-species, and AlSi-species in coals affect the subse-
quent emissions of PM
110
. Clay and quartz minerals completely or
partially fuse to form viscous melt particles at high temperature,
and can react with Ca-species. The melting PM in the viscous ow
can collide with other PM and also can encounter vapor condensa-
tion [12-14].
Coal blending is a ubiquitous technique used by many coal-red
power plants to reduce PM emissions [12,15]. Mechanisms for PM
formation during single coal combustion have been studied exten-
sively; however, the mechanisms that govern the formation of PM
1
and PM
110
during the combustion of coal blends are poorly under-
stood. The emission behavior of a coal blend is not a linear function
of the emission behavior of its constituent coal, and therefore, the
combustion results of blending coals are difcult to predict. Fur-
ther research on the experimental and theoretical work of blended
coal combustion is required if more instructive information is to be
understood [12,15].
0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.04.013
* Corresponding author. Tel.: +81 568 51 9178; fax: +81 568 51 1499.
E-mail address: ninomiya@isc.chubu.ac.jp (Y. Ninomiya).
Fuel 87 (2008) 29973005
Contents lists available at ScienceDirect
Fuel
j our nal homepage: www. f uel r st . com
Our previous studies suggest that the combustion of coal with
different properties yield different PM
10
emissions. In particular,
coal with high concentrations of Ca and/or Fe-species produce
low PM
10
emissions [13,14]. Therefore, combustion of coal blends
with different properties can produce different amounts of PM
10
emissions [15].
In this study, two coals with comparable ranks and different Ca-
species concentration are blended and combusted in air at 1450 C.
This paper aims to study the transformation behaviors among Ca-
species, Fe-species and AlSi-species and their effects on PM
1
and
PM
110
emissions formed during combustion of coal blends.
According to the experimental results, a coalescence-fragmenta-
tion model will be described in a second paper [16]. The modeled
interactions among different minerals and their effects on the for-
mation of PM will be discussed there.
2. Experimental
2.1. Coal preparation and analysis
Two parent coals A and B are ground to less than 100 lm in size.
Prior to combustion, two coals are dried for more than 24 h and
then blended by a rolling blender to form coal A to coal B weight
percents (wt.%) of 5/95, 10/90, 20/80, 30/70, 40/60, and 60/40.
Proximate and ultimate analyses of raw coals are carried out accor-
dance to American Society for Testing and Materials (ASTM) stan-
dards. Elemental composition of low temperature ashes (LTA) of
single and blended coals is determined by X-ray uorescence spec-
trometry (XRF, REGAKU 2100 equipment). LTAs are obtained with
an oxygen plasma reactor (YAMATO PR 300). Computer-controlled
scanning electron microscopy (CCSEM, JEOL JSM-5600) is used to
quantify mineral phases in the coals. The analysis procedure of coal
minerals with CCSEM is described in [17-18].
2.2. Combustion setup and PM collection
Single and blended coal samples are combusted in a lab-scale
drop tube furnace. Combustion temperature is 1450 C. A sche-
matic diagram of the drop tube furnace is described in [17]. Feed-
ing rate of fuels is about 1012 g/h. Residence time of particles in
the combustion zone is about 3 sec. Total airow is 11.5 l/min. Car-
bon is completely combusted under the combustion conditions.
PM samples are collected with a rapid dilution probe rod. The
probe rod is designed not only for collecting the particles but also
for quickly quenching and diluting the particle stream with pure
nitrogen to minimize oxidation as well as particleparticle interac-
tion, and to force the nucleation of vaporized material. A cyclone is
placed on the bottom of the probe rod. The sample particles and
nitrogen are pulled through the probe rod by a vacuum pump con-
nected to a low-pressure impactor (LPI). Almost all PM larger than
3 lm are collected by the cyclone. PM smaller than 3 lm is cap-
tured by the LPI that segregates PM according to their aerodynamic
diameter in the range of 0.0312.1 lm [11,13].
2.3. PM characterization
The size distribution of PM collected in the cyclone is deter-
mined with a laser particle analyzer. The size distribution of ne
PM collected by different Teon lters placed in LPI is combined
with the size distribution of the coarse PM collected by the cyclone
to obtain a total size distribution of total PM. The PM elemental
composition is analyzed by XRF. Scanning electronic microscopy
(SEM: JEOL JSM-5600) with energy dispersive X-ray (EDX) is used
to analyze particle morphology and chemical composition. High-
resolution transmission electron microscopy (HRTEM, JEM2100F,
JEOL) coupled with energy dispersive X-ray spectroscopy (EDX) is
used to characterize the morphology and the chemical composi-
tion of ne particles in PM
110
. The TEM grid is directly placed on
the desired stage of LPI during combustion to collect the PM
110
within 5 min. Particles are observed and analyzed after being dried
in a vacuum chamber [13-14,19]. The mineral composition of PM
1+
is determined by CCSEM [20]. The characterization method for
minerals in PM
1+
using CCSEM is the same as that of coals, de-
scribed in our previous work [11,13,17].
To quantify the distributions of elements in coal minerals and
PM, a novel mineral category has been developed and is listed in
Table 1. The category is developed based on the wt.% of elements
in coal mineral particles or in PM as determined by CCSEM [19-
Table 1
Mineral categories used in this study
Number Category Density Criteria, wt.% (Based on CCSEM analytic results)
1 SiAl 2.60 Si > 5, Al > 5, Ca 6 3, Fe 6 3, Na 6 3, K 6 3
2 Si-rich 2.65 Si > 15, Al 6 5, Ca 6 3, Fe 6 3
3 Ca-rich 2.80 Si 6 5, Al 6 5, Ca > 15, Fe 6 3, P 6 3, S 6 3
4 CaP 3.20 Si 6 5, Al 6 5, Ca > 5, Fe 6 3, P > 5, S 6 3
5 CaSi 3.09 Si > 5, Al 6 5, Ca > 5, Fe 6 3, P > 3, S 6 3
6 CaS 2.50 Si 6 5, Al 6 5, Ca > 5, Fe 6 3, P 6 3, S > 5
7 CaAlSi 2.65 Si > 5, Al > 5, Ca > 3, Fe 6 3, P 6 3, S 6 3
8 CaPAlSi 2.65 Si > 5, Al > 5, Ca > 3, Fe 6 3, P > 3, S 6 3
9 CaSAlSi 2.65 Si > 5, Al > 5, Ca > 3, Fe 6 3, P 6 3, S > 3
10 FeS 5.00 Si 6 5, Al 6 5, Ca 6 3, Fe > 5, P 6 3, S > 5
11 Fe-rich 5.30 Si 6 5, Al 6 5, Ca 6 3, Fe > 15, P 6 3, S 6 3
12 FeSi 4.40 Si > 5, Al 6 5, Ca 6 3, Fe > 5, S 6 3
13 FeAlSi 2.80 Si > 5, Al > 5, Ca 6 3, Fe > 3, P 6 3, S 6 3
14 FeSAlSi 2.80 Si > 5, Al > 5, Ca 6 3, Fe > 3, P 6 3, S > 3
15 FePAlSi 2.80 Si > 5, Al > 5, Ca 6 3, Fe > 3, P > 3, S 6 3
16 CaFeAlSi 2.65 Si > 5, Al > 5, Ca > 3, Fe > 3, P 6 3, S 6 3
17 CaFePAlSi 2.65 Si > 5, Al > 5, Ca > 3, Fe > 3, P > 3, S 6 3
18 CaFeSAlSi 2.65 Si > 5, Al > 5, Ca > 3, Fe > 3, P 6 3, S > 3
19 CaFe 3.00 Si 6 5, Al 6 5, Ca > 5, Fe > 5
20 Na/KAlSi 2.60 Si > 5, Al > 5, Ca 6 3, Fe 6 3, Na > 3 or K > 3
21 Al-rich 4.00 Si 6 5, Al > 15, Ca 6 3, Fe 6 3
22 Na/KCl 1.99 Al 6 5, Ca 6 3, Fe 6 3, Na > 3 or K > 3, Cl > 3
23 CaPSi 3.09 Si > 5, Al 6 5, Ca > 5, P > 5, Ca + P + Si > 30
24 FeSSi 4.40 Si > 5, Al 6 5, Fe > 5, S > 5, Fe + S + Si > 30
25 CaSSi 3.09 Si > 5, Al 6 5, Ca > 5,S > 5, Ca + S + Si > 30
2998 Q. Wang et al. / Fuel 87 (2008) 29973005
21]. In addition to Si, Al, Ca, Fe, Na, and K, elements S, Cl, and P are
also considered in this classication.
2.4. Thermodynamic equilibrium calculations
To predict the fusibility of single and blended coals during com-
bustion, thermodynamic equilibrium calculations are performed
using the computer program FactSage 5.2 with thermodynamic
data taken from the FACT databases [22-24]. Real-gas, non-ideal li-
quid and solid solution models are included. C, H, O, N, SiO
2
, Al
2
O
3
,
CaO, Fe
2
O
3
, Na
2
O, K
2
O, P
2
O
5
, SO
3
, MgO, and TiO
2
in single origin
and coal blend minerals are considered in the equilibrium calcula-
tions. The calculations are performed simulating global fully-oxi-
dizing conditions (i.e. air-to-fuel 1.35) in a furnace under 1 atm.
The proportion of liquid phase produced is evaluated at the exper-
imental temperature of 1450 C.
3. Results and discussion
3.1. Coal properties
The proximate, ultimate and elemental analytic results of coal
minerals are listed in Table 1. The fuel ratio of coals A and B are
1.93 and 2.21, respectively. The content of CaO in the LTAs of the
two coals vary signicantly, with concentration in the minerals
of coals A and B being 15.0 wt.% and 1.43 wt.%, respectively. The
content of Fe
2
O
3
in the minerals of coals A and B is 9.15 wt.% and
6.4 wt.%, respectively. The weight percentage of Al
2
O
3
, SiO
2
, CaO,
and Fe
2
O
3
in the minerals of each single origin and coal blend is
plotted in Fig. 1.
The calculated results (Calc.) in Fig. 1 are calculated from Eq.
(1):
Calc:
W
coalA
C
coalA
W
coalB
C
coalB
100
1
where W is the wt.% of the coal in the coal blend and C is the wt.% of
Al
2
O
3
, SiO
2
, CaO, or Fe
2
O
3
in LTA of the coal.
The experimental results of Al
2
O
3
, SiO
2
, CaO, and Fe
2
O
3
match
their corresponding calculations, which demonstrate the uniform
distributions of minerals in the coal blend.
The analysis of the physical and chemical properties of minerals
in two coals is shown in Fig. 2. Fig. 2a provides total, included, and
excluded mineral distributions. Results show that the included
minerals sized less than 10 lm are comparable. The mineral com-
position of two coals is summarized in Fig. 2b. In coal A, substantial
SiAl and Si-rich compounds are present, in addition to Ca-rich and
CaP compounds that account for 20 wt.% of the composition. Sim-
ilarly, coal B has SiAl and Si-rich compounds that account for
90 wt.% of the composition. FeS and FeAlSi are present in both
coals.
3.2. Characterization of PM collected from single coal combustion
PM samples collected by the cyclone during single coal combus-
tion are analyzed by SEMEDX. Their physical and chemical prop-
erties are summarized in Fig. 3. Particles formed from coal A are
coarse and sticky, and are characterized by stretch, fracture, and
shape-related irregularities, indicating that these particles develop
from ne particles (<10 lm) sticking to the surface of coarse parti-
cles (>10 lm), or from the separate agglomeration by several ne
particles (<10 lm), as shown in Fig. 3a. Particles formed from the
Ca-poor coal B are characterized by discrete spheres with smooth
surfaces derived from the liquid phase, as shown in Fig 3b. The
morphological differences between the two kinds of PM are attrib-
uted to Ca content, since the presence of Ca is the only difference
between coals A and B, as shown in Fig. 3c. The total size distribu-
tion of the PM produced from coals A and B is shown in Fig. 3d. The
amount of coarse particles produced from coal A is much higher
than that from coal B, which is consistent with observations from
SEM.
3.3. Characterization of PM collected from coal blend combustion
Fig. 4 provides a comparison of PM PSDs generated by the com-
bustion of coal blends with their calculated linear results. The lin-
ear results are calculated by Eq. (2):
0 20 40 60 80 100
0
20
40
60
w
t
%
,

o
n

m
i
n
e
r
a
l

b
a
s
i
s
A/(A+B) x100,wt%
Al2O
3
SiO
2
CaO
Fe
2
O
3
Calc.SiO
2
Calc.Al
2
O
3
Calc.CaO
Calc.Fe
2
O
3
Fig. 1. Weight percentage of Al
2
O
3
, SiO
2
, CaO, and Fe
2
O
3
in the minerals of each
single origin and coal blend.
1 10 100
0
20
40
60
80
100
w
t
%
,

o
n

m
i
n
e
r
a
l

b
a
s
i
s
Particle size/m
Total in A
Incl. A
Excl. A
Total in B
Incl. B
Excl. B
a
S
i
-
A
l
S
i
-
r
i
c
h
C
a
-
r
i
c
h
C
a
-
P
C
a
-
P
-
A
l
-
S
i
F
e
-
S
F
e
-
A
l
-
S
i
N
a
/
K
-
A
l
-
S
i
0
20
40
60
80
100
Excl. in B
Incl. in B
Excl. in A
w
t
%
,

o
n

m
i
n
e
r
a
l

b
a
s
i
s
Incl. in A
b
Fig. 2. Physical and chemical properties of minerals in two coals. (a) Total, included,
and excluded mineral distributions; (b) mineral composition of two coals.
Q. Wang et al. / Fuel 87 (2008) 29973005 2999
Na Mg Al Si P K Ca Ti Fe
0
20
40
60
w
t
%
coal A
coal B
1 10 100
0
20
40
60
80
100
w
t
%
Particle size/m
Coal A
Coal B
Coal A Coal B
10m 10m
a
c d
b
Fig. 3. Physical and chemical properties of PM collected during single coal combustion. (a) SEM image of PM formed from coal A; (b) SEM image of PM formed from coal B; (c)
elemental composition of PM produced from coals A and B; (d) total size distribution of PM produced from coals A and B.
1 10 100
0
20
40
60
80
100
Experimental 10/90
W
e
i
g
h
t

p
e
r
c
e
n
t
a
g
e

o
f

P
M
,

%
Particle size/m
Calc. 10/90
1 10 100
0
20
40
60
80
100
Experimental 20/80
W
e
i
g
h
t

p
e
r
c
e
n
t
a
g
e

o
f

P
M
,

%
Particle size/m
Calc. 20/80
1 10 100
0
20
40
60
80
100
Experimental 40/60
W
e
i
g
h
t

p
e
r
c
e
n
t
a
g
e

o
f

P
M
,
%
Particle size/m
Calc. 40/60
1 10 100
0
20
40
60
80
100
Experimental 60/40
W
e
i
g
h
t

p
e
r
c
e
n
t
a
g
e

o
f

P
M
,

%
Particle size/m
Calc. 60/40
Fig. 4. A comparison of PM PSDs generated by the combustion of coal blends with their calculated linear results.
3000 Q. Wang et al. / Fuel 87 (2008) 29973005
Calc:
W
coalA
FR
a;coalA
W
coalB
FR
a;coalB
100
; 2
where Calc. is the calculated value of PM, W is the weight fraction of
coal in coal blends, FR is the wt.% of PM fractions generated during
combustion of the parent coals, based on the total PM generated
and a is the particle size: 1 lm or 10 lm.
Fig. 4 indicates that the experimental PSD of 10/90 is compara-
ble with its calculated value. In contrast, the experimental PSDs
generated during the combustion of coal blends of 20/80, 40/60
and 60/40 differ substantially from their calculated ones, indicat-
ing that the size distributions of the produced PM are not linearly
related to the weight percentage of coal A in the coal blend. More-
over, as concentration of coal A in the coal blend increases, the par-
ticle size of the resultant PM increases.
The amounts of PM
1
, PM
110
and PM
10+
generated by single and
blended coal are measured, respectively, and compared with their
corresponding calculated ones, as shown in Fig. 5. With increasing
concentration of coal A in the blended coals, the emissions of both
PM
1
and PM
110
are reduced compared to their calculated linear re-
sults. For the combustion of coal blends of 40/60 or 60/40, about
30 wt.% of PM
1
and 50 wt.% of PM
110
are reduced and transformed
into larger fractions. Unfortunately, as the concentration of coal A
further increases in coal blends, the emissions of PM
1
and PM
110
increase. Coal A contains the highest concentration of Ca among
all samples. The combustion of coal A produces 22 wt.% of PM
1
10
, which is greater than the 16 wt.% of PM
110
produced from coal
blends of 40/60 or 60/40. Clearly the content of Ca in coal blends
affects the emissions of PM
110
; however, the emissions of
PM
110
are also inuenced by other factors.
Some studies suggest that the liquid phase concentration acts as
a glue in PM formation, and therefore affects the emissions of
PM
110
[22,23,25-27]. Fig. 6a provides the predicted liquid percent-
age depending on the oxide components in the minerals of single
origin and coal blends. The transformation rate of minerals (mainly
referring to clay and kaolinite) from solid to liquid is much shorter
if the local temperature is high enough [12,28]. This is demon-
strated by the SEM images of PM shown in Fig. 3 and Fig. 12 of this
study. These gures provide the shape-related structure formed
from liquid or partial liquid phase. Liquid phase is produced
despite the short residence time (about 3 s). Thermodynamic equi-
librium calculations provide a means for predicting the trends of
the liquid phases production [22,25]. Near the experimental tem-
perature, the order of decreasing liquid content as a function of
coal composition is
coal B < 10=90 < 20=80 < coal A < 40=60 60=40;
which is opposite to the PM
110
emission magnitude. PM
110
de-
creases with increasing content of liquid phase, as shown in Fig.
6b. PM
1
decreases with increasing liquid concentration, except for
coal A, as shown in Fig. 6b. Since S and P are the primary contribu-
tors to the formation of PM
1
[7], the high concentration of PM
1
pro-
duced from coal A may be partially attributed to the high amount of
S and P in the raw coal A, as detailed in Table 2. Based on these re-
sults, the formation of PM
1
can be explained by competing pro-
cesses. The condensation of vapors and the subsequent
accumulation into PM
1
competes with the adhesion of vapors by
the larger liquid particles to prevent the formation of PM
1
. For coal
A, the condensation process is dominant and hence results in high
concentrations of PM
1
emissions.
3.4. Effects of coal blending on the reduction of PM
1
Several studies suggest that PM
1
is primarily formed through
vaporization and condensation (<0.5 lm), together with subse-
0 20 40 60 80 100
1
10
100
Experimental PM1
Experimental PM10
w
e
i
g
h
t

p
e
r
c
e
n
t
a
g
e

o
f

P
M
A/(A+B)X100, wt%
Calc. PM10
Calc.PM1
PM10+
PM1-10
PM1
Part b
Part a
Fig. 5. A comparison of experimentally measured amounts of PM
1
, PM
110
, and
PM
10
generated by single and blended coal with their corresponding calculated
ones. Part a: transformation from PM
1
to PM
1+
; part b: transformation from PM
110
to PM
10+
.
1200 1400 1600
0
20
40
60
80
100
w
t
%

o
f

l
i
q
u
i
d

p
h
a
s
e
Temperature/
o
C
Coal B
10/90
20/80
40/60
60/40
Coal A
0 20 40 60 80 100
1
10
100
PM1-10
PM1
w
t
%

o
f

P
M

Predicted liquid content, wt%
A
B
10/90
20/80
40/60
60/40
A
a
b
Fig. 6. Predicted liquid percentage in the minerals of single and blended coals (a); relationship between predicted liquid percentage and the emissions of PM
1
and PM
110
at
1450 C (b).
Q. Wang et al. / Fuel 87 (2008) 29973005 3001
quent growth by accumulation on the surface of existing particles
(0.51.0 lm) [5,29]. Therefore, the reduction of PM
1
can be attrib-
uted to the transformation of volatilized vapors. Fig. 7 compares
the concentration of elements in PM
1
generated by coal blends of
10/90 and 40/60 to their calculated linear results. The elemental
compositions of 10/90 blends are comparable with their calculated
results. For the coal blend of 40/60, elements S, P, Si, and Al are re-
duced compared to their calculated results. Elements Ca, Na, and K
are reduced to a lesser extent. Therefore, the reduction of these ele-
ments correlates with the reduction of PM
1
. The transformations of
the aforementioned elemental vapors reduce PM
1
during
combustion.
P primarily exists as an included apatite in coal,
CaF
2
3Ca(PO
3
)
2
, which is expressed as CaP in this study. When
heating apatite with C under reduction conditions, part of the P
is volatilized [25].
CaF
2
3CaPO
3

2
10C !CaF
2
" 4P " 10CO " Ca
3
PO
4

2
: 3
Through the boundary layer surrounding the char, P can be oxi-
dized by excess oxygen to form P
2
O
5
.
2P 2:5O
2
!P
2
O
5
: 4
The condensable P
2
O
5
deposits or condenses to accumulate on
the sticky surface of CaAlSi or FeAlSi, which is conrmed by
the micrographs in Fig. 8a and d. Fig. 8a shows the deposition of
P on the sticky surface of CaAlSi. Fig. 8d shows the condensation
and accumulation of vapors, including the vapor of P on the surface
of FeAlSi. Moreover, P
2
O
5
vapor can also adhere to the sticky sur-
face of CaO to form CaO P
2
O
5
with a melting point of 980 C,
which acts as a glue for sticking submicron coarse particles of
CaAlSi and FeAlSi during the collisions of particles, growing
into PM
110
or larger [25]. This is conrmed by the micrograph in
Fig. 8b, which indicates that the sticky Ca and P act as a bridge
to connect CaAlSi with FeAlSi to form large particles.
In addition, the reduction of volatilized Si, Al, Na, Ca, and Fe de-
creases PM
1
. Some studies suggest the vapors are produced by
reaction (5) under localized reducing conditions [2,8].
MO
2
CO ()MO " CO
2
: 5
The reduced PM
1
is partially attributed to the reduction of the
above sub-oxide vapors. Sub-oxide vapors are supposed to be oxi-
dized by excess O
2
in the bulk gas, and subsequently condense,
coagulate and accumulate on the sticky surface of super-micron
particles with a larger area/volume ratio to be nally transformed
into PM
110
, with morphologies comparable to Fig. 8c and d. Addi-
tionally, S is also a primary component of above vapors and can be
captured by the larger particles.
Table 2
Properties of coals
Analysis Coal A Coal B
Proximate analysis (wt.% ad)
Moisture 4.5 5.2
Ash 12.0 9.5
Volatile matter 28.5 26.6
Fixed carbon 55.0 58.7
Fuel ratio 1.93 2.21
Ultimate analysis (wt.%, daf)
Carbon 83.29 84.54
Hydrogen 4.96 5.00
Nitrogen 1.96 1.94
Sulfur 0.99 0.69
Oxygen (by difference) 8.80 7.83
Chlorine 0.0697 0.056
Lower heating value (MJ/kg) 28.18 29.11
Major ash components (wt.%, dry)
SiO
2
40.71 49.80
Al
2
O
3
25.51 36.40
CaO 15.00 1.43
Fe
2
O
3
9.15 6.4
MgO 1.0 0.34
Na
2
O 0.42 0.58
K
2
O 0.48 0.76
MnO 0.11 0.06
TiO
2
1.30 1.32
ZnO 0.00 0.16
P
2
O
5
2.85 0.83
SO
3
3.31 1.57
Si Al Ca FeMg Ti Na K P S Cr Mn Ni
0.0
0.2
0.4
0.6
0.8
1.0
CoalA/Coal B=40/60
w
t
%

o
f

e
l
e
m
e
n
t
Si Al Ca FeMg Ti Na K P S Cr Mn Ni
0.0
0.2
0.4
0.6
0.8
1.0
w
t
%

o
f

e
l
e
m
e
n
t
Calc.
Experimental
Coal A/Coal B=10/90
a
b
Fig. 7. A comparison of the concentration of elements in PM
1
generated by coal
blends of 10/90 and 40/60 to their calculated linear results.
P 23%
Si 12%
S 6 %
Na 8%
Fe-Al-Si
Ca 43% , P 6.8%
Fe-Al-Si
Ca-Al-Si
a b
d c
10m 1m
2m
0.5m
Al 13%
Si 25%
Ca 19 %
Fe 3.5%
P 5.8%
Al-Si
Na 18%
S 27%
K 11 %
Fe 13%
P 16%
Fig. 8. SEMimages of particles in PM
1+
formed from the combustion of coal blend of
40/60.
3002 Q. Wang et al. / Fuel 87 (2008) 29973005
Fig. 9a summarizes the effects of coal blending on the wt.% of P,
S, Al, and Si in PM
1+
. The wt.% of the elements in PM
1+
can be cal-
culated by Eq. (6):
wt:% of interested element in PM
1
100
amounts of the element in PM
1
total amounts of the element in coal minerals
100: 6
The results show that as the wt.% of coal A in coal blends is ini-
tially increased, the wt.% of P, S, Al, and Si in PM
1+
increases. How-
ever, with further increases in the concentration of coal A, the wt.%
of these elements decreases. Higher concentrations of Ca in coal
blends increase the concentration of elements in PM
1+
. For coal A
with the highest concentration of Ca at 15 wt.%, high concentra-
tions of P and S remain as PM
1
and are not transformed to PM
1+
.
Fig. 9b indicates that an increased concentration of liquid phase in-
creases the concentration of P, S, Al, and Si in PM
1+
. The increased
concentration of liquid phase captures more vaporized elements,
and thus PM
1
emissions are reduced accordingly.
3.5. Effects of coal blending on the reduction of PM
110
Fig. 10 compares the experimentally measured concentration of
elements in PM
110
produced from coal blends of 10/90 and 40/60
to their calculated linear results. PM
110
contains high amounts of
Ca, Fe, Al, and Si, and lowamounts of Na, K, P, and S. For coal blends
of 10/90, the calculated results are comparable with the experi-
mental results. Ca, Fe, Al, and Si are signicantly decreased in
PM
110
produced from coal blends of 40/60 in the experimental re-
sults compared to the calculated linear results. Thus, reducing
these elements reduces PM
110
.
Fig. 11 compares the mineral species in PM
10+
produced by the
combustion of single and blended coal. The classication criteria
for the mineral species shown in Fig. 11 are listed in Table 1. The
mineral species in PM
10+
produced from coal blends of 10/90 are
comparable to those formed by coal B combustion. In contrast,
the mineral species in PM
10+
produced from coal blends of 40/60
differ from that of coal A. The CaFeAlSi concentration is
30 wt.% in PM
10+
produced from coal blends of 40/60, but is less
than 10 wt.% in coal A. The results indicate that the reducing con-
centrations of Ca, Fe, Al, and Si are transformed into PM
10+
as the
compound CaFeAlSi during the combustion of coal blend 40/
60. Hence, the concentration of PM
110
is deceased. The morphol-
ogy of the Ca, Fe, Al, and Si in PM
10+
is shown in Fig. 12. Fig. 12a
shows the PM
10+
is agglomerated ne particles of CaAlSi or
FeAlSi particles, or, as shown in Fig. 12b, several ne Ca-rich
or CaAlSi particles adhering to large SiAl particles. These parti-
cles derive from the liquid or partial liquid phase according to the
shape-related structure. Therefore, the collision of primary parti-
cles and their subsequent coalescence is a reasonable agglomera-
tion route for particle growth.
0 20 40 60 80 100
30
40
50
60
70
80
90
100
P
S
Al
Si
W
t
%

o
f

e
l
e
m
e
n
t

i
n

P
M
1
+
A/(A+B) x100, wt%
20 40 60 80
0
20
40
60
80
100
P
S
Al
Si
W
t
%

o
f

e
l
e
m
e
n
t

i
n

P
M
1
+
Liquid content, wt%
a
b
Fig. 9. Effects of coal blending on the wt.% of P, S, Al and Si in PM
1+
(a); and effects of an increased concentration of liquid phase on the concentration of P, S, Al, and Si in
PM
1+
(b).
Si Al Ca Fe Mg Ti Na K P S
0
3
6
9
12
15
Coal A/Coal B=40/60
w
t
%
o
f

e
l
e
m
e
n
t
Si Al Ca Fe Mg Ti Na K P S
0
3
6
9
12
15
Calc.
Experimental
w
t
%
o
f

e
l
e
m
e
n
t
Coal A/Coal B=10/90
a
b
Fig. 10. A comparison of the experimentally measured concentration of elements in
PM
110
produced from coal blends of 10/90 and 40/60 to their calculated linear
results.
Q. Wang et al. / Fuel 87 (2008) 29973005 3003
Fig. 13a shows the transformation tendencies of Ca, Fe, Al, and
Si from PM
10
to PM
10+
with the increasing wt.% of coal A in coal
blends. The elemental wt.% in PM
10+
can be calculated by Eq. (7).
wt:% of interested element in PM
10
100
amounts of the element in PM
10
total amounts of the element in coal minerals
100: 7
The results show that the transformation concentrations of Ca,
Fe, Al, and Si from PM
10
into PM
10+
increase with increasing con-
centration of coal A in coal blends initially but decrease with fur-
ther increasing concentration of coal A. The transformed Ca, Fe,
Al, and Si are illustrated in Fig. 12 as agglomerations of CaFe
AlSi in PM
10+
. Fig. 13b shows transformation trends of Ca, Fe, Al,
and Si from PM
10
to PM
10+
with increasing liquid percentage calcu-
lated at 1450 C. A high concentration of liquid phase transforms
elements from PM
10
to PM
10+
, and PM
110
is reduced accordingly.
For coal A with the highest concentration of Ca, the elemental
transformation concentrations are lower than those coal blends
of 40/60 and 60/40. The explanation for this behavior is that the
Al and Si concentrations in coal A are insufcient to maximize
the liquid content, superseding the benets of high Ca
concentration.
Si-Al
Si-rich
Ca-rich
Ca-P
Ca-Si
Ca-S
Ca-Al-Si
Ca-P-Al-Si
Fe-rich
Fe-Al-Si
Fe-P-Al-Si
Ca-Fe-Al-Si
Ca-Fe-P-Al-Si
Na/K-Al-Si
Ca-Fe
0 10 20 30 40 50 60 70
B
10/90
40/60
A
Weight percentage, %
PM10+
Fig. 11. A comparison of the mineral species in PM
10+
produced by the combustion
of coal B, 10/90, 40/60 and coal A.
Ca-Al-Si
Ca 42%
Al-Si
Fe-Al-Si
Al 28%,
Si 39%
Ca 14%
Fe 9.6%
P 3.4%
10m
5.0m
a
b
Fig. 12. Micrographs of particles in PM
10+
generated by the combustion of 40/60.
0 20 40 60 80 100
20
40
60
80
100
Ca
Fe
Al
Si
W
t
%

o
f

e
l
e
m
e
n
t

i
n

P
M
1
0
+
A/(A+B) x100, wt%
20 40 60 80
0
20
40
60
80
100
Ca
Fe
Al
Si
W
t
%

o
f

e
l
e
m
e
n
t

i
n


P
M
1
0
+
Liquid content, wt%
a
b
Fig. 13. Transformation trends of Ca, Fe, Al, and Si from PM
10
to PM
10+
with the increasing wt.% of coal A in blended coals (a); transformation trends of Ca, Fe, Al, and Si from
PM
10
to PM
10+
with increasing liquid percentage (b).
3004 Q. Wang et al. / Fuel 87 (2008) 29973005
4. Conclusions
This study has the following conclusions:
(1) The different Ca concentrations in coal mineral cause the
morphological differences between the two kinds of PM
formed from coals A and B. Particles formed from coal A are
coarse and sticky. Particles formed from the Ca-poor coal B
are characterized by discrete spheres with smooth surfaces.
(2) PM
10
emissions are not linearly related to the wt.% of the
parent coal in coal blends during combustion. Increasing
Ca concentration in coal blends enhances the liquid concen-
tration produced during combustion and hence affects the
emissions of PM
1
and PM
110
.
(3) PM
1
produced fromcoal combustion is dominated by the ele-
ments of P, S, Al, Si, Na, and K. Furthermore, the transforma-
tions of P, S, Al, and Si from PM
1
to PM
1+
reduce PM
1
emissions. The wt.%of liquidphasegeneratedduringcombus-
tion is the primary factor affecting elemental transformation
to PM
1+
. Mineral concentrations in raw coal also contribute.
(4) PM
110
is dominated by large amounts of Al, Si, Ca, and Fe
with small amounts of P and S. Moreover, the transformation
of Ca, Fe, Al, and Si from PM
10
to PM
10+
with the increasing
Ca content in coal blends reduces the concentration of
PM
110
. Increasing Ca concentration in coal blends increases
the wt.% of liquid phase generated during combustion,
which increases the probability for the collision and coales-
cence of small particles to form larger particles. Particles like
CaFeAlSi or CaAlSi promote the transformation of Ca,
Fe, Al, and Si from PM
10
to PM
10+
, thus a reduction of
PM
110
emissions is realized.
Acknowledgements
The nancial support from Grant-in-Aid for Scientic Research
on Priority Areas (B), 17310054, Ministry of Education, Science,
Sports and Technology, Japan, and the Steel Industry Foundation
for the Advancement of Environmental Protection Technology is
appreciated. The authors acknowledge Mr. Masunori Kawamura
for his assistance with the TEMEDS analysis. Mr. Atsushi Okudaira
and Mr. Tomohito Ito, graduate students in our laboratory are also
thanked for their assistance with the combustion experiments.
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