This effect of the ash constituents has been known for many years. For example, Raask (1982) reported
studies on sulphate capture in ash and boiler deposits in relation to SO2 emissions from firing British
bituminous coals in pulverised-fuel boilers. Species that can be sulphated include sodium chloride
(NaCl), and magnesium and calcium carbonates (MgCO3 and CaCO3). Raask (1982) concluded that, in
coal-fired boilers burning British bituminous coal, an average 15% of the total sulphur in the coal was
retained in the ash and boiler deposits in the form of sulphates. However, later work carried out by the
UK\u2019s Central Electricity Generating Board indicated that this estimate was too high (Gibb, 2000).
For low-rank coals, the fixation of sulphur in the ash may be more effective than for higher-rank coals. At
the 300 MWe Unit 3 of the Ag. Dimitrios power plant, firing Greek lignite with a sulphur content of
0.42\u20130.6%, ash sulphation reduced SO2 emissions from the expected 230 ppm to 120\u2013170 ppm (Kakaras
and others, 1991;1995). The lignite yielded around 18% ash, the ash composition being about one-third
CaO, with an MgO content of more than 4%. Elsewhere, Pleasance and Johnson (1995) reported that for
brown coals from Victoria (Australia), the degree of sulphur fixation ranges from 10 to 70%.
Western US subbituminous coals, particularly those from the Powder River Basin (PRB), are low in
sulphur and high in calcium. Kang and others (1994) give sulphur contents of 0.38% and 0.73% for
Eagle Butte and Wyodak subbituminous coals, with corresponding calcium oxide in ash values of
33.76% and 24.80%. In comparison, a Kentucky No.9 bituminous coal contained 3.67% sulphur and
6.01% CaO in the ash. Thus blending these coals should not only reduce SO2 emissions simply by
dilution, but also possibly capture some sulphur in the higher-calcium ash. The calcium in the PRB
coals is usually atomically dispersed but during char combustion, partially molten aluminosilicate ash
particles on the char surface scavenge the calcium. Computer-controlled scanning electron microscopy
revealed that most of the final ash particles were calcium-rich aluminosilicates. Results of calculations
suggested no thermodynamic barriers to their sulphation in the temperature range 25\u20131200\u00baC, but
entrained flow reactor (EFR) experiments were carried out in order to demonstrate the feasibility of the
capture of sulphur in coal by calcium from the fly ash in a temperature environment similar to that
found in utility boilers. Experiments with ash generated from subbituminous coal in the EFR showed
that sulphur capture with the ash derived from a high-calcium coal was possible, while testwork using a
blend of Kentucky No.9 coal and Eagle Butte coal showed that the amount of SO2 reduced decreased
with increasing amounts of Kentucky No.9 in the blend.
coal from the Powder River Basin. When this as received ash was injected into a flue-gas stream in the reactor at a gas temperature of 1300\u00baC, the SO2 concentration increased from 390 ppm to 520 ppm. This was because the Belle River ash was already sulphated, primarily as calcium sulphate (CaSO4). Above 1200\u00baC, the CaSO4 decomposed, releasing SO2 back into the gas stream. Subsequent experiments were carried out with treated ash at a gas temperature of 1050\u00baC. As soon as the ash feeder was turned on, the SO2 concentration decreased rapidly from 348 ppm to about 322 ppm and thereafter kept decreasing at a slower rate. The rapid decrease in SO2 was attributed mainly to in-flight sulphur capture by ash. The slower decrease reflected the reaction with the deposited ash on the EFR walls. This represented a
A full-scale test was performed at the Belle River Unit 1. Temperatures around 1000\u00baC correspond to
the secondary superheater and first reheater region. The test verified the experimental findings and
showed that about 10% of the SO2 emission was reduced by ash sulphation.
Uzun and others (1995) defined \u2018combustible sulphur\u2019 as the difference between the total sulphur in the
coal and that captured by the ash. Their first attempts to obtain correlations based on total sulphur and
proximate analysis were unsuccessful. However, Uzun and \u00d6zdogan (1997) were able to find
correlations when they were based on the pyritic, organic, and total sulphate sulphur forms. Inclusion of
the CaO content in the correlations also affected the results favourably. Further work also incorporated
the MgO content (Uzun and \u00d6zdogan, 1998). These experiments were not, however, carried out under
combustion conditions. The coal ash samples were prepared according to ASTM standard D3174-89 at
a temperature of 750\u00baC, far lower than the temperatures normally encountered in pulverised-coal
combustion. Increasing the temperature to 950\u00baC resulted in an increase in the combustible sulphur
content, confirming that there are indeed temperature effects. This also implies that the sulphur capture
by ash in pulverised-coal combustion cannot be predicted by equations obtained at lower temperatures.
Uzun and \u00d6zdogan (1998) pointed out that new formulae have to be developed for combustion
conditions that differ from those of their study.
1 gram-molecule of gas occupies a volume of 22.4 litres at 0\u00baC and at 1 atmosphere, and the atomic mass of sulphur is 32. The value obtained can be divided by the emission gas volume to obtain the concentration in ppm.
Other sulphur-emission calculations take into account sulphur capture by ash and boiler deposits. For example, the European Environment Agency (EEA) published a method of determining SO2 emission factors (McInnes, 1996). The calculation procedure is performed in three steps:
The fuel sulphur reacts stoichiometrically with oxygen (O2) to sulphur dioxide (SO2). The result is
the maximum attainable amount of sulphur dioxide (CSO2.max) given by:
CSO2.max= 2 CSfuel
Default values for the sulphur content (CSfuel) in hard and brown coal were provided, based on the
geographical origin of the coal. For example, a sulphur content of 0.9 wt% was given for German Ruhr
bituminous coal, and 0.8 wt% S for German Rhenish brown coal. The EEA document quotes the
sulphur contents on a \u2018maf\u2019 basis (moisture and ash-free), equivalent to \u2018daf\u2019 (dry, ash free).
CSO2.boiler fuel= CSO2.max(1-s)
Therefore, for bituminous coal in a dry-bottom boiler, 5% of the SO2 is captured by the ash, while 1% is captured in a wet- bottom boiler. The brown coal value was an average; in practice a range of 0.05 to 0.60 can occur, depending on the origin of the brown coal.
The boiler emission of sulphur dioxide can be further corrected by the reduction efficiency and
availability of the secondary flue-gas desulphurisation system installed. The EEA compared the
calculated SO2 emission data with measured values from mainly German power stations. These are
shown in Figure 4.
Good correlations between measured and calculated values were claimed for calculations that were only
based on plant- specific data provided by power-plant operators. However, for most of the calculations a
mixture of plant-specific data and default values for missing parameters was used, leading to deviations
from the middle axis. The EEA document claims that, \u2018in particular, strong differences occur for SO2
emissions, which show a tendency to be overestimated\u2019. This is attributed to assumptions with regard to
the default values; for example, the sulphur retention in ash varies greatly depending on the data
However, examination of Figure 4 reveals that there is only one significant overestimate and that the
tendency is tou n d e r e s t i m a t e the SO2 emissions. The data on which Figure 4 is based confirm that the
figure\u2019s axes are correct. The underestimation may be caused by low default values for the sulphur
contents of German coals, or because the default value of 5% SO2 retention in the ash may be too high.
This latter explanation is less likely given that thes value at the M\u00fcnster power station was given as
0.15, and this station was one for which the calculated value (1310\u20131650 mg/m3), although
underestimated, was reasonably close to the measured value (1644\u20131891 mg/m3). For a station at
Karlsruhe, thes value was quoted as 0.4, which seems high, and may account for the underestimate of
1310\u20131650 mg/m3 calculated compared with 1600\u20132000 mg/m3 measured. It is also possible that the
default values for the efficiency and availability of the flue-gas desulphurisation equipment were too
to convert the chloride sodium and carbonate calcium to
sulphates can be expressed in terms of the chloride and
carbonate contents of the coal, assuming no \u2018loss\u2019 of
sodium or calcium to silicates:
where SE is the fraction of total sulphur converted to
sulphate and S, Cl, and CO2 are the sulphur, chlorine,
and carbonate contents on a weight per cent basis.
Raask (1982) allowed for the excess of chlorine over
leachable sodium and potassium, and for the fact that
iron and manganese carbonates in the coal ash would
not form stable sulphates. He also noted that, in practice,
the quantities of sulphates formed are significantly less
as a result of the capture of sodium and calcium by the
fused silica particles in the coal flame. At boiler flame
temperatures of between 1300 and 1500\u00baC, alkali metal
and alkaline earth metal silicates are more stable than
the corresponding sulphates. In fact, as Mraw and others (1983) pointed out, at furnace flame
temperatures, no SO2 absorption by calcium can take place since CaSO4 is thermodynamically unstable.
It becomes stable slightly below 1200\u00baC as the flue gas enters the convection passes of the boiler.
However, the CaO in silicate melts has an extremely low activity that reduces the temperature still
further before CaSO4 becomes stable at the SO2 pressures involved.
An \u2018alkali loss\u2019 term was introduced by Raask (1982): 1\u2013kW2/3, where W is the total mass of ash and the constant k was set at 0.09 based on analytical data for the sulphate content in ash, boiler deposits, hopper ash and so on. The quantity of SO2 emitted in kg per tonne of coal burned was calculated:
Raask (1982) pointed out that the carbonate content of coal is not determined by routine analysis and that analytical data were scarce. An alternative equation uses the acid-soluble alkali and alkaline earth metal content of the coal to calculate the SO2em it ted :
absorption of sulphur dioxide by calcium, sodium and potassium in the ash:
% S capture = 90 (Ca/S) + 30 (Na/S) + 70 (K/S)
where the sulphur capture and the elemental ratios are molar ratios.
Uzun and \u00d6zdogan (1997) obtained several correlations for combustible sulphur with sulphur forms and
the CaO content. The best correlation (with a correlation coefficient of 0.99) was:
SC = -0.130477 CaO + 1.449782 SP + 0.935385 SS + 0.748601 SO
Sc is combustible sulphur, wt%, db
CaO is the calcium oxide content, wt%, db
SP is the pyritic sulphur content, wt%, db
SS is the sulphate sulphur content, wt%, db
SO is the organic sulphur content, wt%, db.
Figure 04 Comparison of measured flue gas
concentrations of SO2 with calculated flue
gas concentrations downstream of the
boiler (McInnes, 1996)
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