Fuel 139 (2015) 720732

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Fuel
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Inhibition of lignite ash slagging and fouling upon the use

of a silica-based additive in an industrial pulverised coal-red boiler.
Part 1. Changes on the properties of ash deposits along the furnace
Bai-Qian Dai a, Xiaojiang Wu a,b, Anthony De Girolamo a, Lian Zhang a,
a
b

Department of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia

R&D Division, Shanghai Boiler Works Co. Ltd., Minhang, Shanghai 200245, China

h i g h l i g h t s
 Adding >4 wt% silica is essential in promoting the agglomeration of ash.
 Formation of friable calcium sulfate is favored by the use of silica additive.
 The capture of Na led to the transformation of Na into coarse bottom ash.
 A portion of Fe was precipitated as discrete grains out of slag matrix.
 Mg was highly crystallised within the slag.

a r t i c l e

i n f o

Article history:
Received 11 March 2014
Received in revised form 15 May 2014
Accepted 25 June 2014
Available online 11 July 2014
Keywords:
Pulverised lignite (Xinjiang) combustion
Slagging and fouling
Silica additive

a b s t r a c t
In this paper, we, for the rst time report the properties of ash deposits collected from the combustion of
lignite mixed with silica additive, in a 30 MWth pulverised-fuel boiler with sub-critical steam conditions.
The combustion test was carried out continuously over ten months, and ash deposits were sampled from
various locations in the boiler. As has been conrmed, the ash-related slagging and fouling have been
controlled effectively. Apart from capturing volatile alkali and alkaline earth metals, silica added in an
excess amount is benecial in mixing with molten liquidus to promote their agglomeration, rather than
adhering to the vicinity of coal burners for slagging. Compared to the formation of abundant Fe2+-slag
that is prone to stick to coal burner vicinity in the raw coal case, the formation of friable calcium sulfate
in reside deposit is favored upon the mixing of silica with coal, which is even predominant in the reside
ash deposit. The calcium sulfate formed is highly layered in a plerospheric structure in which Ca-silicate
is present as the core with calcium sulfate being the shell. The physical adsorption of free Ca on silicate
surface is supposed to enhance its specic surface area for a quicker sulfation. The capture of Na by silica
is also efcient, leading to the transformation of a remarkable portion of Na into coarse bottom ash with
less being sulfated. This in turn alleviates the sulfate relating fouling propensity on the water tube
surface in the convection zone. A noticeable portion of Fe was noticed to remain as discrete grains outside
the Ca-rich slag matrix. In contrast, the majority of Mg is highly crystallised as sub-micrometer Ca/Mgsilicate and oxide particles residing within slag matrix, which in turn increase the viscosity and decrease
the sticking propensity of the molten slag.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
With the depletion of high-rank coals and petroleum, the use of
low-rank subbituminous coal and lignite (i.e. brown coal) has been
receiving increased attention in the energy and mining industries.

Corresponding author. Tel.: +61 3 9905 2592.

E-mail address: lian.zhang@monash.edu (L. Zhang).
http://dx.doi.org/10.1016/j.fuel.2014.06.054
0016-2361/ 2014 Elsevier Ltd. All rights reserved.

China is the largest coal producer and consumer in the world and
the annual coal consumption has been rapidly growing in the past
decade [1]. Recently, one of the largest integrated coal reserves has
been found in Xinjiang area, China, containing more than 390 billion tons of lignite that can be used for more than a hundred years
based on the current annual coal consumption rate [2]. However,
sub-bituminous coal and lignite have notoriously high amounts
of alkali and alkaline earth metals, which are prone to intensify
the ash slagging and fouling propensity in a boiler [35].

721

B.-Q. Dai et al. / Fuel 139 (2015) 720732

The averting of ash slagging has improved remarkably upon the

use of advanced techniques. Most coal red boilers are equipped
with soot blowers that use a high-pressure jet of superheated
steam, saturated steam, water or compressed air to remove ash
deposits [6]. However, the soot blowing is energy-intensive, and
hence, its utilisation negates the overall efciency of a boiler and
causes erosion and damage to water tubes as well [7]. Another
method of reducing fouling is on-line analysis of coal feed properties. Using techniques such as Prompt Gamma Neutron Activation
Analysis (PGNAA), an elemental assay of the coal can be obtained
promptly to feedback information to the mine or preparation plant
to adjust the operating conditions of a boiler, or to blend different
coal together [8].
Apart from coal blending, the use of a fuel additive is another
practical method to minimise ash slagging and fouling propensity
in a boiler. The mineral additive acts as a capturer to mitigate
fouling by capturing certain chemicals that have been linked to
slagging and fouling, particularly alkali and alkaline earth metals
[9,10]. To date, a variety of additives have been examined on different coals in laboratory-scale and pilot-scale facilities. As summarized in Table 1, Locklin et al. reported the use of limestone
additive to reduce the viscosity of slag when low-sulfur coals were
burned in a cyclone-red boiler, at a limestone dosage rate of
10 wt% of the coal feed [11]. A South Australian brown coal was
tested in a 0.35 MW pulverized-fuel furnace for eight hours with
both using clay and dolomite as additives. The dolomite was proven effective in halving the deposit strength, whereas clay was able
to reduce the bond strength and the contents of Na and S in ash
deposit [12]. Loy Yang brown coal has been tested on a 35 kg/h
pulverized-fuel furnace as well as a drop tube furnace. The use of
kaolin was proven effective in reducing the deposit hardness and
stickiness [13,14]. Kyi and Chadwick tried a variety of additives
mixed with Loy Yang and Yallourn coals to clarify the alkali elements capture ability in a mufe furnace. The high levels of alkali
retention have been conrmed for low dosages of additives (1%)
[15]. A bituminous coal was tested on a combustion entrained
reactor with the additive of kaolin and emathllte by Ronald G
et al. They found both additives were effective in reducing sticking
coefcients at 11001300 C [16]. A forestry residue biomass had
been tested on a pilot-scale (35 MW) circulating uidised bed
(CFB) boiler with an additive of kaolin at a relatively low temperature for a continuous operating of seventeen days. The superheater deposition/corrosion and bed agglomeration were reduced
signicantly [17]. As summarized here, to date, most of the information was obtained from lab-scale or at most pilot-scale research
for a very short ash exposure period. In a real boiler, the ash

deposit growth usually takes a number of months. Its formation

is also highly dependent on ue gas ow patterns and temperature
proles which are usually more complex in a real boiler than in
lab-scale facilities. To the best knowledge of the authors, the test
of silica-based additive in a real industrial boiler over a long period
has not yet been conducted. Therefore, the capability of silica on
ash slagging/fouling minimisation is still uncertain, so are the
properties of the ash formed from coal mixed with silica.
This paper aims to clarify the properties of ash deposits in a
30 MWth industrial pulverised coal-red boiler where a lignite
was mixed with 14 wt% nely ground silica. This study is complementary to our previous work for the combustion of raw coal in the
same industrial facility [18]. The combustion test of coal mixed
with additive was continued for approximately ten months. After
the shutdown of the furnace, the ash deposits were collected from
various locations along the furnace, from bottom ash to reside
slag, to ash deposits in convection zone and y ashes exiting the
furnace. Each ash deposit sample was characterised by using
laboratory-based spectrometers including X-ray uorescence
(XRF), X-ray diffraction (XRD), scanning electron microscopies
(SEM) coupled with energy dispersive X-ray (EDX) and Mssbauer
spectroscopy (MS) for iron speciation, and synchrotron-based
extended X-ray adsorption near-edge structure (EXANES) for sulfur
speciation. Thermodynamic equilibrium calculation using FactSage 6.4 was nally conducted to interpret the experimental
observations. This part introduces overall properties of the ash
deposits collected from different positions in the boiler, and the
second part will provide a detailed mechanism regarding the speciation of iron and the separation of magnetic particles from y ash
[19]. Through a detailed characterisation of ash deposits, we aim to
explore new scientic knowledge that cannot be found from
lab-scale studies. Moreover, we expect to clarify and maximise
the utilisation efciency of silica additive in a real industrial boiler
environment.

2. Experiment section
2.1. Properties of lignite coal sample and silica additive
The properties of the lignite tested and its ash fusion temperatures are tabulated in Table 2. Note that, the ash properties were
based on the sample collected by coal ashing in mufe furnace
conducted under the American Society for Testing and Materials
standard (ASTM D3174-12). The as-received coal has relatively
high moisture content, whereas its ash-forming metals account

Table 1
Literature survey on the use of additives to lignite for ash slagging/fouling control.
Coals

Additives

Effects

Experimental setup

Conditions

Time

Refs.

Low-sulfur coals

Limestone

Reduce the viscosity of slag

Cyclone-red boiler

[1]

South Australian
brown coals

Dolomite
Clay

Reduced deposit strength by half

Reduced bond strength and Na and S in
deposit

130 kg/h (0.35 MWth) test

facility

1250 C

8h

[2]

Loy Yang coal

Kaolin
Kaolin
Silica
Alumina

Reduced deposit hardness

Kaolin particularly effective at reducing
stickiness

35 kg/h furnace
Drop tube furnace

1000
1400 C

[3]
[4]

Loy Yang coal

Yallourn coal

Bentonite Kaolin Miclay Pyrophyllite

Diatomite Pumice Overburden

High levels of alkali retention in the ash

with low dosages of additives (1%)

Mufe furnace

1000
1200 C

2h

[5]

Arkwright
Pittsburgh
bituminous

Kaolin Emathllte

Both effective at reducing sticking

coefcient

Combustion/deposition
entrained reactor (CDER)

1100
1300 C

10 min

[6]

Forestry residue
biomass

Kaolin

Reduced superheater deposition and

corrosion and bed agglomeration

35 MW circulating
uidised bed (CFB) boiler

810
840 C

17 days

[7]

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B.-Q. Dai et al. / Fuel 139 (2015) 720732

Table 2
Coal properties and its ash fusion temperature.
Proximate analysis (wt%)
Mar
13

Ad
4.2

Vd
29.3

Ultimate analysis (wt%)

FCd
66.5

Cd
76.3

FT
1420

DT
1240

Hd
2.8

Od
15.9

Nd
0.47

Sd
0.33

HT
1350

FT
1400

Ash fusion temperature (C)

Oxidising atmosphere
DT
1300

ST
1360

HT
1400

Reducing atmosphere
ST
1290

Symbols: ar for as-received basis and d for dried basis. DT deformation temperature, ST soft temperature, HT hemisphere temperature, FT owing temperature.

for 4.2 wt% in total. The sulfur content is also very low, accounting
for 0.33 wt% on the mass basis of dried coal. In addition, the coal
has a relatively high volatile content, which is released at a comparable rate with the published results for bituminous coals [20]. The
char-O2 reactivity of the lignite studied here is much higher than
that of bituminous coal, due to the catalytic effects of its ash-forming metals [20].
For the mufe furnace ash of the raw coal, its melting
commences at 1240 C and 1300 C under reducing and oxidising
environments, respectively. This is relatively low, considering that
coal ame reaches approximately 1500 C in an industrial boiler. In
Table 3 are present the elemental compositions of raw coal ash and
the silica additive. Clearly, the high contents of basic oxides (Ca, Na,
Mg, Fe and K) account for the low melting points of the raw coal
ash. For the silica additive tested, it is exclusively predominated
by acidic SiO2 and Al2O3 with a total amount of 93.9 wt% in total.
Its XRD curve in Fig. S1 in the supporting information (SI) le
suggests the predominance of quartz (SiO2) and a few amount of
kaolin. The other impure elements within the silica additive are
trivial. The microstructure of the raw additive is shown in Fig. S2,
indicative of a crystallised surface for individual particles. The particle size distribution and surface area of the raw silica are shown
in Figs. S3 and S4, indicating a broad size distribution and very
small surface area. In addition, the silica was thermally annealed
at 1300 C in a horizontal tubular reactor to examine if there is
any change on its own structure and phase at high temperature.
2.2. 30 MWth pulverised coal-red boiler for combustion test
The structure of the boiler has been visualised in our previous
paper [18]. Coal particles, either alone or mixed with silica additive, were fed tangentially into the boiler, whereas the hot ue
gas generated passes a variety of tubes from ame zone with an
average temperature of 1300 C through to furnace exist with a
temperature of approximately 130 C. For the combustion of either
raw coal or coal mixed with additive, the airfuel ratio is xed at
1.2 with an unreacted/excess oxygen fraction of 3% in the exhaust
ue gas. Raw coal combustion was rst tested in the period of
AprilOctober 2012, with frequent shutdown and maximum two

Table 3
Raw coal ash and additive compositions, wt%.

SiO2
Al2O3
CaO
MgO
Fe2O3
Na2O
K2O
SO3
Others

Raw ash

Silica additive

23.43
13.76
27
8.83
5
9.94
0.5
9.34
2.2

71.93
21.97
0.22
1.62
1.16
0.01
1.75
0.19
1.15

months for a continuous operation of the boiler. The mixing of coal

with silica was commenced in November 2012, which was
achieved by simply mixing coal and silica at pre-determined mass
ratio prior to entering coal mill. Coal particle size after the mill is
mostly smaller than 90 lm. Coal combustion was continued
without any shutdown until October 2013 when a new 330 MWth
boiler was commissioned to replace the small boiler for internal
power generation. The ash deposits were collected from the same
positions as that conducted for raw coal case, so as to diagnose the
effectiveness of silica and its interaction with ash-forming metals
for the minimisation of slagging and fouling in the boiler.
In order to maintain the continuous operation of the boiler, only
70% of BMCR (Boiler Maximum Continuous Rating) was achieved
under the raw coal combustion conditions, otherwise, the boiler
would be shut down frequently due to severe ash slagging/deposition problems. For the raw coal running at 70% of BMCR, its steam
output reaches approximately 102 t/h. Upon the addition of silica
additive, the steam output was increased to 112 t/h without any
observed changes to ash slagging and fouling in the boiler. The
increase in steam output is partially due to a slight increase in coal
feeding rate from 15.8 t/h for raw coal alone to 17.3 t/h, and
partially attributed to a cleaner surface of all tubes for a less heat
loss by the fouled ash layer. It is also noteworthy that, the slight
increment in coal feeding rate caused a slight, if not negligible
variation in ue gas temperature. For instance, the ue gas temperature at the super-heater outlet was 842.1 C when the additive
was absent, and was changed to around 858.3 C when the additive
was added in. For either raw coal or coal mixed with silica case, the
ue gas temperature below the platen superheater was around
1300 C, which is close to ash fusion temperatures listed in Table 2.
The added silica is suggested to slightly increase coal ame temperature due to its catalytic effect on promoting the cracking of
volatiles into light hydrocarbons [20]. Such an effect is however
marginal, if not negligible here. The variation in coal ame
intensity and ue gas temperature prole upon the use of silica
was not noticed. Therefore, the changes on ash properties to be discussed later cannot be assigned as the effect of temperature in the
boiler. The change on induced fan (IF) opening degree and pressure
rise is rather noticeable. Due to the formation of extra silica-related
y ash particles, the IF opening degree was increased from 83% for
raw coal to 89% for coal mixed with silica, whereas its pressure rise
was raised from 2.1 kPa to 2.36 kPa. The ash deposits sampled
include bottom ash S, Feston tube deposit H (ue gas temperature
756 C), superheater deposit A at 701 C, reheater tube deposit
B of 507 C, economiser deposit C at 428 C, preheater ash
deposit D of 330 C, preheater ash deposit E of 152 C and y
ash F exhausted at 130 C out of the furnace.
2.3. Ash deposit sample characterisation
For elemental analysis by XRF, XRD, MS and XANES, each sample was rst ground to less than 0.038 mm. XRF analysis was conducted by SPECTRO iQ II. A RIGAKU X-ray powder diffractometer
was applied to collect XRD spectra, using Cu Ka radiation (40 kV,
15 mA, Ka1 = 0.13 mm). The samples were scanned with a step size
of 0.01 at 1/min over a 2h range of 290. Quantitative XRD was
conducted based on Rieveld least squares tting method and
through the use of Siroquant 3.1. All the raw spectra and respective
tted curves are illustrated in the SI document.
MS for iron speciation was conducted at room temperature.
Each sample was exposed to a beam of gamma radiation during
the MS analysis, and a detector measured the intensity of the beam
transmitted through the sample. The velocity range of the scanning
here varied from 12 mm/s to 12 mm/s. The source of 57 C in
rhodium was maintained at room temperature. S K-edge XANES
spectra were collected at the National Synchrotron Radiation

B.-Q. Dai et al. / Fuel 139 (2015) 720732

Research Centre (NSRRC) BL16A1 beam line, Taiwan. The X-ray

beam was diffracted by a xed-exit double crystal Si (1 1 1)
monochromator to vary the X-ray energy. The energy scale was
calibrated with reference to elemental S K-edge absorption peak
with energy of 2472 eV. Each spectrum was recorded from about
200 eV below the edge to 250 eV above the edge. A nonlinear
least-squares tting procedure, using linear combination of normalized spectra of standard compounds in the software ATHENA
was used to provide a descriptive information of the forms of sulphur as well as their fractions. More details for this method has
been described in our previous works [21,22].
For sample morphology observation, both optical microscopy
and SEM (JEOL JSM-7001F) were employed. Each sample was
observed as it is, for the measurement of its surface morphology
and elemental composition. In addition, the cross-sections of
numerous ash deposits were observed by a prior grounding. Sample grounding was achieved by rst mounting it in epoxy resins,
which was polymerised subsequently, and nally ground by silicon
carbide paper and diamond paper.
2.4. FactSage thermodynamic equilibrium modelling
The quaternary oxide system of CaOFeOSiO2O2 was
simulated under the conditions of 1300 C and 1 atm, through
the module Phase Diagram in FactSag 6.4. The database of ?Slag_liq, non-ideal gas and solid were chosen. The O2 partial pressure
was set as 0.05 atm, referring to approximately 5% of O2 in ue gas.
The percentage of Na captured by silica was simulated as a
function of silica amount and temperature, on the assumption that
silica additive is pure SiO2, and the aforementioned databases were
used again.

Bottom ash fraction %

14

Experimental

12
10
8
6
4
2
0
0%

2.2%

3%

3.3%

4%

Additive %
Fig. 1. Bottom ash fraction as a function of silica additive amount.

723

3. Results and discussion

3.1. Overall ash properties upon the use of silica additive
The rst series of experiments were designed to optimize the
amount of silica to be mixed with coal. The silica mass percentage,
based on the mass of coal feed, was varied from 0 wt% to 4 wt%,
and each percentage was tested for a combustion period of 2
5 days. Fig. 1 indicates the fraction of bottom ash on the mass basis
of total ash collected as a function of silica addition percentage.
With the increase of silica amount from zero (raw coal case) to
3 wt%, the bottom ash fraction was increased rapidly from around
3 wt% to 9 wt%. A further increase of silica amount to 4 wt% caused
a rather slower rise on the bottom ash fraction. Although it is
envisaged that a portion of the unreacted coarse silica may move
into bottom ash directly, the use of silica apparently promoted
the agglomeration of ash-forming metals in the lignite. The resulting coarse agglomerates should bear a large viscosity and a lower
sticking propensity. The on-site observation has proven the stable
formation of coarse bottom ash and easiness of removing the reside slag by soot blower for the case of adding 4 wt% silica to coal.
For this reason, the silica amount was xed at 4 wt%, and the combustion test was continued for extra ten months. The ash deposits
discussed hereafter refer to this case, unless otherwise mentioned.
Fig. 2 visualises the macro-structures for the cross-section of
bottom ash and re-side slag collected with the addition of silica
to coal. Clearly, the bottom ash is composed of agglomerated clusters in which the solid powders are bridged by molten species
together. The reside ash deposits possess a rather layered structure, in which are embedded the bright round (thus molten) spots.
Such a structure is very friable and hence, it was removed easily by
soot blower. For reference, the raw coal reside ash deposit has a
thick dense initial layer rich in Fe2+-slag, which was stuck to water
tube surface rmly [18]. It was clearly broken by the attack of the
silica additive.
Fig. 3 depicts a comparison of the overall ash deposit compositions along the boiler with and without additive. The use of
additive led to a noticeable shift of a variety of elements including
Fe, Na, Ca and S along the furnace. Specically, the quantity of Fe in
reside ash deposit G is reduced remarkably by the use of silica.
Instead, a large portion of Fe is distributed in the ash deposits
collected from economiser E and y ash F. This is apparently the
major reason causing the aforementioned mitigation of ash reside
slagging. For Na, few of it is present in the re-side slag G for the
case of coal mixed with silica, whereas the majority of it moves
to re-heater ash deposit labelled B. Another noticeable change is
the distribution of S, which is present in reside slag for the case
of coal mixed with silica, in comparison to negligible S in the
raw coal reside slag G. For S in other ash deposits from H through
to D, one can also see an increase on its concentration when compared with respective raw coal ash deposit. Apparently, apart from

Fig. 2. Optical photograph of bottom ash aggregate (a) and reside deposit (b).

724

B.-Q. Dai et al. / Fuel 139 (2015) 720732

with the peak centring at 650 C [23], the shift observed here is
clearly benecial in reducing ash deposits in the convection zone,
thereby enhancing the lifetime of the water tubes exposed at high
temperature.

with additive

without additive

100

80
Fe2O3
CaO
SO3
SiO2
Al2O3
MgO
Na2O

wt%

60

40

20

0
S G H A B C D E F -- S G H A B C D E F

Sample location
Fig. 3. Elements composition of ash deposit samples from S to F for the combustion
of raw coal and coal mixed with 4 wt% additive. The letters on X-axis are for:
bottom ash S, Feston tube deposit H (ue gas temperature 756 C), superheater
deposit A at 701 C, reheater tube deposit B of 507 C, economiser deposit C at
428 C, preheater ash deposit D of 330 C, preheater ash deposit E of 152 C and
y ash F exhausted at 130 C out of the furnace. The results for raw coal were cited
from Ref. [18] with the copyright from American Chemical Society obtained in
February 2014.

5.5
Without additive
With additive

5.0
4.5

B/A ratio

4.0
3.5
3.0
2.5
2.0
1.5

Flame zone

super-heater

convection zone

pre-heater zone

zone

1.0
0.5
0.0

RT

1300

800

700

500

400

320

150

130

o
Deposition temperature / C

Fig. 4. Base to acid ratio for ash deposit as a function of sampling locations. RT
denotes room temperature for bottom ash collection.

being captured by silica, the sulfation of alkali and alkaline earth

metals is also enhanced. These changes altered the basic to acid
ratios of ash deposit along the furnace. As shown in Fig. 4, the basic
to acid ratio is peaked at super heater zone for the raw coal case,
where the temperature ranges from 750 C to 650 C. Such a temperature window is most suitable for ash sulfation, fouling and
tube corrosion. Upon the use of silica additive, the basic to acid
ratios were split at two major positions, one being reside slag in
the combustion zone, and one being economiser ash deposits
formed at approximately 320 C. However, considering that the
correlation of tube corrosion versus temperature bears a bell-shape

3.2. Properties of bottom ash and reside deposit

The XRD spectra referring to crystalline species in bottom ash S
and reside slag G are illustrated in Figs. S5 and S6 in the SI. Table 4
lists the quantitative results obtained from Siroquant tting. Irrespective of the use of silica addition, quartz (SiO2, melting point
(MP) = 1710 C) is the single predominant crystalline present in
bottom ash, followed by anorthite (CaAl2SiO8, MP = 1553 C)) with
a medium amount (1020 wt%). Gehlenite (Ca2(Al(Si,Al)2O7) is the
minor species in raw coal bottom ash, which is accompanied by
hematite (Fe2O3, MP = 1565 C) in the case of silica additive being
mixed with coal. These species should refer to the unreacted silica
or those formed by crystallisation during bottom ash quenching.
Irrespective of the formation route, these crystallised particles
apparently increased the viscosity of ash agglomerates, which are
thus difcult to stick to burner surroundings. The SEM photography for the cross-section of bottom ash in Fig. 5 witnessed the existence of highly crystallised particle that are embedded rmly in
slag matrix. In panel (a) are the unreacted silica crystals encapsulated within dense slag phase. On the other hand, panel (b) demonstrates the abundance of irregular ne particles isolated from slag
phase matrix. Fig. 6 for the amplied elemental mapping of a portion of Fig. 5(b) conrmed that these isolated particles are Fe-rich
and free of Si, Al and Ca that are composed of the slag network.
Apparently, a portion of these precipitates should refer as to hematite detected by XRD. For the inherent iron in coal, it is initially
reduced to ferrous cation (Fe2+) on char surface, which is a good
slag network modier. However, upon the oxidation by ue gas
into ferric cation (Fe3+), it prefers to precipitate out as isolated
species or form ferrite. This is proven by the Phase Diagram for
SiO2CaOFeO at an oxygen partial pressure of 0.05 atm in Fig. 7.
Based on the average ash composition, the raw coal point (open
cycle) falls in the area where slag liquidus and Ca2SiO7 are formed.
Adding silica incurs the formation of solid SiO2 and CaSiO3 (the
dense cycle point), both of which were conrmed by the XRD
results in Table 4. Interestingly, the reside slag compositions, irrespective of the use of silica or not, show a great discrepancy to the
average ash property. That is, the raw coal reside slag falls in the
area predominated by slag and no solid phase formed. Adding silica
moved the reside ash point (open star) to the boundary line for
the formation of solid SiO2(s4) and Fe2O3 (dense star). The extra
Fe2O3 discrete species are not contributed from the silica additive.
SEM observation of the thermally annealed silica at 1300 C in
Fig. S2 (panel (b)) failed to nd any discrete Fe-bearing particles
within it. A detailed discussion on iron speciation and separation
will be discussed in the second part of this study.
The crystalline species in reside ash deposit/slag differ from
bottom ash. For raw coal combustion, wollastonite (CaSiO3,
MP = 1540 C)) is most prevalent, followed by anorthite and
hedenbergite (CaFeSi2O6) with medium content, and stishovite
(SiO2), gehlenite, calcite (CaCO3) and periclase (MgO,
MP = 2832 C) in minor concentration (<10 wt%). The variation of

Table 4
Abundance of crystalline species in bottom ash and re-side deposit, according to Siroquant leave-squares Rieveld tting results.
Sample

Major phase (P20%)

Medium phase (1020%)

Minor phase (<10%)

No additive
With additive

Quartz (SiO2)
Quartz

Anorthite (CaAl2Si2O8)
Anorthite

Gehlenite (Ca2(Al(Si,Al)2O7)
Hematite (Fe2O3) > Gehlenite

No additive
With additive

Wollastonite (CaSiO3)
Anhydrite (CaSO4)

Anorthite > Hedenbergite (CaFeSi2O6)

Stishovite (SiO2) > Gehlenite > Calcite (CaCO3) > Periclase (MgO)
Calcite > Periclase > Magnetite (Fe3O4) > Quartz (SiO2) > Hematite (Fe2O3)

B.-Q. Dai et al. / Fuel 139 (2015) 720732

725

Fig. 5. Morphology of bottom ash collected from coal mixed with silica additive.

Fig. 6. Elemental mapping for a part of photo (b) shown in Fig. 5(b).

(1): Gas_ideal + Aslag_Liq + CaSiO3(s2)

(2): Gas_ideal + Aslag_Liq + Ca2SiO4(s2) + Ca3Si2O7(s)
(3): Gas_ideal + Aslag_Liq + Ca2Si2O7(s)
(4): Gas_ideal + Aslag_Liq + Ca2SiO4(s2) + Ca3Si2O7(s)
(5): Gas_ideal + Ca2SiO4(s2) + Ca3SiO6(s) + Ca2Fe2O5(s)
(6): Gas_ideal +Aslag_Liq + Ca2SiO4(s2)
(7): Gas_ideal + Aslag_Liq + Ca2SiO4(s2) + Ca2Fe2O5(s)
(8): Gas_ideal + Aslag_Liq

Fig. 7. SiO2CaOFeOO2 thermodynamic equilibrium systems for raw coal and the mixing of silica with coal. Temperature 1300 C, O2 partial pressure 0.05 atm. The
symbols: open cycle (raw coal average ash composition); dense cycle (coal mixture average ash composition); open star (composition of reside ash for raw coal); and dense
star (composition of reside ash for coal mixed with silica additive).

chemical formula for Ca(Fe)AlSi crystals reect a heterogeneous

distribution of the ash-forming elements within the raw coal. The
preferential existence of CaAlSi in reside slag reects the fact
for a frequent interaction between these three elements and that

these three elements compose of ash slag network. Fe is another

metal found in reside slag (see Fig. 3), which is however undetectable by XRD. This proves the incorporation of Fe in forms of amorphous species such as Fe2+-slag and Fe3+-slag within ash slag [18].

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B.-Q. Dai et al. / Fuel 139 (2015) 720732

Ca

Si

Al

Fe

Mg

50 m
Fig. 8. Microstructure of re-side deposit G and its elemental mapping.

The minor calcite should be formed during cooling stage, indicating the existence of unreacted CaO (MP = 2899 C) in reside slag
matrix, whereas the presence of periclase should be the evidence
for the difculty of the incorporation of this oxide into slag, when
it co-exists with other metal oxides such as CaO, Fe2O3 and FeO.
Upon the addition of silica to coal, the dramatic changes
occurred for the crystalline structures in reside slag. Anhydrite
(CaSO4) is present as the most prevalent species, accounting for
75 wt% of the total crystals. It is followed by minor species from
calcite to periclase, magnetite (Fe3O4), quartz and hematite in a
descending sequence. The lack of abundant quartz here is further
indicative of the agglomeration of the majority of silica additive
with molten species into large clusters in the bottom ash. A close
review of the XRF results in Fig. 3 indeed suggests a shortage of
silica in the reside ash deposit G formed for the coal mixed with

silica additive. The abundant anhydrite should be originated from

sulfation of the inherent calcium in ue gas and/or the areas such
as water tube surface where the temperature is lower than
1300 C. This however raises a query on why the sulfation of calcium is prompted by the mixing of coal with silica. One probable
explanation can be attributed to an enhanced dispersion of calcium
on silica surface, which in turn improved the contact between calcium and sulfur oxides prior to the sintering of calcium oxide [24].
Fig. 8 visualises the cross-section of reside ash deposit formed
from the case of coal mixed with silica additive. For the macrostructure shown on the top left corner, it indicates a layered and
friable structure for the reside ash deposit formed, which encapsulates spherical particles with varying sizes dispersed highly
across the particle. A close-up view of these particles on the top
right photo reveals different colours (thus different compositions

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B.-Q. Dai et al. / Fuel 139 (2015) 720732

in the SEM backscattered mode) for these dispersed globules. The

elemental mapping photos for individual elements, as shown
below, conrms that CaSO4 is the host matrix for the observed
ash deposit piece. Si is the major metal composing of the discrete
grey globules in CaSO4 matrix, whereas Fe dominates the bright
spots. The round shape for Si-rich particles should refer as to molten Ca-silicate, which proves the aforementioned hypothesis for a
mixing of liquidus and CaSO4 crystals. The silicate liquidus should
act as bond to wet CaSO4 particle and combine them together.
Regarding the discrete Fe-bearing particles, again, they should be
formed by the precipitation of its oxide (such as hematite and magnetite indicated in Table 4). The formation of iron oxide is a major
route for the transformation of inherent iron in coal [25]. Finally,
the dispersion of Mg is noteworthy. It is in portion overlaps with
Si and Ca, implying its incorporation into Ca-silicate. The rest of
Mg is rather free and bears little overlap with others, indicating

the presence of free MgO. This species is also proven by the XRD
quantication results in Table 4. Back to Fig. S2 (panel (b)) for
the thermally annealed silica, the discrete Mg-bearing particles
were not found within it, it is therefore fair to conclude that the
discrete Mg-bearing particles observed here are mostly contributed from the raw coal.
The amplied photography for Si-bearing globule and its elemental mapping are further illustrated in Fig. 9. Interestingly, the
globule was found to compose of a dense body (being molten at
high temperature) and highly crystallised crystals with a size of
approximately 1 lm. As further demonstrated in Fig. 10, the molten background matrix of the globule is dominated by Si, Ca and
Na, which is fully molten from 1300 C onwards. In contrast, Mg
was found to possess a concentration of 6.67 wt% in the crystalline
particles, which is molten by maximum 10 wt% at the boiler operating temperature, 1300 C. The crystalisation of these particles

Si

Al

Ca

Na

Mg

Fe

5.0 m

Fig. 9. Elemental mapping of the molten Si-rich spherical particle in Fig. 8 (EDS analysis for points).

100
Background
Crystalised Particles

Molar percentages of individual elements, %

Crystallised particles

59.05
17.75
1.16
14.15
2.79
5.04
0.08

58.92
14.63
0.00
18.88
6.67
0.90
0.00

80

% Slag_Liquidus

O
Si
Al
Ca
Mg
Na
Fe

Background

Maximum
operating
temperature

60

40

20

0
800

900

1000

1100

1200

1300

1400

1500

1600

Temeprature, C
Fig. 10. Elemental compositions of background matrix and crystallised particles in Fig. 9, and their melting propensity as a function of gas temperature.

728

B.-Q. Dai et al. / Fuel 139 (2015) 720732

Table 5
Abundance of crystalline species for ash deposits from H to F, according to Siroquant least-squared Rieveld tting results.
Sample

Major phase (P20%)

Medium phase (1020%)

Minor phase (<10%)

No
additive
With
additive

Melilite
((Ca,Na)2(Mg,Al)(Si,Al)3O7)
Anhydrite

Gehlenite

Calcite > Anorthite > Wollastonite

Quartz

Anorthite > Periclase > Lime (CaO)

No
additive
With
additive

Anhydrite > Thenardite

(Na2SO4)
Anhydrite

Akermanite (Ca2MgSi2O7) > Gehlenite

Hematite > Quartz > Esseneite (Ca4Fe3Si5Al3O24) > Periclase >

Anorthite > Magnetite (Fe3O4) > Calcite
Esseneite > Gehlenite > Thenardite > Anorthite > Ankerite > Quartz

No
additive
With
additive
No
additive
With
additive

Akermanite > Hematite

Anhydrite > Hematite > Magnetite > Quartz

Periclase > Calcite > Gehlenite > Anorthite > Lime > Thenardite > Kieserite
(MgSO4.6H2O)>Akermanite > Esseneite
Akermanite > Esseneite > Hematite > Gehlenite > Calcite > Magnetite >
Periclase

Lime

Gehlenite > Thenardite > Periclase

Anhydrite > Mirabilite (Na2SO4
10H2O) > Anorthite > Calcite > Akermanite

Anhydrite

Quartz

Hematite > Gehlenite > Thenardite > Anorthite > Magnetite > Periclase >
Kieserite > Akermanite > Lime > Calcite

Anhydrite

Ca

1 mm

50 m

Na

Si

Al

Mg

Fe

Fig. 11. Macrostructure of ash deposit H and its elemental mapping.

can be due to a reduced concentration of Na, and/or an increased

concentration of Mg within it. The enrichment of Mg on slag surface has been reported in a study of the use of MgO as additive
to control ash deposition and particulate matter formation
[26,27]. The mechanism is however still unclear. One probable
explanation is that the free MgO nuclei may diffuse into Ca-silicate
when they get in contact either on char surface or on water tube
wall. By experimental measurement, it has been conrmed that
MgO possesses a diffusivity on the order of 10 6 to 10 5 cm2/s in
Ca-silicate. Increasing temperature and introducing other metals
such as FeOx to reduce the slag viscosity is in favor of promoting
the dissolution of MgO [28]. The molecular dynamic calculation
even suggests a preferential enrichment of MgO nuclei at the interface of CaOSiO2 slag/MgO [29]. The precipitated CaO/MgO-silicate
crystals, as observed here, should bear an amount that is undetectable by XRD.

3.3. Properties of ash deposits in convection and economiser zones

XRD spectra for the ash deposits from Feston tube ash H to y
ash F in exhaust ue gas are depicted in Figs. S7S10 in the SI. Note
that, the Siroquant tted curve for each sample was superimposed
as red colour with the respective measured spectrum. A rather
satisfactory match has been noticed, although y ash samples are
usually quite complex in terms of speciation. The abundances of
the Siroquant quantied crystals as summarized in Table 5. Interestingly, irrespective of ash sampling location, anhydrite is the
major species and/or most abundant in all the ash deposits collected from the case of coal mixed with silica additive. For ash
deposit on Feston tube labelled H (ue gas temperature 900 C),
the Ca-bearing silicates including melilite ((Ca, Na)2(Mg,Al)(Si,Al)3O7), gehlenite and wollastonite formed in raw coal case disappeared once the silica additive was mixed with coal. Another big

729

B.-Q. Dai et al. / Fuel 139 (2015) 720732

Ca

Na

Si

Al

Mg

Fe

10.0 m

Fig. 12. Elemental mapping for the particle coated by sulfate on the surface. Ash particle is labelled H.

Si

Ca

Al

Mg

10.0 m
Fig. 13. Elemental mapping for Ca alumina-silicate particle coated by sulfate on the surface and the precipitation of MgO within the matrix. Ash particle is labelled F (EDS
analysis results).

discrepancy is the replacement of lime as the major species by

anhydrite in y ash F. The same observation was also noticed for
other three ash deposits in which lime and calcite are minor
species in the raw coal case. Both two phenomena are contradictory to our expectation that the added silica should scavenge the
majority of the inherent calcium to form various Ca-silicates, either
as molten slag or as crystallised species, as suggested by the thermodynamic equilibrium prediction in Fig. 7. A complete scavenging of calcium by silica should lead to its immobilisation and
deactivation for any other reactions in the post-ame zone. This
is clearly not the case observed here, which may be attributed to
an extremely short residence time of ash particles in the hot ame

zone. Moreover, given the fact that free lime is mostly disappeared
and sulfated in the case of coal mixed with silica, it is speculated
that the free calcium liberated from coal matrix should be highly
dispersed on silica particle surface. Such dispersion should refer
to physical adsorption in the interlayer spaces of silica, rather than
any chemical reaction for the formation of new species. It is benecial for the sulfation of calcium as the surface for the contact of
calcium to sulfur is enhanced, and the opportunity for CaO particle
to be sintered and self-agglomerated is reduced as well.
The photography for the micro-structure of layered calcium
sulfate is shown in Fig. 11 for its cross-section and elemental mapping. The layered structure of sulfate is evident. Its greyish layer (as

730

B.-Q. Dai et al. / Fuel 139 (2015) 720732

Raw Coal
Coal mixed with silica

50

% Na Sulfated

Relative Intensity [-]

60

F
E
D
C
B
A
H
G
S
CaSO4
Na2SO4

2460

40
30
20
10

2470

2480

2490

2500

2510

Energy Kev

Ash Deposit Location

amplied in middle top row) is predominated by calcium and sulfur, whereas Al and Si are lean. Moreover, Na and S co-exist in the
darkish section residing between the two adjacent CaSO4 layers.
This supports the above speculation that sulfation occurred for
the Ca/CaO lled in the silica interlayers. Apart from layered structure, the coating of CaSO4 on Ca alumina-silicate surface was also
conrmed. Fig. 12 demonstrates a core of Ca-aluminate on the shell
of CaSO4 and Na2SO4. On the other hand, Fig. 13 shows the co-existence of CaSO4 (with a shell thickness of approximately 12 lm)
and Ca alumina-silicate. The core species in these two gures
clearly form a porous Ca-rich skeleton to host a variety of species
including CaSO4, MgO and Na2SO4. Even for the Ca exposed on
the surface of the Ca-rich skeleton, it is also reactive in sulfation.
This is consistent with our previous study on the effect of kaolin
on the sulfation of limestone in a lab-scale drop-tube furnace [29].
Na2SO4 is another species which has been changed dramatically
upon the use of silica. Back to Table 4, one can notice the abundance of Na2SO4 as a major species (thenardite) in ash deposit A
collected from raw coal combustion. This is the principal cause
for ash fouling and corrosion of the superheater tube surface
[18]. However, it is only present as a minor species of <10 wt% in
the respective ash deposit collected from the case of coal mixed
with silica additive. As further detailed by S K-edge XANES spectra
in Fig. 14, one can see that all the ash deposits collected from coal
mixed with silica bear a shoulder peak located at 2485 keV,
which is the ngerprint for the standard CaSO4. The least-squared
tting results in Table 6 supports the abundance of CaSO4 over Na2SO4, irrespective of ash deposit location. By comparing with the
raw coal case results (see Fig. 15), it is clear that the sulfation of
Na is inhibited in nearly all the ash sampling locations except bottom ash and reheater B (507 C). The enhanced Na2SO4 in bottom
ash is due to its agglomeration with other species, which is indeed

Fig. 15. The percentages of Na sulfated at different ash deposits. The stripped bars
are for raw coal and cited from literature [18] with the copyright from American
Chemical Society obtained in February 2014, and the grey bars are for coal mixed
with silica additive.

100

80

% Na Captured

Fig. 14. Sufur K edge XANES spectra for all of the ash samples. Solid curves and
dashed curves are for the experimental measurement and tted spectra,
respectively.

60

1200 oC

40

1300 oC

20

1400 oC

1200 C
1300 C
1400 C
1500 C
1600 C

1500 oC
1600 oC

0
0.1

10

% Silica Additive
Fig. 16. Thermodynamic equilibrium prediction on the percentage of Na captured
as a function of gas temperature and silica additive amount.

benecial for minimizing ash fouling in the convection zone in the

boiler. The increase in Na2SO4 amount in ash deposit B is also
marginal, compared to the dramatic decrease of this species in
other ash deposits.
The decrease in the amount of Na2SO4 can be explained by the
capture of Na vapor by silica additive. In principle, upon the use of
silica additive at a mass percentage close to 5 wt% on the basis of
coal mixture, the Na vapor can be captured completely at the
temperature range of 12001600 C, as substantiated by the
FactSage thermodynamic equilibrium prediction in Fig. 16. This is
proven in Fig. 9 for the elemental mapping of molten silicate globule in the reside ash deposit formed at coal ame zone. The

Table 6
Quantitative sulfur-bearing species in ash deposits.

Bottom ash S
Fire-side ash G
Feston deposit H
Superheater deposit A
Reheater deposit B
Economiser 1 deposit C
Preheater 1 deposit D
Economiser 2 deposit E
Preheater 3 deposit F

Na2SO4

CaSO4

R-factor

Reduced chi-square

% Na sulfated

% Ca sulfated

0.269
0
0
0
0.499
0.227
0.131
0
0

0.731
1
1
1
0.511
0.773
0.869
1
1

0.0075
0.0163
0.0242
0.0004
0.0019
0.0007
0.0158
0.0114
0.0228

0.0071
0.0169
0.0179
0.0003
0.0016
0.0006
0.0157
0.0111
0.0155

14
0
0
0
39
18
10
0
0

10
60
28
40
23
27
44
27
41

731

B.-Q. Dai et al. / Fuel 139 (2015) 720732

Ca

Si

Al

Na

Fe

10 m
Fig. 17. Elemental mapping for molten spherical particle in y ash, which is coated by Ca and Na on the surface.

Table 7
Summary on the changes of ash deposit properties upon the use of 4 wt% silica in an industrial 30 MWth pulverized lignite-red boiler.
Bottom ash
Fireside slag
Ash deposits from Feston tube to boiler exit
Major metals
Ca

Na

Fea
Mg
a

The yield was enhanced signicantly due to agglomeration

Rich in calcium sulfate and easy to be blown off by soot blower
Calcium sulfate formation enhanced, which is less/no corrosive
Scavenged by silica into molten liquidus and crystallised silicate/alumina-silicate
Sulfation enhanced on the surface of silicate particles in convection zone
Calcium sulfate structures: layered and plerospheric
Sulfation extent decreased signicantly
Sulfate formed is partitioned between bottom ash and ash deposits at low temperatures
Sulfate formed is highly diluted by other species
Highly precipitated out of slag matrix
Formation of discrete oxides
Incorporated as ultra-ne crystalline in CaONa2OSiO2SO3 matrix

To be detailed in the second part of this study [19].

encapsulation of Na vapor into molten silicate which further

agglomerate into coarse bottom ash is benecial in reducing ash
fouling propensity in the convection zone. In addition, a portion
of the Na-bearing molten silicate is entrained by ue gas and condensed into superne globules to escape the boiler as y ash F. This
is proven in Fig. 17, where Na and Ca co-exist in a regularly
arranged shape on the particle surface. The mechanisms regarding
the arrangement of these two metals in silicate particle are clearly
worthy of extra research.
In summary, through the test of silica on a 30 MWth boiler for a
continuous operating in ten months, we have for the rst time proven the high effectiveness of the use of approximately 4 wt% silica
on the inhibition of lignite ash slagging and fouling. The use of
4 wt% silica is essential, which maximised the agglomeration of
the inherent ash-forming metals, and the capture of Na vapor into
bottom ash and y ash (thus minimized the formation of corrosive
Na2SO4 in convection zone). In terms of ash deposit properties, a
variety of interesting phenomena, as summarized in Table 7, have
been explored. Most of these phenomena were failed to be fully
justied by the existing thermodynamic knowledge on binary
and tertiary oxide systems. A detailed study is pivotal to promote
the understandings on the fundamental issues such as the kinetics
underpinning the interaction between multiple oxides, and the
changes on the structure of silica additive upon its interaction with
basic oxides. Moreover, as ash formation is a very complex process
involving the multi-physical phenomena, a detailed investigation
with the consideration on uid dynamics such as the combined

use of computational uid dynamic (CFD) software and thermodynamic equilibrium program (e.g. FactSage) [30] is also crucial,
which is underway by us. Finally, it is noteworthy that, the use
of silica as additive is economically attractive compared with the
method of coal blending combustion. As has been conrmed in
another study of us, a minimum fraction of 40 wt% of high-rank
bituminous coal with a vefold price of the silica additive tested
here has to be used to blend with Xinjiang lignite, the cost of which
is obviously high and unaffordable.
4. Conclusions
A detailed sampling and characterization of ash deposits from
various locations in a pulverised-fuel boiler for the combustion of
lignite mixed with silica additive has been conducted in this study.
The combustion test was carried out continuously in ten months
and the boiler used is 30 MWth with subcritical steam conditions.
A variety of interesting phenomena have been observed, which
are far more complex than the conventional binary/ternary oxide
systems to be explained by thermodynamic equilibrium modelling.
The major conclusions are drawn as follows:
(1) Adding no less than 4 wt% silica is essential in promoting the
agglomeration of ash-forming metals into coarse clusters
that can drop out of coal furnace as bottom ash. Apart from
capturing the volatile alkali and alkaline earth metals, silica
added as excess amount is also benecial in mixing with

732

B.-Q. Dai et al. / Fuel 139 (2015) 720732

molten liquidus to promote their agglomeration, rather than

adhering to the vicinity of coal burners for slagging.
(2) Compared to the raw coal case where free lime is largely sintered, the friable calcium sulfate is predominant throughout
all the ash deposits formed upon the mixing of silica with
coal, and even predominant in reside ash deposit. The
calcium sulfate formed is highly layered and even in a plerospheric structure in which Ca-silicate is present as the core
with calcium sulfate being the shell. The physical adsorption
of free Ca on silicate surface is supposed to enhance its specic surface area for a quicker sulfation.
(3) The capture of Na by silica is efcient, leading to the
transformation of a large portion of Na into coarse bottom
ash with less being sulfated. This in turn alleviated the sulfate-relating fouling propensity on the water tube surface
in the convection zone.
(4) A noticeable portion of Fe was noticed to be present as
discrete grains out of slag matrix. On the other hand, Mg
was noticed to highly crytallised as sub-micrometer Ca/
Mg-silicate particles within the slag matrix.

Acknowledgements
The authors are grateful to Australian Research Council (ARC)
for the future fellowship grant (FT0991010), and the Linkage
Infrastructure, Equipment and Facilities Program of the ARC
(LE0989759 and LE110100174). Bai-qian Dai and Xiaojiang Wu
acknowledge the support from Australian Academy of Technological Science and Engineering (ATSE) Joint Co-Ordination Grant (JCG)
for long-term visiting to Monash University in 2012-13. Xiaojiang
Wu thanks National Natural Science Foundation of China (NFSC,
50906055/51276212) for a portion of support on his research in
Monash. The authors also acknowledge the ash deposit sampling
service provided by Hubei Yihua Chemical Co. Ltd., China. The
NSRRC 16 A1 beamline scientist Dr. Ling-Yun Jiang is also thanks
for the operating support.
Appendix A. Supplementary material
The original and Siroquant tted XRD spectra for all the ash
deposit samples are present in this section. This material is available free of charge on-line. Supplementary data associated with
this article can be found, in the online version, at http://
dx.doi.org/10.1016/j.fuel.2014.06.054.
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