SOx emissions and control - 2.5 Predicting sulphur emiss...

Page 1 of 2

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’s 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
0.42–0.6%, ash sulphation reduced SO2 emissions from the expected 230 ppm to 120–170 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 25–1200ºC, 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.

Kang and others (1995) also carried out EFR experiments using coal ash collected from the ESP hopper
of Detroit Edison’s Belle River Unit 2 (St. Clair, MI, USA). The unit burns a Decker subbituminous
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 1300ºC, 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
1200ºC, the CaSO4 decomposed, releasing SO2 back into the gas stream. Subsequent experiments were
carried out with treated ash at a gas temperature of 1050ºC. 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
significant amount of SO2 capture, implying that, in practical coal- combustion systems, potentially
significant reduction by ash deposits is possible.

A full-scale test was performed at the Belle River Unit 1. Temperatures around 1000ºC 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 ‘combustible sulphur’ 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 Özdogan (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 Özdogan, 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 750ºC, far lower than the temperatures normally encountered in pulverised-coal
combustion. Increasing the temperature to 950ºC 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 Özdogan (1998) pointed out that new formulae have to be developed for combustion
conditions that differ from those of their study.

2.5 Predicting sulphur emissions

Despite the evidence for sulphur capture by ash, Okamoto (1998) pointed out that the amount is so
small that it can be neglected for practical purposes. Accordingly, he calculated the SOx emissions as
f ll

http://www.coal.org.uk/catalogues/coalonline/81432/6041/html/6041_30.html 10/9/2551
SOx emissions and control - Page 31 Page 1 of 2

Amount of SOx per tonne of coal (m3) = 1000 kg × (S wt%/100) × (22.4/32)

1 gram-molecule of gas occupies a volume of 22.4 litres at 0ºC 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:

1 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
where:
CSfuel sulphur content of fuel (in mass element/mass fuel [kg/kg])
CSO2.max maximum attainable amount of sulphur dioxide (in mass pollutant/mass fuel
[kg/kg])

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 ‘maf’ basis (moisture and ash-free), equivalent to ‘daf’ (dry, ash free).

2 The maximum attainable amount of sulphur dioxide CSO2.max is corrected by the sulphur retention
in ash s. As a result, the real boiler emission of sulphur dioxide C SO2.boiler fuel is obtained:
C SO2.boiler fuel = CSO2.max(1-s)
where:
C SO2.boiler fuel is the real boiler emission of sulphur dioxide (in mass pollutant/mass fuel [kg/kg])
CSO2.max is the maximum attainable amount of sulphur dioxide (in mass pollutant/mass fuel
[kg/kg])
s is the sulphur retention in ash

The sulphur retention in ash depends on, for example, the fuel characteristics and the temperature inside
the boiler. If there no data for s are available, default values for various fuels are given:

Hard coal Brown coal

Dry-bottom boiler 0.05 0.3
Wet-bottom boiler 0.01

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.

3 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, ‘in particular, strong differences occur for SO2
emissions, which show a tendency to be overestimated’. This is attributed to assumptions with regard to
the default values; for example, the sulphur retention in ash varies greatly depending on the data
availability.

However, examination of Figure 4 reveals that there is only one significant overestimate and that the
tendency is to underestimate the SO2 emissions. The data on which Figure 4 is based confirm that the
figure’s 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 the s value at the Münster power station was given as
0.15, and this station was one for which the calculated value (1310–1650 mg/m3), although
underestimated, was reasonably close to the measured value (1644–1891 mg/m3). For a station at
Karlsruhe, the s value was quoted as 0.4, which seems high, and may account for the underestimate of
1310–1650 mg/m3 calculated compared with 1600–2000 mg/m3 measured. It is also possible that the
default values for the efficiency and availability of the flue-gas desulphurisation equipment were too
high.

http://www.coal.org.uk/catalogues/coalonline/81432/6041/html/6041_31.html 10/9/2551
SOx emissions and control - Figure 04 Comparison of meas... Page 1 of 2

2900 are used, but attempts have been made to estimate the
extent of sulphur capture. For example, Raask (1982)
suggested that the fraction of the total sulphur required
2400
to convert the chloride sodium and carbonate calcium to
sulphates can be expressed in terms of the chloride and
1900 carbonate contents of the coal, assuming no ‘loss’ of
sodium or calcium to silicates:

1400 SE = (0.27 Cl + 0.58 CO2)/S

where SE is the fraction of total sulphur converted to

900
sulphate and S, Cl, and CO2 are the sulphur, chlorine,
and carbonate contents on a weight per cent basis.
400
Raask (1982) allowed for the excess of chlorine over
400 900 1400 1900 2400 2900
leachable sodium and potassium, and for the fact that
Measured values, mg/m3 iron and manganese carbonates in the coal ash would
not form stable sulphates. He also noted that, in practice,
Figure 04 Comparison of measured flue gas the quantities of sulphates formed are significantly less
concentrations of SO2 with calculated flue as a result of the capture of sodium and calcium by the
gas concentrations downstream of the fused silica particles in the coal flame. At boiler flame
boiler (McInnes, 1996) temperatures of between 1300 and 1500ºC, 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 1200ºC 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 ‘alkali loss’ term was introduced by Raask (1982): 1–kW , where W is the total mass of ash and
2/3

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:

SO2em = 20 [S – (0.27 Cl + 0.58 CO2)(1 – 0.09 W )] 2/3

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 SO2 emitted:

SO2em = 20 [S – (0.70 Na +0.41 K + 0.80 Ca + 1.32 Mg)(1 – 0.09 W )] 2/3

where Na, K, Ca, and Mg are the weight percentages of the acid-soluble sodium, potassium, calcium
and magnesium in the coal.

Pohl and others (1997) reported that work at ACIRL in Australia produced the following proportional
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 Özdogan (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

where:

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.

http://www.coal.org.uk/catalogues/coalonline/81432/6041/html/6041_32.html 10/9/2551
SOx emissions and control - Page 34 Page 1 of 2

The presence of calcium chloride however, is not all beneficial, and can potentially cause operational
problems. Blythe and Rhudy (1991) reported experience at two EPRI test facilities in the USA – the
Arapahoe 2.5 MW pilot unit in Denver, CO, and the High Sulfur Test Center (HSTC) at Somerset, NY.
At both plants there were repeated failures of 300-series stainless steel clamps used to attach the bags in
the fabric filters. Failures of stainless steel bag caps and anti-collapse rings were also noted. These
failures were attributed to stress corrosion cracking caused by exposure to chloride. At the Arapahoe
facility, the failures were noted at chloride levels equivalent to 0.2 wt% chlorine in the coal. At the
HSTC, all testing was conducted with a coal chlorine content of only 0.1 wt%.

http://www.coal.org.uk/catalogues/coalonline/81432/6041/html/6041_34.html 10/9/2551