Energy & Fuels 2000, 14, 349-354 349

Index for Iron-Based Slagging for Pulverized Coal Firing

in Oxidizing and Reducing Conditions
A. R. McLennan,† G. W. Bryant,*,† C. W. Bailey,† B. R. Stanmore,‡ and
T. F. Wall†
Cooperative Research Centre For Black Coal Utilization, Department of Chemical Engineering,
University of Newcastle, Callaghan, NSW, Australia, 2308, and Department of
Chemical Engineering, University of Queensland, St. Lucia, Old, Australia, 4072

Received June 16, 1999. Revised Manuscript Received December 1, 1999

A model for the prediction of iron-based slagging precursors from the combustion of iron-
containing coals is detailed. The model accounts for the form of iron (pyrite or siderite), the
distribution of iron within the pulverized coal, temperature, and oxidizing or reducing conditions.
The input required for the model is a CCSEM analysis of the pulverized coal. For oxidizing
conditions, the index predicts similar behavior for pyrite, and siderite-containing coals, with iron
alumino-silicate ash particles becoming sticky at temperatures greater than 1400 °C. This suggests
that for oxidizing conditions, the extent of included iron minerals is the most important factor.
For reducing conditions, the index predicts sticky ash particles are formed at lower temperatures,
as low as 1000 °C for pyrite-containing coals as a result of the decomposition and partial oxidation
of pyrite-forming sticky particles, and 1100 °C for siderite-containing coals. For reducing
conditions, the level of excluded pyrite mineral for pyrite-containing coals and the level of included
iron-containing minerals associated with clays for siderite- and pyrite-containing coals are the
most important factors determining slagging.

Introduction coals have usually no more than a few percent of the

Slagging refers to deposition in the region of the boiler
where radiant heat transfer is dominant, including the
burners, the main boiler waterwalls, the bottom hopper,
and, usually, the bottom of the first bank of superheater
tubes.1 Molten particles deposited on heat exchange
surfaces are retained, whereas much of the dry ash
material rebounds and is re-entrained in the flue gas.2
These ash deposits first undergo a sintering stage, but
as thickness increases, the outer layer of the deposit is
transformed to a tacky material of low viscosity 2 which
can significantly increase the growth rate of deposits.
Subsequently, large masses of semi-molten slag can
build up.2 Boiler slagging experience with pyrite coals
suggests that deposition of molten or semi-fused par-
ticles of pyrite residues may have a significant role in
the initial stages of slagging,3 with severe slagging of
pulverized fuel (pf) boilers usually being associated with
coal ashes rich in iron.2
The more common iron containing minerals found in
coals are listed in Table 1.4 North American and United
Kingdom coals are known to contain iron predominantly
in the form of pyrite.1,5-7 Australian and South African
* Corresponding author.
† University of Newcastle.
‡ University of Queensland.
(1) Couch, G. Understanding slagging and fouling in pf combustion;
IEA Coal Research: London, 1994.
(2) Raask, E., Mineral impurities in coal combustion, behaviour
problems and remedial measures; Hemisphere Publishing: Bristol, PA,
1985.
(3) Bryers, R. W. The physical and chemical characteristics of pyrites
and their influence on fireside problems in steam generators. J. Eng.
Power 1976, 517-527.
mineral matter as pyrite, with siderite generally the
dominant iron-bearing mineral.8,9,10 Indian coals are
known to have low sulfur contents (<0.5%),11 so it would
follow that iron would be mostly in the form of siderite
and clay minerals. Indonesia, with the largest coal
reserves in the South East Asian region,12 also has low
sulfur content coals (<1.0%).13 Typical iron contents
range from 10 to 15% Fe2O3 in ash,14 again likely to be
present primarily as siderite and clay minerals.
(4) Folsom, B. A.; Heap, M. P.; Pohl, J. H.; Smith, J. L. Effects of
coal quality on power plant performance and costs; Energy and
Environmental Research Corporation, Electric Power Research Insti-
tute, Project 2256-1 Final Report, 1986.
(5) Ward, C. R. Mineral matter in the Harrisburg-Springfield (No.
5) Coal Member of the Carbondale Formation, Illinois basin, Ill. State
Geol. Surv, Circ. 498, 1977, p 35.
(6) Spears, D. A.; Caswell, S. A. Int. J. Coal Geol. 1986, 6, 106-
125.
(7) Spears, D. A.; Martinez-Tarazona, M. R. Int. J. Coal Geol. 1993,
22, 1-20.
(8) Ward, C. R. Mineral matter in Australian Bituminous coals; Proc.
Aust. Inst. Min. Metall. 1978, 267, 7-25.
(9) Corcoran, J. F. 1979. In Proceedings of the Conference on
Pulverised Coal Firing: The Effects of Mineral Matter; McStewart, I.,
Wall, T. F., Eds.; University of Newcastle, Newcastle, Australia, L4-
1.
(10) Ward, C. R. Int. J. Coal Geol. 1989, 13, 455.
(11) Sanyal, A.; Roy, C. Impact of coal quality on the design,
operation and emission characteristics of Indian utility boilers, Proc.
Power-Gen International ′96, Orlando, FL., 1996.
(12) Breeze, P. Electricity in South East Asia; Financial Times
Energy Publishing, Pearson Professional Limited. London U.K.,1996.
(13) Soud, H. N. Southeast Asiasair pollution control and coal-fired
power generation; IEA Coal Research: London U.K., 1997.
(14) Osborne, D. PT Kaltim Prima coal mine development, Confer-
ence proceedings of energy efficiency improvements in Chinaspolicy
measures innovative finance and technology development, OECD/
IEA: Paris, 1996; pp 81-99.

10.1021/ef990127d CCC: $19.00 © 2000 American Chemical Society

Published on Web 01/29/2000
350 Energy & Fuels, Vol. 14, No. 2, 2000
Table 1: Common Iron Minerals in Coals, Determined by Mo1 ssbauer Spectroscopy4
mineral chemical formula
goethite R-FeOOH
pyrite FeS2
clay (illite, chlorite)
siderite FeCO3
jarosite (K,Na)Fe3(SO4)2
szomolnokite FeSO4‚H2O
Table 2: Summary of Slagging Indices1,2,4,5
index calculation
ash fusibility 4IDT + HT
5
where IDT ) initial deformation temp
HT ) hemispherical temp
viscosity T250(ox) - T1000(red)
975Fs
where
T250(ox) ) 250 poise temp for oxidizing conditions
T10000(red) ) 10000 poise temp for reducing conditions
Fs ) correlating factor
ash chemistry (Fe2O3 + CaO + MgO + K2O + Na2O) × S <0.6
SiO2 + Al2O3 + TiO2
where S ) % sulfur dry coal
Engineering indices developed from field data using
specific coals are accepted as an industrial standard,
and are presently used as a guideline for the charac-
terization of ash deposition and slagging.15 Such indices
have been summarized in a number of previous studies;
there are three basic types: those based on ash fusion
temperatures, those based on viscosity, and those based
on ash chemistry, an example of each is presented in
Table 2.1-3,15,16 All indices use laboratory ash in the
measurement of the property of interest, which is
prepared by burning a coal sample in a laboratory
muffle furnace at 815 °C. The ash fusibility test (AFT)
determines the temperature at which the various stages
of ash softening and flow take place. The test is
empirical and is based on the judgment of the analyst
as to when the ash reaches and passes through the
defined stages of softening and flow, illustrated by
changes in the profile of an inverted cone of ash. Ash
viscosity is most commonly determined using a rotating
bob immersed in a sample of molten ash in a crucible.
The viscosity as a function of temperature is calculated
from the torque required to maintain a constant angular
velocity of the bob as the crucible is heated. Using a
platinum-rhodium alloy or molybdenum bob and cru-
cible, the viscosity can be determined in oxidizing or
reducing atmospheres.17 The bulk ash chemistry is
determined as the weight percent of elemental oxides
by X-ray fluorescence spectroscopy. However, evaluation
by means of a survey of 130 boiler operators in the
United States and Europe indicated that such indices
were only 50% accurate.18,19
A recent study of the ash fusibility characteristics
indicated poor reproducibility and repeatability for the
(15) Bryers, R. W. Fireside slagging, fouling and high-temperature
corrosion of heat transfer surface due to impurities in steam raising
fuels. Prog. Energy Combust. Sci. 1996, 22, 29-120.
(16) Winegartner, E. C. Coal fouling and slagging parameter book,
No H-86; ASME, 1974.
(17) Reid, W. T.; Cohen, P. The flow characteristics of coal ash in
the solidification range, J. Eng. Power, Trans., ASME, Series A, 1944,
66, 83.
McLennan et al.
occurrence
common in weathered coals, from pyrite oxidation
very common, in most coals
common, especially in low sulfur and higher rank coals
common, especially in low-sulfur and higher rank coals
fairly common, from pyrite oxidation
fairly common, from pyrite oxidation
slagging potential
low medium high severe
>1343 °C 1232-1343 °C 1149-1232 °C <1149 °C
<0.5 0.5-0.99 1.0-1.99 >2.0
0.6-2.0 2.0-2.6 >2.6
determination of ash fusion test temperatures,20 with
the variation in some cases in excess of 200 °C.20 It was
also determined that ash samples reacted at tempera-
tures well below the initial deformation temperature
(IDT), and that at the IDT a substantial proportion (25-
60 wt %) of the sample is liquid. Hence it would appear
that the IDT is not a reliable indicator for the onset of
ash melting.
A limitation of the application of viscosity measure-
ments to predicting slagging is that viscosity can only
be measured accurately for a sample that is predomi-
nantly liquid. Alumino-silicate-based ashes, however,
solidify over a range of temperatures, and may be
partially molten and thus sticky at temperatures below
those for which viscosity can be measured. Similarly, if
a limited portion of the bulk ash melting at low
temperature is responsible for slagging, bulk ash viscos-
ity measurement may not be indicative of slagging
potential. Finally, experimental uncertainties in viscos-
ity measurement of up to (50% primarily as the result
of changes in the composition of the melt due to
reactions between the melt and crucible have been
noted.21
For the slagging index based on bulk ash chemistry,
the slagging enhancement factor incorporating sulfur
was introduced on the basis that much of the sulfur in
slagging coals is present in the form of pyrite, and that
the pyrite residue is an effective fluxing agent. However,
such an index is not expected to predict slagging for
coals with siderite as the principal iron-containing
(18) Barrett, R. E.; Murin, J. M.; Dimmer, J. P.; Mehta, A. K.
Slagging and fouling as related to coal and boiler parameters, Confer-
ence on the Effects of Coal Quality on Power Plants, Electric Power
Research Institute, Atlanta, GA, 1987.
(19) Barrett, R. E. Designing boilers to avoid slagging and fouling,
Power 1990, February.
(20) Wall, T. F.; Gupta, R. P.; Gupta, S.; Creelman, R. A.; Sanders,
R. H.; Lowe, A. Demonstration of the true ash fusibility characteristics
of Australian thermal coals. ACARP Project No. C3093 final report,
1995.
(21) Slag Atlas, 2nd ed.; Eisenhüttenleute, V. D., Ed.; Verlag
Stahleisen GmbH: Germany, 1995.
Index for Iron-Based Slagging for Puliverized Coal Firing
Table 3: CCSEM Analyses Showing Weight Percentages of Alumino-Silicate and Iron Minerals
Coal A
included excluded included
mineral (wt %) (wt %) (wt %)
silicates (SiO2) 0.4 1.7 10.2
alumino-silicates (Al2O3-SiO2) 23.0 52.1 12.4
siderite (FeCO3) 5.8 10.7 3.6
pyrite (FeS2) 0.1 0.2 0 2.4
pyrrhotite (FeS) 0 0 1.1
mineral. Furthermore, as the index is based on the bulk
ash chemistry, which may vary significantly from the
chemistry of the ash particles actually responsible for
slagging, its accuracy is questionable.
Slagging indices are typically based on the analysis
of laboratory ash, which is prepared under markedly
different conditions to those observed for pf combustion.
The high temperatures during pf combustion (1300-
1600 °C) allow the coalescence of included minerals to
produce ash particles which vary significantly in com-
position, and thus melting temperature, compared to the
ash produced from the individual mineral particles. The
laboratory ash is prepared at a lower temperature (815
°C), for which coalescence does not occur. Hence the
analysis is based on ash that is not representative of pf
combustion conditions, and thus cannot accurately
predict the slagging potential. A further limitation of
using laboratory ash is that intermediate ash species,
which may be critical to slagging, cannot be accounted
for. For example, the pyrite mineral forms a low-
melting-point FeO-FeS phase associated with slagging
3 before oxidizing to the Fe O form present in labora-
2 3
tory ash.22
Slagging indices cannot effectively account for differ-
ences in ash behavior for oxidizing and reducing com-
bustion conditions, found in conventional and air-staged
low-NOx combustion, respectively. Although AFT tem-
peratures and viscosity can be measured under reducing
conditions, the measurements are conducted on labora-
tory ash prepared under oxidizing conditions. Low-
melting-temperature phases stable under reducing com-
bustion conditions (such as the FeO-FeS phase derived
from the pyrite mineral) are not present in laboratory
ash, so the indices have a limited application for
reducing conditions.
Previous studies established the effects of reducing
conditions on ash formation mechanisms for iron-
containing pyrite and siderite minerals,23 and the role
of these minerals in coal combustion and gasification.24
The objective of this study was to develop an index to
indicate ash deposition and slagging potential for high-
iron coals in oxidizing and reducing conditions.
Model Development
Using advanced coal characterization techniques such
as computer-controlled scanning electron microscopy
(CCSEM), it is now possible to obtain a good indication
(22) Srinivasachar, S.; Boni, A. A. A kinetic model for pyrite
transformations in a combustion environment. Fuel 1989, 68, 829.
(23) McLennan, A. R.; Bryant, G. W.; Bailey, C. W.; Stanmore, B.
R.; Wall, T. F. Ash formation mechanisms during pf combustion in
reducing conditions. Energy Fuels 2000, 14, 150-159.
(24) McLennan, A. R.; Bryant, G. W.; Bailey, C. W.; Stanmore, B.
R.; Wall, T. F. An experimental comparison of the ash formed from
coals containing pyrite and siderite mineral in oxidising and reducing
conditions. Energy Fuels, submitted.
Energy & Fuels, Vol. 14, No. 2, 2000 351
Coal B Coal C Coal D
excluded included excluded included excluded
(wt %) (wt %) (wt %) (wt %) (wt %)
10.5 0.9 4.4 1.4 2.7
16.1 20.3 17.0 24.4 24.0
14.2 0 0.4 0 2.0
17.9 13.2 11.4 12.7
7.0 0.3 0.3 0.7 0.2
of the proportions of specific minerals and their associa-
tions in a coal sample. Coupled with an understanding
of the ash formation mechanisms during coal combus-
tion and gasification for these minerals, and the effect
of oxidizing and reducing combustion stoichiometries on
these transformations, an index giving an accurate
indication of ash deposition and slagging potential of a
particular coal for either oxidizing or reducing condi-
tions can be developed.
Iron-containing minerals in bituminous coals have
been identified as contributing to deposition, and previ-
ous studies have shown iron mineral ash formation
mechanisms are most affected by oxidizing or reducing
conditions.23 Hence the index developed will focus on
iron-containing minerals, and be most applicable to
bituminous coals of relatively high iron content (>10
wt % Fe2O3 in ASTM ash). The index aims to quantify
the contributions of included/excluded pyrite and sid-
erite minerals to the production of molten sticky ash
particles with potential for sticky type deposition. As
such the index was calculated as the weight percent of
sticky ash particles at a particular temperature multi-
plied by the kilograms of ash produced per tonne of coal,
to include the effect of ash levels and introduce practical
significance. The approach utilized knowledge of included/
excluded pyrite and siderite transformations under
oxidizing and reducing conditions 23 to determine if such
minerals would produce sticky ash particles at a par-
ticular temperature, while CCSEM data (Table 3) was
used to indicate the weight percent of such particles.
The model was based on a number of assumptions as
shown below:
• Excluded pyrite was assumed to be oxidized to
magnetite and hematite for oxidizing conditions, and
form a molten FeO-FeS phase for reducing conditions.23
• Excluded siderite was assumed to be oxidized to
magnetite and hematite for oxidizing conditions, and
to remain as wustite for reducing conditions.23
• The degree of association of included minerals (R)
was assumed to be 0.5. Thus, 50 wt % of included pyrite/
siderite was assumed to be incorporated into iron
alumino-silicate glass, with the remaining 50 wt %
having no contact with alumino-silicates and behaving
as for excluded pyrite/siderite. The figure of 50% was
based on Mössbauer analysis for combustion residues
of float fractions,25 containing predominantly included
minerals, for pyrite and siderite coals, which indicated
between 40 and 60 wt % of total iron was incorporated
into glass phases.
• Equal proportions of included pyrite/siderite and
alumino-silicate were assumed to combine to form iron
alumino-silicate glasssi.e., 50 wt % of included iron
(25) Bailey, C. W. Ash formation involving siderite and performance
of pf fired plants. Ph.D. Thesis. University of Newcastle, Australia,
1999.
352 Energy & Fuels, Vol. 14, No. 2, 2000 McLennan et al.

Figure 2. FeO-SiO2-Al2O3 equilibrium phase diagram.18

Figure 1. FeS-FeO and FeO-Fe2O3 equilibrium phase
diagrams.15-17

mineral incorporated into iron alumino-silicate glass

with 50 wt % of total included alumino-silicate minerals.
Iron in glass is assumed to remain entirely in Fe2+ form
for reducing conditions, with significant proportions
(>50%) oxidizing to Fe3+ form for oxidizing conditions.23
Residence time was assumed to be sufficient for
complete oxidation of iron minerals under oxidizing
conditionssi.e., pyrite/siderite oxidized to magnetite/
hematite, and significant proportions of iron present in
glass oxidized to Fe3+ form.
To establish the temperatures at which such ash
particles become sticky, reference was made to equilib-
rium phase diagrams. The FeO-Fe2O3 phase diagram,26
shown in Figure 1, indicated that melting commenced
for wustite, magnetite, and hematite phases at 1370,
1600, and 1585 °C, respectively. For the FeO-FeS and
Figure 3. Fe3O4-SiO2-Al2O3 equilibrium phase diagram.18
Fe-glass phases, where melting commences at a eu-
tectic temperature and continues over a temperature For an Fe-glass phase ash formed under oxidizing
range, the criteria for the temperature above which ash conditions with iron in both Fe3+ and Fe2+ forms, the
particles become sticky was 25 wt % molten phases. melting behavior can be determined from the Fe3O4-
Referring to the FeS-FeO phase diagram,27,28 also SiO2-Al2O3 phase diagram, shown in Figure 3. For the
shown in Figure 1, it is apparent that at a temperature entire range of typical ash particle compositions, the
of 1000 °C for compositions from 6 to 87 wt % FeO solidus temperature corresponds to the eutectic point
greater than 25 wt % molten phase exists. Previous at 1382 °C. Thermodynamic equilibrium calculations for
work has established the vast majority (>80 number a range of Fe-glass compositions for oxidizing and
%) of FeO-FeS ash particles formed under reducing reducing conditions determined that at a temperature
conditions fall within this composition range,23 so FeO- of 20 °C in excess of the solidus temperature indicated
FeS phase ash particles are assumed to be sticky for by phase diagrams, greater than 25 wt % molten slag
temperatures >1000 °C. phase exists.
As Fe-glass phase ash formed under reducing condi- Having established the temperatures at which the
tions contain iron in the Fe2+ state, the melting behavior various iron-containing ash phases for oxidizing and
can be determined from the FeO-SiO2-Al2O3 phase reducing conditions become sticky, each phase was
diagram, shown in Figure 2.29 The triangular region for assigned a smoothed step function to indicate the mass
typical ash particle compositions 24 is shown, with the fraction of sticky ash, as shown in Figure 4. The onset
hatched sections indicating the solidus temperatures. of formation of sticky particles corresponds to the solidus
temperature. A stickiness factor of 1.0 (or 100% of
(26) Muan, A.; Osborn, E. F. Phase equilibria among oxides in particles being sticky) is assigned to that temperature
steelmaking; : Reading/MA, 1965.
(27) Oelsen, W.; Mitt. K. Wilh. Inst. Eisenhüttenwes. 1961, 32, 741-
where thermodynamic equilibrium calculations indicate
751. 25 wt % slag formation for that particular composition.
(28) Schürmann, E.; von Hertwig, I. O. Gieβerei, techn.-wiss. Beih. For the Fe-glass phase under reducing conditions (i.e.,
1960, 14, 31-36.
(29) Osborn, E. F.; Muan, A. Phase Equilibrium Diagrams for Oxide the FeOn-Al2O3-SiO2 system, Figure 2), it was as-
Systems, Am. Ceram. Soc.: Columbus, OH, 1960. sumed that 30 wt % of ash particles fall within the
Index for Iron-Based Slagging for Puliverized Coal Firing Energy & Fuels, Vol. 14, No. 2, 2000 353

Figure 4. Determination of ash phases sticky as a function

of temperature.

1205-1210 °C, 1083 °C, and 1088 °C regions, and 10

wt % within the 1148 °C region, each contributing to
the function indicated in Figure 4.
The slagging index is then calculated as a function of
temperature using the CCSEM weight percentages of
included and excluded minerals, the functions defined
in Figure 4, the degree of association of included
minerals (R, assumed 0.5), and the ash content of the
coal as follows:

X(T)OX ) [(FeCO3 + FeS2 + FeS)excl*E(T)OX +

(1 - R)*(FeCO3 + FeS2 + FeS)incl*E(T)OX +
R*(FeCO3 + FeS2 + FeS + SiO2 +
SiO2 - Al2O3)incl*D(T)OX] *kg ash/tonne coal

X(T)RED ) [(FeCO3)excl*B(T)RED +
(FeS2 + FeS)excl*A(T)RED +
(1 - R)*(FeCO3)incl*B(T)RED +
(1 - R)*(FeS2 + FeS)incl*A(T)RED +
R*(FeCO3 + FeS2 + FeS + SiO2 +
SiO2 - Al2O3)incl*C(T)RED] *kg ash/tonne coal

Results and Discussion

The values of the index for Coals A, B, C, and D are
plotted for the temperature range 1000-1800 °C for
oxidizing and reducing conditions in Figure 5.
Comparison of the plots for oxidizing conditions
reveals similar behavior for all coals. At approximately
1400 °C the contribution from Fe-glass phase becomes
effective, with a further increase at ∼1600 °C due to
magnetite and hematite. The Fe-glass phase is formed
from the coalescence of included pyrite or siderite and
alumino-silicate minerals, which is dependent on the
proportion of included minerals and their degree of
association. The magnetite and hematite is formed from
excluded pyrite or siderite, and included pyrite or
siderite not closely associated with other minerals. Figure 5. Slagging index for oxidizing and reducing condi-
tions as a function of temperature for (a) Coal A, (b) Coal B,
Hence for oxidizing conditions, ash deposition and
(c) Coal C, and (d) Coal D.
slagging potential is most influenced by the level of
included iron minerals and their degree of association °C is due to wustite derived from excluded siderite and
with alumino-silicates, not by the total iron content. included siderite not closely associated with other
For siderite-containing Coal A the reducing atmo- minerals, ∼200 °C lower than for oxidizing conditions.
sphere plots show the contribution of the Fe-glass phase Hence for siderite-containing coals under reducing
becoming significant at 1100 °C, 300 °C lower than for conditions, the ash deposition and slagging potential is
oxidizing conditions. A further contribution at ∼1370 again most influenced by the level of included iron
354 Energy & Fuels, Vol. 14, No. 2, 2000
minerals and their degree of association with alumino-
silicates, not by the total iron content.
For pyrite-containing Coals B, C, and D the plots show
the contribution of the FeO-FeS phase is significant
at temperatures as low as 1000 °C, 400 °C lower than
for oxidizing conditions. Further contributions to sticky
ash proportions are noted at 1100 °C due to Fe-glass
derived from included pyrite or siderite and alumino-
silicate minerals, and at ∼1370 °C (Coal B) due to
wustite derived from excluded siderite and included
siderite not closely associated with other minerals.
Hence for pyrite-containing coals under reducing condi-
tions, sticky ash particles are formed at low tempera-
tures from both included and excluded pyrite mineral,
thus ash deposition and slagging potential is influenced
by the total iron content.
Under oxidizing conditions, the residence time may
not be sufficient for the complete oxidation of pyrite to
magnetite or haematite,24 as assumed by the model,
which may cause the index to underestimate the mass
of sticky ash. Under reducing conditions, some oxidation
of pyrite and siderite to form magnetite in the early
stages of combustion before oxygen depletion may
occur,13 rather than forming FeO-FeS phase and wus-
tite as assumed by the model, and may cause the index
to overestimate the mass of sticky ash. Considering
these issues, the values given by the index may be
viewed as indicating the extremes of behavior for
oxidizing and reducing conditions. However, incorpora-
tion of a kinetic model for the oxidation of pyrite and
siderite to introduce residence time as a variable would
allow more accurate predictions to be performed using
the index.
Mineral particle size can also have significant effects
on slagging mechanisms. Generally, smaller ash par-
ticles (<5µm) are associated with fouling, while larger
ash particles (>5µm) are associated with slagging. Thus
the larger excluded minerals are likely to produce ash
particles that contribute to slagging. These larger
excluded minerals are also slower to oxidize, further
enhancing their slagging potential. Coalescence of in-
cluded minerals also produces ash particles large enough
to contribute to slagging. However, recent work30 has
shown the degree of coalescence of included minerals
to be primarily dependent on the extent of char frag-
mentation, which in turn is influenced by char struc-
ture. As CCSEM analysis of a coal sample also yields
the particle size of the minerals, consideration of these
effects could be incorporated into the model to further
improve it.
Overall, the index reveals a significant increase in the
ash deposition and slagging potential of high-iron coals
for reducing conditions compared to oxidizing conditions.
At lower temperatures (<1400 °C) the effect is seen to
(30) Wu, M.; Wall, T.; Liu, G.; Bryant, G. Ash liberation from
included minerals during combustion of pulverized coal: The relation-
ship with char structure and burnout. Energy Fuels 1999, 13, 1197-
1202.
McLennan et al.
be greater for pyrite-containing coals than for siderite-
containing coals. The incorporation of the specific
mineral forms and the use of individual mineral ash
formation mechanisms for oxidizing and reducing condi-
tions provides a much more accurate basis for predicting
ash deposition and slagging potential than previous
indices.
Ultimately, the validation of this index with pilot or
full-scale boiler tests would be of considerable benefit.
CCSEM analysis of coals known to have produced
slagging above certain temperatures in full-scale boilers
could be used as input for the model to see if it predicts
slagging at a similar temperature. Pilot-scale tests over
a range of temperatures under oxidizing and reducing
conditions would also allow comparison of slagging
behavior found and that predicted by the index. This
could be accomplished by tapping slag at the base of
the boiler, quenching, and measuring the mass. Dividing
the mass of the slag by the mass of the coal fed at each
test temperature would generate the data points to plot
a curve for comparison to that of the index. If good
agreement were found between the index and boiler
tests, an approximate mass of sticky ash per tonne of
coal (predicted by the index) may be related to the onset
of slagging (in a boiler). The index could then predict
from a coal’s CCSEM data the temperature above which
slagging is likely to occur.
Conclusions
The index successfully combines CCSEM data and
knowledge of ash formation mechanisms to predict ash
deposition and slagging potential for coals with a high
iron content with significantly greater confidence than
previous indices.
For oxidizing conditions, the index predicts similar
behavior for pyrite- and siderite-containing coals, with
iron alumino-silicate ash particles becoming sticky at
temperatures greater than 1400 °C. This suggests that
for oxidizing conditions the level of included iron miner-
als is most important with respect to ash deposition and
slagging potential.
For reducing conditions, the index predicts sticky ash
particles are formed at significantly lower temperatures,
as low as 1000 °C for pyrite-containing coals due to the
products of decomposition and partial oxidation of
pyrite, and 1100 °C for siderite-containing coals. This
suggests that for reducing conditions, the level of
excluded pyrite mineral for pyrite-containing coals and
the level of included iron-containing minerals for sid-
erite- and pyrite-containing coals are the factors which
determine furnace slagging during pulverized coal
combustion.
Acknowledgment. The authors acknowledge the
financial support provided by the CRC for Black Coal
Utilisation, which is in part funded by the CRC’s
program of the Commonwealth Government of Australia.
EF990127D