Chinese J. Chem. Eng.

, 14(6) 784789 (2006)

Application of the FactSage to Predict the Ash Melting Behavior in

Reducing Conditions*
LI Hanxu()a,**, Yoshihiko Ninomiya()b, DONG Zhongbing()a and
ZHANG Mingxu()c
a

Department of Chemical Engineering, Anhui University of Science and Technology, Huainan 232001, China
Department of Applied Chemistry, Chubu University, Kasugai, Aichi 487-8501, Japan
c
Department of Material Science and Engineering, Anhui University of Science and Technology, Huainan 232001,
China
b

Abstract FactSage has been used to predict the ash behavior and ash fusion temperature (AFT) at high temperature under reducing atmosphere conditions. For Huainan coal ash samples, it has demonstrated a good agreement
between the liquid phase formation as the function of temperature and the tested AFT. The tested and predicted flow
temperature (FT) for two typical Huainan coal ashes with the addition of CaO flux are quite fit with the maximum
temperature difference less than 74 which is within acceptable range. It can be concluded that FactSage in combination with X-ray diffraction (XRD) can be used to predict the reactions occurring between minerals, as well as
the mineral transformation and slag formation. This is probably an improved way to interpret melting properties of
mineral matter in coal and assist in quantifying slag formation in gasifier operation.
Keywords ash fusion temperature, FactSage, ash transformation, Huainan coals

INTRODUCTION
The coal ash related problems are major concern
to many coal companies and electrical power utilities[13]. The formation of slagging and fouling deposits in combustion, agglomeration in fluidized beds,
ash slag flow in integrated gasification combined cycleIGCCand other slagging reactors are directly
related to the formation of liquid slag and to the stabilities of solid crystalline phases[4,5]. The traditional
methods used to characterize the high temperature ash
behavior of the coal are becoming increasingly outdated and are unable to accurately predict the behavior
of ash and slag in coal and coal blends in combustion
and gasification technologies[613]. Progresses in
chemical thermodynamic and viscosity models of oxide systems, the development of computational methods, computer software and hardware now make it
possible to accurately predict the phase equilibrium
conditions in complex multi-component coal ash slag
systems[14,15].
Recently, studies on the prediction of ash fusion
temperature (AFT) were undertaken with the aid of
computer thermodynamic model[1619]. FactSage[20]
was introduced in 2001 and was developed jointly by
both the FACT-Win/F*A*C*T and ChemSage/
SOLGASMIX thermochemical packages that were
founded over 28 years ago. The FactSage package
consists of a series of information, database, calculation and manipulation modules that enable one to access and manipulate pure substances and solution databases. FactSage is an extremely powerful tool with

which one can perform a wide range of thermochemical calculations useful to chemical and physical metallurgists, chemical engineers, inorganic chemists,
geochemists, electrochemists, environmentalists, etc.
It provides information on the phases formed, their
proportions and compositions, the activities of individual chemical components and the thermodynamic
properties for all compositions, pressures and temperatures.
Having a significant impact on coal selection internationally (e.g. CRIEPI, ECN-Energy Research
Centre of the Netherlands, EERC-North Dakota Energy & Environmental Research Center, Hongik University in South Korea, Chubu University Japan),
FactSage is already being used in the design of
step-change technologies in the evaluation and selection of coal for entrained flow coal gasification and
blast furnace iron making by research teams in the
world. The most important features of the FactSage
system are the large evaluated multi-component solution databases giving the thermodynamic properties as
functions of temperature and composition. FactSage
contains databases for 15-component oxide/glass solutions, ceramic solution such as spinels, solid and
liquid salt solution, metallic alloy solutions and aqueous solutions, etc. Each of these databases has been
prepared by critical evaluation and optimization of all
available data using appropriate solution models.
In order to understand the ash behavior of
Huainan coals, the FactSage Thermodynamics Model
(FactSage 5.1) was used to evaluate the liquid phase

Received 2005-09-01, accepted 2006-01-08.

* Supported by the Natural Science Foundation of the Education Ministry of Anhui Province (2004kj125) and the Key Project of
Huainan (2003001).
** To whom correspondence should be addressed. E-mail: hxli@aust.edu.cn

Application of the FactSage to Predict the Ash Melting Behavior in Reducing Conditions

amounts and ash transformation at high temperature

under reducing conditions. The theoretical predictions
were also testified by experimental investigations of
ash fusion temperature (AFT) test and X-ray diffraction (XRD) for the quenched ash samples.

As shown in Table 1, the ash composition of

Huainan coal samples is rich in SiO2 and Al2O3
(75%). The contents of TiO2 is higher than 1% on
average, the Na2O and MgO lower than 0.5% and 1%,
respectively. The contents of CaO and FeO vary
greatly from about 1% to 10% with coal samples.
The ground and dried coal was mounted in wax
and allowed to harden. The mount was cross-sectioned
and polished, coated with carbon layer to eliminate the
electrostatic effects, and placed in the computer-controlled scanning electron microscope
(CCSEM) for analysis. Six typical coal samples were
analyzed by JEM-5600 with CDU-LEAP SEM-EDX
and CCSEM. For CCSEM analyses, three magnifications, namely 150 for the 22.0211.0m, 250 for the
4.622.0m and 800 for the 0.54.6m were used
to obtain the backscattered image of samples. The
CCSEM was used to measure the size, composition,
and abundance of mineral grains in the coal.

RESEARCH METHOD
FactSage Thermodynamic Model was used for
predicting multi-phase equilibria, proportions of the
liquid and solid phases in specified atmosphere for the
multi-component system.
Calculation conditions for FactSage Thermodynamic Model:
(1) Chemical composition
The ash composition of Al2O3, CaO, Fe2O3,
Na2O, K2O, MgO, SiO2, SO3, P2O5, TiO2 was input in
the table of the software.
(2) Solution species
FACT-SLAG solution included MgO, FeO, Na2O,
SiO2, TiO2, Ti2O3, CaO, Al2O3, K2O, MgS, CaS, FeS,
Na2S, Na3PO4, Ca3(PO4)2, Mg3(PO4)2, Fe3(PO4)2.
(3) Gas atmosphere
The reducing atmosphere of 60% CO and 40%
CO2 was employed in the FactSage calculation.
(4) Pressure
The pressure for the FactSage calculation was
0.1MPa.
(5) Temperature
The initial temperature and final temperature for
the FactSage calculation were 800 and 1600,
respectively with the interval of 20.

3.2

Ash fusion temperature test

The melting test was carried out under a reducing
condition of 60% CO and 40% CO2. The ash samples
were shaped into triangular cones. The cones were

inserted into a furnace and heated at 5min 1 ramp

rate. The limit temperature of the furnace is 1500.
In order to compare the predicted AFT with the
tested AFT, the AFT of HN115 and HN106 coal ash
with different flux addition contents was tested and
calculated by FactSage respectively.
3.3

Experiment on ash by XRD

A laboratory vertical gas-tight tube furnace apparatus was set up to heat the samples to high temperature under controlled atmosphere. About 1g of ash
samples was heated in the apparatus which was modified to allow rapid heating and quenching of ash samples. The sample was dropped in the furnace and reacted for 5min at desired temperature range from
1050 to 1450, and then was quenched into water.
Total quenching time was normally 5s. Quenched
samples were examined by using Rigaku RINT X-ray
powder diffractometry.

3 EXPERIMENTAL STUDY AND ANALYSIS

3.1 Coal samples
Six typical coal samples, selected from Huainan
coal basin, Anhui Province of China, were ground to
less than 0.063mm (250 meshes). Coal samples are
ashed in air at 815 according to the Japan Industrial
Standard (JIS). All ash samples were analyzed using
Rigaku RINT X-Ray Fluorescence (XRF).
The chemical compositions of the ash samples
analyzed by Rigaku X-ray fluorescence and the melting temperatures of coal ash samples are presented in
Table 1.
Table 1
Coal
HN106

785

Chemical composition and melting temperature for the coal ash samples
Composition, % (by mass)

T,

SiO2

Al2O3

Fe2O3

CaO

MgO

Na2O

K2O

SO3

P2O5

TiO2

DT

ST

FT

39.8

41.8

9.19

1.13

0.36

0.24

2.29

0.71

0.20

3.35

>1500

>1500

>1500

HNC13

42.1

40.2

3.94

5.77

0.59

0.41

1.13

1.78

1.22

2.26

>1500

>1500

>1500

HN115

42.3

34.5

6.17

8.55

1.00

0.21

0.76

3.20

0.55

2.24

1335

1360

1400

HN119

42.0

36.9

3.21

9.93

0.44

0.37

0.17

3.82

0.2

2.08

1434

1451

1480

KL1

47.1

35.3

4.72

5.67

0.75

0.26

1.33

2.22

0.19

1.96

1450

1500

>1500

HNP01

50.1

32.9

8.42

1.37

0.62

0.45

2.17

1.00

0.34

1.51

1425

1495

>1500

Expressed as mass fraction (%) equivalent oxide, dry basis.

Chinese J. Ch. E. 14(6) 784 (2006)

Chinese J. Ch. E. (Vol. 14, No.6)

786

4 RESULTS AND DISCUSSION

4.1 The mineral matter composition of Huainan
coal samples
The composition of mineral matter in Huainan
coals can be seen from Table 2. The mineral chemical
composition of Huainan coal includes the following
main groups: kaolinite, montmorillonite, quartz, pyrite,
calcite, dolomite, unknown groups and other minor
mineral matter. The most abundant mineral matter in
Huainan coal is that of the aluminosilicate clay minerals with quartz. They account for more than 60% of
the total mineral matter in coal. Pure kaolinite melts
more slowly than the other clay minerals because of
Table 2
Category

the more restricted chemistry and the absence of

cations such as K, Na and Ca. Therefore, the AFT of a
coal is mainly impacted by the contents of kaolinite in
a coal sample and the contents of cations such as K,
Na, Fe and Ca in minerals of coal (K, Na, Fe and Ca
which are not in the structure of aluminosilicate).
During the ash fusion process, quartz starts to dissolve
slowly in the aluminosilicate matrix of coal ash. Although smaller quartz grains fuse and are assimilated
in slag more readily, larger quartz grains may persist
longer in slag phase. Therefore, quartz as a main mineral matter in Huainan coals contributes to high AFT
of Huainan coals. Carbonates generally formed in coal

The mineralogical composition in six Huainan coal

Composition, % (by mass)

XM

HN115

HN119

KL1

HN106

HN113

quartz

4.29

4.1

3.6

0.79

1.22

iron oxide

1.58

0.65

0.48

0.36

periclase

0.02

0.06

0.03

rutile

0.44

0.03

0.42

0.41

0.15

alumina

0.38

1.47

0.71

0.75

0.62

2.96

calcite

1.79

5.93

11.57

3.01

0.16

8.63

dolomite

1.37

4.93

0.6

1.4

0.12

ankerite

0.55

1.39

0.49

0.1

kaolinite

32.67

50.15

67.63

64.99

55.31

70.92

montmorillonite

7.1

1.01

0.51

1.12

0.42

0.21

K Al-silicate

8.79

2.86

8.63

11.8

0.47

Fe Al-silicate

0.47

0.34

3.59

0.54

1.04

Ca Al-silicate

0.05

0.67

0.19

0.3

0.01

1.85

Na Al-silicate

0.03

0.79

0.18

1.67

aluminosilicate

0.28

0.14

0.05

0.07

0.04

0.14

mixed aluminosilicate

0.05

0.05

0.33

Fe silicate

0.05

Ca silicate

0.06

0.13

0.15

0.16

Ca aluminate

0.07

0.04

pyrite

10.53

12.25

6.03

2.94

10.06

0.73

pyrrhotite

1.07

0.1

oxidized pyrrhotite

0.22

0.01

0.27

0.45

0.24

gypsum

5.55

0.2

0.05

0.36

0.26

apatite

0.13

0.09

0.47

Ca-Al-P

0.09

NaCl

0.07

0.08

0.08

0.35

KCl

0.13

0.12

0.41

0.03

0.01

0.29

gypsum/Al-silicate
Si-rich

0.48

0.15

0.22

0.06

Ca-rich

0.07

0.11

1.55

0.1

0.11

0.06

Ca-Si rich

0.05

unknown

22.05

10.78

6.78

7.13

17.49

7.45

100

100

100

100

100

100

totals
December, 2006

Application of the FactSage to Predict the Ash Melting Behavior in Reducing Conditions

following the coalification process are typically found

in veins. Calcium, from calcite, may interact with
transforming clay minerals to produce calcium-rich
aluminosilicate ash particles and lower the AFT. The
variation of pyrite content in Huainan coals indicates
the different geological conditions during the coalification process. Pyrite in coals can have a significant
influence on ash fusion process. It decomposes and
fuses at a relatively low temperature.
4.2

FactSage calculation and analysis

The FactSage calculations were performed from
800 to 1600. Fig.1 shows clearly the mass percent of liquid phase as the function of temperature for
six typical Huainan coal ash samples. Although the
amount of liquid phase is fairly low at 1000, a percentage of which is definitely present, this temperature
is not reflected by AFT analysis. The mass percentage
of liquid phase formed during the heating process
varied with coal ash samples over the temperature
ranges. For HN115 and HN119, the initial liquid formation temperature is at about 1000. With an increase in temperature, the mass percentage of liquid
phase increases quickly by 75% of the overall material
for HN115 at 1400 and HN119 at 1450 respectively, which is quite fit for the tested AFT. For
HN106, the initial liquid formation temperature is
higher than that of HN115 and HN119 at about 1070
. From 1070 to 1110, the liquid phase increases
very sharply from very low percentage to 35%. Over
1110, the formed liquid increases smoothly by 63%
at 1600, which means about 40% solid present in
the slag and demonstrates why the HN106 AFT is so
high.

Figure 1

Mass percentage of liquid phase for representative Huainan coal ash samples
- - HN115; - - - - HN119; HNC13;
- - - KLI; HNP01; - HN106

Figure 2 shows the main calculation results for

ash transformation of HN115 coal with the temperature increase. The data shows that melilite
(Ca,Na)2(Al,Mg,Fe2+)(Si,Al)2O7, feldspar [XAl(1-2)Si(3-2) O8 , X in the formula can be sodium, and/or potassium, and/or calcium], quartz (SiO2), mullite
(Al6Si2O13), cordierite (Mg2Al4Si5O18), AlPO4, leucite
(KAlSi2O6), rutile (TiO2), ilmenite (FeO)(TiO2) was
formed at 800. As the temperature increases to
about 1000, liquid starts to form. About all melilite
and 50% mullite phase react to form feldspar phase
which has significant effect on the ash fusion charac-

787

teristics. From 800 to 1000, the proportion of

feldspar phase increases smoothly. At about 1000,
the proportion of feldspar phase increases sharply and
reaches maximum at temperature 1020. At temperature over 1020, the proportion of feldspar phase
and quartz decreases smoothly which results in a rapid
increase in the proportion of liquid phase. Quartz disappeared at 1200. Feldspar phase disappeared at
1400 which has excellent agreement with the tested
AFT (see Table 1). For temperature increase from over
1400 to 1600 the mass percentage of mullite
decreases from 23% to 3.4% and leucite begin to decline from 3% to 1.5%.

Figure 2 The ash transformation of HN115 coal as the

function of temperature under reducing condition
melilite; feldspar; SiO2 quartz; A16Si2O13 mullite;
KAlSi2O6 leucite; TiO2 rutile; (FeO) (TiO2) ilmenite;
SiO2 tridymite; + slag liquid; mullite

4.3 AFT measurements and the FactSage predictions

Two typical Huainan coals, HN115 with FT
1400 and HN106 with FT higher than 1500, were
selected for the comparison of tested FT and predicted
FT with the addition of CaO flux. An equivalent CaO
level of 8%, 15%, 20%, 25%, 30%, 35%, 42% of ash
mass were selected to estimate the results. The predicted FT was defined as the temperature at which the
formed liquid phase reaches 75% of the total material.
The comparison results are shown in Table 3. The results show clearly that the measured FT and the predicted FT are quite close with the maximum temperature difference less than 74 which is within acceptable range.
4.4 The experiments investigation of ash transformation by XRD
Figure 3 shows the main mineral components
change of HN115 coal ash at different temperature
under a simulated gasification environment (60%CO,
40%CO2).
As temperature increases, thermal decomposition,
transformation and interaction and phase change occur
among the components. Around 1150, anorthite
(CaAl2Si2O8) becomes stable probably due to partial
melting of the phase assemblage. Quartz and anhydrite
decrease while mullite increases. From 1150 to
Chinese J. Ch. E. 14(6) 784 (2006)

Chinese J. Ch. E. (Vol. 14, No.6)

788
Table 3
Ash samples

Comparison of the tested FT and the predicted FT by FactSage

Measured FT,

Predicted FT,

Temperature difference,

HN115

1400

1389

11

HN115(CaO,8%)

1445

1451

HN115(CaO, 15%)

1340

1396

56

HN115(CaO,20%)

1280

1302

22

HN115(CaO,25%)

1280

1294

14

HN115(CaO, 30%)

1310

1384

74

HN115(CaO,42%)

>1500

1481

HN106

>1500

>1600

HN106(CaO,8%)

1470

1470

HN106(CaO,15%)

1450

1418

32

HN106(CaO,20%)

1360

1326

34

HN106(CaO, 25%)

1310

1288

22

HN106(CaO, 30%)

1310

1364

54

HN106(CaO,42%)

1500

1512

12

Figure 3

The XRD patterns of HN115 coal ash at different temperature under reducing atmosphere (Q-Quartz, M-Mullite,
AN-Anorthite, G-Gehlenite)
T, : 11150; 21250; 31350; 41450

1350, quartz phase decreases sharply and anorthite

contents show the tendency of first increasing greatly
then decreasing. The formed mullite phase shows the
slow declining tendency with temperature over 1250.
Above 1350 the major minerals identified are mullite and non-crystalline phase. The transformation results for quartz, anorthite, mullite and non-crystalline
phase obtained from XRD are fairly consistent with
the FactSage results. The XRD findings were further
supported with FactSage calculations and indicated
that feldspar formation (including anorthite) correlated
with slag formation at temperatures around 1000.
It can be concluded from these comparisons that
FactSage, in combination with XRD can be used to
predict the reactions occurring between minerals, as
well as the ash transformation and slag formation.
This could probably be an improved way to interpret
flow properties of mineral matter in coal and assist in
quantifying slag formation in gasifier operation at
temperatures not reflected by AFT analyses.
December, 2006

CONCLUSIONS
(1) FactSage has been an important tool to predict the ash behavior and AFT at high temperature
under reducing atmosphere conditions.
(2) Huainan coal ash samples have demonstrated
a good agreement between the liquid formation as the
function of temperature and the tested AFT as well as
the ash transformation tendency with the changes in
temperature. Two typical Huainan coals have been
selected for the comparison of tested FT and predicted
FT with the addition of CaO flux. The results show
clearly that the measured FT and the predicted FT are
quite fit with the maximum temperature difference
less than 74 which is within acceptable range.
(3) The ash transformation results by FactSage
calculation are consistent with the results by XRD. It
can be concluded that FactSage in combination with
XRD can be used to predict the reactions occurring
between minerals, as well as the mineral transformation and slag formation. This is probably an improved

Application of the FactSage to Predict the Ash Melting Behavior in Reducing Conditions

way to interpret flow properties of mineral matter in

coal and assist in quantifying slag formation in gasifier operation at temperatures not reflected by AFT
analysis.

ACKNOWLEDGEMENTS
This work was supported by the key project of
Huainan Municipal Government, Anhui Province
(Project No.2003001) and the project of Japanese
Government Loan. The authors acknowledge the contributions made by the members of Ninomiyas Lab,
Chubu University and the Ash Chemistry Lab of Anhui
University of Science and Technology.

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REFERENCES
1

2
3
4
5
6
7

Jak, E., Hayes, P.C., Thermodynamic modelling of the

coal ash systems in black coal utilization, In: Proceedings of 18th Pittsburgh Coal Conference 2001, Newcastle,
Australia ( 2001).
Ninomiya, Y., Sato, A., Ash melting behavior under coal
gasification conditions, Energy Convers. Magmt, 38,
14051412(1997).
Yamashita, T., Tominaga, H., Asahiro, N., Modeling of
ash formation behavior during pulverized coal combustion, IFRF Combust. J., 8, 117(2000).
Patterson, J.H., Hurst, H.J., Ash and slag qualities of
Australian bituminous coals for use in slagging gasifiers,
Fuel, 79, 16711678( 2000).
Skrifvars, B.J., Laurn, T., Hupa, M., Korbee, R., Ljung,
P., Ash behaviour in a pulverized wood fired boilerA
case study , Fuel, 83, 13711379(2004).
Gray, V.R., Prediction of ash fusion temperature from
ash composition for some New Zealand coals, Fuel, 66,
12301239(1987).
Kucukbayrak, S., Ersoy, M.A., Haykiri, A.H., Guner, H.,
Urkan, K., Investigation of the relation between chemical composition and ash fusion temperatures for some
Turkish lignites, Fuel Sci. Technol. Internat., 11,
12311249(1993).

14

15
16
17
18
19

20

789

Llyod, W.G., Riley, J.T., Zhon, S., Risen, M.A., Ash fusion temperatures under oxidizing conditions, Energy
and Fuels, 7, 490494(1995).
Seggiani, M., Empirical correlations of the ash fusion
temperatures and temperature of critical viscosity for
coal and biomass ashes, Fuel, 78, 11211125(1999).
Yin, C., Luo, Z., Ni, M., Cen, K., Predicting coal ash
fusion temperature with a back-propagation neural network model, Fuel, 77, 17771782(1998).
Huggins, F.E., Kosmack, D.A.,Huffman, G.P., Correlation between ash-fusion temperatures and ternary equilibrium phase diagrams, Fuel, 60, 577584(1981).
Huffman, G.P., Huggins, F.E., Dunmyre, G.R., Investigation of the high temperature behavior of coal ash in
reducing and oxidizing atmospheres, Fuel, 60, 585
597(1981).
Goni, C., Helle, S., Garcia, X., Gordon, A., Parra, R.,
Kelm, U., Jimenez, R., Alfaro, G., Coal blend combustion: Fusibility ranking from mineral matter composition, Fuel, 82, 20872095(2003).
Yan, L., Gupta, R.P., Wall, T.F., The implication of mineral coalescence behavior on ash formation and ash
deposition during pulverized coal combustion, Fuel, 80,
13331340(2001).
Yin, C.G., Luo, Z.Y., Ni, M.J., Cen, K.F., Predicting
coal ash fusion temperature with a back propagation neural network model, Fuel, 77, 17771782(1998).
Rhinehart, R.R., Attar, A.A., Ash fusion temperature: A
thermodynamically-based model, Am. Soc. Mech. Eng.,
Petroleum Division, 8, 97101(1987).
Kondratiev, A., Jak, E., Predicting coal ash slag flow
characteristics, Fuel, 80, 19892000(2001).
Qiu, J.R., Li, F., Zheng, C.G., Mineral transformation
during combustion of coal blends, Int. J. Energy Res.,
23, 453463(1999).
Jak, E., Degterov, S., Zhao, B., Pelton, A. Hayes, P., Coupled experimental and thermodynamic modelling studies
for metallurgical smelting and coal combustion systems,
Metal. Trans., 31B, 621630(2000).
Bale, C.W., Chartrand, P., Degterov, S.A., FactSage
thermochemical software and databases, Calphad, 26,
189228(2002).

Chinese J. Ch. E. 14(6) 784 (2006)