Main mineral melting behavior and mineral reaction mechanism at molecular level

of blended coal ash under gasication condition

Xiaojiang Wu
a,b
, Zhongxiao Zhang
a,
, Yushuang Chen
c
, Tuo Zhou
c
, Junjie Fan
c
, Guilin Piao
d
,
Nobusuke Kobayashi
d
, Shigekatsu Mori
d
, Yoshinori, Itaya
d
a
School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
b
Shanghai Electric Power Generation Group, Shanghai 201100, China
c
Department of Power Engineering, University of Shanghai for Science & Technology, Shanghai, 200093, China
d
Department of Chemical Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan
a b s t r a c t a r t i c l e i n f o
Article history:
Received 29 January 2010
Received in revised form 4 June 2010
Accepted 23 June 2010
Keywords:
Blended coal ash
Ash fusion characteristics
Mineral transition
Quantum chemistry
The main mineral melting behavior and mineral reaction mechanism at molecular level of Chinese blended
coal ash under gasication condition (30% H
2
, 66% CO, 4% CO
2
) from 1073 K to 1573 K were studied through
the ASTM test, X-ray diffraction (XRD), ternary phase diagram system and quantum chemistry calculation
with ab-initio calculations. The results show that with increasing blending mass fraction of low ash fusion
temperature (AFT) ash (ash B), the location of blended ash in ternary systems is transferred from the mullite
region to the anorthite region, as the dominant crystal mineral of blended ash at around DT (XRD analysis) is
also transferred from mullite to anorthite. The calcium-bearing minerals, such as anhydrite, calcite etc., can
react with mullite and the precursors of mullite (metakaolinite etc.), which is one of the main refractory
minerals in high AFT ash (ash A), and is converted into low-melting minerals (anorthite, gehlenite, and
fayalite etc.) in the temperature range between 1273 K and 1403 K. The reaction between mullite and CaO to
form anorthite plays a signicant role in decreasing AFTs of blended coal ash A/B. It is because the chemical
activity of the highest occupied molecular orbits (HOMO) in mullite cluster is stronger than that of the
lowest unoccupied molecular orbits (LUMO) in mullite cluster, the Ca
2+
as electron acceptor can easily enter
into the crystal lattice of mullite mainly through O (7) and O (12) and cause the rupture of bonds Al (1)O
(13) (in the [AlO
6
]
9
-octahedron) and Al (8)O (13) (in the [AlO
4
]
5
-tetrahedron), which are weaker than
any other bonds in crystal lattice of mullite. Finally, the entrance of Ca
2+
can force mullite to transform to
anorthite by the effect of Ca
2+
, and the entered Ca
2+
is located in the center of [SiO
4
]
4
-tetrahedron ring in
the anorthite crystal lattice. Taking the [SiO
4
]
4
-tetrahedron, which is composed of Si (70), O (78), O (48),
O (91), O (86) as an example, the Ca
2+
can capture the partial electronics of O (86) and cause the bond
length (B.L.) of bond Si (70)O (86) to become longer and unstable.
2010 Elsevier B.V. All rights reserved.
1. Introduction
China is the world's largest producer and user of coal, the demand
of coal has been rapidly growing in the past 10 years [1]. Entrained
ow gasier has been greatly improved as one of the most important
clean coal technologies in China, since it not only can satisfy the
growing demand of primary energy but also can supply electricity,
liquid fuels, hydrogen and other chemical materials if needed, with
low pollution levels in China [2,3]. For prevailing slagging entrained
owgasiers, such as Shell, Texaco, Preno, GSP etc., the AFT (FT, ow
temperature) of feeding coal must be lower than the operating tem-
perature (1673 K) for safe operation with a molten slag [3,4]. Chinese
coals usually have relatively high total ash content, around 2728%, as
well as high AFT (FTN1673 K). High AFT coals account for about 55% of
the annual output and 57% of the retained coal reserves in China [5].
As a result, those high AFT coals would be expected to require either
adding ux agents, such as limestone, Fe
2
O
3
and K
2
CO
3
etc. or
blending with low AFT coals. As compared with the method of adding
ux agents, coal blending is a good method for high AFT coal to
provide a consistent feedstock of fuel for slagging gasier because
there is no increase of ash content and corresponding oxygen
consumption, which is necessary to melt added ux agents [6,7].
Thus, it is necessary to clarify the melting behavior and fundamental
melting mechanism of blended coal ash under gasication conditions
for a continuous successful safe operation of slagging combustors and
slagging gasiers when gasifying blended Chinese coal. In gasiers,
organic materials in coal are completely combusted and gasied at
high temperature (14731873 K) and high pressure (3.04.5 MPa),
and the mineral matters in coal would transform into ash and also
undergo chemical reaction, and morphology changes; and eventually
Fuel Processing Technology 91 (2010) 15911600
Corresponding author. Tel.: +86 13501618961; fax: +86 21 34207274.
E-mail address: zhzhx222@163.com (Z. Zhang).
0378-3820/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.06.007
Contents lists available at ScienceDirect
Fuel Processing Technology
j our nal homepage: www. el sevi er. com/ l ocat e/ f upr oc
fusion at high temperature [8,9]. The relationships between AFT and
the chemical and mineral compositions of coals and coal ashes have
been extensively studied through ASTM test, chemical analysis,
scanning electron microscope (SEM), energy dispersive X-ray ana-
lyzer (EDX), X-ray diffraction (XRD) and phase diagrams theory etc.
[1014]. Previous studies show that the mineral matters in ash and
their melting behavior plays a signicant role during ash melting
behavior at high temperature. In general, the main refractory minerals
in coals and coal ashes are quartz (SiO
2
), metakaolinite (Al
2
O
3
2SiO
2
),
mullite (3Al
2
O
3
2SiO
2
) and rutile (TiO
2
) etc., while the main uxing
minerals are anhydrite (CaSO
4
), anorthite (CaOAl
2
O
3
2SiO
2
), gehle-
nite (2CaOAl
2
O
3
2SiO
2
), K-feldspars (KAlSi
3
O
8
), Ca silicates and
fayalite (2FeOSiO
2
), almandite (3FeOAl
2
O
3
3SiO
2
) etc. [15,16].
Especially for calcium- and iron-bearing minerals, such as anhydrite,
calcite (CaO), hematite (Fe
2
O
3
) and wustite (FeO) etc., they would act
as the key factors in uxing aluminosilicates and lowering MP
(melting point) of ash during coal combustion and gasication
[16,17]. Furthermore, various mineral matters in ash will also react
with each other complexly to form some eutectic mixtures that start
to melt and cause ash melting mechanism of blended coal ash to
become more complicated at high temperature [16,17]. The melting
behaviour of coal mineral is a complex process: the blending of coals
inevitably makes it even more complex.
Recently, with the development of quantum chemistry theory and
computer technology, the semi-experimental and ab-initio computa-
tional methods have become a powerful tool to investigate the
molecular surface chemical characteristics and chemical reaction
mechanism of various minerals at a molecular level [18,19]. In the
area of fuel science, the computational program has been applied to
simulate the molecular structure of coal [20,21], which has a guiding
signicance to provide an insight into the interaction mechanism
between gas molecule and coal or char molecule in coal liquefaction
[22,23]. In the eld of mineral matters, atomistic simulation tech-
niques were used to investigate the interaction mechanism between
mineral and absorber, such as heavy metal ion [24,25]. The main
atomic orbital populations of some frontier molecular orbits, covalent
bond level of main atoms and other properties of minerals or minerals
after absorption of heavy metal ion can be obtained directly through
ab-initio density functional calculation method [2628]. Li J. et al [29]
has used ab-initio density functional calculation method to guide the
selection of appropriate uxing agent to reduce AFT of coal ash.
Therefore, it seems that it is possible to investigate the complicated
interaction mechanism of minerals in blended coal ash at molecular
level through ab-initio density functional calculation method.
Through quantum calculation of main minerals (refractory or uxing
minerals) in ash, some important information on mineral reaction
process during heating, such as reaction activity sites, atomic net
charge, a particular molecular orbital energy level etc., can be
obtained to provide an insight into the main interaction mechanism
of minerals in ash. In order to clarify the fundamental mineral
transition mechanism of blended ash under gasication condition,
blended coal ashes of one typical Chinese high AFT coal ash and one
typical Chinese low AFT coal ash with different blending ratios at
various temperature levels under gasication condition (30% H
2
, 66%
CO, 4% CO
2
) were obtained and their corresponding mineral com-
positions were analyzed by XRD analysis in detail. Furthermore, the
molecular chemical characteristics of main minerals, such as mullite,
anorthite etc., were also studied by quantum chemistry calculation to
provide an insight into the main mineral reaction mechanism of
blended ash at molecular level under gasication conditions. For the
current research, only the molecular chemical characteristics of
mullite and anorthite have been studied. Further calculation on
other minerals such as genhlenite, wustite, hercynite (FeOAl
2
O
3
),
fayalite etc., would take place to completely interpret the fundamen-
tal interaction mechanism of minerals in blended ash during heating
under gasication condition.
2. Material and methods
2.1. Coal sample
Two typical Chinese bituminous coals A and B with different AFTs
were selected for use in this work. One is high AFT coal and the other is
lowAFT coal. Coal samples were ground to less than 75 m(under 200
meshes) in diameter. Laboratory ash samples (1088 K/1 h, under air)
were prepared from crushed coal samples and an ash oxide anal-
ysis was determined in accordance with Chinese national standards
(GB-210). The AFT test, which can provide four temperatures (DT, ST,
HT and FT) that characterize the fusibility behavior of laboratory
ash was performed in both oxidizing and a simulated gasication
environment (30% H
2
, 66% CO, 4% CO
2
) according to Chinese national
standard (GB/T219-1996). The ash chemical composition of test coals
is illustrated in Table 1. A number of blended ash samples were
prepared on mass basis with a similar SiO
2
/Al
2
O
3
ratio and different
FeO
n
or CaO levels in blended ashes A/B. The normalized composition
of ashes A, B and their blended mixtures are respectively shown on the
appropriate position in the CaOSiO
2
Al
2
O
3
and FeOSiO
2
Al
2
O
3
ternary phase diagram system (Fig. 1 (a) and (b)). The initial mineral
composition of ashes A and B at 1073 K is also shown in Fig. 2.
2.2. Experimental details
The blended ash samples A/B with various blending mass ratios (20,
40, 60 and 80 wt.%) of ash B were prepared and mixed well before
carrying out the experiment. The AFT test of ashes A, Bandtheir blended
ashes A/B was performed based on Chinese national standard under
both oxidizing (air) and a simulated gasication environment (30% H
2
,
66% CO, 4% CO
2
) in a HR-4 ash fusion testing apparatus (HR-4, Henan
Province). Furthermore, in order to investigate the mineral transition
behavior of blendedashA/Bunder gasicationcondition, around1 g ash
samples (ashes A, B and blended ashes A/B) were spread out in a layer
(about 5 mm thickness) and heated to reach various temperatures
(1073, 1173, 1273, 1373 1473 and 1573 K) in an electric furnace (Fig. 3)
under a simulatedgasication environment with20 K/minheating rate,
respectively. When temperature reached the predetermined tempera-
ture, eachsample was taken out and quenchedin water quickly to avoid
the crystal phase changes of ashes A, B and their blended ash A/B [30].
Some ash samples at various temperatures were dried and ground into
a powder of required particle size in a carnelian bowl for XRD analysis
(D/Max PC 2550, Japan).
2.3. Quantum chemistry calculation
In order to provide an insight into the mineral transition process in
the conversion of mullite into anorthite when heating blended ash A/
B under gasication condition, the quantum chemistry calculation
with ab-initial density function theory B3LYP method [31] was
employed to calculate the surface chemical characteristics of mullite
and anorthite at molecular level. In practice, the KohnSham theory
Table 1
Ash composition of coal ashes A and B.
Ash composition, wt.% A B
SiO
2
50.62 43.41
Al
2
O
3
39.3 12.23
Fe
2
O
3
3.70 16.54
CaO 0.70 12.08
MgO 0.20 2.56
SO
3
0.10 7.82
TiO
2
1.12 0.65
K
2
O 0.64 0.54
Na
2
O 0.27 0.74
P
2
O
5
0.36 0.16
1592 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
Fig. 1. Representation of ashes A, B, C and their corresponding blended ashes on the ternary phase diagram. (a) Ternary phase diagram CaOSiO
2
Al
2
O
3
system. (b) Ternary phase
diagram FeOSiO
2
Al
2
O
3
system.
1593 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
can be applied in several distinct ways depending on what is being
investigated. In the chemistry eld, one popular functional is known
as BLYP (from the name Becke for the exchange part and Lee, Yang
and Parr for the correlation part). Even more widely used is B3LYP
which is a hybrid functional in which the exchange energy, in this case
from Becke's exchange functional, is combined with the exact ener-
gy from the HartreeFock theory [31]. The Gaussian 03 package
(631 G(d, p) basis set) [32] was used in this study. Through quantum
chemical calculation, some important information on surface chemical
characteristics of minerals at molecular level, such as reaction activity
sites, bond order (B.O.), the highest occupied molecular orbital (HOMO)
and the lowest unoccupied molecular orbital (LUMO) etc., can be
obtained. Mullite belongs to the orthorhombic system, with cell
dimensions: a=7.60 , b=7.68 , c=2.88 and the space group is
Pbam. The primitive cells of mullite with the lattice parameters are
chosenfromthe study of Takayuki [33]. Anorthite belongs tothe triclinic
system, with cell dimensions: a=8.19 , b=1.29 , c=1.42 and the
space group is P1. The primitive cells of anorthite with the lattice
parameters are chosen from the study of F. F. Franklin and R. P. Donald
[34]. In order to avoid higher false charge, the Oatoms, which are on the
Fig. 2. The XRD patterns of ashes A and B.
Fig. 3. Schematic diagram of experimental system. 1gas bottle; 2owmeter; 3mix room; 4value; 5electric furnace (~1873 K); 6temperature control box; 7ash sample/
(blended ash); 8samples(at different temperatures).
1594 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
cell edge of mullite/anorthite were saturated by H atoms to obtain
electric neutrality [35,36]. The atomic cluster of mullite and anorthite
can be written as [SiAl
4
O
10
H
9
] and Ca
8
[Al
16
Si
16
O
64
H
14
] respectively.
3. Results and discussion
3.1. Fusibility of blended coal ash A/B during heating under gasication
conditions
Lines AB on the ternary phase diagrams (CaOSiO
2
Al
2
O
3
and
FeOSiO
2
Al
2
O
3
) represent the range of blended ash A/B composi-
tion (Fig. 1 (a) and (b)). As it is can be seen fromFig. 1, the initial bulk
ash composition of ash A (high AFTs, DTN1773 K) is located in the
mullite region of both CaOSiO
2
Al
2
O
3
and FeOSiO
2
Al
2
O
3
phase
diagrams, while the anorthite region of CaOSiO
2
Al
2
O
3
and the
tridymite region of FeOSiO
2
Al
2
O
3
are ash B's locations. Along with
the increasing mass fraction of ash B in blended ash A/B, the bulk ash
chemical composition of blended ash A/B changes along with the
straight line AB from the mullite region to the anorthite region in the
CaOSiO
2
Al
2
O
3
system and from the mullite region to the tridy-
mite region in the FeOSiO
2
Al
2
O
3
system. The relationship
between AFTs of blended ash A/B and their corresponding liq-
uidus temperatures from the phase diagrams (CaOSiO
2
Al
2
O
3
and FeOSiO
2
Al
2
O
3
) under both oxidizing and gasication con-
ditions are shown in Fig. 4. As it can be seen from Fig. 4, the
experimental AFT curves of blended ashes A/B would closely parallel
the liquidus temperatures fromthe CaOSiO
2
Al
2
O
3
phase diagram
under oxidizing atmosphere, as well as the liquidus temperatures
from the FeOSiO
2
Al
2
O
3
phase diagram under gasication condi-
tions. The AFTs of those blended coal ashes A/B whose normalized
chemical composition is located near the boundaries between
two mineral regions or triple points are lower and changed more
evidently than that of those blended ashes A/B whose normalized
chemical compositions are far away from the boundaries or triple
Fig. 4. Relationship between AFTs of blended ashes and liquidus from phase diagrams. (a) Oxidizing atmosphere. (b) Reducing atmosphere.
1595 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
points in the ternary phase system. Therefore, in order to decrease
the AFT of high AFT coal, the optimum mixture ratio of blended ash
is near the boundaries or triple points in the CaOSiO
2
Al
2
O
3
or FeO
SiO
2
Al
2
O
3
phase diagram.
3.2. Main mineral transition behavior of ash A and B during heating
under gasication conditions
The main mineral transitions in ashes A, B and their blended ashes
A/B under gasication conditions from1073 K to 1573 K are discussed
based on Fig. 5 and the 3D graphical visualization of XRD results,
which are given in Fig. 6. As it can be seen fromFig. 2, when compared
with the initial identied minerals in ash B at 1073 K, ash A is mainly
composed of quartz and muscovite (KAl
2
AlSi
3
O
10
(OH)
2
) and a small
amount of rutile (TiO
2
). Also, there are no identied lowMP minerals,
such as calcite, rankinite, anhydrite, anorthite, dioposide and augite
(Ca(Mg,Fe)Si
2
O
6
), but these are identied in ash B. The main mineral
transitions that occurred during heating between 1073 K and 1573 K
in ash A are mullite, quartz, wustite and hercynite etc. (Figs. 5 and 6
(a)). With increasing temperature, mullite is formed and increased
due to the decomposition of metakaolinite (Al
2
O
3
SiO
2
) when the
temperature is higher than 1273 K [37]. When temperature rises to
1573 K, mullite is the dominant and single crystalline phase in ash A
because of the high MP of mullite (MP, 2123 K Fig. 6 (a)). The
other minerals in ash A, such as quartz, wustite and hercynite etc.,
decreased and disappeared with the increase of temperature (Figs. 5
and 6 (a)). Quartz is also one of the main refractory minerals with high
MP (MP, 1983 K) in coal and coal ash. However, under reducing
conditions, the refractory nature of quartz or its polymorphs can be
compromised because of lime, wustite and other calcium or iron-rich
minerals (anhydrite, pyrite, siderite (FeCO
3
)) which can react strongly
with quartz to a yield mixture of anorthite, wollastonite(CaOSiO
2
),
rankinite, fayalite and silicate melts in ash [38]. Under reducing
condition, wustite is formed at around 1173 K mainly due to the
decomposition of hematite and siderite [39]. With further increase of
temperature, wustite starts to react with mullite and quartz etc., to
form fayalite and hercynite etc., at around 12731373 K. As it can be
seen from Figs. 5 and 6, the XRD peak of wustite in both ashes A and B
decreases at around 1173 K, and meanwhile the XRD peak of fayalite,
almandite and hercynite increases. For low AFT coal ash B, the main
mineral transition that occurred during heating between 1073 K and
1573 K are anorthite, quartz, anhydrite etc. (Figs. 5 and 6 (d)). As it
can be seen fromFigs. 5 and 6, anorthite starts to formas the products
from anhydrite, alumina and silica at around 11731373 K, and
meanwhile the decomposition of anhydrite also occurred at around
11731373 K [37]. Anorthite becomes stable at around 1273 K, while,
the XRD peak of anorthite decreases with further increase of
temperature above 12731373 K probably due to partial melting of
the phase assemblage [37]. Above 1573 K ash B is completely molten
(Fig. 6 (d)). The decrease in intensity of the mineral matters as a
function of temperature is not only a decomposition of some mineral
phases, but also the formation of liquid (slag) because of some
minerals with low-melting point in ash B, such as anorthite, rankinite,
fayalite, almandite etc.
3.3. Main mineral transition behavior of blended ash A/B during heating
under gasication conditions
For blended ashes A/B, The Ca-, Fe-, Na- and Mg-bearing minerals
in ash B, such as anhydrite, wustite, albite and augite etc., can react
with quartz and mullite, which are mainly refractory minerals in ash
A, to formsome lowMP minerals such as anorthite, hercynite, fayalite
etc., at above 1373 K [37]. Therefore, with increasing blending ratio of
ash B in blended ash A/B, the peak value of mullite at various
temperatures decreases and new low MP minerals, such as anorthite,
fayalite etc., are formed and increased in the temperature range of
12731573 K when compared with the main mineral composition of
ash A at various temperatures (Figs. 5 and 6). When the blending ratio
of ash B reaches 40 wt.%, it is because the bulk ash chemical com-
position of blended ash A/B still is located in the mullite region of both
the CaOSiO
2
Al
2
O
3
and FeOSiO
2
Al
2
O
3
phase systems, the main
crystal mineral at high temperature (1573 K) is still mullite except for
the lower peak value of mullite than that of mullite in ash A at 1573 K
(Fig. 6 (a) and (b)). Though some portions of the initial active melts
such as anorthite, hecynite, fayalite etc., with low viscosity are also
formed in blended ash A/B (40% B+60% A) in the temperature range
from 1423 to 1468 K (Figs. 5 and 6 (b)), those melts do not dissolve
the refractory mineral phases completely such as mullite, cristobalite,
cordierite etc. In that case (40% B+60% A), mullite and anorthite
coexist in the temperature range of 14231463 K (Fig. 6 (b)). When
the blending ratio of ash B reaches 80 wt.%, it is because the location of
blended ash A/B in CaOSiO
2
Al
2
O
3
phase diagram has been changed
from the mullite region to the anorthite region, the mullite crystalline
phase disappeared and anorthite, rankinite, fayalite etc., become the
dominant crystal minerals of blended ash A/B in the temperature
range of 12681468 K (Figs. 5 and 6 (c)). Along with increasing mass
fraction of ash B in blended ash A/B, the content of calcium- or iron-
bearing minerals will increase and react with some main refractory
Fig. 5. Main minerals change of ashes A, B and blended ash A/B as a function of temperature under gasication conditions.
1596 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
minerals in ash A, such ash mullite and quartz etc., to form low MP
minerals (anorthite, wollastonite, fayalite, hercynite etc.). The main
mineral reactions of ashes A, B and their blended ash A/B during
heating at gasicaiotn condition are shown as follows:
hematiteFe
2
O
3

e
1173K
FeO + O
2
reducingcondition 1
anhydriteCaSO
4

N 1273K
CaO + SO
3
2
mullite3Al
2
O
3
2SiO
2
+ CaO
e
1403K
anorthiteCaO Al
2
O
3
2SiO
2

3
anorthiteCaO Al
2
O
3
2SiO
2
+ CaOgehlenite2CaO Al
2
O
3
2SiO
2

4
quartzSiO
2
+ CaO wollastoniteCaO SiO
2
5
wollastoniteCaO SiO
2
+ CaOAlite3CaO SiO
2
6
quartzSiO
2
+ FeO
1173
e
1273K
clinoferrosiliteFeO SiO
2
7
clinoferrosiliteFeO SiO
2
+ FeO
1173
e
1273K
fayalite2FeO SiO
2

8
mullite3Al
2
O
3
2SiO
2
+ FeO
1273
e
1473K
fayalite2FeO SiO
2

+ hercyniteFeO Al
2
O
3

9
anorthiteCaOAl
2
O
3
2SiO
2
+ FeO
1273
e
1473K
fayalite2FeOSiO
2

+ hercyniteFeOAl
2
O
3
+ almandite3FeOAl
2
O
3
3SiO
2

10
Among these main mineral reactions, the mineral reaction (3) is
especially noteworthy because it will play a signicant role in mullite
(melting point, MP=2133 K) transformed to anorthite (MP=
1826 K). Therefore, for current research, the molecular surface
chemical characteristics of mullite and anorthite were rstly focused
on to analyze the fundamental mineral reaction mechanism of
blended ash A/B. Further calculation on other minerals in ash would
take place to complete the database for fully understanding melting
mechanism of coal ash/blended ash at high temperature.
3.4. Reaction activity of mullite cluster
The HOMOand LUMOmaps of mullite are shown in Fig. 7. As it can
be seen from Fig. 7, the HOMO of mullite is almost constituted of
Fig. 6. Integral intensities of main minerals of ashes A, B and their blended ash A/B as function of temperature.
1597 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
oxygen atoms, especially the oxygen atoms O (7) and O (12), which
connect with Si (16). The LUMO of mullite is mostly constituted of Al
(1), Al (8) and corresponding connected oxygen atoms, such as O (3),
O (9), O (13) and O (14). Based on the frontier orbital theory, the
frontier orbits in the HOMO or LUMO have more chemical reactivity
than any other orbits and play a key role in the chemical reaction of
minerals on the molecular level [40]. In order to clarify the frontier
orbits in the mullite molecular structure, the bond order (B.O.),
population (Pop.), net charge (N.C.) and bond length (B.L.) of HOMO
and LUMOin the mullite molecules are shown in Table 2. According to
the B.O.(P(A)) and B. L. (R(A)) in mullite, the B.O. of bond Al (1)O
(13) is lower than that of Al (8)O (13), Si (16)O (7), Al (8)O (14)
and Si (16)O (12), and the B.L. of bond Si (16)O (12) is shorter than
that of Al(8)O(14), Si (16)O (7), Al (8)O (13) and Al (1)O (13).
Therefore, the covalent bond of Si (16)O (12) is the strongest in
mullite, because of the highest B.O. (0.6650) and the shortest B.L.
(0.16673 ), whereas the bond of Al (1)O (13) is the weakest in
mullite because of the lowest B.O. (0.2630) and the longest B.L.
(1.9752 ). It is because the O (13) has a relatively low net charge
(absolute value) than that of O (12), O (14) and O (7) (Table 2), the
relatively large electronic cloud is mainly located around O (13) and
the relatively large overlapping electronic cloud density is located
on bond Al (1)O (13). Therefore, cations as electron acceptors, such
Ca
2+
, Na
+
etc. can easily enter into the crystal lattice of mullite from
the HOMO atoms, such as Si (16), O (5), O (7), and O (12) and cause
bond Al (1)O (13) to break.
3.5. Reaction activity of anorthite cluster
The HOMO and LUMO maps of anorthite are shown in Fig. 8. As it
can be seen fromFig. 8, the HOMOof anorthite is almost constituted of
oxygen atoms, especially the oxygen atoms O (31), O (42) and O
(101), which connect with Al (15). The LUMO of anorthite is mostly
constituted of Ca (55), Al (19), Al (57), Al (59) and corresponding
connected oxygen atoms, such as O (35), O (91), O (97), and O (99).
Based on the frontier orbital theory, the frontier orbits in the HOMOor
LUMO have more chemical reactivity than any other orbits and play a
key role in the chemical reaction of minerals on the molecular level
[40]. In order to clarify the frontier orbits in anorthite molecular
structure, the B.O., Pop., N.C., and B.L. of HOMO in anorthite molecules
are shown in Table 2. According to the B.O.(P(A)) and B. L. (R(A)) in
anorthite, the B.O. of bond Al (15)O (31) is lower than that of
Al (15)O (42) and Al (15)O (101), and the B.L. of bond Al (15)O
(101) is shorter than that of Al (15)O (42) and Al (15)O (31).
Therefore, the covalent bond of Al (15)O (101) is the strongest in
anorthite, because of the highest B.O. (0.5657) and the shortest B.L.
(1.74023 ), whereas the bond of Al (15)O (31) is the weakest in
anorthite because of the lowest B.O. (0.3719) and the longest B.L.
(1.84206 ). It is because the O (31) has a low net charge (absolute
value) relative to that of O (42) and O (101) (see Table 2), the
relatively large electronic cloud are mainly located around O (31) and
the relatively large overlapping electronic cloud density is located on
bond Al (15)O (31). Therefore, cations as electron acceptors, such
Fig. 7. HOMO and LUMO maps of mullite surface structure. (a) HOMO map of mullite
surface structure. (b) LUMO map of mullite surface structure.
Table 2
The bond order (B.O.), population (Pop.), net charge (N.C.) and bond length (B.L.) of
mullite and anorthite.
Atom Population Net charge Bond Bond order Bond length
(Pop.) (N.C.) (B.O.) ()
Mullite
Si (16) 1.5410 1.6930
O (7) 0.9930 1.0960 Si(16)O(7) 0.6540 0.17183
O (12) 1.3320 1.3080 Si(16)O(12) 0.6650 0.16673
Al (1) 2.1200 2.0420 Al(1)O(13) 0.2630 1.9752
Al (8) 1.9690 2.0080
O (3) 1.3590 1.2960 Al(8)O(3) 0.5750 0.17009
O (9) 1.1190 1.1870 Al(8)O(9) 0.6025 0.16734
O (13) 0.7060 0.7690 Al(8)O(13) 0.4530 0.18386
O (14) 1.1470 1.1980 Al(8)O(14) 0.6620 0.16843
Anorthite
Si (70) 1.2399 1.3646
O (48) 0.6535 0.7888 Si(70)O(48) 0.8001 1.6389
O (78) 0.6160 0.7153 Si(70)O(78) 0.7706 1.6762
O (86) 0.6135 0.7923 Si(70)O(86) 0.7366 1.6890
O (91) 0.6641 0.7734 Si(70)O(91) 0.9646 1.6113
Al (17) 1.041261 1.17357
O (33) 0.713516 0.83238 Al(17)O(33) 0.6715 1.69097
O (40) 0.654882 0.77044 Al(17)O(40) 0.3041 1.99228
O (99) 0.681562 0.90540 Al(17)O(99) 0.6545 1.70259
Al (15) 1.231309 1.33275
O (31) 0.572465 0.64076 Al(15)O(31) 0.3719 1.84206
O (42) 0.675449 0.85678 Al(15)O(42) 0.4536 1.80488
O (101) 0.532719 0.68454 Al(15)(101) 0.5657 1.74023
1598 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
Ca
2+
, Na
+
etc. can easily enter into the crystal lattice of anorthite from
the HOMO atoms, such as Al (15), O (31), O (42), and O (101) and
cause the bond Al (15)O (31) to break.
3.6. The stability of mullite and anorthite cluster
The optimized structure of mullite crystal is shown in Fig. 7. It can
be seen that the mullite molecule cluster mainly consisted of one
[SiO
4
]
4
-tetrahedral, one [AlO
6
]
9
-octahedron and three [AlO
4
]
5
-
tetrahedrals. The Ca
2+
as electron acceptor can easily enter into the
lattice of mullite from oxygen atoms O (7), O (12), which connect
with Si (16) and cause a transformation from mullite to anorthite.
Therefore, when mullite reacts with other minerals, which contain
Ca
2+
cations, the electrons that connect with oxygen in the HOMO of
mullite are prone to lean to the Ca
2+
to reach the electric-charge
balance and nally cause the change of mullite crystal properties to
form anorthite by the entrance of Ca
2+
.
As it can be seen from Fig. 7, the anorthite molecules mainly
consisted of eight-membered [SiO
4
]
4
-tetrahedral rings and eight
[AlO
4
]
4
-tetrahedrals. The Ca
2+
is mainly located in the cavity of the
eight-membered [SiO
4
]
4
-tetrahedral rings. Taking the [SiO
4
]
4
-
tetrahedron, which is composed of Si (70), O (78), O (48), O (91),
and O (86) (see Fig. 4) as an example, the B.O. of bond Si (70)O (86)
in the [SiO4]
4
-tetrahedron is lower than that of Si (70)O (78),
Si (70)O(48) and Si (70)O(91), as well as the B.L. of bond Si (70)O
(86) is longer than that of Si(70)O(78), Si(70)O(48) and Si(70)O
(91) (Table 2). Therefore, the bond of Si (70)O (86), which connects
with Ca
2+
in the [SiO4]
4
-tetrahedron is the weakest bond. According
to the mulliken atomic populations [41] in [SiO4]
4
-tetrahedron, the
order of that is O (91)bO (48)bO (78)bO (86), the atom of O (86),
which connects with Ca
2+
has the highest value of mulliken pop-
ulation. The Ca
2+
can capture the electron, which composes the S
orbital of bond O
br
Si and causes the unstable state of anorthite.
4. Conclusions
(1) Coal ash melting temperature can be decreased by ash
blending effectively. The phase equilibrium diagram can be used to
explain the phase transformation of ash mineral from mullite to
anorthite. In order to decrease the AFT of high AFT coal, the optimum
mixture ratio of blended ash is near the boundaries or the triple points
in CaOSiO
2
Al
2
O
3
and FeOSiO
2
Al
2
O
3
phase diagram.
(2) With increasing blending mass fraction of ash B, the location of
blended ash A/B in the ternary systems is transferred fromthe mullite
region to the anorthite region, and the dominant crystal mineral of
blended ash A/B at around DT temperature is also transferred from
mullite to anorthite. The calcium-bearing minerals, such as anhydrite,
calcite etc., can react with mullite, which is a major refractory mineral
in ash A, to form low-melting minerals (anorthite, fayalite and
gehlenite etc.) in the temperature range from 1273 K to 1403 K and
cause the AFT of blended ash A/B to become lower. When the blending
mass ratio of ash B reaches 80%, all of the mullite in ash A reacts with
calcium-bearing minerals in ash B and forms anorthite, In this case
(80% ash B+20% ash A), the AFT of blended ash A/B is decreased
sharply.
(3) Based on quantum chemical calculation of the mullite and
anorthite molecular structure, some fundamental information on
mineral reaction between mullite and Ca
2+
has been obtained. The
Ca
2+
as electron acceptor can easily enter into the crystal lattice of
mullite from O (7) and O (12), which connect with Si (16) and cause
the rupture of bond Al (1)O(13) and Al (8)O (13). Finally, the Ca
2+
,
which entered the mullite is located in the center of [SiO
4
]
4
-
tetrahedron ring in anorthite. Taking the [SiO
4
]
4
-tetrahedron, which
is composed of Si (70), O (78), O (48), O (91), and O (86) as an
example, the Ca
2+
can capture the partial electronics of O (86) and
cause the B.L of bond Si (70)O (86) to become longer and unstable.
Nomenclature
AFT Ash fusion temperature
ASTM American society for testing and materials
B.L. Bond length
B.O. Bond order
DT Deformation temperature
EDX Energy dispersive X-ray analyzer
FT Flow temperature
HOMO Highest occupied molecular orbits
HT Hemispherical temperature
LUMO Lowest unoccupied molecular orbits
MP Melting point
N.C. Net charge
Pop. Population
Fig. 8. HOMOand LUMOmaps of anorthite surface structure. (a) HOMOmap of anothite
surface structure. (b) LUMO map of anorthite surface structure.
1599 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600
SEM Scanning electron microscopy
ST Softening temperature
XRD X-ray diffraction
Acknowledgements
This research was partially supported by the National Natural
Science Foundation of China (50906055) and China Postdoctoral
Science Foundation (20090450571) in China. The authors also
acknowledge the project members and may people relevant to this
project.
References
[1] T. Attwood, V. Fung, W.W. Clark, Market opportunities for coal gasication in
China, J. Cleaner Prod. 11 (2003) 473479.
[2] A.G. Collot, Matching gasication technologies to coal properties, Int. J. Coal Geol.
65 (2006) 191212.
[3] A.J. Minchener, Coal gasication for advanced power generation, Fuel 84 (2005)
22222235;
H.X. Li, F.L. Chen, Coal blending to reduce the ash fusion temperature of high
fusability Huainan coal, J. China Coal Soc. 27 (2002) 529533.
[4] H.X. Li, Y. Ninomiya, Z.B. Dong, M.X. Zhang, Application of the FactSage to predict
the ash melting behavior in reducing conditions, Chin. J. Chem. Eng. 14 (2006)
784789.
[5] X.J. Wu, N. Kobayashi, G.L. Piao, Y. Itaya, S. Mori, Discussing of Chinese coal
resources and coal gasication process with high ash fusion temperature coal,
Proceedings of the 43th coal conference in Japan, KAOCHI, Japan, 2006, pp. 5354.
[6] G.W. Bryant, G.J. Browning, H. Emanuel, S.K. Gupta, R.P. Gupta, J.A. Lucas, T.F. Wall,
The fusibility of blended coal ash, Energy Fuels 14 (2000) 316325.
[7] J.H. Patterson, H.J. Hurst, Ash and slag qualities of Australian bituminous coals for
use in slagging gasiers, Fuel 79 (2000) 16711678.
[8] H. Liu, C.H. Luo, M. Toyota, S. Kato, S. Uemiya, T. Kojima, H. Tominaga, Mineral
reaction and morphology change during gasication of coal in CO
2
at elevated
temperatures, Fuel 82 (2003) 523530.
[9] J. Barroso, J. Ballester, L.M. Ferrer, S. Jimenez, Study of coal ash deposition in an
entrained ow reactor: inuence of coal type, blend composition and operation
conditions, Fuel Process. Technol. 87 (2006) 737752.
[10] S.V. Vassilev, K. Kitano, S. Takeda, T. Tsurue, Inuence of mineral and chemical
composition of coal ashes on their fusibiliy, Fuel Process. Technol. 45 (1995)
2751.
[11] S.V. Vassilev, G.M. Eskenazy, C.G. Vassileva, Behaviour of elements and minerals
during preparation and combustion of the Pernik coal, Bulgaria, Fuel Process.
Technol. 72 (2001) 103129.
[12] S.V. Benson, E.A. Sondreal, J.P. Hurley, Status of coal ash behavior research, Fuel
Process. Technol. 44 (1995) 112.
[13] R.P. Gupta, T.F. Wall, I. Kajigaya, S. Miyamae, Y. Tsumita, Computer-controlled
scanning electron microscopy of minerals in coal-lmplications for ash deposition,
Prog. Energy Combust. Sci. 24 (1998) 523543.
[14] W.J. Song, L.H. Tang, X.D. Zhu, Y.Q. Wu, Y.Q. Rong, Z.B. Zhu, S. Koyama, Fusibility
and ow properties of coal ash and slag, Fuel 88 (2009) 297304.
[15] S. Gupta, M. Dubikova, D. French, V. Sahajwalla, Characterization of the origin and
distribution of the minerals and phases in metallurgical cokes, Energy Fuels 21
(2007) 303313.
[16] C.G. Vassileva, S.V. Vassilev, Behaviour of inorganic matter during heating of
Bulgarian coals 2. Subbituminous and bituminous coals, Fuel Process. Technol. 87
(2006) 10951116.
[17] J.R. Qiu, F. Li, Y. Zheng, C.G. Zheng, H.C. Zhou, The inuences of minerals behaviour
on blended coal ash fusion characteristics, Fuel 78 (1999) 963969.
[18] S.G. Chen, R.T. Yang, Unied mechanism of alkali and alkaline earth catalyzed
gasication reactions of carbon by CO
2
and H
2
O, Energy Fuels 11 (1997) 421427.
[19] W.G. Richards, D.L. Cooper, Ab Initio Molecular Orbital Calculations for Chemists,
Oxford University Press, New York, 1983.
[20] T. Takanohashi, H. Kawashima, Construction of a model structure for upper
freeport coal using13 CNMR chemical shift calculations, Energy Fuels 16 (2002)
379387.
[21] G.A. Carlson, Computer simulation of the molecular structure of bituminous coal,
Energy Fuels 6 (1992) 771778.
[22] T. Takanohashi, K. Nakamura, M. Lino, Computer simulation of methanol swelling
of coal molecules, Enery Fuels 13 (1999) 922926.
[23] A. Montoya, F. Mondragon, T.N. Truong, CO
2
adsorption on carbonaceous surfaces:
a combined molecular modeling and experimental study, Prepr. Symp.-Am.
Chem. Soc., Div. Fuel Chem., vol. 46, 2001, pp. 217219.
[24] Y. Zhou, H.L. Hong, Q.J. Bian, L.W. Fan, Reactivity of tourmaline by quantum
chemical calculations, J. Wuhan Univ. Technol.-Mater. Sci. Ed. 22 (2007) 673676.
[25] N.H. De Leeuw, S.C. Parker, H.M. Sithole, P.E. Ngoepe, Modeling the surface
structure and reactivity of pyrite: introducing a potential model for FeS
2
, J. Phys.
Chem. B 104 (2000) 79697976.
[26] J.M. Costa, J.M. Lluch, The use of quantum mechanics calculation for the study of
corrosion inhibitors, Corros. Sci. 24 (1984) 929933.
[27] C. Lee, W. Yang, R.G. Parr, Development of the ColleSalvetti correlation-energy
formula into a functional of the electron density, Phys. Rev. 37 (1988) 785.
[28] H.L. Hong, R.J. Xiao, X.M. Min, Reaction activity of kaolinite surfaces: quantum
chemistry calculations, J. Wuhan Univ. Technol.-Mater. Sci. Ed. 18 (2003) 912.
[29] J. Li, M.F. Du, Z.H. Zhang, R.Q. Guan, Y.S. Chen, T.Y. Liu, Selection of uxing agent for
coal ash and investigation of fusion mechanism: a rst-principles study, Energy
Fuels 23 (2009) 704709.
[30] C.G. Vassileva, S.V. Vassilev, Behaviour of inorganic matter during heating of
Bulgarian coals 1. Lignites, Fuel Process. Technol. 86 (2005) 12971333.
[31] A. Montoya, T.N. Truong, A.F. Sarom, Spin contamination in hartree-fock and
density functional theory wavefunctions in modeling of adsorption on graphite,
J. Phys. Chem. A 104 (2000) 61086110.
[32] J.B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure Methods,
Gaussian Inc., Pittsburg, PA, 1996.
[33] T. Ban, K. Okada, Structure renement of mullite by the Rietveld method and a
newmethod for estimation of chemical composition, J. Am. Ceram. Soc. 75 (1992)
227230.
[34] F.F. Franklin, R.P. Donald, The anorthite crystal structure at 410 and 830 C, Am.
Mineralog. 58 (1973) 665675.
[35] F.W. Averill, D.E. Ellis, An efcient numerical multicenter basis set for molecular
orbital calculation: application to FeCl
4
, J. Chem. Phys. 59 (1973) 64126418.
[36] Z.J. Yi, T.Y. Liu, Q.R. Zhang, Y.Y. Sun, First-principles study on the origin of optical
transitions to be associated with F colour centers for PbWO
4
crystals, J. Electron.
Spectrosc. Relat. Phenom. 151 (2006) 140143.
[37] J.C. van Dyk, S. Melzer, A. Sobiecki, Mineral matter transformation during Sasol
Lurgi xed bed dry bottom gascation-utilization of HT-XRD and FactSage
modelling, Miner. Eng. 19 (2006) 11261135.
[38] G.P. Huffman, F.E. Huggins, G.R. Dunmyre, Investigation of the high-temperature
behaviour of coal ash in reducing and oxidizing atmospheres, Fuel 60 (1981)
585597.
[39] T.F. Zeng, J.J. Helble, L.E. Bool, A.F. Sarom, Iron transformations during
combustion of Pittsburgh no.8 coal, Fuel 88 (2009) 566572.
[40] H. Fujimoto, S. Inagaki, Orbital interaction and chemical bonds polarization in
chemical reactions, J. Am. Chem. Soc. 99 (1977) 74247432.
[41] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made
simple, Phys. Rev. Lett. 77 (1996) 38653868.
1600 X. Wu et al. / Fuel Processing Technology 91 (2010) 15911600