Ash Formation and Deposition From A Victorian

Fuel Processing Technology 53 Ž1998.
215–233
Ash formation and deposition from a Victorian

brown coal—modelling and prevention
a,) b
H.B. Vuthaluru , T.F. Wall
a
Department of Chemical Engineering, The UniÕersity of Adelaide, Commerce and Research Precinct,
35 – 37 Stirling Street, Thebarton SA 5031, Australia
b
Department of Chemical Engineering, The UniÕersity of Newcastle, UniÕersity DriÕe,
Callaghan NSW 2304, Australia
Received 28 February 1997; accepted 22 September 1997
Abstract
Experiments were conducted in a drop-tube furnace to determine the ash character and to
measure ash deposition for Loy Yang brown coal and the same coal treated with aluminium
lactate. A series of experiments on sized fractions, using the same stoichiometry Ž20% excess air.,
gas temperatures Ž1000–12508C. and surface temperatures of the deposition probe Ž500–8008C.
allowed direct comparison of results for the treated and untreated coals. The results show that
treatment with aluminium reduces the amount of sodium-rich fine ash and also causes an overall
reduction in the ash-size distribution when compared to the untreated coal. The treated coal was
markedly less fouling and slagging, particularly at a deposit probe temperature of 7008C.
Thermodynamic calculations and experimental data ŽXRD, FTIR. indicate that the added alu-
minium in the treated coal led to the formation of aluminium-rich phases such as MgAl 2 O4 and
sodium aluminosilicates. The reduction in fouling and slagging is probably due to the decrease in
the sodium chloride and the formation of aluminium-rich phases. q 1998 Elsevier Science B.V.
Keywords: Fouling; Slagging; Sodium; Ash formation; Deposition; Modelling; Brown coal
1. Introduction
Ash fouling of boiler tube surfaces during the combustion of low-rank coals is a
serious operating problem for power stations. The nature of the fouling depends on coal
)
Corresponding author. Fax: q61-8-8303-3648.
0378-3820r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII S 0 3 7 8 - 3 8 2 0 Ž 9 7 . 0 0 0 4 7 - 7
216 H.B. Vuthaluru, T.F. Wall r Fuel Processing Technology 53 (1998) 215–233
properties for a given boiler design and operating conditions. In pf combustion of brown
coal, fouling and slagging are particularly sensitive to sodium levels. Studies have been
conducted by several researchers w1–8x on understanding and controlling the fouling
problems associated with the firing of lignites and brown coals. In these studies, much
emphasis was placed on the effect of additives in controlling deposit formation on boiler
tubes, especially of aluminium additives, to reduce sodium-related fouling. The treat-
ment of coal with soluble aluminium proves to be an effective method for controlling
fouling from Victorian brown coal w9–11x. Because of the hydrophilic nature of brown
coal, coal can readily be treated with soluble aluminium salts in aqueous media. Most of
the ash-forming constituents are present as carboxylate-bound ionic species and thus
inorganics in an aqueous coalrwater slurry would be expected to migrate from the
aqueous phase through the pores of the coal particles into the coal matrix w12x. Research
has been carried out at the State Electricity Commission of Victoria ŽSECV. on the
extent of aluminium retention by brown coals and the likely impact of the aluminium on
the ash-formation chemistry of the treated coals w13x.
The thermal conditions prevailing in pulverised-coal-fired boilers change widely and
depend on several aspects which include, mode of firing, coal rank, firing rate and the
extent of fouling of boiler. For a typical Victorian-brown-coal-based Loy Yang Power
station, calculated thermal history Žtimertemperature. of gas and fly ash has been
reported by Brockway et al. w14x. The calculated thermal history indicate that the
residence time of the burning coal particle in a flame region is ; 1 s Žcorresponding to a
peak flame temperature of 12708C.. This is followed by a fairly uniform temperature
decrease during the next 2.5 s to a furnace exit temperature of 10708C. The fly ash
formed, and volatile species travel with flue gas through these changing thermal regions.
For simulating closely the thermal conditions prevailing in a pulverised-coal-fired boiler,
a vertical drop-tube furnace has been employed for the present studies.
In the present work, experiments have been carried out to determine the influence of
gas temperature on the ash chemistry of untreated and treated Loy Yang brown coals
and to observe the deposition behaviour of the coals on a probe placed at the end of a
drop-tube furnace. In this way, data were obtained on the relative effects of aluminium
treatment on the ash chemistry and, from this, effects could be deduced relating the
influence of aluminium on the ash chemistry. The experiments carried out on untreated
and treated coals were:
Ži. Variation of furnace temperature and collection of ash with a quench probe. The
small-sized ash was separated with a cyclone and collected with a filter.
Žii. Collection of deposits at one furnace temperature by varying probe surface
temperatures to test the effects of condensation of sodium compounds on deposit
formation.
This paper presents results on the treatment of Loy Yang brown coal with soluble
aluminium and subsequent changes to the ash character. From the experimental results
and with thermodynamic equilibrium calculations, an attempt has been made to the
describe the ash formation for the tested coals.
H.B. Vuthaluru, T.F. Wall r Fuel Processing Technology 53 (1998) 215–233 217
2. Experimental
2.1. Characteristics of coal
Victorian brown coals are generally characterised by a high moisture content, low ash
yield and high oxygen content. The inorganic constituents in these coals exert an
important influence on the performance of these coals in power station boilers. For
several years, the formation of ash deposits during the combustion of Victorian brown
coal has been a subject of extensive study w14x. Problems have been encountered with
ash deposits from Loy Yang coal in power station boilers.
The pulverised coal used in this study is a Victorian brown coal from the Loy Yang
coal field from bore LY2479. This is typical high-sodium coal containing discrete
mineral particles ŽSiO 2 ., particularly in size from about 8 to 80 m m w10x. The other
ash-forming elements, Na, Mg, Ca, Fe, Al, Cl and S, are usually bound within the coal
matrix to oxygen functional groups. The models used for thermodynamic calculations
consider the silica particles being separated from the burning coal particles. Silicates
may form through gas–solid reactions Že.g., sodium species with solid silica particles,
w15x.. Silicates in deposits may Žalso. form through reactions in deposits, for instance, by
the capture of ash particles by Žsticky. silicate particles.
2.2. Preparation of coal samples
About 100 kg of pulverised Loy Yang coal brown coal from bore LY2479 was
elutriated to remove fine particles. The coal was separated into three size cuts using an
18 in. Sweco Vibroenergy Separator operating in a continuous mode with a screw
feeding coal system. Coal retained as the 43–90 m m cut was used as the untreated coal
for the experiments reported in this paper.
The sized coal was treated with a solution of aluminium lactate. A waterrcoalrad-
ditive slurry was prepared by adding aluminium lactate Ž0.2 wt.% of coal. to 140 ml of
water at 708C. Air-dried coal Žabout 60 g. was slowly added while stirring for 30 min at
708C and allowed to settle. The solid was washed with about 100 ml of hot water and
then dried at 1008C in an oven. The characteristics of the treated and untreated coals are
given in Table 1.
2.3. Combustion experiments
The coal samples Žboth treated and untreated. were burnt in the drop-tube furnace at a
rate of 4–5 g hy1 . Gas temperatures chosen were 10008C, 11008C and 12508C. Details
of the drop-tube furnace and temperature profiles are given in Ref. w4x. The experiments
were conducted to obtain two sets of ash samples. The first set of experiments
concentrated on collecting cyclone ash and the submicron ash. However, the second set
of experiments specifically dealt with the collection of deposits. These experiments were
done mainly to determine the deposition behaviour of the two coals at a furnace
temperature of 12508C and at deposit probe temperatures of 5008C, 6008C, 7008C and
Table 1
Analyses of untreated and treated coal samples
Sample Coal ultimate analysis Coal minerals Coal inorganics Other
Ž% d.b.. Ž% d.b. Ž% d.b.. Ž% d.b..
Designation C H N S SiO 2 Na Mg Ca Fe Cl Al 2 O 3
Untreated coal 65.4 4.8 0.5 0.28 0.64 0.46 0.14 0.08 0.45 0.41 0.07
Treated coal 65.4 4.8 0.5 0.28 0.53 0.13 0.11 0.06 0.33 0.12 0.4
8008C. The details of the ash-sampling system and the deposit probe used for the two
sets of experiments are given below.
2.3.1. Ash-collection system

Gases and ash particles were collected by a water-cooled quench probe w4x. The gases
were cooled by air at a rate of 600–9008C sy1 . The coarse ash was separated in a
cyclone and the submicron ash was collected on a filter paper Ž47 m m diameter
Millipore, type AW03 paper.. The cooling with air is not as rapid as the helium-fed
quench probe and it is expected to influence the particle collection to some extent by the
increased evaporation and interaction periods with vapors.
2.3.2. Deposit probe

A deposit probe was placed at the bottom of the furnace, with the gas temperature at
12508C. Ash and gaseous condensable species were collected on a removable target disc
placed on top of the air-cooled deposit probe as shown in Fig. 1. The calculation of
Stoke’s number for the drop-tube furnace indicated that the particles greater than 9–11
m m would impact on this deposition probe. The temperature of the probe was main-
tained at the desired temperature by controlling the air-flow rate. At the end of each run,
the target disc was removed from the probe and shaken to remove the loosely held ash
and the deposit was examined using Scanning Electron Microscopy ŽSEM.. The ash
remaining after shaking the disc was defined as adhered ash.
2.4. Analysis of coals and ash samples
2.4.1. Ash particle size

Ash and coal samples were sized using Malvern particle size analyzer. The ash
samples were dispersed in isopropanol to avoid dissolving any water-soluble species that
may be present.
2.4.2. Chemical analysis

The coal samples were analysed for acid-extractable inorganics by mixing a weighed
portion of coal with dilute HCl and analysing the filtrate using atomic absorption
spectroscopy. Minerals, sulphur and chlorides in coal were analysed by XRF. Chlorides
and sulphates in ash samples were analysed by stirring the ash sample in water and
Fig. 1. Deposition probe.
determining SO4y and Cly, using ion-chromatography, Na, Ca, Mg, Al and Fe by atomic
absorption spectroscopy ŽAAS. or ICP.
2.4.3. X-ray microprobe analysis (SEM–EDX)

Samples collected in the cyclone were examined using a Jeol JSM-840 scanning
electron microscope with a KEVEX Si ŽLi. energy-dispersive X-ray detector. The
energy-dispersive X-ray system ŽEDAX. was used for elemental analysis of individual
ash particles. The instrument has been calibrated with standard mineral phases prior to
performing elemental analyses on ash samples. Whole ash particles were also examined
for their shape by Scanning Electron Microscopy ŽSEM..
2.4.4. Infrared spectra of laboratory ash samples

Coals were ashed at 8008C in a muffle furnace and the ashes were examined with
infrared spectroscopy and XRD to deduce any changes that may be exerted by the
additive on the ash chemistry. Infrared spectra were recorded using KBr pellets with
Perkin–Elmer IR and FTIR Spectrometers.
3. Results and discussion
3.1. Aluminium treatment of brown coals
Treatment of the coal slurry with aluminium compound caused a decrease in the
levels of sodium and chloride and an increase in the level of ionic aluminium in the coal
matrix, as analysed by atomic absorption spectroscopy w10x. Loss of sodium and chloride
occurs mainly by the extraction of sodium chloride into the aqueous phase of the slurry.
The uptake of aluminium ions appears to take place via chelation by functional groups
w16x.
SEM studies carried out on treated and untreated Loy Yang coal samples show an
uneven distribution of inorganics within the particles, reflecting the different maceral
compositions of the coal grains. No direct correlation could be found between an uptake
of aluminium and the loss of inorganics. A careful examination was made of silica
within the coal grains, including a direct comparison under identical conditions between
a silica standard, untreated coals and treated coals, using computer correction for
background levels. No silica could be found above the background level of five samples
examined. SEM studies of the external characteristics of the same coal samples revealed
silica and clay particles and the bulk composition was comparable to the bulk analyses
for that coal.
3.2. Laboratory ashes
Ashing coal in a muffle furnace produces an ash with similar ‘bulk’ characteristics to
that of fly ash collected in the precipitators of pilot-scale and full-scale furnaces w13x.
Infrared spectra of such ashes have been studied to obtain information on the overall
effects of additives on the ash chemistry w17x. Increases in the aluminium content of the
coal have caused marked changes in the 700–400 cmy1 absorption region, showing that
these ashes form the spinel MgAl 2 O4 with increasing levels of Al. The spectra are
typical for aluminium ashes with some sodium sulphate and relatively small amounts of
silicates. Because the ash is produced at about 8008C, Na 2 SO4 would form but with
little sodium silicate. The spectra indicate that levels of 0.2–0.3% aluminium may be
sufficient to cause the Loy Yang coal to be non-fouling.
Table 2
Mass of ash samples collected with gas temperature Žuntreated coal.
Gas temperature Ž8C. Cyclone ash Žg. Filter ash Žg.
1000 0.061 0.008
1100 0.059 0.010
1250 0.053 0.008
Table 3
Mass of ash samples collected with gas temperature Žtreated coal.
Gas temperature Ž8C. Cyclone ash Žg. Filter ash Žg.
1000 0.048 0.002
1100 0.046 0.035
1250 0.040 0.007
3.3. Total ash collected

A series of experiments were carried out in which the ash was separated by a cyclone
and fine ash particles collected by a filter. Ash was collected at three furnace tempera-
tures, 10008C, 11008C and 12508C, from treated and untreated coals. Tables 2 and 3
indicate the split of the ash samples with gas temperatures for both untreated and treated
coal runs. The total quantity of ash collected was 0.06 g. This is 50–60% of the
expected ash from the total coal burnt. Factors which contributed to the losses were:
–A small proportion of the ash was not extracted through the sampling system.
–Condensation of sodium on the exposed exit cone of the water cooled, coal feeder
probe.
–Difficulty in complete recovery of ash from the ash collection systems.
3.3.1. Ash from untreated coal
The ash collected from the cyclone consists of relatively larger ash particles Žonly
20–40% wrw smaller than 40 m m. whereas the filter ash consists of small ash particles
Žless than 5 m m.. The cyclone ash is formed mainly from the minerals Žquartz and clay.
and the non-volatile inorganics in the coal ŽMg, Ca and Fe.. The fine ash is formed
mainly from the volatile components ŽNa, Cl and S. in the coal. SEM data shows that
the ash collected by the cyclone consists mainly of silica, iron, calcium and some
sodium. The ash particles are relatively large, round particles and melting was seen at
higher temperatures. The ash particles collected at 12508C consisted of silica-rich ash
with molten particles high in Si, Fe and Na, indicating the formation of complex molten
phases. A relatively large number of small iron-rich particles and sodium chloride
particles are also observed. Ash collected at 12508C also contains large particles coated
with crystallised iron oxide. At lower temperatures, round silica particles coated with a
layer of iron oxide are also observed w9x. These particles may have formed by the
condensation of iron oxide on the molten surface of silica particles w18,19x.
The filter ash samples consists mainly of sodium, chloride, sulphur and some
magnesium. The filter ashes contain some ash particles with iron, magnesium and silica.
Filter ash samples from experiments run at 10008C and 11008C contain some particles
that are high in both chloride and sulphur and these may result from the condensation of
hydrochloric and sulphuric acids. A large number of discrete NaCl crystals about 5 m m
in size are observed in the filter ash samples. X-ray diffraction of the filter ash collected
at 11008C furnace temperature revealed that the principal crystalline phases were NaCl,
Na 2 SO4 and Na 21 MgCl 3 ŽSO4 .10 .
The bulk of the filter ash would be formed by condensing NaCl and Na 2 SO4 species.
The quenching and cooling effects of the sampling probe may cause a significant
amount of these vapours to undergo homonuclear condensation and thus form submicron
ash particles. The relative amount of sulphur to chloride increased with furnace
temperature, suggesting that sodium sulphate formation is favoured at lower gas
temperatures. Crystalline phases of sodium sulphate are clearly observed along with
mixed NarClrS and NarMgrClrS species. The samples are probably formed by the
condensation and subsequent gas–solid phase reactions between sodium chloride and
SO 2rSO 3 in the gas phase. A significant number of small ash particles containing iron
and magnesium are observed. Such small particles may result from either fragmentation
of coal during combustion or fume formed from the vaporisation of these inorganics
w18,19x.
3.3.2. Ash from treated coal

Ash collected in the cyclone from treated coal differed markedly from the untreated
coal ash. A lower proportion of round silica particles was observed, indicating that few
of the extraneous silica particles had melted or had formed complex molten phases. A
larger proportion of iron particles was noted, generally less than 10 m m in size Žat
12508C. and as part of fluffy agglomerates Žat 11008C.. The ash at 10008C was ‘dry’ in
appearance, with almost all silica particles unchanged and a significant proportion of
fluffy skeletal particles that are rich in Al were observed. Relatively large Žabout 20
m m. silica particles with small FerAl containing particles agglomerated onto the surface
were observed. At 11008C a larger proportion of the ash consisted of fluffy, skeletal ash
with large, unchanged silica particles and round iron-rich particles. At 12508C many of
the silica particles were covered with smaller iron and AlrFerCarSi particles which
had become molten. The filter ash at 12508C contained crystalline phases of NaCl,
Na 2 SO4 , Na 21 MgCl 3 ŽSO4 .10 and MgFeAlO4 . The filter ash contained fewer crystals of
NaCl Ž5 m m in size., a great deal more fluffy, skeletal material containing AlrFe with
S, Cl, Na and some particles high in Fe and S. At 12508C more mixed NarClrS
particles were observed, with a number of submicron iron-rich particles, and many
particles with Fe, S, Cl, Na, Al and some Si, Mg and Ca.
The size distribution of ash samples collected in the cyclone changed significantly for
the treated coal. SEM data indicated that the aluminium-containing coal forms smaller,
lacy ash particles and these are mostly less than 10 m m w9x. At a gas temperature of
12508C the ash particles have become relatively larger although the size distribution is
Table 4
Quantities of adhered ash collected
Temperature of target disc Ž8C. Untreated coal Treated coal
Weight of deposit Weight of deposit
Žg. and Ž% of ash. Žg. and Ž% of ash.
500 0.0028 Ž2.7. 0.0031 Ž1.3.
600 0.0065 Ž6.3. 0.0034 Ž3.3.
700 0.0164 Ž15.8. 0.0061 Ž5.9.
800 0.0178 Ž17.1. 0.0112 Ž10.8.
Plate 1. Deposition probe at 5008C.
smaller than that for the untreated coal at the same furnace temperature. It is likely that
at 12508C a larger number of sticky particles form and coagulation and particle capture
may cause an increase in ash-particle size.
Plate 2. Deposition probe at 6008C.

The size and composition of the filter ash is markedly different for the treated coal.
The main cause is the reduced level of sodium and chloride in the treated coal, leading
to a reduction in the amount of NarClrS fume produced.
Fig. 2. Sketches of deposition probe at a gas temperature of 12508C.

3.4. Deposits formed on a target disc

3.4.1. Deposits from untreated coal
The quantities of deposited ash Žadhered ash. on the target disc for all experiments
are presented in Table 4. About 50–60% of impacted ash particles deposited onto the
target disc. A ring of condensed salts was observed on the deposit probe when the
untreated coal was burnt Žsee Plates 1 and 2, Fig. 2.. No condensed salts were observed
with the runs carried out at a probe temperature of 8008C. The melting point of NaCl is
1073 K Ž8008C. and thus the crystalline NaCl and higher deposit weight may be due to
the formation of liquid NaCl on the target disc. The vapour pressure of Na 2 SO4 in the
temperature range of 700–9008C is sufficient for condensation to occur. The sulphur
content of the deposits is higher than the chloride content and this may be due to further
sulphation of deposited sodium compounds during the experiment.
The iron content of the adhered deposit was high and apparently increasing with
probe temperature. Calculations Žsee Section 4. suggest that calcium ferrites, magnesium
ferrites and iron oxides, along with sodiumrmagnesium silicates, would make up the
bulk of the deposits. If the sodium were distributed between chloride and sulphur, very
little would be thermodynamically favoured to form silicate phases and SEM data shows
that there is ample Mg available for this in the deposits. IR and XRD data of deposits
and ashes collected in pilot scale test furnace show, for LY 2479, the following phases
w20x: MgFe 2 O4 , MgAl 2 O4 , MgFeAlO4 , Mg 2 SiO4 , CaMgŽSiO 3 . 2 , Al 2 Si 2 O5 , 3Al 2 O 3 P
2SiO 2 , Na 6 Ca 2 Al 6 Si 6 O 24ŽSO4 . 2 , NaAlSiO4 , Na 2 Si 2 O5 .
3.4.2. Treated coal
The deposited particles appeared to be less molten and loosely agglomerated. No ring
of condensed salts was observed ŽFig. 2., and at temperatures below 8008C the weight of
adhered ash was about half that of the untreated coal ŽTable 4.. SEM results indicate that
fewer molten silica particles had formed. This result is supported by thermodynamic
calculations which show that the lower Na content of the coal will lead to lower sodium
silicate formation w4x. The deposits contain more aluminium rich phases and it is felt that
the formation of sodium aluminosilicates, by the reaction of molten sodium silicate and
alumina, had caused a reduction in the extent of molten phases. The appearance of the
deposits was that of ash particles covered with ‘fluffy’ deposits, while the ash which
would not adhere to the deposit suggests that the presence of aluminium has inhibited
the formation of iron-rich phases. Iron has been observed in a number of slags from Loy
Yang coals. The phase MgFeAl 2 O4 has been identified by XRD in ash from the treated
coal w10x. This suggests that aluminium may form ‘dry’ iron phases and thus further
prevent slagging and fouling.
Overall the deposits are low-sodiumriron and high-aluminium phases which do not
appear to adhere strongly, suggesting a large reduction in slagging would result from
aluminium treatment.
4. Calculations
Computational methods dealing with ash formation and deposition can be very
complicated and the validity of the results often depend on assumptions made regarding
ash-formation mechanisms and simplifications in the way deposition-phenomena are

treated. Ash-formation descriptions from brown coals w13x is based on the assumption
that the ash-forming constituents in brown coal, being discrete mineral particles ŽSiO 2 .
and inorganics Žsuch as Na, Mg, Ca, Fe, Al, Cl and S. present in the coal matrix, are
bound to functional groups such as carboxylates.
The minerals undergo flame transformation as a result of heating, while the inorgan-
ics in a coal particle undergo complicated phase-formations and transformations within
the burning char particles, with sodium chloride and sulphur rapidly volatilised to
undergo gas-phase chemistry to form sodium compounds w13x. Some release of magne-
sium and perhaps iron is believed to occur during brown coal combustion w21x. Thus the
spectrum of ash particles emerging from a coal flame consists of gas-phase sodium
species, small sub-micron iron and magnesium particles, ash particles with
MgrAlrCarFe phases and silica particles which may have undergone gas–solid
reactions with sodium hydroxide. Mg, Fe, Ca, Si and K have been reported to vaporize
during Beulah lignite coal combustion w22x. The large number of sub-micron ash
particles from volatilised MgrFe Žand perhaps from fragmented aluminium ash parti-
cles. need to be considered in greater detail. Their role in condensation processes
involving sodium species is important and they may also be captured on sticky surfaces
and by molten silicate particles ŽFig. 3..
Fig. 3. Descriptive model showing ash formation.

Calculations on the phases within ash particles and deposits would require informa-
tion on the ways that all ash particles may interact, since any solid-phase formation
requires that the reactants are in contact with each other. Thus solid transformations may
occur once the ash particles are deposited on a surface, provided the temperature is
sufficient for chemical reaction.
4.1. Thermodynamic calculations and modelling
Thermodynamic calculations have been performed for the following two ‘models’:
Ži. reactions only between inorganics in a coal particle, restricting silicate formation to
reactions between silica and sodium species Žunmixed model.;
Žii. include inorganics and silica Žmixed model..
4.1.1. Fly ash from the untreated coal

The inorganics Mg, Fe, Ca and Al are calculated as solid phases in fly ash, Na, Cl
and S forming sodium salts and silicates by reactions between the gaseous sodium
species and solid silica. The relative molar concentrations of each species for the models
are presented in Tables 5 and 6. The measured values for SrCl in filter ashes are
presented in Table 7.
The phases predicted for MgrFerCa are experimentally identified by infrared
spectra of laboratory ashes, consistent with published observations w17x and reflecting
the large amounts of iron-rich particles in cyclone ash as observed by SEM. The molten
Na 2 SO4 predicted in mixed phases by the calculation is particularly interesting, since
the amounts at 1500 K are much higher than if the salt were to form as a single phase
ŽTable 6.. Relatively higher levels of sulphur have been observed in ash particles which
Table 5
Relative molar concentrations of major phasesa for the discrete mineralsrinorganics in untreated coal
Žunmixed model.
Temperature ŽK. Fly ash phases Silicates Sodium species
1400 Fe 2 O 3 0.1511 Na 2 Si 2 O5 0.1020 NaClŽg. 0.259ey03
Fe 3 O4 0.0165 Na 2 Si 2 O5 0.0773 NaOHŽg. 0.583ey04
MgFe 2 O4 0.1419 SiO 2 0.2212 Na 2 SO4 Žg. 0.488ey06
CaFe 2 O4 0.0528 Na 2 SO4 0.618ey01
MgO 0.1267
Fe 3 O4 0.0276 Na 2 Si 2 O5 0.0972 NaOHŽg. 0.226ey04
CaFe 2 O4 0.0771 Na 2 SO4 0.902ey02
MgO 0.1420
Fe 3 O4 0.0393 Na 2 SiO 3 0.0787 NaOHŽg. 0.536ey04
CaFe 2 O4 0.0866 Na 2 SO4 0.771ey03
MgO 0.1503
a
Solids unless noted Žg.; molar concentrations are for solids or gases of major phases.
Table 6
Relative molar concentrations of major phasesa for the discrete mineralsrinorganics in untreated coal Žmixed
model.
MgFe 2 O4 0.0765 CaSiO3 0.0771 Na 2 SO4 Žg. 0.109ey06
CaFe 2 O4 0.0019 MgSiO 3 0.0769 Na 2 SO4 0.771ey03
Mg 2 SiO4 0.0389
SiO 2 0.1173
Mg 2 SiO4 0.0411
SiO 2 0.0960
Mg 2 SiO4 0.0425
SiO 2 0.1243
a
had melted. At 1400 K the amount of sodium sulphate predicted in mixed phases is
comparable to the amount of NaCl present ŽTable 6., whereas if sodium sulphate were
considered as a single phase the concentration is predicted as 0.1 of NaCl. At
1250–1300 K, which is close to the lowest temperature of the drop-tube furnace, the
mixed phase and single phase models give similar predictions although mixed-phase
calculations indicate NaCl and NaOH will also be present.
4.1.2. Fly ash from the treated coal

Similar calculations were performed for the treated coal. The relative molar concen-
trations of each species for all the models are presented in Tables 8 and 9. The measured
values for SrCl in filter ashes are presented in Table 10. The major features are higher
Al 2 O 3 levels in the coal, slightly lower Mg levels and lower NarCl. The unmixed
model allows Fe, Mg, Al and Ca to form oxide compounds, while SiO 2 and Na species
Table 7
Comparison of measured and calculated molar ratios of S to Cl in filter ash for concentrations similar to
drop-tube Žuntreated coal.
Temperature Ž8C. Measureda Calculated
1000 1:1 1:0.7
1100 1:5 1:4
1250 1:7 1:16
a
Accuracy within "10%.
Table 8
Relative molar concentrations of major phasesa for the discrete mineralsrinorganics in treated coal Žunmixed
model.
MgAl 2 O4 0.1402 Na 2 SO4 0.134ey01
Al 2 O 3 0.0415
MgAl 2 O4 0.1377 Na 2 SO4 0.121ey02
Al 2 O 3 0.0429
MgAl 2 O4 0.1356 Na 2 SO4 0.106ey03
Al 2 O 3 0.0462
a
may form silicates. The results are consistent with infrared spectra of laboratory ashes
which show the formation of MgAl 2 O4 with increasing aluminium content of the coal.
Calculations with the mixed model showed that the most favoured phases are
NaAlSiO4 , MgAl 2 O4 , CaMgSi 2 O6 and the oxides SiO 2 , Fe 2 O 3 and Al 2 O 3 ŽTable 9..
Alumina and silica, with Mg phases, account for the bulk of the aluminium. Indeed, over
Table 9
Relative molar concentrations of major phasesa for the discrete mineralsrinorganics in treated coal Žmixed
model.
1400 Fe 2 O 3 0.2503 NaAlSiO4 0.1106 NaClŽg. 0.634ey04
Fe 3 O4 0.0351 CaSiO 3 0.0661 NaOHŽg. 0.244ey05
MgAl 2 O4 0.0931 MgSiO3 0.0608 Na 2 SO4 Žg. 0.107ey06
MgFe 2 O4 0.0447 SiO 2 0.1519 Na 2 SO4 0.135ey01
Al 2 O 3 0.0486 CaMgSi 2 O6 0.0140
MgFe 2 O4 0.0471 SiO 2 0.1668 Na 2 SO4 0.126ey02
Al 2 O 3 0.0515 CaMgSi 2 O6 0.0131
MgFe 2 O4 0.0464 SiO 2 0.1928 Na 2 SO4 0.103ey03
Al 2 O 3 0.0554 CaMgSi 2 O6 0.0123
a
Table 10
Comparison of measured and calculated molar ratios of S to Cl in filter ash for concentrations similar to
drop-tube Žtreated coal.
Temperature Ž8C. Measureda Calculated
1000 8:1 9:1
1100 5:3 2:5
1250 1:1 1:500
a
Accuracy within "10%.
the temperature range 1300–1500 K, 10–20% of the aluminium is connected with

NarSi phases and about 50% forms MgAl 2 O4 , the remainder being mainly Al 2 O 3 . The
major silicate phase for the treated coal, at 1500 K is CaMgSi 2 O6 . These results indicate
that if silica were considered part of the coal particle and could undergo the chemical
reactions with the inorganics during the char-burning stage, a number of aluminium
silicate phases would form including the sodium aluminosilicate, but the reduction in
fouling would result from a combined alumino-phase formation and reduction in sodium
species. All calculations show that iron-rich phases would have a major impact on the
ash chemistry.
Modelling of the Na 2 O–SiO 2 system w23x shows that at 12008C a solidrliquid phase
boundary composition at Na 2 O ) 0.2 mole fraction. The treated coal has a molar ratio
of Na 2 O to SiO 2 of about 0.2:1 and would just form a liquidrsolid mixture if all the
silica were available for the reaction with all the sodium. It is most likely however, that
a large portion of sodium would be tied up as NaCl, while the surface of the silica
particles would represent the concentration of SiO 2 available for reaction. The treated
coal is likely to form less Na 2 SiO 3 than the untreated coal. Experimental data show that
fewer silica particles have undergone melting than in the untreated coal runs.
It should be mentioned here that the thermodynamic calculations which have been
performed predict equilibrium composition of reaction products and thereby ignore
kinetic effects. Apart from being limited by the assumption of equilibrium, thermody-
namic predictions are also confined by the accuracy of the data. However, the qualitative
behaviour is relatively insensitive to inaccuracies in the data.
4.1.3. Deposits from coal samples
The deposit formation from the coal was assumed to occur through capture of all
solid and liquid species on the surface. This provided a basis for the thermodynamic
modelling of the phases formed from the ash and gaseous species at the chosen
temperature. The gas temperature will determine the composition of the ash and
gas-phase species which would impact onto the fouling probe. The temperature of the
probe would be important in subsequent transformations that may occur after deposition,
condensation and molten phase formation of sodium salts.
4.1.3.1. Untreated coal runs. At a gas temperature of 12508C, the composition of the fly
ash and the vapour species is that shown in Table 6. The silicates and other solid phases
would not be expected to undergo further transformations, but the sulphate and chloride
levels may, by the condensation of chloride and sulphate, and further displacement of
chloride from NaCl by SO 2 in the gas phase. The formation of molten NaCl at about
8008C Žmelting point of NaCl. would further complicate matters and crystal formation
has been noted in the deposits.
4.1.3.2. Treated coal runs. The calculated species shown in Tables 8 and 9 may form
deposits at the levels of sodium, sulphur and chloride observed during drop-tube
experiments. The lower levels of fouling observed for the treated coal would result from
a lower relative amount of sodium silicates, larger amounts of aluminium phases and
lower relative amounts of sodium salts.
5. Conclusions
The treatment of a high-fouling and slagging brown coal with soluble aluminium has
been found to:
Ži. Reduce the amount of sub-micron ash, due to a reduction in the amounts of
sodium and chloride through greater capture of sodium salts on alumina particles
Žheterogeneous condensation. and the formation of sodium aluminosilicates.
Žii. Cause an interaction between the molten silicate particles and aluminium-contain-
ing ash which has probably formed sodium aluminosilicates. The increased amounts of
aluminium-containing phases and aluminium silicate formation has markedly reduced
the slagging tendency of the treated coal.
Žiii. Decrease the amount of ash which adhered to the deposit probe, indicating a
marked reduction in fouling of surfaces. Relative to the untreated coal, the treated coal
produced the greatest reduction in deposit weight at 7008C.
Thermodynamic calculations indicate that the ash-formation process outlined in the
descriptive model is appropriate for brown coal. Burning char particles normally reach
temperatures which may lead to molten ash phases on the burning particles. Silicates are
unlikely to form within the char because no silica has been detected within the coal
particles. Most of the silica particles exist as discrete particles and supports the unmixed
calculations. Silica particles however may form molten sodium silicates, and the molten
surface of these particles may then interact with other finer ash particles to form sodium
aluminosilicates as shown in the descriptive model. The experimental and theoretical
approach employed in the present work is also suitable for other high-sodium low-rank
coals.
It is evident from the above conclusions that the ash-related problems associated with
the utilisation of brown coals can be controlled and prevented by pretreating the coal
with aluminium prior to firing them in power station boilers.
Acknowledgements
The authors wish to thank the staff of the Coal Evaluation Section ŽAnalytical Group.
and Materials Chemistry Section, State Electricity Commission of Victoria, for their
assistance, especially with coal preparation, analysis and ion-chromatography analysis.
The authors like to acknowledge the following colleagues of University of Newcastle for
their cooperation: R.P. Gupta for helpful discussions, T. Farrugia for advice on ash
sample analysis, and G. Weber and D. Phelan for their instructions on SEM analysis.
The authors also like to thank Dr. J.M. Vleeskens and Dr. G. Domazetis for their
valuable suggestions.
References
w1x A.J. Lowe, D.J.A. McCaffrey, D.G. Richards, Fuel Processing Technol. 36 Ž1993. 47–53.
w2x E.R. Lindner, A. Kosminski, C. Taylor, R.G. Williams, Effects of additives on fouling behaviour
characteristics of South Australian brown coals, in: Proceedings of Australian Coal Science Conference,
University of Adelaide, 16–18 May 1988, pp. B2:11.1–B2:11.14.
w3x S. Devine, G. Mackay, Studies of ash deposit to metal tube bonding, NERDDP project 1045, State
Electricity Commission of Victoria, Research and Development Dept., Report No. NDr89r053, 1989.
w4x H.B. Vuthaluru, Sodiumrash reactions during pulverised coal combustion—Treatments and additives to
control deposition, PhD thesis, Department of Chemical Engineering, University of Newcastle, Australia,
1992.
w5x H.B. Vuthaluru, R.P. Gupta, T.F. Wall, Sodium reaction with kaolin, silica and alumina, Presented at the
Joint International Conference on Coal Combustion, The Combustion Institute, Sydney, September 1991.
w6x H.B. Vuthaluru, G. Domazetis, T.F. Wall, J.M. Vleeskens, Fuel Processing Technology, submitted for
publication.
w7x H.K. Hein, in: The effects of mineral matter, Proceedings of Pulverised Coal Firing, Dept. Chemical
Engineering, University of Newcastle, Paper L15.1–34, 1979.
w8x H.K. Hein, Fouling and Slagging Resulting from Impurities in Combustion Gases, in: R.W. Bryers ŽEd..,
Proceedings of the Engineering Foundation Conference, 12–17 July 1991, New England College, New
Hampshire, 1991, pp. 69–83.
w9x H.B. Vuthaluru, G. Domazetis, T.F. Wall, J.M. Vleeskens, Fuel Processing Technol. 46 Ž1996. 117–132.
w10x G. Domazetis, G. Kitanovic, Minimising ash fouling from high sodium brown coals, Volume 2b:
Treatment of low rank coals with soluble aluminium compounds, NERDDP Project 1167, End of Grant
Report, State Electricity Commission of Victoria, Research and Development Department, Report No.
NDr90r056, 1990.
w11x G. Domazetis, Fly ash formation and sulphation during the combustion of brown coal, NERDDP Project
933, End of Grant Report, State Electricity Commission of Victoria, Research and Development
Department, Report No. NDr88r048, 1988.
w12x L.E. Paulson, W.W. Fowkes, Changes in ash composition of North Dakota lignite treated by ion
exchange, US Department of the Interior, Bureau of Mines, Report 7176, 1967.
w13x G. Domazetis, Ash formation from inorganics in Victorian brown coal, Proceedings of the 1985
International Conference on Coal Science, 389 Ž1985..
w14x D.J. Brockway, A.L. Ottrey, R.S. Higgins, in: R.A. Durie ŽEd.., The Science of Victorian Brown Coal:
Structure, Properties and Consequences for Utilisation, Chap. 11, pp. 597–650.
w15x E.R. Lindner, A study of sodium-ash reactions during the pulverised coal, PhD thesis, Department of
Chemical Engineering, University of Newcastle, Australia, 1988.
w16x R.H. Kadlec, G.A. Keoleian, Metal Ion Exchange in Peat and Water, in: C.H. Fuchsman ŽEd.., Elsevier
Applied Science Publ., New York, 1986.
w17x G. Domazetis, Use of infrared spectroscopy in the characterisation of precipitator ash, State Electricity
Commission of Victoria, Research and Development Department, Report No. SOr84r82, 1984.
w18x R.J. Quann, A.F. Sarofim, in: Proceedings of the Nineteenth Symposium ŽInternational. on Combustion,
The Combustion Institute, Pittsburgh, PA, 1982, pp. 1429–1440.
w19x J. Helble, M. Neville, A.F. Sarofim, in: Proceedings of the 21st Symposium ŽInternational. on Combus-
tion, The Combustion Institute, Pittsburgh, PA, 1986, pp. 411–417.
w20x S. Devine, X-ray diffraction examination of six samples from 100-h furnace a33 using LY2479 coal,
State Electricity Commission of Victoria, Research and Development Department, Test Report No.
CEr87r06, 1987.
w21x A. Campisi, Application of graphite-furnace AAS for investigations of the release of inorganic species
from coal particles, State Electricity Commission of Victoria, Research and Development Department,
Report No. S0r88r131, 1988b.
w22x A.A. Boni, R.C. Flagan, J.J. Helble, T.W. Peterson, A.F. Sarofim, S. Srinivasachar, J.O.L Wendt,
Transformations of inorganic coal constituents in combustion systems, Report to US Department of
Energy, Pittsburgh, Contract No. DE-AC22-86PC-90751, 1989.
w23x J.W. Hastie, D.W. Bonnell, High Temp. Sci. 19 Ž1985. 275.

Ash Formation and Deposition From A Victorian

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Fuel Processing Technology 53 Ž1998.

Ash formation and deposition from a Victorian

0378-3820r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

2.1. Characteristics of coal

2.2. Preparation of coal samples

2.3. Combustion experiments

2.3.1. Ash-collection system

2.3.2. Deposit probe

2.4. Analysis of coals and ash samples

2.4.1. Ash particle size

2.4.2. Chemical analysis

Fig. 1. Deposition probe.

2.4.3. X-ray microprobe analysis (SEM–EDX)

2.4.4. Infrared spectra of laboratory ash samples

3. Results and discussion

3.1. Aluminium treatment of brown coals

3.2. Laboratory ashes

3.3. Total ash collected

3.3.2. Ash from treated coal

Plate 1. Deposition probe at 5008C.

Plate 2. Deposition probe at 6008C.

Fig. 2. Sketches of deposition probe at a gas temperature of 12508C.

3.4. Deposits formed on a target disc

ash-formation mechanisms and simplifications in the way deposition-phenomena are

Fig. 3. Descriptive model showing ash formation.

4.1. Thermodynamic calculations and modelling

4.1.1. Fly ash from the untreated coal

4.1.2. Fly ash from the treated coal

the temperature range 1300–1500 K, 10–20% of the aluminium is connected with

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