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ISSN 1018-5593

European Commission

technical coal research

THE ROLE OF FUEL ADDITIVES

TO CONTROL ENVIRONMENTAL EMISSIONS
AND ASH FOULING

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 5

European Commission

technical coal research

THE ROLE OF FUEL ADDITIVES

TO CONTROL ENVIRONMENTAL EMISSIONS
AND ASH FOULING

British Coal Corporation

Coal Research Establishment
Stoke Orchard
Cheltenham
Gloucestershire GL52 4RZ
United Kingdom

Contract No 7220-EC/846

FINAL REPORT

(Ad
Directorate-General
Energy PARI EUROP. Biblioth,
1994 N.£UR 14893 EN
C J.
 Published by the
EUROPEAN COMMISSION

Directorate-General XIII
Telecommunications, Information Market and Exploitation of Research
L-2920 LUXEMBOURG

LEGAL NOTICE
Neither the European Commission nor any person acting on behalf of the Commission
is responsible for the use which might be made of the following information

Catalogue number: CD-NA-14893-EN-C

ECSC — EC — EAEC, Brussels • Luxembourg, 1994

 III

SUMMARY

It ¡s well known that the inorganic components of coal are responsible for the serious slagging and
fouling problems associated with certain combustion processes. For instance, the alkali metals
(sodium and potassium) are commonly associated with fouling deposits and fluidised bed
agglomeration. Numerous fuel additives are currently available commercially which are claimed to
alleviate these problems. In addition, it is claimed that many of these additives can reduce the
levels of undesirable emissions such as S0 2 and NO,. Such additives, if the claims are accurate,
can reduce costly boiler outages, reduce the need for expensive FGD systems and generally
improve coals' marketability.

However the claims made for additives are rarely backed up by scientific evidence and the main
objective of this project has therefore been to test the effectiveness of the available additives at
reducing ash fouling and slagging, and NO, and/or SO, emissions in FBC, stoker fired and, to a
lesser extent, PF combustion. Where the claims were found to be justified, it was also an objective
to determine the mechanism involved.

Seventeen fuel additives were selected for this study. These were chosen to cover the range of
additive formulations available in the UK and claimed to reduce fouling/slagging and/or emissions
of NO, and S0 2 . They were characterised using chemical techniques and XRD and their effect on
the kaolinite/sodium reaction studied in laboratory thermal interaction studies. Their effects on ash
fusion characteristics and ash sinter strengths were also investigated in laboratory studies. The
effect of the additives on alkali bonded fouling and emissions was then investigated using a 9 kW
and a 150 kW underfeed stoker and a laboratory scale FBC. The results of the laboratory stoker
studies from selected additives were subsequently confirmed on a 2 MW chaingrate stoker. The
effect of copper oxychloride and kaolinite were also assessed on a pilot scale PF combustor.

The study concluded that, in general, the claims made for fuel additives were not justified. Only
copper oxychloride fulfilled its claim to reduce slagging of iron rich coals during PF combustion by
modifying the crystallinity of the slag. Magnesium containing additives were found to have no
effect on fouling in FBC but a detrimental effect on fouling in stokers. The deposits increased in
both quantity and strength. The use of magnesia in stokers is therefore not recommended.

Kaolinite was shown to have potential as an antifoulant for stokers and, to a lesser extent, FBC
systems. Fouling deposits in stokers were found to be reduced in both strength and quantity when
kaolinite was premixed with the coal. It may therefore be particularly beneficial if used in
conjunction with soot blowers. Injection of kaolinite into the boiler was shown to be unsuitable
as the airborne particulates loading was unacceptably increased. Kaolinite would therefore ideally
need to be added to the coal during the preparation process. The study suggested that kaolinite
may not be suitable for use in PF systems as the tests on the 150 kW PF combustor indicated an
increase in molten bonding material in deposits from the kaolinite treated coal. However, laboratory
studies indicated that the effect of kaolinite in PF systems can be dependent upon the ash
composition of the coal used. Tests indicated that none of the other additives would have any
effect on fouling in stokers or FBC.

The studies indicated that only limestone, dolomite or additives containing Ca(0H)3 have any effect
on S0 2 emissions from FBC. In the latter case, use of limestone would be more cost effective.
 CONTENTS

Pgqg NP,

SUMMARY

1. INTRODUCTION . 1

1.1 General Background and Objectives 1

1.2 Study Approach 1
1.3 Background to Fuel Additives for Coal-Fired Systems 2

1.3.1 Factors affecting the choice and use of fuel

additives 2
1.3.2 Additives for treating high temperature
corrosion problems 3
1.3.3 Additives for treating low temperature
combustion problems 8
1.3.4 Additives for reducing particulate emissions 8
1.3.5 Additives for reducing gaseous emissions 9
1.3.6 Additives as combustion enhancers 10

2 EXPERIMENTAL 10

2.1 Coal Selection 10

2.2 Coal Preparation and Analysis 10

2.2.1 Coal preparation 10

2.2.2 Coal analysis 11

2.3 Additive Selection and Analysis 11

2.4 Laboratory Coal/Additive Interaction Studies 12

2.4.1 Ash fusion studies 12

2.4.2 Heat treatment of coal/additive mixes 12
2.4.3 Heat treatment of mineral/additive mixes 12
2.4.4 Thermal analysis - mass spectroscopy 13
2.4.5 Ash sinter strength tests 13

2.5 Fluidised Bed Combustion Studies 14

2.5.1 The effect of fuel additives on fouling 14

2.5.2 The effect of additives on gaseous emissions 15

2.6 Stoker Fired Combustion Studies 15

2.6.1 Laboratory scale underfeed stoker 15

2.6.2 Pilot scale underfeed stoker 16
2.6.3 2 MW chaingrate stoker 16
2.6.4 1.12 MW mini-coking stoker 18

2.7 Pilot Scale Pulverised Fuel Combustor 18

3 RESULTS AND DISCUSSION 20

3.1 Additive Characteristics and Claims 20

3.2 Laboratory Coal/Additive Interaction Studies 21
 VI

CONTENTS (continued)

Page No.

3.2.1 Ash fusion studies 21

3.2.2 Heat treatment of coal/additive mixtures 22
3.2.3 Heat treatment of mineral/additive mixtures 23
3.2.4 Thermal analysis • mass spectroscopy 25
3.2.5 Ash sinter strength tests 25

3.3 Fluidised Bed Combustion Studies 26

3.3.1 The effect of fuel additives on fouling 26

3.3.2 The effect of fuel additives on gaseous emissions 29

3.4 Stoker Fired Combustion Studies 30

3.4.1 Laboratory underfeed stoker 30

3.4.2 Pilot scale underfeed stoker 31
3.4.3 2 MW chaingrate stoker 32
3.4.4 1.12 MW mini-coking stoker 37

3.5 Pilot Scale Pulverised Fuel Combustor 38

3.5.1 Additive E 38
3.5.2 Additive P 39

3.6 General Discussion on the Effectiveness of Commercial Activities 39

4 CONCLUSIONS 40

5 REFERENCES 42

Tables I to LX 47

Figures 1 to 31 101

Plates 1 to 4 133
 1
1 INTRODUCTION
1.1 General Background and Objectives
It Is well known that the inorganic components of coal are responsible for the serious slagging and
fouling problems associated with the combustion of certain coals111. For instance, the alkali metals
(sodium and potassium) are commonly associated with fouling deposits and fluidised bed
agglomeration121. Numerous fuel additives are currently available commercially which are claimed
to alleviate these problems. In addition, it is claimed that many of these additives can reduce the
levels of undesirable gaseous emissions such as S0 2 and NO«. The existence of effective additives
to alleviate fouling and slagging would reduce the need for costly boiler shutdowns, thereby
improving the marketability of high slagging or fouling coals. Effective additives to reduce
environmentally sensitive emissions, such as NO, and S0 2 , would avoid the need for expensive
control technology such as FGD in order to comply with emission targets. Coal's position as an
acceptable and competitive energy source would therefore be improved.

The claims made for commercial fuel additives are, however, often backed by little if any
scientific evidence. In addition, existing literature on the effectiveness of fuel additives for coal
fired systems is often conflicting. The objectives of this project have therefore been to test the
effectiveness of the available additives at reducing ash fouling and slagging, and NO, and/or S0 2
emissions in FBC, stoker fired and, to a lesser extent, PF combustion. Where the claims were
found to be justified, it was also an objective to determine the mechanisms involved. A few non
commercial materials were also included in the programme (eg limestone and dolomite to reduce
S0 2 and kaolinite to reduce the levels of available sodium).
1.2 Study Approach
The assessment of the ability of additives to reduce fouling has concentrated on the additives'
effect on the alkali metals, in particular sodium. Previous work'31 has shown that, during
combustion, alkali metals vaporise and subsequently condense on heat exchange surfaces as low
melting "sticking" alkali sulphates and/or chlorides. These then act as the glue which both initiates
deposition and bonds the growing deposit together.
It has been shown'41 that a proportion of the coal sodium reacts with the clay mineral
kaolinite (AI2Si20,(OH)4) during combustion, forming phases such as nepheline (NaAISi04) and
hauyne ((Na,Ca)l(Si,AI),2024(S04)2). The sodium "fixed" in this manner is therefore unavailable for
deposit formation. The proportion of "fixed" sodium can be calculated from the amount of
insoluble sodium in the combustion products, as in the original coal all of the sodium is water
soluble.
Previous work has shown'881 that the proportion of unreacted or soluble sodium in the
combustion products is related to the kaolinite/(Na20 + xCaO + yMgO) molar ratio (where x - 0 . 6 7 ,
y «0.54), in the coal. This ratio has also been shown to be related to the mass of above bed
fouling deposit from an Encomech FBC and the qualitative extent of fouling in a Robey chaingrate
stoker. These results suggest that the amount of soluble sodium in the combustion products is
related to the coal's fouling potential. This relationship has been extensively used to assess the
effect of additives on fouling in the laboratory studies of coal/additive interactions and the
laboratory scale FBC and stoker fired combustion studies.
The techniques used included investigating the effect of additives on the solubility of
sodium in ashed coal/additive mixtures and mineral/additive mixtures, thermal analysis • mass
spectroscopy (TA-MS) and combustion studies on a 70 mm FBC, a 9 kW underfeed stoker and a
150 kW underfeed stoker. Additives which had a significant effect in some or all of the tests were
then assessed on a 2 MW chaingrate stoker and a 1.12 MW mini-coking stoker (the latter under
commercial conditions). The objective of these larger scale studies was to confirm the prediction
that additives which decrease or increase the extent of sodium solubility in the laboratory will
reduce or exacerbate fouling respectively when used on boilers which are more representative of
"real" systems. The influence of mode of additive addition was also briefly investigated in these
tests. During these larger scale studies a quantitative assessment of the extent of fouling was
made.
The effect of additives on fouling in higher temperature regimes and on slagging were
assessed using ash fusion tests, sinter strength tests and limited tests on a 150 kW version of a
PF combustor.
The effect of additives on emissions of NO, and S0 2 was assessed using the 70 mm FBC
and the 9 kW underfeed stoker.
Due to the large number of additives in the programme (twelve were originally chosen but
the number was later extended to seventeen as new ones became available), not every additive
was subjected to every test. In particular, few of the additives which did not claim to reduce
emissions were tested for this and where there were two or more additives of similar composition,
often only one additive was tested. Claims to reduce soot were only qualitatively assessed and
claims to increase combustion efficiency were considered beyond the scope of the project.
1.3 Background to Fuel Additives for Coal-Fired Systems
1.3.1 Factors affecting the choice and use of fuel additives
Numerous factors need to be considered when attempting to cure a combustion problem by the
use of additives. The most important are the nature, quantity and mode of application of the
additive, the nature of the fuel, and parameters affected by boiler design and operation such as
residence times, temperature gradients and the efficiency of air, fuel and additive interactions.
The parameter 'nature' of the additive includes particle size, chemical and physical form and
thermal history as well as composition. All of these factors affect additive performance171. Additive
particle size affects the surface area, the number of particles per unit weight and transportation of
the additive through the combustor. Smaller particles have larger surface areas, greater numbers
of particles per unit weight and subsequently a greater additive to coal contact potential. Larger
particles tend to impact on heat exchange tubes and/or drop out of the gas stream as it cools in
passing through the boiler systems and may be more suitable for treating problems near the
furnace. Finer particles will generally be swept past the tubes, dropping out in the cooler regions
or being conveyed out to the stack and may therefore be more effective for treating cold end
problems.
The chemical and physical form of an additive, together with its thermal history, influences
the particle porosity/density and hence its available surface area. For example, hydroxides and
carbonates decompose endothermically upon heating, yielding low density sponge like particles
which are readily transported through the boiler.
High temperatures may sinter the particle surface although volatile additives, such as
copper oxychloride, are unaffected by sintering and can be effectively added with the coal.
Injecting other additives outside the flame envelope minimises the sintering effect but limits the
available reaction time.
An additive may be added continuously or intermittently, either by mixing with the coal or
injecting into the gas stream. Intermittent application has the advantage of producing, for short
periods, a high ratio of additive to coal ash which can markedly change the composition of the ash
deposited on the boiler tubes. This strategy has been used effectively for copper oxychloride,
magnesium oxide and limestone.
In general it is preferable to use additives on a cleaned boiler although claims are made that
existing boiler deposits can be alleviated by their use. However, this could exacerbate the boiler
condition by increasing the ash burden and affecting the heat transfer equilibrium.
The interdependence of the various parts of the combustion system must be considered
when using additives, for example, some additives aimed at reducing fouling can reduce ESP
efficiencies by adversely affecting fly ash resistivity. These and other factors important in the
selection and use of additives are discussed further in Radway and Hoffman (1987)'7'.
1.3.2 Additives for treating high temperature combustion problems
During combustion, the mineral matter present in coal is transformed mainly into ash with lesser
amounts of volatile products. The coarser ash particles fall to the base of the furnace whilst the
volatiles, together with the finer ash particles, are swept out of the furnace in the flue gas.
Depending on their composition, the ash particles may be partially or completely molten at the high
combustion temperature, giving them a tendency to stick to one another and to the components
of the boiler. The deposits formed are divided into two types: slagging deposits which form in the
sections of the boiler subjected to radiant heat (eg the furnace walls) where the ash is molten,
forming a partially mobile liquid layer; and fouling deposits which form in the convectiva sections
of the boiler (eg the superheater and économiser tubes) and are not necessarily molten. Fouling
is usually initiated by the condensation of volatile alkali sulphates formed during combustion. The
low melting sulphate matrix acts as a 'flypaper', collecting ash particles which slowly sinter
together and form a hard bonded deposit. Deposition of molten alkali sulphates on tube surfaces
can also cause metal corrosion. Slagging and fouling cause poor heat exchange and impede gas
flow, leading to load reduction and eventual shut down.
 The use of additives to alleviate high temperature deposition and corrosion problems in oil

fired systems is well developed and generally successful1*'. However, less consistent results have

been obtained in coal fired systems.

Laboratory tests have been used to evaluate the potential of fuel additives to alleviate

fouling. In particular, the sinter strength test" 10 ', used to estimate ash fouling propensities, has

been adapted to test the effect of additives on sintering by determining the strength of sintered

pellets of ash and additive mixtures111'. MgO, CaO and dolomite were all found to reduce ash

fouling propensities under the test conditions.

Dixit (1978)' 12 ' proposed a 'friability index' to characterise the physical properties of coal
ash deposits.

m
if « (-=! x s .

where I, = friability index

Ba = wt % (Na 2 0 + K 2 0 + CaO + MgO + Fe 2 0 3 ) of deposit

Aa = wt % (Al 2 0 3 + Si0 2 + Ti0 2 ) of deposit

S,„4 = sulphate content of deposit
A lower index corresponds to a more friable deposit. It was proposed that additives such
as magnesia may alleviate fouling by decreasing the sulphate content of the deposit, although this
theory has not been widely accepted.

Effective additives may not necessarily reduce the quantity of ash deposited, but may alter
its physical characteristics making it more friable and easily removed by soot blowers.
Fuel additives are said to alleviate deposition and corrosion problems by one or more of the
following mechanisms:
1. Modification of the ash fusion temperature (eg MgO or CaC0 3 ).
2. Inducing crystal growth in'liquid phases in a deposit to increase viscosity and thus reduce
slagging (eg copper oxychloride).
3. Removal of an individual component essential to deposit formation (eg SO, using MgO,
alkali sulphates using diatomaceous earth).
4. Physical disruption of a deposit by forming weak cleavage planes (eg vermiculite).
Slaaoino and Corrosion of Radiant Surfaces
Modification of coal ash fusion temperatures. The fusion temperature of coal ash can be modified
by changing the ratio of acidic to basic components in the ash (Figure 1). The required additive
dosage, however, is often high (several % by wt of coal) making the process uneconomic. Smaller
quantities of additives may be sufficient to alter the surface properties of the ash which can
subsequently affect deposit formation.
 Slag viscosity reducing additives which lower ash fusion temperatures are occasionally used
in cyclone and slag tap boilers in order to maintain the flow of molten slags'131. The slagging
characteristics of a bituminous coal ash can be estimated from the following relation'11:

Rd * a
W
where Rd « rate of slagging
Y, » fluxing of components of the ash (Na20, CaO, FeO)
1-Y, - infusible components (Si02, Al203)
a ■ constant
b « rate index
Increasing the proportion of fluxing components, such as limestone, reduces the viscosity
of the ash'131. Other components which are reported to be effective as fluxing agents include iron
ore, fluorite (CaF2) and boron containing compounds such as colemanite and ulexite'12,141. However,
iron ore can produce iron-rich slags which are highly reactive and can attack refractory linings
whilst fluorite and boron compounds can yield environmentally unacceptable products111. All the
same, boron compounds have been widely tested and their effects patented'14'.
Figure 1 demonstrates that ash fusion temperatures can also be increased by changes in
ash composition. Slagging problems in dry bottom combustors burning sodium rich lignites and
sub-bituminous coals (whose ash composition constitutes >50% basic oxides, see Figure 1) can
be effectively reduced by the addition of calcium based additives such as limestone or dolomite'1".
Some promising results have also been obtained in the US with manganese and magnesium oxides
in preventing slagging by bituminous coals'1'■"'.
Nucleation enhancing agents The primary mechanism responsible for consolidating hard bonded
high temperature deposits is sintering of the ash particles via viscous flow'11. The use of nucleation
enhancing additives to increase deposit crystallisation and viscosity, thereby reducing the adhesion
between the bonded deposits and the boiler tubes, was first tested on coals by James and Fisher
(1967)'1". Copper, an accepted nucleation inducing metal, in the form of copper oxychloride
(paratacamite), was used. E xtensive trials followed later in the United Kingdom'1'1, France1201, and
in Finland'311. Tests on small PF and stoker-fired power stations in the United Kingdom using copper
oxychloride generally produced significant improvements. However, it was demonstrated*32,11 that
copper oxychloride is only effective on iron-rich coals (> 10 - 20% Fe 2 0, on ash), producing a more
friable deposit which could easily be removed.
Kiss. Lloyd and Raask. 1972""; 1975 IMI and Livingston, Sanyal and Williamson (igSS) 02 '
have proposed possible mechanisms for the effect of copper oxychloride based on experimental
results. Copper oxychloride is partially volatilised in coal flames as chloride'1*'241. Subsequently the
copper chloride condenses on, and is dissolved in, the surface layers of the silicate rich ash
 particles. Cuprous oxide produced by the reaction 4CuCI + Si02-»SiCI4 + 2Cu20 can be reduced
to metallic copper by iron oxides and sulphides present in the melt.
eg Cu20 + 2FeO ■* Fe 2 0, + 2Cu
2Cu20 + FeS - S0 2 + 4Cu + Fe
The copper precipitates and initiates crystallisation of iron-rich spinels and/or hematite,
particularly on the deposit surface and pore surface. This increases the slag viscosity,
consequently reducing the rate of ash sintering and slagging"'. In addition, factors including
microcrack formation due to uneven changes in the coefficient of thermal expansion of the melt
caused by small scale variations in copper concentrations, lead to a more friable deposit. The
copper concentrates in the outer layers of the ash1261 with the result that only low dosage rates (2-
45 ppm copper) are required, added either as a dry powder or a water slurry.
The use of copper oxychloride has declined in the UK since the early 1970's with the
progressive closure of small coal fired power stations where it was effectively applied. Similar and
more recent tests on larger (800 MW) boilers have been less successful1".
Fouling and Corrosion of Convection Surfaces
Additives used to control the fouling and corrosion of convectivo surfaces in coal-fired plant are
based on one or more of several elements, the most common of which are calcium, magnesium,
aluminium, silicon and manganese. These elements, added as single compounds or in various
compound combinations, are said to control high temperature deposits by raising ash melting
temperatures and/or by removing components essential for deposit formation eg S0 3 . Addition
rates in the range 50 ppm to 5% of the coal feed have been reported, with performance being
related to ash composition. Improved performance has been noted with intermittent application
(in some cases directly on to heat transfer surfaces) immediately after soot blowing126"'.
Addition of calcium, usually in the form of limestone, to basic ash coals, in particular alkali
rich lignites, reduces ash fouling by forming higher melting, more friable, less tenacious deposits
(Figure 1) in dry bottom boilers. This has the effect of enhancing soot-blower cleaning
6 26 2 28 28301
effectiveness" ' - ' - . However, the high doses of limestone used to reduce sulphur oxide
emissions may adversely affect fouling performance of units firing bituminous coals, by lowering
ash fusion temperatures and increasing the amount of fouling deposits"".
Early attempts to reduce fouling with magnesia (MgO) produced some beneficial results,
but mainly with uneconomical^ large dosage rates (eg 0.4 - 3% wt on coal)'9"1. The intermittent
addition of high concentrations of MgO1361 reduced the overall quantity required whilst maintaining
effective control of fouling. More recent work, by Radway and Boyce (1978)" 4 ', in which fine
Mg(OH)2 particles were injected above the flame envelope in the combustor, produced some
improvements in deposits at much lower concentrations (50-1250 ppm). Reasons given were
increased particle surface area, less particle sintering and reduced particle loss with the bottom ash.
Subsequent reports on the effectiveness of magnesium based compounds in controlling fouling and
corrosion of convective surfaces have given conflicting results l , , " , 2 , M 3 ". Limited trials using oxide
mixtures, eg MgO/AI20,, Al 2 0,/Ti0 2 have been reported to more effective than single
compounds11'""). Magnesium oxide mixtures containing alumina may form a spinel, MgAI204,
which produces a more friable deposit which is more easily removed by soot-blowing112,1".
The mechanisms by which magnesia and other oxides affect high temperature deposits are
uncertain, although four possible theories have been proposed1341. These are:
1. Preferential deposition of a high melting point protective layer on the convective surfaces.
2. Reducing SO, formation by masking the catalytic iron oxide surfaces in the combustor'1,401.
3. Reaction with SO, either in the gas stream ahead of, or on, the convective surfaces'401.
4. Formation of more stable complexes with alkali sulphates eg NajMg 3 (S0 4 ), l,MM2> .
The most probable reaction mechanism appears to be gas phase reaction of the additive
with SO,, as a direct relationship has been found between MgO injected into the furnace and the
reduction in condensable SO, at the air heater inlet1341.
It is likely, however, that other mechanisms are also partly responsible for any noted
effects, for example, physical adsorption of the molten sulphates'37,43' and the production of higher
melting point compounds in the sticky alkali-rich ash surfaces layers as a result of the addition of
further alkali (see Figure 1).
Mechanisms 1 and 2 and reactions with SO, on convective surfaces are less likely as fly
ash has been shown to effectively mask tube surfaces1441 and no increase in MgO or SO, has been
found in high temperature deposits obtained during additive trials1341.
Attention was focused on calcium chloride as an anti-fouling additive due to its use as an
antifreeze agent during the transport and storage of coal in winter. Investigations carried out to
assess the possible detrimental effects of extra chlorine on the boiler fouling and low temperature
corrosion found, unexpectedly, that in many cases boiler deposits had become more friable
although not less abundant14". It has been suggested that the CaO produced from thermal
decomposition of CaCI2 in the furnace deposits preferentially, producing a weak cleavage plane at
the metal surface*46'. Only small quantities of calcium chloride were used ( - 0 . 0 1 % per wt coal),
usually added intermittently.
Other compounds which may affect high temperature deposition by restricting SO, levels
include organo-manganese compounds, antimony trioxide and zinc oxide. Manganese compounds
have been used effectively in oil fired boilers to improve combustion efficiency, though they appear
to be less effective for coal. However, volatile methyl-cyclopentadienyl manganese tricarbonyl has
been found to reduce ash slagging and fouling of high sulphur bituminous coals'1". Manganese
oxide (Mn,04) acts as a catalyst for carbon combustion, inhibits oxidation of magnetite (Fe,04) and
may react with sulphur oxides. Consequently, the catalytic oxidation of S0 2 to SO, by hematite
(Fe20,) will be reduced. The reduction in ash fouling and slagging are unlikely to have been
achieved through ash fusion temperature modifications at the very low dosages used, ~20g Mn
per ton coal.
 Studies have shown that antimony trioxide (Sb20,)M7' and zinc oxide148,48,60' were effective
in reducing fouling and corrosion problems by inhibiting catalysis of SO, to SO,. Treatment rates
for antimony of 50 to 500 ppm would probably have to be reduced to ensure that stack emissions
are below the threshold limit value.
Sorbent materials including silica gel, kaolinite, diatomaceous earth, bentonite, mica and
bauxite may also remove components essential to deposit formation by adsorption, their
effectiveness being related to surface area and temperature1"'6162,83,84'6'. Diatomaceous earth,
bauxite and, for temperatures <700°C, kaolinite were found to be the most promising for reducing
fouling problems.
Vermiculite and other expandable materials have been investigated as possible additives to
control fouling and corrosion of convectiva surfaces'7,16,68'. Vermiculite adheres to deposits and,
at temperatures above 630°C, expands up to fifteen times its original volume, providing weak
cleavage planes and disrupting the deposit, which is then readily removed by soot-blowing.
Vermiculite's performance, however, deteriorates at gas temperatures >1090°C and is also
dependent on the source of the material. Severe wear problems have been encountered in the
feeding equipment and care is needed in handling the material as it may contain up to 1 %
asbestiform tremolite.
1.3.3 Additives for treating low temperature combustion problems
Low temperature (cold end) problems include corrosion, acidic emissions (both caused by H2S04)
and fouling of air channels by aggregates made from ash and condensed H 2 S0 4 m . Magnesium
based additives are used successfully to reduce these problems in oil fired boilers187' but results
have been less consistent in coal fired systems. However, in general S0 3 , and therefore H2S04,
can be reduced by magnesium additives134,36,M'. Reduction of cold end problems is also a beneficial
side effect of adding limestone to boilers to reduce S0 2 emissions or fouling with alkali rich
lignites1681. Other additives which have been tested include methyl-cyclopentadienyl manganese
tricarbonyl and MnO'18,69,67' which are suggested to work by inhibiting oxidation of magnetite to
hematite, thereby restricting the catalytic conversion of S0 2 to SO, by hematite"7,801; and injection
of anhydrous ammonia18". The latter requires careful dosage control as too much can give rise to
ammonium bisulphate which is corrosive and can cause fouling1821.
1.3.4 Additives for reducing particulate emissions
Additives are widely used to improve ESP efficiency by modifying ash resistivity and cohesiveness
(ash conditioning)11,14,83,84'. No conditioning agent is universally applicable but SO, or compounds
which decompose in the flame to give SO, (eg H2S04, ammonium sulphate or bisulphate, or
sulphamic acid) are the most widely used114,86,88,87-68,70,71'. Ash resistivity is reduced by the
production of a thin conducting layer of H2S04 on the ash particles. Ammonia172,73,74-78,78"' and
triethylamine'78,78,80,81,82' have also been used but with less consistent results. Too much ammonia
may also cause fouling problems'78'. Use of solid additives is rare, but magnesium based additives
can reduce SO, levels in systems where too much SO, results in loss of charge and ash particle
re-entrainment'"'. Other additives which are claimed to reduce ash resistivity include alkali metal
carbonates and sulphates, ferric sulphate and phosphorous pentoxide"-1*-4'-*4'"-"'171. A fuller
111
account of additives for E SP's can be found elsewhere .
1.3.5 Additives for reducing oaseous emissions
Calcium based sorbents
The practice of adding limestone or dolomite directly to the fuel or by injection into the furnace
chamber to control sulphur oxide emissions from combustion plant, particularly from FBC units is
well documented1**1. Limestones and dolomites from different sources very considerably in their
ability to capture S0 2 , and studies have shown that the calcium content and the porosity of the
calcined rock are the major factors affecting their performance as sorbents1**'. Criteria to be
considered when selecting sorbents are discussed in detail by Ulerich'**'.
The carbonates calcine rapidly between 700° and 900°C, causing major structural
changes.
Limestone CaC03ll) -» CaO,., + C02lB,
Dolomite CaCO,.MgC03lll ■* CaO,,, + MgO„, + 2C02ls,
The sorbent porosity increases during calcination, enhancing diffusion of S0 2 and 0 2 into
the pores. Sulphation then occurs, reducing the sorbent porosity.
Limestone CaO,,, + S02ls, + y»02(Ql-» CaS04„,
Dolomite CaO,,, + MgOte, + S02(B, + %02|Q, -+ (>775°C) CaS04l„ + MgO„,
MgO is largely unaltered due to the instability of MgS04 above 775°C at atmospheric
pressure1901.
The sulphation reaction is diffusion controlled '*". A shell of impervious CaS04 forms,
blocking the pores and eventually terminating the reaction '*". The reaction is also temperature
dependant, the optimum temperature being 800-900°C. At higher temperatures the reactivity of
the lime is reduced due to sintering of the particle surface and above 1200°C calcium sulphate is
unstable.
The performance of some sorbents can be enhanced by heat and chemical treatments " 2I .
The addition of chlorides, particularly sodium chloride, can induce structural re-arrangements giving
optimum pore distribution for reactions with S0 2 '**'.
The development of low NOx staged combustion has renewed interest in sorbent addition in PF
combustion as the flame temperature is lower and sulphur may be captured in the reducing zone
via the following reaction "".
CaO + HjS ■* CaS + H 2 0
Limited studies have also been carried out on the use of calcium based sorbents in coal-fired
IM
stokers '.
Economically it is important to keep sorbent additions low in order to minimise both raw material
costs and spent sorbent disposal costs.
 10

Calcium Free Additives

The reported use of calcium free additives to reduce gaseous emissions is very limited. Additions
of sodium compounds, such as sodium hydroxide, sodium carbonate and bicarbonate to coal gave
w6,,e
reductions in S0 2 emissions of up to 70% '. However, and not surprisingly, all of the
compounds significantly increased boiler fouling.
Additions of MgO, organomanganese compounds, NH„ ZnO and Si0 2 have variously been
demonstrated to reduce SO, levels in flue gases. Reports that various commercial additives affect
reductions in SOx and NOx were not substantiated in a review by Krause et.al"".
1.3.6 Additives as Combustion Enhances
Soot deposits and high carbon ashes can occur with hard to burn coals, or ageing inefficient
l>7 >
boilers. Combustion enhancers can potentially increase plant efficiency by up to 2.5% - ",
improve ESP performance, reduce SO, levels and even reduce ash deposits by producing more
oxidising conditions which may result in higher ash fusion temperatures.
Numerous metal compounds, particularly the chlorides, have been shown to act as combustion
enhancers but few have been widely assessed on coals '"'. Copper compounds appear to be the
most effective although studies ',001 suggest that chloride ions may be the active agent, depressing
the ignition temperature and thus extending the coal particle burn time. KNO, has been shown to
reduce the ignition temperature of coal n 0 " and is the active ingredient in many commercial "anti
soot" additives. Possible mechanisms for the action of combustion enhancers have been proposed
by Havard and Kaush.'1021
2 EXPERIMENTAL
2.1 Coal Selection
Initally six UK bituminous coals were selected for use in both the laboratory coal/additive interaction
studies and the laboratory scale combustion studies. These coals were chosen to cover a range
of ash, chlorine, sulphur and sodium contents, as well as a range of observed behaviours during
utilisation. Four further coals and a second grade of one of the original coals were later used for
the studies on the pilot scale rigs and small industrial boilers. These coals were included as they
were either more suitable for the boiler being used or were readily available at the boiler site.
2.2 Coal Preparation and Analysis
2.2.1 Coal Preparation
The six coals used for the laboratory interaction and combustion studies (250kg of each of Coals
I, IIa, IIb, III, IV and V) were individually homogenised in a ribbon blender to minimise future
sampling problems. During the blending a representative sample was collected which was
subsequently used for characterisation and analysis. The remaining coal was stored in sealed
barrels for later use. Coal for the laboratory coal/additive interaction studies was then crushed to
-212/ym. Coal for the laboratory scale fluidised bed combustion studies was prepared to -355 +
180//m. As this can result in some selective fractionation of the mineral matter, a representative
sample was taken from each sized coal for subsequent analysis.
 11

The 9 kW underfeed stoker is designed to burn pearl grade coal (nominally 6-12mm) and so a pearl
grade of Coal I was used for these studies. This coal was also sampled for analysis.
The larger quantities of coal required for the 150 kW underfeed stoker (Coals III, IV and V)
and the 2MW chaingrate stoker (Coal III) were mixed mechanically. A sample was taken for
analysis from each batch of mixed coal for the 150 kW underfeed stoker. Analytical samples from
the 2MW chaingrate stoker studies were obtained by sampling the coal from the feed stream at
regular intervals during each test. Analytical samples were taken from each delivery lorry for the
1.12 MW mini-coking stoker (Coal VII). No facilities were available at this site to mix the coal,
although fairly good mixing was expected to occur as the coal is blown into the bunker.
The coals used for the pilot scale PF combustor, (Coals VII and IX) were milled to PF grade
(nominally 70% < 75//m) immediately prior to use and sampled for analysis.
2.2.2 Coal Analysis
The chemical analyses for each coal used in this project are given in Tables I to Vili. A separate
analysis is given for each test in the mini-coking stoker and chaingrate stoker studies.
Proximate analyses (moisture, ash and volatile matter) were determined using a Leco MAC-410
automatic analyser. Carbon, hydrogen, nitrogen, carbon dioxide and chlorine contents were
determined according to BS procedures <1°", and oxygen indirectly determined by difference. Total
sulphur was determined using a Leco SC-32 Sulphur Determinator. Sulphate and pyritic sulphur
l1031
were determined according to BS procedures and organic sulphur determined indirectly by
difference. The BC rank code classification uses volatile matter and Gray King coking values as
criteria of rank, however, it is not applicable for coals with ash contents 2 1 0 % ad. The ash
analyses were calculated from elemental compositions determined by inductively coupled plasma
spectroscopy using a Perkin Elmer ICP/6000 Spectrometer. Ash fusions were measured under a
reducing atmosphere using the British Standard Ash Fusion Test n03>.

The Kaolinite/(Na20 + 0.67CaO + 0.54MgO) molar ratio was calculated as follows:

Na 2 0, K 2 0, CaO, MgO and Al 2 0, on ash were converted to moles in the coal.
Then

I l l l t e
' -T72ÌT

and

¡Caolinite « yţi20, - - ^ i illite

The molar values were then entered into the equation above.
2.3 Additive Selection and Analysis
Twelve additives were originally selected for investigation, but this was expanded to seventeen
during the course of the project as new formulas were introduced. The range of additives selected
covered all of the main chemical types of fireside additives presently or about to be marketed in
 12

the UK, aimed at reducing slagging/fouling and/or emission problems in industrial boilers. The
additives also included three naturally occurring materials (limestone and dolomite (SO, sorbents)
and (caolinite (potentially an anti foulant).
Ash and moisture were determined using a Leco MAC-410 automatic analyser and Si, Al, Fe, Mg,
Ca, Na, K, Mn, Ti, P, Cu, Pb and Cr where applicable determined by inductively coupled plasma
spectroscopy using a Perkin Elmer ICP/6000 spectroscopy. Nitrate was determined by ion
chromatography, and C, H and N using a Carlo Erba CHN analyser. Additives M and N were
analysed using gas-liquid chromatography. Chlorine was determined using combustion techniques
and XRD data obtained using a Siemens D500 Diffractormeter with Cu K. radiation.
2.4 Laboratory Coal/Additive Interaction Studies
2.4.1 Ash Fusion Studies
The effect of the solid additives on the bulk melting characteristics of coal high temperature ash
(HTA) was studied using the British Standard Ash Fusion test ,1MI . HTA was prepared by heating
•212¿rm coal in air at 815°C according to the BS procedure and was mixed with each additive in
a proportion corresponding to the manufacturer's maximum recommended dosage on the coal.
Kaolinite (Additive P) was mixed at dosages corresponding to 1 and 2% w/w on the coal and the
limestone and dolomite (Additives I and J respectively) were mixed at dosages corresponding to
2:1, Ca:S ratio on the coal and 5% on the coal.
The ash fusion test is an empirical test used to simulate the behaviour of coal ash when
heated in contact with a reducing (or oxidising) atmosphere. The data is frequently used to assess
the quality of coals with respect to furnace slagging. The ground ashes (<63/sm) were formed into
pyramidal cones with the aid of a dextrin binder and heated in a tube furnace, at 5°C min'1 from
1000°C under a reducing atmosphere (50:50 mixture of hydrogen and carbon dioxide). The
temperatures of initial "deformation", formation of a "hemisphere" and complete "flow" were
noted.
Additives which gave a result outside the acceptable variation of the test at the
recommended dosage were then re-tested using higher concentrations in order to separate real
effects from normal variations by establishing trends.
2.4.2 Heat Treatment of Coal/Additive Mixtures
Selected additives were mixed in varying proportions (0-5%w/w) with Coal I (-212//m) and ashed
at 815°C for 6 hours. Samples of the pure additives were also ashed. All the resultant ashes were
refluxed in high purity water for six hours, filtered and analysed for sodium, potassium, calcium and
magnesium.
2.4.3 Heat Treatment of Mineral/Additive Mixes
In order to investigate the potential of additives to encourage or restrict the kaolinite/sodium
reactions during combustion, mixtures of kaolinite (4g), Na2S04 (1g), (giving a slight excess of
kaolinite over sodium on a molar basis) and additive (1g) were ashed for 6 hours at 850°C and
1150°C to represent FBC and stoker fired combustion respectively. The resultant ashes were
 13

examined by XRD to identify the crystalline phases present. In addition, 1g samples of each ash
were refluxed in high purity water for three hours, filtered and analysed for sodium and potassium.
The (caolinite used was Grade E china clay from ECC International Ltd (Additive P) and the Na2S04
was analar grade from BOH chemicals.
2.4.4 Thermal Analysis • Mass Spectroscopy
Thermal analysis • mass spectroscopy (TA-MS) studies were carried out on mixtures of low
temperature ash (LTA) from Coal I and 10% w/w of selected additives.
The LTA was produced by oxidising coal at low temperatures under oxygen plasma using
a Plasmaprep 300 system. The TA-MS was carried out using a Stanton Redcroft STA780
thermogravimetric analyser interfaced with a VG quadrupole mass spectrometer. The samples (10-
30mg) were heated in flowing air (50ml min-1) at a heating rate of 15K min1. A heated capillary
transfer line was used to sample 20ml min ° of the gas to the quadrupole mass spectrometer. This
was operated in a multiple ion monitoring mode which permitted the simultaneous monitoring of
H 2 0 (m/z 18), C0 2 (m/z 44) and S0 2 (m/z 64). These evolution profiles were correlated with the
conventional thermogravimetric data obtained at the same time in order to generate the TA-MS
l1Ml
profiles . A mineral mix standard was prepared using samples of "pure" anhydrite, calcite,
dolomite, kaolinite, muscovite mica, pyrite and siderite. The characteristic decomposition
temperatures of these components were subsequently used to assign peaks in the profiles for coal
LTA.
2.4.5 Ash Sinter Strength Tests
Sintering of ash particles is an important bonding mechanism in the formation of fouling deposits,
in PF combustion. A modification of Barnhardt and Williams sintered pellet test110" was used to try
to measure the effect of different types of additives on the extent of sintering of ash particles.
Selected additives were mixed in varying concentrations with coal HTA and also with coal
ground to -212//m. The coal/additive mixtures were then ashed at 815°C to allow interaction
between the coal minerals and the additives. 0.75g quantities of each resulting ash or
HTA/additive mixture were mixed with 0.16g deionised water and pressed in a mould for 10
seconds at 30 bar pressure. The resulting pellets were fired at 1100°C overnight to allow sintering
to occur. After cooling slowly, the compressive strengths of the pellets were measured using an
Ingstrom mechanical test machine. Three pellets were made from each ash in order to obtain an
average result. Selected pellets were then examined by qualitative XRD and scanning electron
microscopy in order to investigate the reasons for the differing pellet strengths.
Pellets were also made from samples of deposits collected from the 150kW underfeed stoker and
the 2MW chaingrate stoker when fired with and without Additive P (Kaolinite). The tube deposits
from the underfeed stoker were ashed at 815°C to remove residual carbon and then ground to
-212/ym prior to pelletisation. The deposits from the chaingrate stoker were already ground to
 14

•75pm and had a negligible carbon content so no extra preparation was necessary. The amount
of ash used per pellet was increased to 0.8g for the underfeed stoker deposits and 1.0g for the
chaingrate deposits to maintain the required height to diameter ratio in the resulting pellets.
2.5 Fluidised Bed Combustion Studies
2.5.1 The effect of Fuel Additives on Fouling
Fluidised bed combustion studies were carried out on a 70mm laboratory scale FBC. A schematic
diagram of the FBC is given in Figure 2 and the reactor is shown in more detail in Figure 3.
The test procedure involved fluidising 300g of sand bed material (-500 + 250pm) in a silica glass
reactor with air preheated to 500°C. Bed temperature was maintained at a constant 850°C with
the aid of external heating elements wound round the reactor. Coal (-355 + 180pm) was fed from
a vibratory feeder directly into the fluidised bed via a gas cooled coal feed tube. A flow of nitrogen
was used to force the coal into the bed and prevent combustion in the feeder tube. This effectively
diluted the oxygen content of the fluidising gas to 17% v/v. Silica glass probes (10mm diameter),
equipped with thermocouples were positioned in the reactor free board in order to collect
representative deposits.
An isokinetic sampler was used to continuously sample - 4 % of the flue gas from a
position between the reactor exit and the cyclone. The sample gas subsequently passed through
a bubbler containing H 2 0 2 (3% v/v solution). The remaining flue gas passed through a glass
cyclone to collect fly ash and finally a dry ice cooled condenser.
Approximately 300g of coal was burned during each test at a feed rate of approximately
lOOg/h. Additives were pre-mixed with the coal typically at a dosage of 0.5% w/w.
During the course of each test, flue gas samples were taken at hourly intervals and
analysed for 0 3 , N2, C0 2 and CO by gas chromatography. Upon completion of the test, the solid
fly ash and bed sand materials were recovered from the cooled reactor. Aqueous samples, which
included the bubbler and condensate solutions and those resulting from dilute nitric acid washings
of the reactor and associated glassware and the silica glass probes, were filtered, made up to a
fixed volume with ultrapure water .and then retained in plastic containers for subsequent analysis.
A summary of the mass balance conditions is given in Table IX.
Three main classes of combustion product were recovered from the tests. These were a
"condensed/deposited material" primarily recovered from the walls of the reactor, coal feeder tube
and the probes. This was considered to be representative of material that had been volatilised
during combustion and subsequently condensed on cooler reactor surfaces. The "fly ash"
represented material that had been elutricated from the fluidised bed while the "sand" included
material retained in the fluidised bed. 25g of each bed material and 2g of each fly ash were
refluxed in ultrapure water for 6 hours, filtered and then made up to 250ml for subsequent analysis
for Na, K, Ca and Mg.
Similar experiments were carried out with various concentrations of Additive P (Kaolinite)
premixed with the coal using a limestone or dolomite bed instead of a sand bed. In order to
 15

maintain a constant volume of bed material, only 215g of limestone or 235g of dolomite was used
in place of the 300g of sand usually used. In all cases the bed material was sized to -500 +
250//m. The limestone used was from Dimmocks Cote (Additive I) and the dolomite was from
Tadcaster (Additive J). Analysis of the limestone and dolomite are given in Table X.
2.5.2 The Effect of Additives on Gaseous Emissions
A modified 70mm FBC was used to assess the effect of selected additives on gaseous emissions
of S0 2 , NO and N 2 0. The unit is shown schematically in Figure 4. The main differences to the
system described in Section 2.5.1 are the use of a double screw feeder rather than a vibration
feeder to feed the coal into the reactor, and the more elaborate gas sampling system. This involved
passing the portion of gas used for analysis through a coarse quartz wool plug, 2 cyclones and
finally a 1//m filter to remove particulates. Moisture was then removed by a magnesium Perchlorate
trap and the cleaned gas analysed for N20 using a Shimadzu ECD analyser, NO using a Signal
Series 4000 chemiluminescence analyser and S0 2 using an ADC infra-red analyser. CO, C02> 0 2
and N2 were also determined. Gas compositions were monitored at 800°, 850°, 900° and 950°C
after allowing the FBC to equilibrate at each temperature.
Coal was fed into the reactor at a nominal 50g/h and the bed materials used consisted of
sand, limestone or dolomite. Additives were pre-mixed with the coal typically at a dosage of 0.5%
w/w on the coal.
2.6 Stoker Fired Combustion Studies
2.6.1 Laboratory Scale Underfeed Stoker
Effect of Additives on Fouling
Conventional stoker fired combustion was simulated on a laboratory scale using a 9kW underfeed
stoker fired domestic boiler, shown in Figure 5. The unit is designed to burn pearls grade coal
(nominally 6-12mm). Minor modifications were made to the unit to facilitate gas sampling from
the flue and the collection of deposits on both silica glass and gas cooled metal probes. These
were inserted into the boiler convective passes and their surface temperatures monitored by
thermocouples attached to the probes.. Attempts were made to monitor SO, levels with a Severn
Science SO, meter but this was later abandoned as the measured levels were too low dppm) for
any differences to be seen.
Additives were pre-mixed with the coal (pearls grade Coal I, an analysis of which is given
in Table IV) at twice the manufacturer's recommended dosage and the coal burned at
approximately 1.3kg/h for 8 hours (full fire). Gas samples were collected at intervals and analysed
for CO, C0 2 , N2 and 0 2 . After each test, the bottom ash was removed, deposit was collected from
the probes and scraped from the heat exchanger surfaces, and "fly ash" recovered from the
entrance to the flue. Ig samples (-212/um) of each material were refluxed in ultra pure water for
3 hours, filtered and made up to 100ml for subsequent analysis.
A limited number of additives were also assessed on the 9kW underfeed stoker for a 5 day
period to assess the effect of selected additives on more mature deposits. The unit was run at full
 16

fire during each working day and kindled overnight. Attempts were made to monitor particulate
emissions during this period using a small scale ESP and to monitor any decline in boiler efficiency
over the week. The former was not successful as the ash resistivity was too low, causing the unit
to repeatedly cut out.
This apparatus had been used extensively in a previous ECSC Project1" and was known to
result in acceptable repeatability in terms of the values obtained from soluble sodium recovery.
The Effect of Additives on Gaseous Emissions
A further 8 hour test was carried out on the 9kW underfeed stoker for additives which are claimed
to affect gaseous emissions. Additives were premixed with each coal at twice the manufacturer's
recommended dosage and the boiler was run at full fire during each test. A portion of the flue gas
was filtered and transferred to British Coal's mobile emissions laboratory via a heated line (to
prevent loss of S0 2 ). Water vapour, S0 2 , CO and C0 2 were measured using infra-red gas
analysers, while 0 2 was measured using a paramagnetic oxygen analyser. NO, was measured
using a chemiluminescent NO, analyser and total hydrocarbon emissions measured using a flame
ionisation detector. After an initial equilibration period lasting several hours, gas levels were logged
in 25 minute runs, each consisting of 50 measurements for each gas, taken at 30 second intervals.
3 such runs were carried out during each test.
2.6.2 Pilot Scale Underfeed Stoker
Longer deposition studies were carried out on a 150kW underfeed stoker in a reverse flame boiler.
The boiler is shown schematically in Figure 6. Additive P was pre-mixed with the Coal III and IV,
at 1 %w/w and Coal VI in various concentrations.
Each test consisted of burning 1.3 -1.7 tonnes of coal on a precleaned boiler over a period
of 12 days. The boiler was run at full fire during each working day (10 periods of 8 hours) and
kindled (minimum combustion rate) overnight and over the weekend. Each morning the bottom ash
was removed and weighed and the automatic tube cleaning mechanism operated 10 times. The
tube cleaning mechanism consisted of a metal spiral inside each heat exchange tube which was
pushed down the tube by compressed air when the cleaning mechanism was operated. The metal
spirals scrape the insides of the tubes clean. The deposit was then collected and weighed. At the
end of the test the cleaning mechanism was operated 20 times to remove as much as possible of
the remaining deposit. The bulked tube deposit and bottom ash were then sampled for analysis.
1g samples of the ash and deposit (-2l2//m) were refluxed in ultra pure water, filtered and made
up to 100ml for analysis. C0 2 was monitored at intervals during each test.
2.6.3 2MW Chainarate Stoker
General
The test programme was carried out on a Proctor chaingrate stoker installed in a Danks boiler (rated
at 5000lb/h) in the site boiler house. The boiler is shown schematically in Figure 7. The initial
programme consisted of four nineteen day trials with the boiler being shutdown at weekends.
 17

The boiler was thoroughly cleaned prior to each test. The boiler tubes, furnace tube, rear
tube plate and refractory surfaces in the reversal chamber were all brushed and vacuumed. All ash,
grits, dusts and deposits were removed from the boiler and the cyclone emptied. Approximately
70 tonnes of a washed smalls grade of Coal III (Coal 1Mb) was burned during each test (chosen due
to the high fouling tendency noted in previous test work"1). The boiler was run at approximately
75% M CR during each test (grate speed 8, bed height 4"). All grate ash and cyclone fines
off-takes were weighed and sampled throughout each test. Reversal chamber fines were removed,
weighed and sampled at each weekend shutdown, and stack emissions were monitored and
sampled at intervals using the BCURA technique. The coal feed was sampled twice a day and COa
levels,and backend and flue temperatures monitored periodically. The coal analyses for each test
are given in Table VII.
At the end of each trial the remaining grits/ashes were collected and weighed. The deposits
were photographed, weighed and removed for analysis. Typical locations from which deposits
were collected are illustrated in Figure 7. The coal, combustion products (grate ash, cyclone fines,
reversal chamber fines, smoke box fines and stack ash) and deposits were characterised using
chemical techniques and X-ray diffraction (XRD). Elemental solubilities were determined by
extracting samples of the combustion products/deposits in ultrapure water for 6 hours (1g of
-75//m material). The mixture was then filtered, made up to 100ml and analysed for sodium,
potassium, calcium and magnesium.
Trial with Additive C
The recommended mode of addition of this additive was injection into the secondary air stream.
However, as the Danks boiler did not have a secondary air system, attempts were made to inject
into the air stream at the front of the boiler. Unfortunately, this adversely affected the fire and it
was only possible to inject the additive into the reversal chamber. It is recognised that this was
not ideal due to the short residence time, however, it was an acceptable compromise as addition
with the coal prior to combustion was unacceptable to the manufacturers as the majority of the
additive would be lost with the'grate ash. The average dosage over the test period was
0.15% w/w (approximately 3 times the normal recommended dosage).
Trial with Additive B
During this trial (Trial 3), Additive B (iron carbonate) was injected intermittently into the flame at
the front of the grate (for 10 seconds every hour), as per the manufacturer's recommendations.
The average dosage over the test period was 0.12% w/w (approximately 3 times the normal
recommended dosage).
Trials with Additive P
This additive was mixed with the coal prior to combustion to ensure intimate contact between coal
and additive. The dosage used was approximately 1.5% w/w. Due to technical problems this trial
(Trial 4) had to be abandoned after 15 days and a second series of tests were carried out at a later
date to complete the assessment of Additive P (Kaolinite).
 18

The second series of tests were 15 day trials, due to the high fouling propensity of the coal
which had made running for 19 days difficult in the original series of tests. Three trials were
carried out, consisting of an additional control trial (Trial 5), a trial with approximately 1.5% w/w
(caolinite mixed with the coal prior to combustion (Trial 6) and a test with (caolinite injected into the
flame at the front of the boiler (Trial 7). The operating conditions and test procedures were the
same as for the 19 day trials with the following exceptions: stack ash emissions were not
monitored and, for the trial with (caolinite injection, a spell of cold weather prevented the normal
weekend shutdowns, instead during this trial, the boiler was run continuously for 15 days.
Continuous injection of kaolinite was attempted, but not achieved during this trial due to the
tendency of the kaolinite to "rathole" in the hopper. This resulted in the intermittent addition of
larger dosages. The overall dosage over the trial period was approximately 0.5% w/w.
2.6.4 1.12 MW Mini-coking Stoker

The test programme was carried out on a Proctor mini-coking stoker installed in a Hartley and
Sugden 1.12 MW Black Diamond medium pressure hot water boiler supplying heat to domestic
residences. The boiler is shown schematically in Figure 8.
The programme consisted of a 35 day control trial followed by a similar period burning coal
which had been premixed with 1 % w/w of Additive P (kaolinite). The coal used was Coal VII, the
analysis is given in Table VI.
The boiler was cleaned prior to each test. Flue gas oxygen content was monitored, and
furnace and flue gas exit draughts recorded during each test in order to determine if the smoke
tubes were starting to block due to deposit formation. Hour timers on the stoker and induced
draught fan allowed total boiler running times for high and low fire to be calculated. The boiler was
briefly shut down 16 days into each test for an interim inspection of the tube plate. Cyclone fines
and grate ash were sampled daily from the grate ash and cyclone bins during each test.
After each test, the reversal chamber fines were removed and sampled (Figure 8) and the
tube plate inspected and photographed. The tube plate deposit was then removed and weighed
and samples of all the combustion' products analysed. The sodium solubilities of the combustion
products were determined by refluxing 1g of each material (-75 //m) in ultra pure water for six
hours. The resultant mixtures were then filtered, made up to 100 ml and analysed for sodium.
2.7 Pilot Scale Pulverised Fuel Combustor
Pulverised fuel combustion was simulated on CRE PF ash deposition rig (ADR) which is designed
to model a 150 kW highly rated front wall-fired utility boiler. It was designed to study the ash
deposition characteristics of power station grade coals under furnace operating conditions. The
rig is illustrated in Figure 9 and described briefly below. A comprehensive description can be found
elsewhere'106'.
Coal is milled to PF grade (nominally 70% <75//m) and transferred to a storage hopper via
a vacuum pump system. The coal is conveyed from the hopper via a rotary valve to a loss-in-
weight screw feeder. The feeder delivers coal at a pre-determined rate (17.7kg/h for these tests)
 15

to a vibrating tray. The tray conveys the coal to an ejector where it is entrained in a stream of
primary combustion air. The coal/air stream is then conveyed to the burner by a flexible hose.
Secondary air, preheated to 250°C, is introduced tangentially to the coal/primary air stream. The
burner fires into a refractory lined chamber which has several observation ports on one side,
allowing access for the deposition probe. A schematic diagram of the deposition probe tip is given
in Figure 10. The probe is air cooled and deposit was collected on both a metal coupon and a
mullite coupon (a mullite sleeve attached over the second metal coupon). The metal coupon had
been preheated to 900°C for 1 hour to allow the surface to oxidise and be more representative of
metal boiler tube surfaces, whilst the mullite (AI6Si20„) was used to represent an existing layer of
deposit. Both types of coupons were weighed prior to fitting to the deposition probe. The
"upstream" and "downstream" temperatures of the metal coupons were monitored by means of
thermocouples inserted into "pockets" in the coupons. The mullite coupon's temperature was
expected to approach that of the gas stream. After the combustor had equilibrated at the desired
conditions, the assembled probe was inserted for 1 hour. At the end of this period it was removed
and allowed to cool prior to being dismantled. Immediately after removal of the probe, the gas
temperature was measured using a LAND suction pyrometer (type SU6/H/12/2.0). Oxygen
concentration was monitored continuously during the test using an ADC paramagnetic oxygen
analyser.

The additives tested on this unit were Additives E and P. Coal VIII was used (the analysis
is given in Table VIII) with Additive E, chosen due to its iron rich ash (necessary to the proposed
mechanism for Additive E). The additive was added by first mixing it into a small quantity of coal
(~100g) by hand and then mixing this into increasingly larger quantities of coal until the entire
quantity of treated coal was finally mixed using a drum roller.
The probe conditions aimed for during the test were 1300°C gas temperature and 3% Oa,
to represent oxidising conditions, 1100°C gas temperature and 3% 0 2 and 1300°C gas
temperature and 1 % 0 2 to represent reducing conditions. Deposit samples were collected under
each of these conditions for both the untreated coal and coal premixed with lOOppm w/w of
Additive E. The actual conditions at which the deposits were collected are given in Table X.
After the deposit had been collected and the probe cooled, the metal coupon was removed,
weighed and the deposit brushed off. The mullite coupons had shattered in each case so the
deposit could not be quantified in these cases. Deposit was brushed off the remaining portions of
mullite.
Each deposit was powdered and examined by XRD to identify the crystalline phases
present. Pieces of the mullite coupons were sectioned and polished and their micro-structures
examined in plane and cross polarised reflected light, using a reflected light microscope. The same
specimens were then examined using scanning election microscopy (SEM) and EDAX analysis to
confirm the composition of individual phases. Deposits from the metal probe were examined in
their powdered form.
 20

Additive P was pre-mixed(1 %w/w) with the pulverised Coal IX (Analysis is given in Table
VIII) using the drum roller. The available time on the rig was short so deposits were collected on
metal and mullite coupons at only 1 condition (1190°C gas temperature, 3% 0 2 and a probe
temperature of 550°C) with, and without, Additive P. The resulting deposits were collected and
analysed using XRD and SEM.
3 RESULTS AND DISCUSSIONS
3.1 Additive Characteristics and Claims
Results of the chemical and XRD analysis of the seventeen additives is given in Table XI. A
summary of the main claims for these additives is given in Table XII. The additives can be roughly
categorised according to composition as follows:-
a. Magnesium based CD, F (0,Q)
b. Calcium based H. I., J.
c. KNO, based K. L, 0, Q
d. Iron based A, B, N
e. Miscellaneous E, G., P.
* Additives G, I, J and P are not marketed as commercial additives, but are either used or have
been tested as such..
Additives C, D, F and, to a lesser extent, 0 and Q are MgO or Mg(OH)2 based and are all
claimed to reduce fouling. The literature suggests the following possible mechanisms:-
a. Reduction of gaseous SO,, subsequently limiting the production of sticky alkali
sulphates ,4°'.
b. Formation of higher melting point compounds such as K2Mg2(S04),, rather than the low
,39 42
melting Na2S04 ' '
c. Physical absorption of the molten alkali sulphates'371.
Additives I and J (limestone and dolomite respectively) are primarily used to reduce S0 2
emissions by reacting to produce solid CaS04 as shown below110"
CaO,-»CaO + C0 2
CaO + S0 2 + %0 2 -»CaS0 4
The CaS04 then remains in the ash.
Limestone and dolomite can also reduce slagging and fouling when added to basic ash coals
(e.g alkalic rich lignites) by raising the ash fusion temperature.
Additive H is also claimed to reduce SO, in a similar manner to limestone. However, as the calcium
in this additive is already present as CaS04, such reductions are unlikely.
The KNO, based additives are predominantly claimed to reduce soot and work by lowering
the coal's ignition temperature.11011 A reduction in soot is claimed to reduce fouling deposits as a
more oxidising environment gives rise to higher ash fusion temperatures.
Additive L also claims to reduce cold end acidity problems and reduce S0 2 and SO, emissions by
the following mechanisms:-
 21

H2S04 ¡s neutralised by:-

Ca(OH)2 + HjS0 4 - CaS04 + 2H 2 0
MgO + HjSO« -• MgS04 + H20
2NH, + H2 S0 4 -» (NH4)2S04
SO, concentrations are lowered by:-
KNO, + S0 2 ■* KNOj + SO,
MgO + SO, + MgSO, + 0 2 -»2MgS0 4
SO, is reduced by:-
MgO + SO,-»MgS0 4
Ca(OH)2 + SO, •* CaS04 + H 2 0
The recommended dosage (150g/tonne) is far too small for the mechanisms to significantly
affect SO, or SO, levels. Injection of Ca(OH)2 or MgO into the cold end of the boiler might reduce
the acid related cold end problems. However, this additive would not be used in this way as it is
predominantly a soot remover and therefore needs to be added in the combustion chamber.
Additive K also contains a small amount of copper oxychloride (tested separately as Additive E).
Copper oxychloride is reported to reduce slagging during the combustion of iron rich coals by
nucleating crystallisation of iron rich spinel and/or hematite, thereby increasing the slag
viscosity. , , , ' 1 , M 2 1 ""' 2 4 '
The iron based additives A and B are claimed to reduce fouling and soot emissions. Iron
compounds can have a catalytic effect on combustion which in turn could reduce soot. A
reduction in sooty deposits would then result. No acceptable mechanism has been proposed as
to why these additives might reduce ash deposits as claimed.
Additive N contains ferrocene which is believed to catalyse combustion, thereby improving
combustion efficiency. No mechanism has been proposed by the manufacturers for the claimed
reduction in ash deposits.
Additive M is claimed to improve combustion efficiency, reduce emissions of NO, and SO,
and reduce fouling problems. No sensible mechanisms have been put forward by the
manufacturers. Instead total destruction of the undesirable elements (S, N, Na and CO,) is claimed.
Additive P (Kaolinite) should reduce alkali based fouling deposits by reacting with sodium
during combustion, reducing the amount available to form sticky alkali sulphates.
3.2 Laboratory Coal/Additive Interaction Studies
3.2.1 Ash Fusion Studies
The results of the HTA/additive mixture ash fusion tests are given in Tables XII to XVII. The vast
majority of the commercial additives had no effect at the recommended dosages and, in most
cases, no effect at up to ten times the recommended dosage. Only Additive D had any effect and
this was only noticeable at 10 times the recommended dose ( 1 % w/w) with Coal I. The non
commercial additives had far more effect, mainly due to the larger dosages used which can
significantly alter the bulk composition of the ash mixture. The melting point of an ash is related
 22

to the basic to acidic component ratio of the ash (See Figure 1). For coals I, III, IV and V, adding
5% limestone or dolomite (Additives I or J respectively) increases the melting point of the ash. For
example, adding 5% limestone to coal V ash changes the proportion of basic components in the
ash from 36.2% to 62.3% of the total acid and base. This moves the base/acid ratio to the right
on Figure 1 with a consequent rise in ash melting temperature. The compositions of the ashes
from Coals Ha and lib are such that increasing the proportion of base moves the composition closer
to the minimum ash melting temperature. Similarly, 1 % w/w of Additive D with Coal I HTA was
sufficient to alter the base to acid ratio such that a noticeable change in fusion temperature was
produced. Additive P increased the fusion temperatures of Coal IIa, IIb and Coal V HTA slightly and
Coal IV considerably, while reducing the fusion temperature of Coal I. Again this is due to the 1
or 2% w/w of kaolinite added being sufficient to significantly alter the base to acid ratio of the
resulting ash mixture.
The results suggest that Additives P, I or J may affect the fusion characteristics of coal ash
during combustion due to the significant quantities added. Depending upon the coal ash
composition, this may increase or decrease the potential of the coal for fouling or slagging, by
increasing or decreasing the stickiness of the ash particles. Commercial additives are unlikely to
affect ash fusion characteristics in combustion as the amounts added are small. Adding larger
dosages would be uneconomic and the same effect could be achieved by adding non commercial
materials such as limestone or kaolinite, depending on the coal ash composition.
3.2.2 Heat Treatment of Coal/Additive Mixtures
The effect of selected additives on the ability of the coal to render sodium and potassium water
insoluble was investigate by ashing and extracting coal/additives mixtures. The resulting
concentrations of soluble sodium and potassium in the extracts are given in Tables XIX and XX
respectively. The results from the extractions of ashed pure additives have been used to correct
the results in order to remove the contribution made by the additives themselves. Any change in
the nature of the coal sodium or potassium, caused by interactions with the additives, can then be
determined.
Additives C, O and F (based on Mg(OH)2) all produced a progressive increase in soluble
sodium with increasing additive concentration (Figure 11). This is attributed to magnesium
competing successfully against the sodium for reaction with the kaolinite. More sodium is therefore
left "unfixed". The levels of soluble sodium are significantly less with Coal IV with Additive C
compared to Coal I, due to the higher kaolinite /(Na20 + 0.67CaO + 0.54MgO) molar ratio of Coal
IV. Additive P (Kaolinite) significantly decreased the level of soluble sodium as expected, as the
kaolinite/(Na20 + 0.67CaO + 0.54MgO) molar ratio is significantly increased and more of the
sodium in the coal can be "fixed" as nepheline.
Soluble potassium levels were slightly increased with Additives C, D and F with Coal I and
markedly increased with Additive C with Coal IV (Figure 12). This is attributed to a proportion of
the potassium in the illite (a potassium bearing clay) being exchanged for magnesium during the
 23

ashing process. The effect is much less pronounced with Coal I which contains only 3% illite(w/w
on the mineral matter, as determined by normative analysis) compared to Coal IV which contains
in excess of 29% illite.
An increase in soluble sodium (Figure 13) was noted with increasing amounts of Additive
L (mainly KNO, and Ca(OH)2). This is attributed to the potassium and the lesser amounts of
calcium in this additive, competing for reaction with the available kaolinite. A large increase in
soluble potassium was also noted with Additive L, predictable due to the high levels of KNO, in this
additive. Additives B and H had very little effect on the soluble sodium levels. A decrease in
soluble sodium was noted with increasing proportions on Additive M. Accompanying this was an
equal increase in soluble potassium. The overall level of soluble alkali was unaffected. It is
possible that this additive encourages exchange of sodium with potassium in the heat altered clays.
Additive N appears to have reduced soluble sodium levels. However, there was no trend with
increasing dosage, so this result cannot be considered conclusive.
3.2.3 Heat Treatment of Mineral/Additive Mixtures

The crystalline phases identified in the ash by XRD are given in Table XXI. Soluble sodium, as a
percentage of total input, and total soluble alkalis (Na + K), as the number of moles x 10*, are given
in Table XXII. In the absence of additive, there is no measurable reaction between Na2S04 and
kaolinite at 850°C (100% Na solubility). XRD indicates that Na2S04 is unchanged whilst kaolinite
becomes amorphous. The small amounts of quartz, muscovita and microcline observed were
present as impurities in the kaolinite.
The small reductions in sodium solubility with the three magnesium based additives at
850°C (Additives C, D and F) indicates initiation of a limited reaction between the Na2S04 and
kaolinite. The phase produced was not identified by XRD and is therefore either amorphous or not
present in sufficient quantity. The only extra phase identified was periclase (MgO) from the
unreacted additive. The small reduction in soluble sodium with magnesium additives is the opposite
effect to the increase in soluble sodium noted at higher temperatures, due to the reaction of
magnesium with kaolinite reducing the amount of kaolinite available to "fix" the sodium. It is
possible that the presence of certain elements (e.g. magnesium or potassium) encourages reaction
of sodium and kaolinite to form nepheline. The three KNO, based additives (Additives K, L and 0)
have induced a significant amount of reaction between the sodium and kaolinite at 850°C
(between 38 and 55% of the sodium has reacted) producing a potassium bearing nepheline phase
|(Na,K)AISiO«) and/or hauyne ((Na,Ca)t(Si,AI)12024(Si04)2). Reaction between magnesium and
kaolinite has also been increased with the MgO rich Additive 0, forming forsterite (Mg2Si04) instead
of periclase. Unreacted additive has decomposed to potassium oxide (K20).
The results suggest that the Na2S04/kaolinite interaction is a simplistic viewpoint. In this
study, no reaction occurs between the pure Na2S04/kaolinite at 850°C, while in an FBC, where the
residence times are far shorter, in excess of 70% of the total sodium is typically insolubilised. The
results also suggest that the presence of other elements may therefore have a considerable effect
 24

on sodium/kaolinite interactions, possibly by forming solid solutions (e.g. potassium rich nepheline)
which may be more stable than the pure phases.
The results indicate that the presence of KNO, can increase the reaction between sodium
and kaolinite at 850°C. This could potentially reduce fouling in FBC as long as the total 'available'
alkali in the system is also reduced.
As potassium is usually already incorporated in certain clay minerals (e.g. illite) in UK coals,
little is available for volatilization and deposit formation. With the addition of significant amounts
of potassium (as KN03), measuring the total soluble alkali (Na + K) becomes important. The results
in Table XXII indicate that the total soluble alkali is reduced for all 3 KNO, additives at 850°C, and
especially for Additives L and 0. The excess potassium is incorporated into the nepheline. KNO,
may therefore have some potential to reduce fouling in FBC.
However, the reduction in total soluble alkali with KNO, is not that large and the reduction
in soluble sodium (or lack of) achieved with pure Na2S04/kaolinite is not typical of an FBC system
as mentioned previously. It is likely that sufficient elements are already present in coal ash to
encourage the kaolinite/sodium reaction in FBC and additional KNO, is unlikely to improve the
situation. However, it was decided that the possibility that KNO, additives can reduce soluble
sodium levels in FBC would be examined when assessing the additives on the laboratory FBC
(Section 3.3.1).
The results in Table XXII indicate that Additives A, B, E, H and M had little, if any, effect
on the extent of reaction between sodium and kaolinite at 850°C and the only additional phases
identified by XRD were the thermal decomposition products of the additives (e.g. tenorite, CuO,
from Additive E).
At 1150°C, nearly all the Na2S04 reacts with the kaolinite in the absence of additives,
producing nepheline (NaAISi04) and some mullite (AI6Si203) from the excess kaolinite. As expected,
the three magnesium based additives reduced the extent of reaction between sodium and kaolinite
as magnesium competed for reaction with the kaolinite, producing forsterite (Mg2Si04) and spinel
(MgAljOJ. However, the presence df periclase and nepheline, together with the absence of
significant quantities of other sodium bearing phases, suggests that the reaction between MgO and
kaolinite is less favourable than that between Na2S04 and kaolinite.
The three KNO, based additives again reduced the soluble sodium, still producing a
potassium bearing nepheline. The presence of leucite (KAISi20«) however, suggests that the
nepheline is now less potassium rich then at 850°C, and that the potassium aluminosilicate is now
stable. The smaller reduction in soluble sodium obtained with the MgO containing Additive 0 is
presumably due to the competing effect of magnesium increasing the sodium solubility. With all
three KNO, containing additives, the total soluble alkali has now increased compared to the control
sample, indicating that these additives are unlikely to beneficially affect fouling in stokers.
 25

A reduction in soluble sodium at 1150°C was noted with Additive B. This suggests that
iron carbonate can increase the reaction between sodium and (caolinite. Additives A and M
produced minimal, and probably not significant, reductions in soluble sodium.
Some increase in soluble sodium solubility, rather than the reduction found, had been
expected with Additive H (CaS04.2H20 based) due to the competing effect of calcium which
reacts with kaolinite to form anorthite (CaAI2SiO,) as indicated by the XRD and past work.
However, CaSO« is fairly stable at 1150°C, which may explain its lack of reaction with the
kaolinite.
Additive E caused the ash to fuse and insufficient was recoverable for the aqueous
extractions. However XRD indicated that some reaction between the copper and the kaolinite had
occurred, yielding copper aluminium oxide (CuAI204). The amounts of this additive used in practise
(approximately 10 ppm) are too small for this reaction to be significant in real systems or for the
ash fusion temperature to be affected.
3.2.4 Thermal analysis • mass spectroscopy
TA-MS was used to investigate the interaction of the fuel additives with coal mineral matter (as
low temperature ash (LTA)). In particular, the effect of additives on the reaction between kaolinite
and coal sodium was studied. Reaction between the sodium (present in LTA as Na2S04) and the
clay minerals is studied using TA-MS by monitoring the evolution of S0 2 at around 713°C and
908°C (illustrated by the Coal I LTA profile shown in Figure 14). Addition of kaolinite (Additive
P) intensifies these peaks (Figure 14) due to the increased proportion of sodium fixed. These peaks
are absence when 10% of Additive C is added to the LTA (Figure 14) indicating that the reaction
between the sodium and clay is retarded. A similar effect is observed for Additives D, F, H and L,
all of which contain either magnesium or calcium phases. These results confirm the competitive
reaction of calcium and magnesium with kaolinite thereby decreasing the kaolinite/sodium reaction.
However, Additive L also contains large amounts of potassium (as KNO,) and the reduction in S0 2
peak may be wholly or partly due to the reaction of potassium with the kaolinite. Normally the
potassium content of a coal need not be taken into consideration as it is already present in
association with the clay mineral illite.
No effect upon the TA-MS profiles was observed with Additives 6, M or N when added to
Coal I LTA.
3.2.5 Ash sinter strength tests
Ash sinter strength tests have been used to assess the effect of additives on the extent of sintering
in deposits. Results for the Coal III HTA/additive mixes and the coal/additive mixes are given in
Tables XXIII and XXIV respectively. XRD analyses of selected pellets are given in Table XXV. A
strong positive correlation was noted between pellet strength and proportion of Additive P
(kaolinite) for the Coal III HTA/additive mixtures (Figure 15). This suggests that kaolinite may
increase the strength of sintered deposits with this composition. The XRD of the 20% kaolinite
pellet shows the presence of less crystalline phases than in the other pellets. Hauyne
 26

((Na,Ca)8(S¡,AI),2024(S04)2) and pyroxene were absent and the results suggest that the presence
of additional (caolinite has led to the formation of more nepheline and anorthite at the expense of
hauyne, often regarded as an "intermediate" phase in deposits. It is possible that the increased
nepheline content is responsible for the stronger bonding, or it may be due to the inherent strength
of the additional kaolinite. SEM studies to investigate if the kaolinite had led to increased
interparticular bonding failed to identify differences between any of the pellets.
Only marginal differences in pellet strengths were noted with Additives B, C and M in the
Coal III HTA/additive pellets. In addition, no differences were noted in the crystalline phases
present in the SEM analysis.
A significant decrease in pellet strength was observed with increasing Additive C content
in the Coal lib/additive pellets. Conversely a small increase in pellet strength was noted with
increasing Additive C content with the Coal V/additive pellets (Figure 15). No trend in strength was
noted with Additives M or P with either of these coals. Only single concentrations were tested
with Coals III and IV. A small increase in strength was noted with Additive P and Coal III, this may
be due to normal test variability, or to the effect noted with the Coal HTA/additive mixtures. None
of the other results with these two coals are sufficiently different to be significant.
Results of the strength tests using deposits from the underfeed stoker and the chaingrate
stoker are given in Tables XXVI and XXVII. The results indicate a reduction in strength with
kaolinite for the chaingrate deposits (Coal 1Mb) and with Coal III for the underfeed stoker deposits.
This is in contrast to the increase observed with kaolinite and Coal III HTA described above.
However, the coal compositions used in the combustion trials are somewhat different to the coal
used in the laboratory studies and the deposits used are not the same composition as the bulk coal
ash, having been fractionated in the boiler. This is likely to account for the difference in trend as
the effect of an additive seems to be dependent upon the ash composition. Kaolinite increased the
strengths of the pellets made with deposits from the underfeed stoker and Coals IV and VI.
The differences observed with the same additives on different coals suggest that, like the
ash fusion test, the observed effect depends upon the bulk ash composition. It appears likely that
Additive P (kaolinite) and Additive C (Mg(OH)2) (when used in unusually large dosages) may either
increase or decrease deposit strength by increasing or decreasing the strength of the interparticular
bonding. Due to the small quantities usually added, it is unlikely that any of the commercial
additives will affect sintering in boiler deposits and use of larger quantities would be uneconomic.
3.3 Fluidised Bed Combustion Studies
3.3.1 The effect of Fuel Additives on Fouling
Thirteen of the additives were tested using the laboratory FBC to assess their effect on alkali
bonded fouling. The additives tested were B, C, D, F, H, K, L, M, O, Q (0.5% w/w) and
N(0.1 %w/w) and the coals used were Coal I and IV. Coal I was chosen as it has a high tendency
to cause fouling problems, while Coal IV is a relatively low fouling coal. Additives I and J
(limestone and dolomite) were also tested by replacing the normal sand bed with the sorbent.
 27

The recoveries of water soluble sodium, potassium, calcium and magnesium in the
combustion products are given in Tables XXVIII and XXIX. The recoveries of soluble sodium are
illustrated in Figure 16 for Coal I and Figure 17 for Coal IV. The proportion of soluble sodium
obtained with untreated Coal ! (14.5 -19.3%) is approximately double that obtained with Coal IV
(5.6 - 8.5%). This is attributed to differences in their mineralogies. Both coals contain a similar
amount of sodium, but the kaolinite/(Na20 + 0.67CaO + 0.54MgO) ratio is much higher for Coal
IV than for Coal I. Coal I contains less clay and more calcium to compete with sodium for reaction
with the kaolinite, resulting in a greater proportion of "unfixed" sodium. This results in Coal I's
greater fouling tendency.
Use of either Additive I or J as a bed material resulted in a vast increase in soluble sodium
with both coals (55-60% for Additive I and 43-48% with Additive J) and there is now little
difference between the soluble sodium values from the two coals. The vast excess of calcium (and
magnesium with Additive J) results in very little of the sodium being "fixed" by the kaolinite. The
increase in soluble sodium suggests a corresponding increase in fouling tendency which agrees with
the increased fouling noted in commercial boilers when using limestone or dolomite sorbents. With
both coals, the increase in soluble sodium is less marked with dolomite than with limestone. This
effect has also been noticed in commercial boilers, where the increase in fouling was found to be
less with dolomite than with limestone, even when the Ca: S ratio was the same (i.e. more
dolomite than limestone). In both cases, the largest increase in soluble sodium is in the fly ash.
For the other 11 additives, the variations in soluble sodium compared to the untreated coals are
all quite small. None of the additives have resulted in any marked decrease in soluble sodium levels
and therefore none would be expected to reduce fouling. There are some small increases in soluble
sodium with some additives, notably H and L, but these might be due to natural variability and
experimental error. However, if the increase with Additive H is real, it may be due to the relatively
high chlorine content of this additive which is known to increase soluble sodium levels in FBC. The
KNO, additives did not produce a reduction in soluble sodium levels as found in the mineral/additive
extraction study (Section 3.2.2). .As discussed in this section, the reduction in soluble sodium
levels occurring in FBC is naturally much higher than in the mineral/additive study and does not
require additional potassium to induce it.
No increase in soluble sodium was noted with the magnesium rich additives (C,D,F) as
might have been expected. The kaolinite/(Na20 + 0.67CaO + 0.54MgO) molar ratio has been
shown to be less accurate for FBC, especially for added phases which have less chance to react
than the inherent coal minerals.
The potassium, calcium and magnesium solubility results are also given in Tables XXVIII and
XXIX, but these results are considered less significant for indicating fouling potential. Large errors
are observed in the potassium results with Coal I. The low percentage of potassium in this coal
and the comparatively high amount in the bed sand leads to large percentage errors.
 28

A comparison of the analyses of the fly ashes and bed sands from these experiments
indicates that the magnesium based additives produced a corresponding increase in MgO in both
the sand and the fly ash (a greater percentage increase was noted in the sand). Additive H
(predominantly CaS04.2H20) resulted in an increase in both calcium and sulphur in the fly ash.
With the exception of Additive M, all the commercial additives were used in dosages far in excess
of the recommended dosage during this study. Even less effect would be expected when used at
the recommended dosages.
As indicated by the above results and observed in commercial boilers, the use of large
quantities of limestone or dolomite to reduce SO, emissions during combustion may exacerbate or
initiate fouling problems by significantly increasing the levels of soluble sodium in the system,
particularly in the fly ash. As (caolinite is the principle component that "fixes" sodium during
combustion, kaolinite was added to coals to be burned with limestone (Additive I) or dolomite
(Additive J) beds in the laboratory FBC to see if the level of soluble sodium could be reduced back
to acceptable levels.
Coals I, IV and V were used with 0, 1, 5 and 10% kaolinite pre-mixed with the coal. The
recoveries of water soluble sodium for each system are given in Table XXX and are illustrated in
Figures 18 to 22.
With Coals IV and V a general reduction in soluble sodium with increasing kaolinite content
was observed except for 1 % kaolinite with Coal IV (limestone and dolomite bed) and 10% kaolinite
with Coal V which deviated from the predicted trend. The 1 % kaolinite/Coal IV result is within
experimental error of the untreated coal result in both cases, indicating little change with the lowest
dosage of kaolinite. The high result with 10% kaolinite/Coal V may possibly be due to problems
encountered feeding the coal during the 10% kaolinite runs. This led to periods of unblocking the
feeder while the added kaolinite could be elutricated from the bed. Attempts to repeat this run had
to be abandoned as the kaolinite/coal mixture repeatedly blocked the coal feeder system. With
Coal I there appeared to be little relation between the percentage of kaolinite added and the total
soluble sodium. The reason for this is not apparent. In all cases there was a reduction in the
soluble sodium deposited on the reactor surface (See Figures 23 to 25) and it is possible that
variations in the proportion of fly ash recovered are responsible for some of the variability in the
results.
The reductions in soluble sodium obtained were not sufficient to regain the low soluble
sodium levels of the coal/sand systems. This is attributed to the excessive quantities of
calcium/magnesium present in such systems competing for reaction with the kaolinite. It is also
considered that the kaolinite added to such systems is less effective than that already present in
the coal, perhaps because the added kaolinite, being very fine ( < 10//m), is likely to be elutricated
from the bed quickly, while kaolinite associated with the coal is likely to have a longer residence
time and consequently more opportunity to react with the sodium being released.
 29

3.3.2 The Effect of Fuel Additives on Gaseous Emissions

Results of the gaseous emissions tests are given in Tables XXXI to XXXIII for NO (g), N2O(g) and SO2(g)
respectively. It can be seen that in all cases NO,,, concentrations increased with increasing
temperature whilst N2Ow concentrations declined. This inverse linear relationship between NO and
N 2 0 is characteristic of the interrelated formation mechanisms of NO and N 3 0 (See Figures 26
& 2 7 ) ( 1 0 8 ) . Of the additives tested, Additives C, D, L, N, O and P had no significant effect on N2O
or NO levels. Additive H had no effect on N2O but appeared to reduce NO emissions.
However, the significance of this is uncertain. There is no obvious mechanism by which this
additive can reduce NO, however, it does contain NH4CI which would decompose to give NH,.
Adding ammonia to the free board can reduce NO by the DeNO. reaction (2NO + 4NH, + 20 2 -»
3N 2 -i- 6H 2 0) when the gas temperature is sufficiently high. However, it has been shown that NH,
added to the bed can also increase NO."0*'
NO levels were significantly increased by the use of a limestone (Additive I) or dolomite
(Additive J) bed, whilst N2O was significantly decreased. This has been observed elsewhere (108_
and it is believed that CaO interferes with the reaction pathways for the formation of NO and N20
shown in Figures 26 and 27 by catalysing the reaction of HCN to NH, or NH2 radicals, thus
excluding the formation of NCO which is a necessary intermediate for the formation of N2O. The
NH, formed from the HCN is readily oxidised,
e.g. CaO + 2HCN - Ca(CN)2 + H2O
Ca(CN)2 + 3H2O - CaO + 2CO + 2NH2
NHj + OH -• NH2 + H 2 0
NH2 + OH -» NH + H20
NH + OH - N + H20
2N + 0 2 -»2NO
Additive P had no significant effect on NO or N2O emissions with either the limestone or
dolomite bed.
As expected SO2 emissions were significantly reduced by the use of a limestone or dolomite
bed (from around 200ppm to less than 20ppm). The mechanism by which this occurs is well
known(107) namely:-
CaCO3 -» CaO + CO2
CaO + SO2 + 1 / 2 O2-»C a SO4
The CaSO« is then retained in the ash.
A reduction in S0 2 was also obtained with Additive L. This additive contains 17% Ca(OH2)
which dehydrates to give CaO and reduces S0 2 in the same manner as limestone. The reduction
in SO2 was less than that obtained with limestone or dolomite due to the lower amount present
(0.5% w/w). In practice, the recommended dosage of 0.015% w/w for Additive L is too low for
any measurable reduction in SO2. Use of limestone or dolomite would be considerably cheaper than
adding larger dosages of Additive L.
 30

3.4 Stoker Fired Combustion Studies

3.4.1 Laboratory Scale Underfeed Stoker
Effect of Additives on Foulino
Fifteen additives were assessed on 1 day tests on the underfeed stoker. The water solubilities of
sodium, calcium, magnesium and potassium in the combustion products are given in Table XXXIV.
The sodium solubilities are shown in Figure 28. The results indicate that several of the additives
have increased the proportion of soluble sodium, namely Additives C, D, F, K and N. The increase
in water soluble sodium with Additives C, D and F can be attributed to the extra magnesium
competing with the sodium for the available kaolinite., More of the sodium therefore remains
"unfixed". Only a marginal increase was observed with limestone (Additive I) where a larger
increase was expected due to calcium's ability to react with kaolinite. The increase with Additive
K (KNO3) was not unexpected as potassium can also react with kaolinite, but a corresponding
increase with Additive L (also predominantly KN03) was not observed. Instead a small decrease
was noted. The increase in soluble sodium with Additive N was unexpected and not easily
explained.

Additive M produced unusually variable results. There is some evidence that this may be
due, at least in part, to the shedding of a large quantity (315g) of iron oxide scale from the heat
exchanger during cleaning after one of the tests. This would be expected to take any base layer
of Na2S04 with it. This level of cleaning is not normally achieved and could possibly be due to the
additive which does claim to improve cleanability. The mass of heat exchanger deposit was about
25% higher with Additive M in the second two tests, compared to the two control tests, indicating
either increased deposition or improved cleanability.
Significant reductions in soluble sodium were noted with Additive P (kaolinite) and Additive
B (iron carbonate). The kaolinite reacts with the available sodium, thus reducing its solubility. No
explanation is available for Additive B.
XRD was carried out on deposits collected from an air cooled metal probe suspended
between the heat exchanger surfaces. In all cases, the phases identified were halite (NaCI), sodium
sulphate (Na2S04), hematite (Fe203), thenardite (Na2S04), anhydrite (CaS04) and magnetite (Fe203).
No new phases were identified in any of the tests with additives.
Attempts to observe any changes in S0 3 levels in the flue gas (a claim made for a possible mode
of action of MgO based additives) were unsuccessful as the levels monitored were at the limits of
detections of the equipment.
A comparison of the analyses of the solid combustion products allows the fate of the
additives to be seen. The five magnesium additives (C, D, F, O, Û) increased the magnesium
content of all the solid combustor products, whilst the potassium from the 4 KN0 3 additives (K,
L, O, Q) was found only in the cooler heat exchanger deposit and stack ash. The limestone
increased the calcium content of all the products, but was found to be mainly retained in the bed
ash. The other additives had little effect on the combustion product compositions.
 31

Similar mass balance studies were carried out on the 9kW underfeed stoker on 5 of the
additives for 5 days, in order to give the deposit more time to develop. The results of the water
solubility calculations are given in Table XXXV and the sodium solubilities illustrated in Figure 29.
It can be seen that there is only a small decrease in soluble sodium with Additives L and
B. This suggests that either the 1 day results were not representative or that the effect noted only
occurs in the initial stages of deposition. The increase in soluble sodium with Additive N in the 1
day day tests has also become an insignificant decrease in the 5 day test.
Additive M produced an increase in soluble sodium, contradicting the decrease found in the
coal/additive study in Section 3.2.2, but the increase cannot be considered significant due to the
large variability in results encountered with this additive. Additive H had no effect in either the 1
or 5 day tests.
Effect of additives on oaseous emissions
The S0 2 and NOx results (corrected to 6% oxygen, dry, to eliminate false trends due to dilution
by varying levels of excess air) were statistically analysed using One Way Analysis of Variance.
This enabled a statistical comparison between the results obtained for each additive trial and the
control. Results are given in Table XXXVI. Natural limestone was the only additive which
significantly reduced S0 2 and NOx under the prevailing conditions. The reduction in NOx emissions
was unexpected but suggests mildly reducing conditions in which NOx is removed via the following
mechanism00":
CaO + S0 2 -»CaSO,
CaSOj + 2NO -» CaS03(NO)j
CaS0,(N0) 2 -»CaS0 4 + N2 + % 0 2
Under oxidising conditions S0 2 is removed via the mechanism'1071:
CaCO, -• CaO + C0 2
CaO + S0 2 + %0-»CaS0 4
The reduction was not large as CaS04 becomes unstable at these temperatures.
Additive N was found to significantly increase S0 2 emissions but the mechanism is unclear. None
of the other additives produced any significant effects.
3.4.2 Pilot Scale Underfeed Stoker
Previous work1" had shown that Additive P (kaolinite) consistently reduced the soluble sodium
levels on the 9 kW underfeed stoker with a range of UK coals. A similar study was carried out on
the 150 kW underfeed stoker in a series of 12 day tests.
Additive P was added to Coals III, IV and VI at a dosage of 1 %w/w. Additive B was also
added to Coal VI at 0.06% w/w, twice the recommended dosage.
The amounts of heat exchanger deposit collected, both in terms of actual mass and as a
percentage of the total ash recovered, are given in Table XXXVII. The predicted reduction in
deposit mass was apparent with Additive P for Coals VI and IV. No change was found with Coal
III. Although every attempt had been made to achieve good mixing of the additive into the coal,
 32

it is believed that the mixing was insufficient as tests with Additive P on Coal III on the 2MW
chaingrate stoker (described in Section 2.4.3) had already shown a reduction in deposition with
Additive P.
The elemental solubilities of the combustion products are given in Table XXXVIII and the
expected reduction in total soluble sodium with Additive P was only found with Coal VI. This
appears to be due to large variations in the soluble sodium recovered in the bottom ash. The
soluble sodium in the heat exchanger deposit (Figure 30) followed the expected trend of a reduction
in soluble sodium where a reduction in ash deposited was observed.
Additive B produced a reduction in percentage ash deposited and soluble sodium in the heat
exchanger deposit but not deposit mass or total soluble sodium, adding to the conflicting evidence
for this additive.
A series of similar tests was carried out with 0, 0.5, 2 and 5% w/w Additive P with Coal
VI in order to find an optimum dosage. The amounts of deposit collected, as a percentage of ash
recovered are given in Table XXXIX. It is evident that, although deposition was less with Additive
P, there was no overall trend with dosage. This may again be due to mixing problems. The sodium
solubilities are given in Table XXXX.
The expected trend of decreasing soluble sodium with increasing kaolinite was observed
for the 0.5, 2 and 5% tests. However the 0% test was unexpectedly low. The soluble sodium
levels for the combined tests with Additive P and Coal VI are shown in Figure 31. It is not possible
to select an optimum dosage level from these results.
3.4.3 2MW Chaingrate Stoker
General
Additives C, B and P were assess on the 2MW chaingrate stoker to confirm that additives which
can reduce soluble sodium levels in laboratory scale studies (Additive P) would reduce fouling on
full sized stoker fired boilers and additives which increased soluble sodium levels in laboratory
studies (Additive C) would increase fouling.
The coal analyses for each ruh are given in Table VII. There was some variation in coal
composition between the tests as it was not possible to mix and store sufficient coal on site for
all the tests. Most significant were the variations in ash content (from 8.4 to 14.5% ad) and the
high chlorine content (1.3% ad) in the coal used to test Additive C. The coal ash compositions
were fairly similar however, with Na20 on ash ranging from 1.4-2.0% w/w. Sulphur contents
ranged from 0.85 to 1.2% w/w whilst CV and ash fusion temperatures were all fairly similar.
The combustion products from each trial (grate ash, smoke box fines, cyclone fines,
reversal chamber fines, stack ash and deposits) were characterised to identify any changes caused
by the additives, and also to determine the fate of each additive where possible. Analytical results
and product masses are given in Tables XXXXI to LII. The analyses were compared to the
corresponding coal ash analyses in order to assess any enrichments or depletions in specific
elements. As expected, there was a general trend of depletion of the more volatile species (Na,
 33

K, SO]) for products from the hotter regions eg. grate ash. In comparison an enrichment of the
same elements was detected in products from the cooler regions (eg. stack ash, smoke box fines,
tube plate deposits, material from inside the smoke tubes) due to the condensation of alkali
sulphates.

Additive C
Examination of the combustion product analyses from this trial indicates that the additional
magnesium is distributed between several of the combustion products. The smoke box fines and
cyclone fines both show a moderate increase in MgO compared to the coal ash, whilst a much
larger increase is observed in the stack ash (29.7% on ash compared to 2.5% in the coal ash)
indicating that a significant proportion (-10%) of the magnesia leaves the system via the stack.
Significant increases in MgO content are also noted in the tube plate and tube plate base deposits,
as well as the material from inside the smoke tubes. Examination by XRD of the crystalline phases
in the deposits from the water cooled surface (Table LUI) (tube plate, inside the smoke tube,
powder from inside the furnace tube) suggests that much of the additive has reacted to form
langbeinite (KMg2(S04),). Magnesium sulphate was also identified as a minor phase in the material
from the base of the tube plate deposit. The sodium and mixed sodium/potassium sulphates
normally found in these deposits were not identified except in the powder from the furnace tube
(prior to the magnesia injection point). No magnesium alumino-silicate was positively identified to
confirm a reaction between kaolinite and the magnesium, although there were a few unidentified
phases in the deposits (one of which was tentatively identified as magnesio-anthophyllite
(MgSi,022(OH)j). The majority of the deposits also contained some non-crystalline material. The
remainder of the crystalline phases found in the deposits were the normal mix of feldspar, hematite
and anhydrite typically associated with such deposits.
The total mass of deposit recovered from this trial was 111 kg (compared to 107kg from
the control trial). In terms of total ash throughput (to allow for the different quantities of coal
combusted and their differing ash contents), 1.4% w/w of the total ash was deposited during the
trial with Additive C compared to 1.1% w/w with no additive. The majority of this increase was
attributed to the mass of tube plate deposit (14.4kg compared to 8.4kg) and material from inside
the smoke tubes (65.8kg compared to 47.8kg). Examination of the smoke tubes after each trial
revealed that the tubes were restricted but not blocked after the control trial. In contrast many
tubes were completely blocked after the trial with Additive C. In the last few days of the trial the
tubes had become so restricted that it was necessary to turn the boiler down and increase the air
supply to maximum in order to complete the test. In addition, in the last week, no particulates
were able to reach the cyclone as the tubes were so blocked. The tube plate deposit was less
friable than normal and it was not possible to clean the smoke tubes with the normal mechanical
cleaner. Both factors indicate the presence of stronger than normal bonding in the deposits. It was
 34

therefore concluded that under these conditions, Additive C had the predicted detrimental effect
on fouling.
Elemental solubilities for the combustion products were calculated in order to determine
whether the increase in soluble sodium observed in laboratory studies with Additive C were
repeated on a larger scale. The results are given in Table LIV. Both increases and decreases in
sodium solubility were noted in various combustion products when compared with the control test,
but the total soluble sodium increased from 4 . 1 % with the control to 5.4% with Additive C,
therefore following the predicted trend.
Additive C was therefore found to detrimentally affect fouling by increasing the strength
and quantity of deposit. This agrees with the results of the laboratory interaction experiments and
tests on the 9 kW underfeed stoker.
Additive B
The relatively small proportion of Additive B (iron carbonate) added (0.12% w/w) makes it difficult
to determine its fate from the chemical composition of the combustion products. It is possible that
the higher Fe,0 3 content in the tube plate base deposit, compared to the control trial, may be due
to the Additive B addition (Tables XXXXVII and XXXXIX). XRD (Table LIN) indicates the presence
of yavapaiite (KFe(S04)2) in this deposit which may indicate that some interaction has occurred
between the coal ash and Additive B. However, the yavapaiite may also be due to a reaction
between the metal of the tube plate and the deposit. The latter seems the most probable
explanation, as yavapaiite was later identified in the same deposit from Trial 4 (Additive P). Further
comparison of the phases identified in the deposits by XRD (Table LIII) indicates the presence of
hauyne (Na,Ca)g(Si,AI)12024(S04)2) and anhydrite (CaS04) in deposits from some of the hotter
regions (side and rear walls, inside of the rear arch). In the control test such phases were only
identified in deposits from water cooled surfaces. The chemical compositions of these deposits
also show corresponding increases in sulphate content. The reasons for this are not clear, but may
indicate lower temperatures during the trial with Additive B, as anhydrite and hauyne are not stable
at the temperatures normally attained on these hotter surfaces.

The total mass of deposit recovered from this trial was 91kg compared to 107kg from the
control trial. In terms of total ash throughput, 1.3% w/w was recovered as deposit with
Additive B, compared to 1.1 % w/w for the control. An examination of the tube plate after the trial
revealed that the extent of tube blockage and ease of cleaning was not noticeably different from
the control trial. Neither was the friability of the tube plate deposit noticeably different. Additive B
does not appear to have had any beneficial effects on fouling under the test conditions.
Elemental solubilities for the combustion products are given in Table LIV. Some reductions
in sodium/potassium solubilities, compared with the control test, were found in the cyclone fines,
smoke box fines and reversal chamber fines while the other products showed little change or a
slight increase in sodium solubility. Total soluble sodium was 4.3% compared to 4 . 1 % for the
 35

control. The reduction in soluble sodium found in some of the laboratory studies was therefore not
evident upon larger scale testing.
In this study, Additive B had no measurable effect on boiler fouling. The slight increase in
fouling observed compared to the control test was predictable due to the slight variation in coal
composition between these trials (see Use of a Mineralogicai Index page 36).
Additive P
Kaolinite is a naturally occurring constituent of UK coals (typically accounting for 25 to 70% w/w
of the mineral matter) and it is therefore not possible to identify the fate of the additional kaolinite
added in Trials 4, 6 and 7 from chemical analysis or XRD of the combustion products. The
crystalline phases identified by XRD (Table LIII) were generally the same as for the control trial.
Feldspars, quartz and hematite were present in the majority of the deposits, with sodium or mixed
sodium/potassium sulphates being identified in the deposits from the cooled heat exchange
surfaces. Anhydrite was again identified in some of the deposits from the hotter surfaces, possibly
suggesting slightly milder conditions than the control trial, whilst yavapaiite was again identified
in the tube plate base deposit (previously identified with Additive B). This further suggests that,
as mentioned previously, yavapaiite is probably formed by an interaction between the condensed
alkali sulphates and the metal of the tube plate. Boron phosphate was identified in the material
from inside the smoke tubes. This is sometimes found in deposits from coal combusted under
reducing conditions (eg. coking stokers) and may therefore be indicative of localised reducing
conditions during this trial.

Comparison of the total masses of deposits recovered from the control trial (Trial 5) and
the trial when kaolinite was premixed with the coal shows that there was a significant reduction
in deposit mass from 63kg (control) to 52kg (Trial 6). In terms of total ash throughput, this had
decreased from 1.7% w/w for the control to 1.2% w/w (Trial 6). The predicted reduction in
deposition was therefore observed when kaolinite was premixed with the coal.
However, with injection of kaolinite, the total mass of recovered deposit rose to 68kg,
although this still represented a drop in the percentage of ash throughput from 1.7% to 1.4%.
Examination of the tube plate after each trial indicated that the smoke tubes were less
restricted after Trial 6, compared to the control (Trial 5). The tube plate deposit was still fairly
substantial for kaolinite premixed with the coal, but the deposit was noticeably more friable than
normal and some "birds nests" had fallen off during the trial. In addition, the normally abundant
white alkali sulphate rich base layer of the tube plate deposits was almost entirely absent
suggesting the presence of less bonding material. Kaolinite may therefore be particularly effective
when used in conjunction with sootblowers.
After injection of kaolinite, the tube plate deposit was noticeably worse than normal with
large, extremely friable, low density white deposits. The abundance of white clay in the reversal
chamber and the lack of particulates in the cyclone (only 6kg was collected over the entire test
 36

period), suggests that the majority of the kaolinite settled out in the reversal chamber, either as
fines or as deposit.
The elemental solubilities of the combustion products are given in Table LIV. From the
laboratory studies additional kaolinite would be expected to reduce the soluble sodium in the
combustion products and this was found for the majority of the samples. The total percentage of
soluble sodium was reduced from 4.6% for the control to 2.9% with premixed kaolinite and 1.9%
with kaolinite injection. A significant decrease in soluble sodium upon kaolinite addition was
therefore obtained.

Kaolinite was therefore found to reduce fouling when premixed with the coal, by reducing
both the strength and quantity of deposits. This suggests that kaolinite may be particularly
beneficial when used in conjunction with sootblowers.
When injected above the bed kaolinite only marginally reduced the extent of deposition and
unacceptably large volumes of extremely friable low density deposit were produced. The soluble
sodium was significantly reduced as predicted but fouling was not. It is believed that this is due
to the increased airborne particulates loading. When injected, the kaolinite reacted with the sodium
as predicted but remained airborne. A significant proportion of the extra particulates were of the
correct size (probably as a result of agglomeration) to impinge and deposit on the tube plate. When
premixed with the coal the reacted kaolinite remained in the grate ash. This emphasises the need
to consider physical as well as chemical factors in deposit formation when assessing the effect of
additives.
Use of a Mineralogica! Index
In Section 2 it was stated that additives which increased the kaolinite/(Na30 + 0.67CaO + 0.54MgO)
molar ratio of the coal's mineralogicai components will reduce the amount of available (soluble)
sodium in the system and thereby reduce fouling. The kaolinite/(Na20 + 0.67CaO + 0.54MgO) molar
ratio for the coals or coal/additive mixtures used in these trials are given in Table LV, along with
the percentage of the total ash deposited and the total percentage of soluble sodium in the system.
For the first three tests (control, Additive C, B) the predicted order of fouling (and total
soluble sodium) was:
control < B < C
Comparison of the actual percentages of ash deposited and soluble sodium shows this
ordering was obtained. Additive C increased deposition by reducing the
kaolinite/(Na2O + 0.67CaO + 0.54MgO) molar ratio (originally 0.72), consequently increasing the
amount of sodium available for bonding deposits (the soluble sodium).
Additive B has no effect on the kaolinite/(Na2O + 0.67CaO + 0.54MgO) molar ratio and the
reduction in soluble sodium noted in laboratory studies was not repeated in these trials. Instead,
the extent of sodium solubility and deposition were slightly higher than the control trial probably
due to the small variation in coal composition.
 37

For the tests which involved kaolinite, the kaolinite/(Na30 + 0.67CaO + 0.54MgO) molar ratio
suggested that the order of fouling and soluble sodium would be:-
injected < premixed < control
This is indeed what was observed for the soluble sodium results, however the order
obtained for deposition was premixed < injected < control. This is believed to be due to the
system being overloaded with large quantities of airborne particulates of the correct size to drop
out in the reversal chamber. The system is therefore no longer comparable with the other tests
as an important physical variable (airborne particulate loading) has been changed significantly. The
mineralogical index was therefore found to correlate well with both the amount of soluble sodium
and extent of fouling when other physical factors are equal.
3.4.4 1.12 MW Mini-coking Stoker
After favourable results were obtained on the 2MW chaingrate stoker using Additive P (kaolinite)
premixed with the coal, a field trial was set up to assess the performance of the additive under
commercial conditions. The original test programme consisted of a 16.5 day control test (in the
absence of additional kaolinite) followed by a similar period burning coal which had been premixed
with 1 % w/w of Additive P. However, after the control test, there were no significant deposits
on the convection tube plate and it is believed that the composition of the delivered coal had
changed. Unfortunately, it was not possible to confirm this as coal samples were not available
prior to the test period. It was decided to continue with the programme, but extend the duration
of each test to approximately 35 days in order to try and build up significant amounts of deposit.
The chemical analyses of the combustion products are given in Table LVI. In both cases
the analyses show a reduction relative to the coal ash in the more volatile sodium and potassium
in the products from the hotter regions (eg grate ash and reversal chamber fines) and a
corresponding increase in the products from the cooler regions (eg tube plate deposit) due to the
condensation of alkali sulphates.
There was very little formation of tube plate deposit during either test and no restriction
in draught was observed. Only 200g of deposit was collected from the control trial and 130g from
the test with kaolinite. This is a 35% reduction but, as the amounts are so small, it is difficult to
assess if the reduction is significant. Less deposition would be expected from the control trial if
the additive had no effect, as the stoker ran for a lower percentage of the time at full fire during
this test (40% compared to 66%). In addition the mineralogical index
(kaolinite/(Na2O + 0.67CaO + 0.54MgO) molar ratio) was higher for the control test coal (1.5
compared to 1.3 for the untreated kaolinite test coal). The mineralogical index has been shown
to relate to the extent of fouling"', although fouling is rarely extensive for coals where the index
is significantly greater than one. In such coals, there is a relatively high natural kaolinite content
which results in most of the sodium being fixed. This is consistent with the minimal amounts of
deposits formed in both the reported tests. Addition of 1 % kaolinite increased the mineralogical
index to 1.84 for the Additive P test, which would indicate that fouling should be less extensive
 38

for this test, as was indeed found. The results are therefore consistent with previous work, which
showed a reduction in alkali bonded fouling deposits with kaolinite addition, but the amounts of
deposits were so minimal that the results cannot be considered conclusive.
Sodium solubilities for each product are given in Table LVII. There is a small reduction in
sodium solubility with kaolinite in the grate ash and reversal chamber fines, but a small increase
in the other combustion products. However, the sodium solubilities are low (26-33%) in both the
tube deposits ( > 8 0 % is more typical in extensive deposits) indicating that the high levels of
kaolinite in both cases have fixed the majority of the sodium, resulting in the low levels of
deposition. The overall sodium solubility for each test could not be calculated as it was not
possible to weigh the combustion product off-takes at this site.
3.5 Pilot Scale Pulverised Fuel Combustor
3.5.1 Additive E
A summary of boiler/probe conditions is given in Table X. The crystalline phases identified in the
deposits by XRD are given in Table LVIII and LIX for the undoped and Additive E doped trials
respectively. All the samples contained quartz, hematite, mullite and a glassy phase. In addition,
all contained spinel phases from the magnetite • hercynite solid solution series. As Al 2 0, replaces
Fe2Oj in the solid solution, the position of the diffraction peak moves to higher values of 20, making
it possible to estimate the approximate composition of the spinel phase. Some samples contained
more than one spinel.
Both the Additive E doped and the undoped slag samples contained significant amounts of
the spinel phases. There was no noticeable variation with conditions of deposition. Several of the
slag samples from the metal probes also contained various forms of iron chromium oxides which
were attributed to contamination with oxide scale from the probe surface.
Optical and SEM examinations revealed no significant differences between samples adhering
to the mullite coupons and those recovered from the metal probes. All indicated that the ash had
been molten at some stage. The ash on the mullite probe was well bonded to the ceramic with
evidence of chemical attack. All samples contained an appreciable quantity of a glassy phase, with
undissolved quartz and iron oxide. In addition, the glass had detrified to give well defined
crystalline phases such as mullite and spinel. All samples contained rounded pores, indicating that
the slag had been very fluid at some stage.
The undoped samples all showed a random distribution of the iron-rich spinel phase, with
an absence of spinels on the surface of particles and internal pores (Plate 1 ). Sections of the doped
samples again showed nucleation and growth of iron-rich spinel panicles, but these tended to form
almost continuous layers on the surface of particles and pore walls (Plate 2). This would indicate
that Additive E had started to alter the nature of the slag. It has been postulated that the
mechanism by which Additive E reduces slagging problems is by increasing slag viscosities via the
nucleation and growth of iron rich spinel phases on the exposed surfaces of deposits and pores.
This mechanism only works on coals with a high iron content but from these results it appears that
 39

Additive E may indeed help alleviate slagging problems in PF boilers combusting iron rich coals.
This is thought to be the first time such behaviour has been observed using a small scale PF burner.
3.5.2 Additive P
The crystalline phases identified in the deposit samples are given in Table LX. The samples were
all fairly similar, each containing quartz, mullite, hematite and anhydrite with the exception of the
second sample with (caolinite on the ceramic coupon which contained anorthite instead of
anhydrite. The SEM study shows that much of the material had been molten at one point (shown
by the presence of spherical particles in all the deposits). Plates 3 and 4 show the deposits from
the ceramic coupon with and without Additive P respectively. It is apparent that, although molten
bonding material is present in both samples, there is far more material in the deposit from the
kaolinite treated test. This is in agreement with the results of the sinter strength test which
indicated that kaolinite can increase in strength of bonding in high temperature deposits if the ash
composition is correct. The deposits from the metal coupons were less molten due to the probe's
air cooling system. However, there was still more molten bonding material in deposits from the
kaolinite treated test. It is therefore concluded that, for coals of this composition (Coal IX, Table
VIII), kaolinite has a detrimental effect on deposition in PF boilers.
3.6 General Discussion of the Effectiveness of Commercial Additives
Deposition and emission problems which can occur during coal combustion have resulted in the
development of a variety of fuel additives. The effectiveness of these additives in alleviating such
problems has been the subject of this study.

The use of additives such as limestone sorbents to reduce SO, emissions or fly ash
conditioning agents to improve ESP efficiency and reduce particle emissions is well developed and
routinely used in many coal fired combustion plants around the world. Other successful uses of
additives include the use of limestone or boron based additives to reduce ash fusion temperatures
thereby improving slag flow in wet bottom boilers (used commercially on a limited scale), and the
use of limestone to reduce fouling in combustors burning alkali rich lignites and sub-bituminous
coals.
In other areas the use of additives has been less successful and commercial additives are
generally viewed with much scepticism. The results of this project suggest that such opinions are
in most instances justified. Of the commercial additives tested, only Additive E (copper
oxychloride) fulfilled its claim. The results indicated that it would reduce slagging problems during
the PF combustion of iron rich coals by modifying the crystallina of the slag.
None of the commercial additives which claimed to reduce fouling showed any consistent
ability to reduce the level of available sodium in either the FBC or the stoker fired systems and are
therefore unlikely to reduce alkali bonded fouling. Instead, all the Mg0/Mg(0H) 2 bearing additives
were found to increase soluble sodium levels in stoker fired systems. It was demonstrated using
the 2MW chaingrate stoker, that such additives actually result in both increased quantities of
fouling deposits and stronger deposits. The use of magnesium rich additives in stoker fired systems
 40

is therefore not recommended. The laboratory studies indicate that magnesium's detrimental effect
on fouling results from its ability to react with kaolinite, reducing the amount of kaolinite available
to "fix" sodium.
Kaolinite was the only material tested which showed any potential to reduce alkali bonded
fouling. Tests on the 2MW chaíngrate stoker demonstrated that kaolinite could reduce both the
extent and strength of fouling deposits when premixed with the coal. Good mixing was shown to
be important. Premixing kaolinite with the coal at a commercial site is unlikely to be viable as good
mixing is both difficult to achieve and labour intensive and few sites would be wiling to carry out
the necessary procedure. Injection of kaolinite was unfortunately found to be less satisfactory due
to the increased air borne particlulates loading leading to increased deposition (albeit of very friable
deposits). Kaolinite may have some potential as an antifoulant if added to coals at the coal
preparation plant • eg. during the preparation of blends - and could be particularly beneficial if used
in conjunction with soot blowers.
The effect of kaolinite and magnesium in stokers appeared to relate well to the
kaolinite/(Na20 + 0.67CaO + 0.54MgO) molar ratio, where a higher ratio is equated with less
fouling.
Additives were only found to affect ash fusion properties or sinter strengths if added in quantities
sufficient to alter the bulk composition of the resultant ash. This effectively rules out any beneficial
effects from the commercial additives, all of which are added in minute amounts (generally less that
0.1 % w/w). Larger amounts are uneconomic. The cheaper naturally occurring materials can affect
fusion temperatures economically and this is the basis for the use of limestone to reduce fouling
during the combustion of alkali rich lignites. However, these fuels are not used in the UK and
limestone detrimentally affects fouling propensities for UK coals. Tests with kaolinite in the ash
deposition rig suggest that increased slagging would be observed if used in PF combustors.
There was also little evidence for reduction in NO, or S0 2 emissions with commercial
additives. Limestone and dolomite reduced S0 2 in FBC as expected while raising NO levels and
reducing N 2 0 levels. Additive I reduced S0 2 emissions when added at many times the
recommended dosage. However, this is due to its Ca(OH)2 content and the same result can be
achieved more cost effectively with a moderate addition of limestone. Only Additive H caused any
measurable reduction of NO levels and only on the FBC at many times the recommended dosage.

4. CONCLUSIONS
1. A combination of laboratory scale and small industrial scale combustion tests was shown
to be a valuable method for fuel additive evaluation. Prescreening additives on laboratory
scale combustors allowed large numbers of tests to be carried out quickly and relatively
cheaply with closely controlled conditions while larger scale tests allowed the more
promising results to be confirmed using larger scale combustion equipment.
 41

2. It was demonstrated that kaolinite has the potential to reduce alkali bonded fouling in
stokers. Laboratory studies indicated that available sodium levels are reduced by a reaction
between the kaolinite and the sodium (generally to produce nepheline). Studies on the
2MW chaingrate stoker confirmed that this corresponded to reduced quantities of lower
strength deposits when kaolinite was premixed with the coal.
3. Mode of additive addition was shown to be an important factor influencing the
effectiveness of an additive. Premixing kaolinite with the coal produced a reduction in both
available sodium and extent of deposition, whilst injection of kaolinite reduced the available
sodium without reducing deposition significantly. This was attributed to the resultant
increase in the airborne particulate loading.
4. Magnesium (MgO or Mg(OH)2) containing additives were shown to detrimentally affect
fouling in stokers. Laboratory studies indicated that this was due to magnesium competing
against sodium for reaction with the available kaolinite, resulting in increased amounts of
sodium available to bond deposits. Studies on the 2MW chaingrate stoker confirmed that
this corresponded to increased quantities of stronger deposits.
5. The kaolinite/(Na20 + 0.67CaO + 0.54MgO) molar ratio of the coal and additive was
shown to relate well to the extent of fouling on the 2MW chaingrate stoker except when
other boiler parameters (such as airborne particulate loading) were significantly altered.
6. None of the other commercial additives consistently altered soluble sodium levels on the
9kW stoker and are not expected to affect alkali bonded fouling.
7. None of the commercial additives affected sodium solubilities in the FBC tests and the
kaolinite/(Na,0 + 0.67CaO + 0.54MgO) molar ratio appears less applicable under such
conditions. Consequently magnesia containing additives are unlikely to detrimentally affect
fouling.
8. Fouling in FBC will be significantly increased by limestone or dolomite, both of which
dramatically increased soluble sodium levels. This corresponds with the increased fouling
observed in commercial FBC with limestone sorbents. The increase in soluble sodium was
less with dolomite than with limestone, however the reasons for this behaviour are
unknown.
9. Adding kaolinite to the FBC with either a limestone or dolomite sorbent was shown to
reduce soluble sodium levels when sufficient is added, but not back to presorbent levels.
This implies that fouling may be reduced but not eliminated. The effect was not consistent
with all coals.
10. Studies in the pilot scale PF combustor indicated that copper oxychloride has the potential
to reduce slagging during the PF combustion of iron rich coals by modifying the slag
structure. This is thought to be the first time evidence had been obtained for such
behaviour on a small scale rig.
 42

11. Of the commercial additives tested, only Additive L reduced SO, emissions from the FBC
due to its Ca(OH)2 content. The same effect could be achieved far more cost effectively
using limestone or dolomite.
12. A small but consistent decrease in NO emissions from the FBC was observed with Additive
H. A possible, but unconfirmed, explanation for such behaviour is that NH, produced by
the decomposition of the additive takes part in DeNO, reactions in the freeboard zone.
13. SO, and N 2 0 emissions were reduced by limestone or dolomite additions to the FBC while
NO was increased.
14. None of the commercial additives tested significantly reduced NOx or S0 3 emissions from
the underfeed stoker.
15. Ash fusion studies showed that ash melting characteristics were only affected when the
base/acid ratio of the bulk ash was significantly altered. The direction of the change was
dependent upon the ash composition and could be predicted. None of the commercial
additives could be expected to significantly affect ash fusion temperatures at their
recommended dosages.
16. Ash sinter strengths were significantly affected by large concentrations of magnesium or
kaolinite. The extent of the effect appeared to be dependent upon the ash composition.
17. Kaolinite was observed to detrimentally affect fouling/slagging in PF combustors for the
coal tested, by increasing the amount of molten bonding material. The effect may be
dependent upon coal composition.

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 45

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 46

89. Ulerich, N.H., Newby. R.A., Vaux, W.G. and Keairns. P.L.. 1983. "FBC design and
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p.226.
 47

TAßlg I

ANALYSES OF THE COALS USED IN THE LABORATORY FBC TESTS

(-355 + IBOt/M FRACTIONS)

Coal

1 Ila IIb III IV V

BC Coal Rank Code No 801 701 N/A 802 802 902
Proximate Analvsis. % m/m (adl
Moisture 8.8 4.2 4.9 5.2 9.6 4.1
Ash 3.3 6.4 12.6 3.4 4.0 4.2
Volatile Matter 35.4 34.6 32.2 33.7 34.8 38.0
Fixed Carbon 52.5 54.8 50.3 57.7 51.6 53.7

Low Temperature Ash, % m/m (ad) 4.4 7.9 14.9 4.3 4.5 5.5

Calorific Value kJ/kg daf 33660 34380 33880 34040 33830 ND

Cokina ProDerties
BS Swelling Number 1 4K 2% 1 1 1
Gray-King Coke Type D G D C C B

Ultimate Analsvis. % m/m

C dmmf 81.9 84.3 84.2 84.4 83.0 82.0
H 6.0 5.9 5.8 5.24 5.42 5.8
0 9.2 6.4 6.6 7.3 8.5 9.1
N 1.7 1.9 1.9 1.66 1.79 1.5
CI db 0.8 0.6 0.5 0.72 0.45 0.25
C0 2 0.60 0.04 0.27 0.34 0.14 0.46
S Total 1.09 2.00 2.26 0.86 1.39 1.69
S Pyritic 0.2 0.74 1.04 0.1 0.3 0.26
SS0 4 0.02 0.09 0.11 0.0 0.0 0.02
S Organic " 0.87 1.17 1.11 0.76 1.09 1..41

Alkali/Alkaline Earths. % m/m

Na 0.18 0.18 0.20 0.19 0.18 0.06
K 0.01 0.15 0.37 0.03 0.10 0.01
Ca 0.60 0.07 0.29 0.30 0.16 0.38
Mg 0.04 0.04 0.10 0.07 0.06 0.08
Rs N/A 0.8 0.8 0.7 0.7 1.0
Rf N/A 1.4 0.7 5.8 2.7 1.0
Ash Fusion Temperatures
(reducing atmosphere)
Deformation Temp °C 1040 1070 1120 1050 1050 1090
Hemisphere Temp °C 1110 1220 1230 1090 1110 1240
Flow Temp °C 1170 1400 1300 1100 1140 1310

ad air dried
db dry basis
dmmf dry mineral matter free
ND not determined
Rf see text
Rs see text
daf dry ash free
N/A not applicable
 48

TABLE II

ASH ANALYSES OF THE COALS USED IN THE LABORATORY FBC STUDIES

( - 355 + 180i/in FRACTION)

Coal 1 Ha lib III IV V

S¡02 17.6 42.8 46.1 28.6 36.8 28.5

Al 2 0, 12.4 27.5 26.8 16.7 24.7 24.8
Fe20, 11.7 18.1 14.8 15.4 17.5 13.4
CaO 23.4 1.4 3.1 11.6 5.1 12.2
MgO 1.7 1.0 1.3 3.3 2.1 3.2
Na20 6.6 3.7 2.0 7.0 5.1 1.7
K20 0.3 2.7 3.4 1.1 2.7 0.3
TiOj 0.8 1.1 1.0 0.8 0.9 1.1
Mn,0 4 0.2 <0.1 <0.1 0.3 0.1 0.4
P20, 0.7 0.2 0.3 0.9 0.2 0.6
SO, 23.9 0.4 1.1 12.7 3.3 12.5
Kaolinite. .26 1.66 1.28 .39 1.55 .71
(Na20 + .67CaO + .54MgO)

TABLE III

ANALYSES OF THE COALS USED IN THE LABORATORY COAL/ADDITIVE INTERACTION STUDIES

Coal

I Ila IIb III IV V

% w/w

Moisture ad 8.9 4.5 4.0 5.4 9.5 4.3

m
Ash 3.3 8.2 15.3 3.4 4.4 4.0

Sulphur (total) db 0.87 2.08 2.31 0.88 1.49 1.69

Chlorine db 0.70 0.60 0.45 0.69 0.50 0.26

Ash Analvsis % w/w

Si0 3 % on ash 16.9 43.5 ♦7.3 30.2 39.0 29.3

Al 2 0, 12.8 27.8 26.9 18.1 25.2 24.8
Fe20, 15.3 18.0 14.1 15.1 15.8 13.3
CaO 23.8 1.6 2.8 10.6 4.7 12.3
MgO 1.6 1.1 1.3 3.2 1.9 3.1
Na20 6.2 3.6 1.5 6.3 4.3 1.6
K20 0.4 3.1 3.7 1.1 3.2 0.6
 49 ,

TAPIE lY
ANALYSIS OF PEARLS GRADE OF COAL I USED ON THE 9 KW UNDERFEED STOKER

Proximate Analysis
Moisture %ad 8.2
Ash ■
2.9
■
Volatile Matter 35.9
m
Fixed Carbon 53.0
Volatile Maner %daf 40.3

Calorific Value
U/kg (daf) 33735

Ultimate Analvsis

Carbon % 83.1
Hydrogen dmmf 5.21
Oxygen 8.8
Nitrogen 1.63

Total Sulphur %db 0.95

Sulphate as S 0.01
Pyritic S 0.15
Organic S 0.80
Chlorine 0.74
Carbon Dioxide 0.33
Mineral Matter 3.84

Ash Analvsis (% on ash)

SiOa 20.2
AIA 16.6
Fe20, 13.9
CaO 18.2
MgO 2.0
Na20 6.6
K20 0.2
TiOa 0.9
Mn,04 0.2
PA 1.5
SO, 18.9
 50

TABLE V

ANALYSIS OF COAL VI FROM THE 150 KW UNDEREED STOKER TESTS

Moisture %ad 3.9

Volatile Matter %daf 37.2
Ash %ad 4.0
Total H a 0 %ar 6.6
C %ad 75.1
H %ad 5.2
CI %ad 0.70
CaO % on ash 7.6
MgO % on ash 1.5
Na20 % on ash 2.2
KjO % on ash 1.3
SO, % on ash 6.0

TABLE VI

ANALYSES OF COAL VII FROM THE MINI-COKING STOKER TRIALS

Additive P Control Trial

Trial

Moisture % ad 5.6 5.2

Ash % ad 4.3 4.7

S!02 % on ash 36.4 40.1

Al 2 0, 26.5 27.6
Fe20, 20.1 16.7
CaO 4.2 3.5
MgO 1.0 0.9
Na20 5.4 4.6
K20 1.5 1.8

Kaolinite molar 1.3 1.5 I

(Na20 + 0.67Ca0 + 0.54Mg0) ratio
Na20 % on coal 0.23 0.22 |
 TABLE VII

ANALYSES OF COAL 1MB FROM THE CHAINGRATE STOKER TRIALS

Control Trial with Trial with Control Trial with Trial with Ï
Trial Additive B Additive C Trial Additive P Additive P 1
(coal only) (coal only) (coal + (injected coal 1
additive) only) |
Moisture % aa 5.5 5.8 5.1 6.1 5.8 4.5
Ash %aa 11.6 '8.6 14.5 11.9 8.4 13.0
LOI % db 87.7 90.8 ND ND ND ND
Volatile Matter % ad 31.4 ND ND ND ND ND

Total Moisture % ar 10.2 10.1 9.9 11.4 12.3 10.8

Calorific Value kJ/kg daf 33626 33540 33300 33400 33500 33480

Ash Fusion Range °C

Deformation Temperature 1180 1190 1190 1190 1190 1190
Hemisphere Temperature 1210 1210 1220 1210 1220 1220
Flow Temperature 1250 1280 1270 1275 1265 1265

Carbon % ad 72.42 69.75 ND ND ND ND

Hydrogen % ad 5.10 4.78 ND ND ND ND
Nitrogen % ad 1.52 1.44 1.37 ND ND ND
Total Sulphur % db 1.01 1.00 0.94 0.88 0.85 1.2
Chlorine % ad 0.80 0.70 1.32 0.71 0.7 0.6
Carbon Dioxide % ad 0.72 0.57 0.93 ND ND ND

SiO, ' % on ash 46.0 45.4 50.0 45.6 42.4 47.4 I

Al203 24.8 23.3 23.6 21.8 24.1 25.1 |
Fe2O3 9.8 9.7 9.7 11.5 13.3 9.4 |
CaO 5.7 6.1 5.5 6.3 7.1 5.3 |
MgO 2.4 2.5 2.5 2.6 2.6 2.4 I
Na20 1.7 2.0 1.5 1.6 2.0 1.4 |
K20 3.4 3.0 3.1 3.2 2.7 2.8
TiO, 0.9 1.0 0.9 0.9 0.8 1.0
Mn,0 4 0.2 0.2 0.2 0.2 0.2 0.2
P 2 0, 0.5 0.4 0.5 0.3 0.4 0.3
|so, 4.4 5.7 4.3 5.4 5.9 4.3
|Kaolinite/(Na2O+ .67CaO + .54MgO) Moilar Ratio 0.72 0.64 0.68 0.52 0.76 1.03

ND • not determined
 52

TABLE VIII

ANALYSIS OF THE COALS USED ON THE 150 KW PF COMBUSTOR

Coal VIII Coal IX

Moisture <fc ad 4.3 12.8
Ash «%ad 7.5 8.2
Volatile Matter «fcdaf 37.3 41.2
Calorific Value IcJ/kg daf 34380 33030
% <75¿/m 61
Ash Fusion (oxidising atm)
Deformation Temperature »c 1270 1385
Hemisphere Temperature »c 1380 1430
Flow Temperature »c 1420 1460
Ash Fusion (reducing atm)
9
Deformation Temperature C 1100 1240
Hemisphere Temperature »c 1210 1330
Flow Temperature »c 1300 1380
SiO, % on ash 41.1 50.3
AIA 28.4 27.1
FeA 21.6 8.5
CaO 1.8 4.2
MgO 1.1 1.5
Na20 3.0 1.8
K20 3.2 2.2
Ti02 0.9 1.5
Mn,0, <0.1 <.2
PA 0.2 0.7
SO, 0.9 2.4
 53

TABLE IX

MASS BALANCE CONDITIONS FOR THE LABORATORY SCALE FLUIDtSED BED TESTS

Bed Temperature 850-860°C

Run Time 180 min
Coal Feed Rate 100 g/h
Fluidising Gas Air (17% v/v0 2 l
Fluidising Gas Velocity 0.5 m/s @ 850°C {5 x min. Fluidising Velocity)
Probe Temperatures 500-550°C
Typical Flue Gas Compositions 02 8-10%v/v
N2 82% v/v
C02 7 - 9 % v/v
CO < 0 . 1 % v/v

TABLE X

SUMMARY OF PF COMBUSTOR/PROBE CONDITIONS

Run Additive Collection Gas Temp of Temp of 0 2 /% Mullite

Identifier E/ppm Time/hr Temp Upstream Side of Downstream Side v/v Remaining
°C Metal Coupon of Metal Coupon
U1 0 1295 860 595 3.0
U2 0 1280 890 695 2.7 •
U3 0 1170 875 725 3.0 •
U4 0 1180 735 0.9 X
U5 0 1180 860 685 1.1 X
T1 100 1300 880 580 3.0 •
T2 100 1295 860 790 3.1 •
T3 100 1190 875 600 3.6 •
T4 100 1345 620 1.1
T5 100 .5 1300 980 -2 •
 TABLE XI

ANALYSES OF FUEL ADDITIVES

f Additive XRD Chemical Analysis [

Mineral Formula Major/Minor % as Calculated % (ad) except loss on ignition |
Phase from Chemical (LOI) (db)
Analysis
A Magnetite Fe304 Major - H20 = 0.0 Fe - 67.5'
Hematite Fe20, Major - Ash - 99.6 Si02 •= 3.4
Quartz Si02 Minor 3.4 LOI = 0.4 CaO = 0.4
Ankerite Ca(Fe.Mg)(CO,)2 Poss -
B Fe 2 0, - 56.7
Siderite FeCO, Major 68-80% H20 = 0.1 CaO - 2.0
Ankerite Ca(Mg.Fe) C0,) 2 Minor Ash - 71.4 MgO - 1.9
LOI = 28.5 K20 - 0.3
CO, - 30.2
C MgO - 69.8
Brudte Mg(0H)2 Major - H20 - 1.6 SiO, - 1.6
Periclase MgO Minor Ash - 70.7 CI = 0.35
- LOI - 28.2 Al 2 0, - 0.3
Fe 2 0, - 0.8
CaO - 0.7
Na20 - 0.3
K20 - 0.1
S0 4 - 0.29
D Perclase MgO Major 80% H20 - 1.6 MgO - 80
Corundum Al 2 0, Minor 6.7 Ash - 91.1 Al 2 0, = 6.7
Anhydrite CaS04 Minor 3.7 LOI - 7.4 CaO - 1.5
E Paratacamite Cu2(OH),CI Major - H20 - 1.0
Potassium Calcium 17K3P04.3Ca,(P04), Poss " Ash - 62.5
Phosphate LOI - 36.8

Fe = 67.5% present as oxides Fe203, Fej04 i n unknown proportions

 Additive XRD
Mineral Formula Major/Minor % as Calculated % (ad) except loss on ignition
Phase from Chemical (LOI) (db)
Analysis
F Brudte Mg(OH), Major 49.2% H 2 0 = 0.6 MgO = 34.0
Gibbsite AI(OH), Major 48.9% Ash = 68.2 Al 2 0, = 32.0
j Cornelite
De villine
Cu„CI4(SO4)(OH)32.3H20
CaCu4(S04)2(OH),.3H20
Poss
Poss
- LOI - 31.4 SiO, = 0.7
CaO = 0.4
Cu « 0.1
S - 0.15
CI = 0.28
G N/A Liquid Methylcyclopentadienyl Manganese
Tricarbonyl
H Gypsum CaS0 4 .2H 2 0 Major 42.7% H20 - 7.8 Si0 2 = 18.8
Quartz SiO, Major 18.8% Ash = 67.2 CaO - 13.9
Sal Ammoniac NH4CI Major 7.2% LOI - 27.1 A l 2 0 , . - 6.5
Anhydrite CaS04 Minor - Fe 2 0, - 3.2
Epsomite MgSO4.7H20 Poss - MgO - 4.0
Millozevichite AI 2 (S0 4 ), Poss - Na20 = 0.4
U1
Hydromolysite FeCI3.6H20 Poss K20 - 0.4
in
Ti02 - 0.3 0
SO, - 26.8 |
CI = 4.8 1
1 Calcite CaCO, Major 85.3 H20 = 1.3 CaCO, - 85.3 I
Quartz Si0 2 Minor - Ash « 51.9 MgCO, « 3.1
LOI = 47.4 Fe 2 0, - 1.1
J Dolomite Ca.Mg(C03)2 Major - H20 -= 0.2 CaCO, - 57.1
Calcite CaC0 2 Minor - Ash « 55.5 MgCO, - 40.6
Quartz SiO, Minor * LOI - 44.3 Fe 2 0, - 0 . 5

K Nitre KNO, Major 75.0 H 2 0 - 1.1 K - 29.0

1 Paratacamite Cu2(OH),CI Minor 1.8 Ash « 46.3 Cr = 2.2
Sulphur S Minor 2.4 LOI - 53.2 Pb = 1.1
S - 2.4
Cu - 1.1
11 Portlandite Ca(0H) 2 Major 17.0 H2) - 5.1 K = 19.5
H Nitre KNO, Major 51.0 Ash - 47.9 Ca - 8.2
Cornalite KMgCI, Poss LOI - 49.5 Mg - 2.8
CI - 0.61
| NH 4 = 1.6
 Additive XRD Chemical Analysis
Mineral Formula Major/Minor % as Calculated % (ad) except loss on ignition
Phase from Chemical (LOI) (db)
Analysis
M N/A Liquid Complex mixture of branched and
unbranched hydrocarbons - average
composition CH,
CH,CH2CH3CH(CH2)ieCHJ
i —
N N/A Liquid 3% Ferrocene (Active ingredient) |
97% Xylenes and (Solvent) 1
ethyl benzene |
0 Periclase MgO Major 32.5% H20 - 0.2 SiO, - 0.8
Nitre KNO, Major 67% Ash = 60.6 Fe 2 0, - 0.3
LOI = 39.2 CaO - 0.6
MgO - 32.5
CO, - 0.57
K 2 0 - 31.2
CI - 0.6
Ul
BP Kaolinite AI2Si206(OH)4 Major H20 - 0.5 SiO, - 49.6
Muscovite KAI2Si,AI010(OH)2 Minor Ash - 89.1 Al 2 0, - 34.6
LOI - 10.4 Fe,0, - 1.2
MgO - 0.2
Na20 - 0.2
K 2 0 - 3.2
S - 0.06
, CI - 0.03
0 Periclase MgO Major 22.5% LOI - 42.2 SiO, - 0.2
Nitre KNO, Major 34.3% H20 - 1.8 Al 2 0, - 0.6
Ash - 56.7 Fe,0, - 1.4
CaO - 0.3
MgO - 22.5
Na,0 - 0.7
K 2 0 - 31.9
P 2 0, - 0.1
SO, - 6.3
CI » 0.06
S - 1.26
 57

TABLE XII

SUMMARY OF CLAIMS MADE FOR THE SELECTED ADDITIVES

Additive Reduces Reduces Increases Reduces Reduces Reduces Reduces

Slagging Fouling Combusion Soot Corrosion NOx SO,
Efficiency Emissions Emissions
A / /
B / /
C / /
D • / / / /
E •
F • • /
G • • /
H • • / /
1 /
J /
K • /
L • • • •
M • / • /
N • / •
0 • • •
P •
Q • /
 58

TABLE, P I

ASH FUS'ON TEMPERATIIRFS OF HTA/AnniTIVF MIXTtlRFS

CM! I

Additive Dosage Deformation Hemisphere Flow Tempi

% w/w Temp °C Temp °C
°C
NONE 0 1020 1110 1120
B .03 1010 Collapsed 1110
C .05 1020 Collapsed 1120
D .1 1040 1110 1120
E .008 1020 1120 1130
F .08 1020 1110 1120
K .013 1020 Collapsed 1120
♦NONE 0 1040 1110 1170
A .015 1040 1180 1230
H .08 1040 1210 1270
1 5 1070 1380 1390
1 2:1 Ca:S 1150 1320 1330
J 2:1 Ca:S 1190 collapsed 1460
•NONE 0 1080 1150 1180
A .15 1060 1140 1170
B .3 1080 1150 1180
D .5 1180 1220 1310
D 1 1240 >1400 >1400
H .4 1100 1170 1200
H .8 1130 1170 1200
L .075 1060 1150 1210
L .15 1060 1170 1210
•NONE 0 1080 1210 1330
P 1 1050 1190 1220
P 2 1120 1140 1150
0 .1 1160 1220 1290
Acceptable variation of test 30 30 40
• new batch of HTA so new control test
 59

TABLE XIV

ASH FUSION TEMPERATURES FOR HTA/ADDITIVE MIXTURES

Coal Ha

Additive Dosage Deformation Hemisphere Flow Temp

% w/w Temp °C Temp °C
°C
NONE 0 1070 1220 1400
A .015 1010 1160 1200
B .03 1010 1180 1360
D .1 1080 1210 1390
E .008 1040 1210 1260
F .08 1030 1160 1180
1 5 1030 1080 1110
K 0.13 1040 1200 1240
L 0.15 1070 1210 1380

•NONE 0 1000 1190 1230

B .06 1070 1220 1280
B .15 1020 1180 1240
K .026 1000 1200 1260
K .065 1010 1200 1240
H .08 1040 1170 1230
•NONE 0 1090 1250 1350
A .075 1110 1290 1330
A .15 1080 1210 burst
E .04 1090 1250 1330
E .08 1110 1300 >1400
F .4 1090 1310 >1400
F .8 1120 1280 1350
•NONE 0 1090 1250 1410
P 1 1130 1260 1430
P 2 1130 1290 1460
0 .01 1090 1210 1370
•n<iw batch of HTA sci a new control test
 60

TABLE XV

ASH FUSION TEMPERATURES FOR HTA/ADDITIVE MIXTURES

Coal lib

Additive Dosage Deformation Hemisphere Flow Temp

% w/w Temp °C Temp °C
°C
None 0 1120 1230 1300
A .015 1100 1200 1250
B .03 1150 1210 1270
C .05 1050 1210 1310
D .1 1050 1200 1270
E .008 1140 1210 1290
F .08 1100 1200 1270
1 2:1 Ca:S 1110 Collapsed 1220
1 5 1100 1130 1180
J 5 1130 1160 1230
K .013 1050 1220 1280
L .015 1120 1210 1290
•NONE 0 1010 1220 1250
A .075 1020 1200 1220
A .015 1010 1220 1240
C .25 1010 1210 1250
C .5 1010 1200 1230
D .5 1020 1210 1240
D 1 1020 1190 1220
K .065 1010 1220 1240
K .13 1010 1220 1240
NONE 0 1140 1250 1400
P 1 1080 1270 1450
P 2 1180 1290 1480
0 .01 1110 1250 1390
Acceptable Test Variation 30 30 40
* new batch of HTA so a new control test
 61

TABLE XVI

ASH FUSION TEMPERATURES FOR HTA/ADDITIVE MIXTURES

Coal III

Additive Dosage Deformation Hemisphere Flow Temp

% w/w Temp °C Temp oC
°C
None 0 1030 Collapsed 1090
A .015 1020 Collapsed 1090
B .03 1040 Collapsed 1100
C 0.05 1030 1090 1110
D 0.1 1040 Collapsed 1100
E .008 1020 Collapsed 1090
F .08 1030 Collapsed 1100
H .08 1020 Collapsed 1100
1 5 1090 1320 1390
J 5 1130 Collapsed 1360
K .013 1020 Collapsed 1090
L .015 1040 Collapsed 1100
Acceptable test variation 30 30 40

TABLE XVII

ASH FUSION TEMPERATURES FOR HTA/ADDITIVE MIXTURES

Coal IV

Additive Dosage Deformation Hemisphere Flow Temp

% w/w Temp °C Temp °C
°C
None 0 1000 1110 1140
A .015 1010 1110 1130
B .03 1010 1120 1150
C .0.05 1020 1090 1120
D 0.1 1030 1100 1130
E .008 1000 1105 1120
F .08 1000 1110 1130
H .08 1000 1110 1120
I 5 1060 1330 1340
J 5 1130 Collapsed 1300
K .013 1000 1110 1130
L .015 1020 1110 1110
•None 0 1060 1100 1200
P 1 1100 1200 1300
P 2 1190 1250 1350
0 .1 1060 1120 1200
Acceptable test variation 30 30 40
* New batch of HTA so new control test
 62

TAPIE XVIII
ASH FUSION TEMPERATURES FOR HTA/ADDITIVE MIXTURES

CoalV

Additive Dosage Deformation Hemisphere Flow Temp

% w/w Temp °C Temp °C
°C
None 0 1090 1240 1310
A .015 1080 1230 1300
B .03 1070 1220 1310
C 0.05 1070 1210 1270
D 0.1 1080 1220 1260
E .008 1060 1230 1280
F .08 1070 1230 1290
1 2:1 Ca:S 1170 1390 1420
J 5 1350 1360 1380
J 2:1 Ca:S 1140 Collapsed 1350
K .013 1080 1230 1300
L .015 1070 1230 1290
*None 0 1270 1300 1350
P 1 1280 1310 1340
P 2 1240 1340 1390
0 .01 1270 1300 1350
' New batch of HTA so new control test 30 30 40
- Acceptable variation of test
 63

TABLE XIX

SOLUBLE SODIUM IN EXTRACTS FROM COAL/ADDITIVE ASHES (WITH COA

ADDITIVE ADDITIVE CONCENTRATION, % w/w |

0 0., 0.25 0.5 | 1.0 5.0 100
Uncorrected ppm Sodium f

B 139 113 114 109 111 123 9

C 125 155 188 213 224 298 13
D 116 138 148 173 189 274 17
F 129 150 159 146 180 254 14
H 118 135 118 - 90 121 3
L 149 151 167 130 175 217 18
M 121 - - 126 90 63 0
N 121 • • 72 65 81 0
P 121 - • 51 23 4.4
C (coal IV) 0.7 1.7 5.7 13.2 67.4 128.8 »

Corrected for (average of

Additive several results)
B 129 113 114 108 119 114
C 129 155 188 212 222 285
D 129 138 147 171 186 257
F 129 150 158 145 178 240
H 129 135 117 - 90 118
L 129 151 166 128 171 213
M 121 - - 126 90 63
N 121 - • 72 65 81
P 121 - - 51 23 4
C (coal IV) 0.7 1.5 5.4 11.9 64.8 115.8
 64

TABLE XX

SOLUBLE POTASSIUM IN EXTRACTS FROM COAL/ADDITIVE ASHES (WITH COAL I)

ADDITIVE ADDITIVE CONCENTRATION , % w/w

0 0., 0.25 0.5 1.0 5.0 100
Uncorrected ppm Potasium

B 23.5 3.4 3.2 13.0 5.4 15.0 6.8

C 1.1 1.2 2.2 3.1 3.7 6.7 3.8
D 0.6 1.5 2.6 3.0 4.9 10.2 2.8
F 1.8 2.1 3.9 4.2 5.1 9.9 2.2
H 1.8 2.6 5.3 - 6.9 10.4 3.2
L 2.4 13.8 39.4 93.0 201 792.4 65.7
M 0.7 - - 1.3 12.2 83 0
N 0.7 - • 2.0 15.6 2.0 0
P 0.7 - • 2.1 3.5 1.1 1.4
C (coal IV) 1.4 2.2 3.5 8.1 25.6 48.0 3.8
Corrected for (average of several
Additive results)
B 1.5 3.3 3.8 12.3 4.0 8.2
C 1.5 1.2 2.0 2.7 2.9 2.9
D 1.5 1.5 2.5 2.7 4.3 7.4
F 1.5 2.1 3.8 4.0 4.7 7.7
H 1.5 2.6 5.1 • 6.3 7.2
L - 1.5 0.7 6.5 27.3 69.6 135.4
M 0.7 - - 1.3 12.2 83
N 0.7 - - 2.0 15.6 2.0
P 0.7 - - 2.0 2.2 0
C (coal IV) 1.4 2.2 3.3 7.7 24.8 44.2
_ _ _
 65

TABLE XXI

PHASES INDENTIFIED IN ASHED ADDITIVE/MINERAL MIXES

Phases (M - MAJOR, m - MINOR)

ADDITIVE 850°C 1150 »c

None Sodium sulphate Na2S04 M Nepheline NaAISi04 M

Quartz SiO, m Mullite Al e Si 2 0„ m
Muscovite KAI2SijAI0,0(0H)2 m Quartz SiOj m
Microcline KAISijO, m
A Sodium sulphate M Nepheline M
Quartz m Mullite m
Muscovite m Quartz m
Microcline m Hematite m
Magnetite Fe304 m
B Sodium sulphate M Nepheline M
Hematite M Hematite M
Quartz M Mullite m
Muscovite m Quartz m
Microcline m

C Periclase M Nepheline M
Sodium sulphate M Periclase M
Muscovite m Forsterite Mg2Si04 m
Quartz m Spinel MgAI204 m
D Periclase M Nepheline M
Sodium sulphate m Periclase M
Quartz m Spinel m
Muscovite m Forsterite m
Microcline m Mullite m

E Sodium sulphate M Cuprite Cu20 M

Tenorite CuO M Copper aluminium oxide CuAI204 M
Quartz m Tenorite m
Muscovite m •
Microcline m

F Periclase M Nepheline M
Sodium sulphate M Spinel m
Quartz m Forsterite m
Muscovite m Periclase m
Microcline m Mullite m
H Sodium sulphate M Nepheline M
Quartz M Anorthite CaAI2Si20, m
Muscovite M Quartz m
Microcline m Hauyne (Na,Ca),|Si,AI)12024(S04)2 m
Mullite m
K Sodium sulphate M Nepheline (Na.K)AISi04 M
Quartz M Leucite KAISijO, m
Nepheline (Na,K)AISi04 m
Muscovite m
Potassium oxide m
Microcline m

Fused
 66

TABLE XXI CONT'D

PHASES (M - MAJOR, m « MINOR) I

L
ADDITIVE

Quartz
850°C

M Nepheline
1150°C 1
(Na.K)AISiO« M
Hauyne M Hauyne M
Muscovite m Leucite m
Microcline m
Nepheline (Na,K)AISi04 m
M Sodium sulphate M Nepheline M
Quartz M Mullite m
Muscovite m Quartz m
Microcline m
Hematite m
0 Quartz M Nepheline M
Nepheline M Leucite m
Hauyne M Forsterite m
Muscovite m Spinel m
Forsterite m
Microcline m
 67

TABLE XXII

SOLUBLE SODIUM AND TOTAL SOLUBLE ALKALI AS A PERCENTAGE

OF TOTAL PRESENT IN ASHED MINERAL/ADDITIVE MIXTURE S

,„■—„■
850°C 1150°C
ADDITIVES
SOLUBLE . SOLUBLE Na + K SOLUBLE SOLUBLE Na-t-K
SODIUM/% (MOLESxlO4) SODIUM (MOLESxlO4)
None 100 144 0.3 0.4

A 101 146 0.2 0.3

B 96 139 <0.1 0.2

C 83 121 2.1 3.6

D 75 110 2.8 4.8

E 93 135 - -

F 84 122 0.9 1.4

H 94 138 <0.1 0.2

K 62 107 <0.1 0.7

L 48 80 <0.1 0.8

M 89 130 0.2 0.3

0 45 87 0.1 3.4
 68

TABLE XXIII

ENSILE STRENGTHS OF PELLETS MADE FROM COAL III HTA AND ADDITIVES FIRED AT HOO°C

Additive Additive Concentration Tensile Strength

(% w/w) (kPa) (Mean of 3)
None . 4.6
P 2 5.8
P 5 6.7
P 10 7.7
P 20 11.5
P 100 12.7
C 5 3.8
0 5 5.8
B 5 4.5
M 10 3.9

TABLE XXIV

TENSILE STRENGTHS OF PELLETS MADE FROM ASHED COAL/ADDITIVE MIXTURES

FIREDAT1100°C

COAL ADDITIVE CONCENTRATION/ STRENGTH (kPa) SD

% w/w
lib None 0 18.0 1.38
P 3.2 18.8 10.14
P 6.5 13.4 2.88
P 13.0 13.2 2.54
P 26.0 17.2 4.74
C 3.2 8.4 1.75
C 6.5 10.1 1.75
C 13.0 5.9 1.95
C 26.0 3.3 0.89
M 3.2 15.2 2.08
M 6.5 3.0 0.10
M 13.0 21.8 4.55
M 26.0 14.3 2.37
V None 0 3.3 0.08
P 4.3 5.3 0.39
P 8.7 3.0 0.25
P 17.4 4.9 0.36
P 34.8 4.2 0.50
C 8.7 3.0 0.06
C 17.4 5.7 1.33
C 34.8 7.5 0.35
M 4.3 3.7 0.02
M 8.7 2.6 0.12
M 17.4 3.7 0.45
III None 0 2.4
P 9 3.1 0.47
C 9 2.8 0.30
M 9 2.6 0.13
IV None 0 12.7 5.23
P 9 12.5 2.17
C 9 10.6 0.93
M 9 11.8 0.94

Standard deviation
 69

TABLE XXV

X-RAY DIFFRACTION ANALYSIS OF SELECTED ASH/ADDITIVE PELLETS (COAL HI)

ADDITIVE CRYSTALLINE PHASES IDENTIFIED

None Hauyne (Na,Ca),(Si,AI)12O24(SO4)2
Hematite Fe2O3
Nepheline NaAISiO«
Anorthite CaAI2Si203
Pyroxene (Diopside) Ca(Mg,Fe,AI)(Si,AI)20, f
20% w/w P Anorthite j
Hematite
Nepheline
5% w/w B Hauyne
Anorthite
Hematite
Nepheline
Pyroxene (Diopside)
5% w/w C Hauyne
Pyroxene (Diopside)
Anonhite
Nepheline
Hematite
5% w/w 0 Hauyne
Nepheline
Hematite
Anorthite
Pyroxene (Diopside)
10% w/w M Hauyne
Hematite
Nepheline
Anorthite
Pyroxene (Augite) Ca(Mg,Fe)Si206
 70

TABLE XXVI

TENSILE STRENGTHS OF PELLETS MADE FROM THE 150 KW UNDERFEED STOKER

TUBE DEPOSITS

Coal % w/w Strengths/kPa Strength/kPa

Additive (Fired at 1100°C) (Fired at 800°C)
(Mean of 3) (Mean of 3)
III None 6.7 0.5
III 1%P 5.6 0.3
IV None 4.8 0.8
IV 1% P 5.9 0.8
VI None 4.0 0.5
VI 1% P 5.2 0.6
VI 0.06% B 2.1 0.3

TABLE XXVII

ENSILE STRENGTHS OF PELLETS MADE FROM THE CHAINGRATE STOKER DEPOSITS

(FIRED AT 800°C. ALL RESULTS A MEAN OF 3)

Additive Tube Plate Deposit Material Inside

Smoke Tubes
None 6.5 6.6
1.5%, P Premixed 5.4 5.7
0.5%, P Injected 3.0 0.4
0.12% B 4.0 6.3
0.15% C ND 6.2

ND - not determined
 71

TAPIE XXVIII
RECOVERIES OF WATER SOLUBLE COMPONENTS IN FLUIDISED BED COMBUSTION PRODUCTS

tCoal D

Additive Sample Na K Ca Mg
%ir i coal recovered as soluble

None Condensed/Deposited Material 6.5 87.1 3.1 1.1

(average of 4 Fly Ash 1.7 18.8 5.4 ND
runs) Sand 10.2 69.6 8.0 ND
TOTAL 18.4 175.5 16.5 1.1

B Condensed/Deposited Material 9.1 110 3.1 1.3

Fly Ash 2.8 33 4.3 ND
Sand 10.8 0 12.7 ND
TOTAL 22.7 143 30.1 1.3

C Condensed/Deposited Material 7.5 101 2.1 3.0

Fly Ash 5.4 68 6.2 ND
Sand 4.4 ND 4.9 ND
TOTAL 17.3 169 13.2 3.0

D Condensed/Deposited Material 7.3 106 2.8 3.7

Fly Ash 4.7 56 4.9 ND
Sand 8.1 ND 11.0 ND
TOTAL 20.1 162 18.7 3.7

F Condensed/Deposited Material 8.3 113 3.4 7.5

Fly Ash 4.4 50 7.3 ND
.Sand 9.3 ND 11.1 ND
TOTAL 22.0 163 21.8 7.5

H Condensed/Deposited Material 10.4 125 3.6 2.0

Fly Ash 3.4 35 7.2 ND
Sand 11.2 ND 13.3 ND
TOTAL 25.0 160 24.1 2.0

K Condensed/Deposited Material 11.6 7 2.8 0.5

Fly Ash 3.5 33 3.4 ND
Sand 8.8 45 19.2 ND
TOTAL 23.9 85 25.4 0.7

M Condensed/Deposited Material 5.2 97 2.8 0.7

Fly Ash 1.1 29 7.0 ND
Sand 6.6 79 10.3 ND
TOTAL 12.9 205 20.1 0.7

M Condensed/Deposited Material 7.4 96 3.8 3.6

Fly Ash 0.9 15 4.2 ND
Sand 7.6 61 9.1 ND
TOTAL 15.9 172 17.1 3.6
N Condensed/Deposited Material 7.9 119 3.6 1.3
Fly Ash 2.1 29 7.7 ND
Sand 9.7 87 8.2 ND
TOTAL 19.7 235 19.5 1.3

0 Condensed/Deposited Material 4.5 7.7 1.6 1.6

Fly Ash 2.9 4.5 3.5 ND
Sand 11.5 ND 18.0 ND
TOTAL 19.0 12.2 23.2 1.6

ND • not detected
 72

TAPIE CT
RECOVERIES OF WATER SOLUBLE COMPONENTS IN FLUIDISED BED COMBUSTION PRODUr

(Cpgi IV)

Additive Sample Na K Ca Mg

% in coal recovered as soluble

None Condensed/Deposited Material 2.0 4.3 1.7 .5
(average of 4 Fly Ash 2.9 3.4 8.7 ND
runs) Sand 2.5 2.8 21.1 ND
TOTAL 7.4 10.5 31.5 .5
B Condensed/Deposited Material 5.8 4.9 1.0 0.8
Fly Ash 0.2 6.7 7.5 ND
Sand ND ND 19.7 ND
TOTAL 6.0 11.6 28.2 0.8

C Condensed/Deposited Material 1.9 6.0 3.3 4.2

Fly Ash 6.0 14.3 10.5 ND
Sand 1.4 5.1 19.0 ND
TOTAL 9.3 25.4 32.8 4.2

D Condensed/Deposited Material 1.9 5.0 3.5 5.2

Fly Ash 6.1 16.1 9.4 0.1
Sand ND ND 19.2 ND
TOTAL 8.0 21.1 32.1 5.3
F Condensed/Deposited Material 1.2 5.0 0.8 11.4
Fly Ash 3.0 10.5 12.2 ND
Sand 0.6 5.1 15.8 ND
'TOTAL 4.8 20.6 28.8 11.4
H Condensed/Deposited Material 11.8 5.7 1.7 2.4
Fly Ash 1.7 6.8 19.5 ND
Sand ND 2.9 18.2 ND
TOTAL 13.5 15.4 39.4 2.4
K Condensed/Deposited Material 2.7 26.9 0.5 ND
Fly Ash 1.1 9.0 3.5 ND
Sand 1.4 ND 21.2 ND
TOTAL 5.2 35.9 25.2 ND
L Condensed/Deposited Material 3.9 4.8 1.8 0.5
Fly Ash 3.6 2.6 10.4 0.4
Sand 4.6 2.7 20.6 0.7
TOTAL 12.2 10.1 32.8 1.6
L Condensed/Deposited Material 2.0 2.1 3.0 1.7
Fly Ash 9.3 5.1 40.9 1.0
Sand 3.1 1.8 24.4 0.7
TOTAL 14.4 8.9 68.3 3.4
M Condensed/Deposited Material 2.5 5.2 1.9 1.0
Fly Ash 3.2 5.3 9.5 ND
Sand 3.6 4.5 23.6 ND
TOTAL 9.3 15.0 35.0 1.0
N Condensed/Deposited Material 1.6 4.8 3.3 2.5
Fly Ash 3.7 5.8 10.3 ND
Sand 2.5 4.1 19.2 ND
TOTAL 7.7 14.7 32.8 2.5
 73

Additive Sample Na K Ca Mg

% in coal recovered as soluble

0 Condensed/Deposited Material 1.7 5.5 5.9 7.6
Fly Ash 4.1 7.8 7.8 2.2
Sand 3.1 4.3 22.8 1.0
TOTAL 8.9 17.7 36.5 10.9
Q Condensed/Deposited Material 0.5 2.3 23 9.8
Fly Ash 4.8 11.8 152 0.5
Sand NO ND 71 0.1
TOTAL 5.3 14.0 246 10.5

NO - not detected
 74

TABLE XXX

RECOVERIES OF SOLUBLE SODIUM IN THE COMBUSTION PRODUCTS FROM SORBENT BED

TESTS ON THE FBC

Coal Bed Material Additive P Aqueous Fly Ash Bed Ash Total

% w/w of coal feed % of input recovered as soluble sodium

Sand 0 5 1 11 17
Limestone 0 22 24 8 54
Limestone 1 19 40 8 67
Limestone 5 12 42 5 59
Limestone 10 6 31 4 41
Dolomite . 0 5 31 7 43
Dolomite 5 4 46 8 58
IV Sand 0 0 0 8.5 8.5
IV Limestone 0 8 44 7 59
IV Limestone 1 7 45 12 64
IV Limestone 5 2 38 7 47
IV Limestone 10 1 36 5 42
IV Dolomite 0 8 31 8 47
IV Dolomite 1 6 40 7 53
IV Dolomite 5 2 35 6 43
IV Dolomite 5 1 26 5 32
V Sand 0 0 0 1.5 1.5
V Limestone 0 9 62 11 82
V Limestone 1 5 53 9 67
V Limestone 5 2 27 12 41
V Limestone 10 2 49 8 59
 75

TABLE XXXI

NO.,. EMISSIONS FROM THE LABORATORY FBC WITH COAL IV

Bed Material Additive Bed Temperature/0 C

800 850 900 950

NO/ppm sd/ppm NO/ppm sd/ppm NO/ppm sd/ppm NO/ppm sd/ppm
Sand None 145 27 195 22 220 30 255 29
Sand C 145 28 185 11 215 9 240 16
Sand D 145 13 175 15 200 17 220 10
Sand H 100 20 130 25 150 28 180 27
Sand L 150 12 175 6 200 19 220 18
Sand N 145 6 180 11 205 9 225 4
Sand 0 165 22 205 30 235 28 255 31
Sand P 130 2 160 7 195 3 220 4
Limestone(l) None 365 31 395 50 425 69 435 35
Limestone(l) P 395 86 430 47 465 29 485 25
Dolomite (J) None 370 142 435 94 480 49 500 57
Dolomite! J) P 305 46 375 73 455 133 500 101

TABLE XXXII

. N,0,Q, EMISSIONS FROM THE LABORATORY FBC WITH COAL IV

Bed Material Additive Bed Temperature/0 C

800 850 900 950
N20/ppm sd/ppm N20/ppm sd/ppm N20/ppm sd/ppm NjO/ppm sd/ppm
Sand None 45 . 36 » 25 . 14 m
Sand C 46 31 38 26 29 22 19 16
Sand D 41 1.7 32 3.1 23 4.4 14 4.1
Sand H 37 5.3 33 7.1 21 2.9 13 1.9
Sand L 41 2.1 32 2.1 19 0.2 10 0.5
Sand N 40 2.1 33 1.2 23 2.1 15 1.3
Sand 0 45 26 • 36 20 26 16 11 3.6
Sand P 42 - 34 - 23 • 14 •
Limestone(l) None 7.1 .8 5.8 .9 3.1 1.4 1.9 .4
Limestone(l) P 5.8 - 5.4 - 3.7 • 2.8 .
Dolomite(J) None 14 3.5 7.7 2.4 3.8 .8 2.9 .3
Dolomite(J) P 17 1.1 13 4.3 4.8 .2 4.0 .4
 76

TABLE XXXIII

SO.,,,, EMISSIONS FROM THE LABORATORY FBC WITH COAL IV

Bed Material Additive Bed Temperature/°C

800 850 900 950

SO2/ppm SO2/ppm SO2/ppm SO2/ppm

Sand None 180 230 260 280

Sand C 155 190 210 230
Sand D 185 210 235 270
Sand H 230 265 295 260
Sand L 95 130 145 150
Sand N • 195 220 230 240
Sand 0 150 200 235 265
Sand P 180 210 240 240
Limestone(l) None <20 <20 <20 <20
Limestone(l) P <20 <20 <20 <20
Dolomite(J) None 20 20 20 20
Dolomite(J) P 20 20 20 20
 tftewr-
*S
77

TABLE XXXIV
ELEMENTAL SOLUBILITIES IN COMBUSTION PRODUCTS FROM THE 9 KW UNDERFEED STOKER
(1 DAY TESTS)

1 Additive Combustion Product % recovered as soluble I

Na K Ca Mg
None Bottom ash 4 8 14.2 .8
Heat exchanger deposit 26 18 .7 .3
'Fly ash' 4 7 .5 <.1
TOTAL 34 33 15.4 1.1
None Bottom ash 24 28 15.8 .7
Heat exchanger deposit 14 4 1.0 .9
'Fly ash' 4 1 0.6 <.1
TOTAL 42 33 17.4 1.6
A Bottom ash 4 11 5.8 .8
Heat exchanger deposit 21 19 .8 .7
'Fly ash' 3 2 .2 <.1
TOTAL 28 32 16.8 1.5
B Bottom ash .3 14 8.5 .8
Heat exchanger deposit 4.6 15 .4 .4
'Fly ash' .8 3 .2 <.1
TOTAL 5.7 32 9.1 1.2
C Bonom ash 31 2.7 12.3 .3
Heat exchanger deposit 24 4.2 .7 1.6
'Fly ash' 6 .9 .8 <.1
TOTAL 61 7.8 13.8 1.9
D Bottom ash 18 16 11.6 .2
Heat exchanger deposit 30 11 .9 1.7
'Fly ash' 3 2 .3 <.1
TOTAL 51 29 12.8 1.9
E Bonom ash 12 13.7 .6
Heat exchanger deposit 34 .9 1.3
'Fly ash' 2 .6 <.1
TOTAL 48 15.2 1.9
F Bonom ash 71 22.0 .4
Heat exchanger deposit 26 .8 2.4
'Fly ash' 6 .6 <.1
TOTAL 103 23.4 2.8
Bonom ash 5 9 14.6 .7
H Heat exchanger deposit 32 9 1.0 .9
'Fly ash' 2 1 .2 <.1
TOTAL 39 19 15.8 1.6
1 Bonom ash 21 8 15.5 1.2
Heat exchanger deposit 25 8 .2 .2
'Fly ash' 3 2 .1 <.1
TOTAL 49 18 15.8 1.4
K Bonom ash 18 4 17.6 .6
Heat exchanger deposit 30 13 .8 1.6
'Fly ash' 5 2 .6 <.1
TOTAL 53 19 19.0 2.2
L Bonom ash 9 20 8.7 .5
Heat exchanger deposit 15 7 .6 1.1
'Fly ash' 1 1 .2 <.1
TOTAL 25 28 9.5 1.6
 78

Additiv« Combustion Product % recovered as soluble |

Na K Ca Mg
M Bottom ash 43 27 24.0 .7
Heat exchanger deposit 16 4 1.1 2.6
'Fly ash' 9 6 1.6 2.3
TOTAL 68 37 26.7 5.6
M Bottom ash 10 30 16.7 .6
Heat exchanger deposit 28 23 3.5 4.9
'Fly ash' 3 2 .6 <.1
TOTAL 41 55 20.8 5.5
M Bottom ash 1 5 12.4 .8
Heat exchanger deposit 15 46 1.2 1.8
'Fly ash' 8 26 1.5 .1
TOTAL 24 77 15.1 2.7
N Bottom ash 36 6 28.5 .7
Heat exchanger deposit 44 6 3.6 1.1
'Fly ash' 9 2 .9 <.1 |
TOTAL 89 14 33.0 1.8 fl
0 Bottom ash
Heat exchanger deposit
3
22
4
23
15.3
1.0
' 1.2'8 |1
'Fly ash' 14 17 1.6
TOTAL 39 44 17.9 2.1 I
P Bottom ash 10 5 27.5 .9
Heat exchanger deposit 7 5 .6 1.9
'Fly ash' 2 1 1.0 1.0
TOTAL 19 11 29.1 3.8
Q Bottom ash 9 12 20.1 .6
Heat exchanger deposit 22 26 1.2 1.6
'Fly ash' 7 6 1.2 .2
TOTAL 38 44 22.5 2.4
 79

TABLE XXXV

ELEMENTAL SOLUBILITIES IN COMBUSTION PRODUCTS FROM THE 9 KW UNDERFEED STOKER

(5 PAY TESTS)

Additive Combustion Product % recovered as soluble

Na K Ca Mg
None Bottom ash 17 5 5.9
Heat exchanger deposit 36 12 1.1
'Fly ash' 4 2 .4 <.1
TOTAL 57 19 7.4 .9
None Bottom ash 17 16 6.0 .4
Heat exchanger deposit 37 41 1.1 .5
'Fly ash' 5 7 .4 <.1
TOTAL 59 64 7.5 .9
B Bottom ash 22 5.4 18.3 .6
Heat exchanger deposit 25 3.1 1.3 1.1
'Fly ash' 7 2.5 .7 .2
TOTAL 54 11 20.3 1.9
H Bottom ash 11 5 10.5 .4
Heat exchanger deposit 39 87 1.4 .6
'Fly ash' 9 43 .3 .2
TOJAL 59 17 12.2 1.2
L Bottom ash 16 9 12.7 .5
Heat exchanger deposit 28 20 1.0 .8
'Fly ash' 7 6 .7 <.1
TOTAL 51 35 14.4 1.3
M Bottom ash 33 12 12.3
Heat exchanger deposit 7 24 2.0
'Fly ash' 34 6 0.7
TOTAL 74 42 15 1.3
N Bottom ash 16 5 15.4 .5
Heat exchanger deposit 28 3 1.3 .9
'Fly ash' 5 1 .7 .1
TOTAL 50 9 17.4 1.5
 80

TABLE XXXVI
NOx AND SO. EMISSIONS FROM THE 9 KW UNDERFEED STOKER

Additive NOx/ppm (6% 02. dry) SOa/ppm (6% 0 2 , dry)

x of means x of means
None 300 510
A 320 490
B 320 510
C 270 500
D 290 480
H 300 540
1 •220 •420
L 260 470
M 270 470
N 320 ••600

Significantly lower than the control at the 95% level

Significantly higher than the control at the 95% level

TABIE XXXVH

TUBE DEPOSIT FORMED ON THE 150 KW UNDERFEED STOKER

Conditions Deposit as %
Deposite Mass/kg Total Ash Recovered
Coal % w/w
Additive
Coal III None 11.5 7.0
Coal III 1% P 11.7 7.0
Coal IV None 6.7 9.1
Coal IV 1% P 5.5 4.5
Coal VI None 7.7 12.6
Coal VI 1% P 6.8 9.2
Coal VI 0.06% B 8.5 7.3
 81

TABLE XXXVIII

RECOVERIES OF WATER SOLUBLE COMPONENTS IN THE COMBUSTION PRODUCTS FROM THE

150 KW UNDERFEED STOKER

Coal Additive Combustion Product % in coal recovered as soluble

Na K Ca Mg

III None Bottom ash 2 4 6 .5

Heat exchanger deposit 2 2 4 1.5
TOTAL 4 6 10 2.0

III P Bottom ash 4 3 7 .6

Heat exchanger deposit 2 1 4 1.5
TOTAL 6 4 11 2.1

IV None Bottom ash 5 2 10 .6

Heat exchanger deposit 3 1 4 .6
TOTAL 7 3 14 1.2
IV P Bottom ash 7 2 10 .6
Heat exchanger deposit .5 .5 1 .5
TOTAL 7.5 2.5 11 1.1

VI None Bottom ash 12 40 9 1.5

Heat exchanger deposit 3 6 6 1.4
TOTAL 15 46 15 2.9
VI P Bottom ash 10 23 13 1.6
Heat exchanger deposit 1 2 4 1.6
TOTAL 11 25 17 3.2
VI B Bottom ash 15 56 29 1.5
Heat exchanger deposit 1 4 3 1.1
TOTAL 16 60 32 2.6
 82

TAPIE XWX.
IBE DEPOSIT RECOVERED FROM THE 150 KW UNDERFEED STOKER WITH COAL VI AND
VARYING PROPORTIONS OF ADDITIVE P

Additive P Deposit as % of Total 1

(% w/w) Ash Recovered
0 6.0
0.5 3.8
2 5.6
5 4.0

TABLE XXXX

RECOVERIES OF WATER SOLUBLE SOLDIUM AND POTASSIUM IN THE

OMBUSTION PRODUCTS FROM THE 150 KW UNDERFEED STOKER WITH COAL VI AND
DIFFERENT PROPORTIONS OF ADDITIVE P

% Additive P Combustion Product % Recovered as Soluble

Na K
0 Bottom ash 6 3
Heat exchanger deposit 2 1
TOTAL 8 4
0.5 Bonom ash 16 8
Heat exchanger deposit 4 2
TOTAL 20 10
2 Bottom ash 7 5
Heat exchanger deposit 2 2
TOTAL 9 7
5 Bottom ash 6 4
Heat exchanger deposit 2 1
TOTAL 8 5
 TABLE XXXXI

ANALYSES OF COMBUSTION PRODUCTS FROM THE CHAINGRATE STOKER TRIAL 1 (CONTROL)

Combustion Mass H20 Ash %ad

Product kg %ad %ad
SiO, Al 2 0, Fe 2 0, CaO MgO Na 2 0 K20 Ti0 2 Mn,0 4 P*0, SO,
i
Grate ash 1720 0.3 90.7 44.3 23.8 9.5 5.4 2.3 1.4 2.7 0.9 0.2 0.5 0.5

Reversal chamber 503 0.1 99.9 47.7 25.2 10.2 5.5 2.1 1.9 3.0 1.0 0.1 0.5 2.5
fines

Smoke box fines 25 0.2 93.6 33.4 17.5 8.2 5.4 1.5 4.5 7.6 0.8 0.1 1.5 13.2

Cyclone fines 197 0.4 . 88.6 36.4 20.3 8.8 5.7 1.6 2.7 4.1 0.9 0.1 1.0 6.2

Stack ash 138 1.1 89.7 25.7 13.3 11.2 6.4 1.3 4.1 6.2 0.9 0.1 2.4 14.5

TABLE XXXXII 00
co

ANALYSES OF COMBUSTION PRODUCTS FROM THE CHAINGRATE STOKER TRIAL 2 ADDITIVE C

I Mass H20 Ash %ad

1 Product
Combustion %ad %ad
kg
Si0 2 Al 2 0, Fe 2 0, CaO MgO Na 2 0 K20 TiO, Mn,0 4 P,O. so,
Grate ash '660 0.7 78.3 39.6 20.3 8.5 4.5 2.0 1.3 2.1 0.8 0.1 0.3 0.6 i
Reversal 150 <0.1 99.2 50.6 24.9 9.6 5.3 2.4 1.9 3.0 1.0 0.1 0.4 1.8 I
chamber fines

Smoke box fines 20 0.4 91.3 33.9 15.8 9.8 4.9 4.8 3.3 5.0 0.8 0.1 0.9 12.4

Cyclone fines 255 0.5 80.7 40.1 18.8 8.0 4.4 2.2 2.0 2.8 0.9 0.1 0.4 2.8

Stack ash 249 0.9 86.6 20.7 10.3 6.2 5.2 25.7 2.2 2.9 0.7 0.1 1.6 8.9
 TABLE XXXXIII

ANALYSES OF COMBUSTION PRODUCTS FROM THE CHAINGRATE STOKER TRIAL 3 ADDITIVE B

% ad |
Combustion Mass H20 Ash
Product kg %ad %ad Na2O K20 Ti0 2 Mn3O4 P2O6 SO, |
SiO2 Al2O3 Fe 2 0, CaO MgO

39.0 20.5 8.3 4.3 2.0 1.4 2.4 0.8 0.2 0.4 1.0
Grate ash 6350 0.7 80.0

25.0 10.0 4.6 2.0 2.1 3.3 1.0 0.2 0.5 2.2
Reversal 638 0.1 98.4 48.3
chamber fines
27 3.9 6.5 0.8 0.2 1.1 13.0
0.3 90.3 32.9 16.5 9.9 4.5 1.6
Smoke box fines
270 2.0 2.7 0.9 0.2 0.6 3.5
0.5 78.5 35.4 18.4 7.6 4.9 1.6
Cyclone fines
119 1.2 0.1 2.6 10.4
0.8 83.5 29.6 12.9 9.3 8.7 1.7 2.6 4.0
H Stack ash

TABLE XXXXIV

ANALYSES OF COMBUSTION PRODUCTS FROM THE CHAINGRATE STOKER TRIAL 5 (CONTROL)

H20 Ash % ad
Combustion Mass
Product kg %ad %ad K20 TiO2 Mn3O4 P2O6 SO,
SiO2 Al 2 0, Fe 2 0, CaO MgO Na 2 0

11.0 6.4 2.4 1.6 2.2 0.9 0.2 0.4 0.4

Grate ash 3360 0.4 89.5 44.4 21.8

8.8 6.2 2.3 2.3 2.8 1.1 0.1 0.4 2.6

Reversal 234 0.1 99.2 48.5 25.1
chamber fines

18.4 10.4 6.5 1.9 2.9 3.8 0.1 0.1 0.9 9.9
Smoke box fines 19 0.4 88.9 38.2

17.7 8.1 5.5 1.7 2.3 2.7 0.9 0, 0.6 5.1

Cyclone fines 78 0.4 79.2 36.6

V
 TABLE XXXXV

ANALYSES OF COMBUSTION PRODUCTS FROM THE CHAINGRATE STOKER TRIAL 6 ADDITIVE P

Combustion Mass H20 Ash %ad

Product kg %ad %ad
Si0 2 Al,0, Fe 2 0, CaO MgO Na?0 K20 Ti0 2 Mn,0 4 P,0, SO,

Grate ash 3930 0.4 86.8 42.3 23.4 8.9 ' 4.9 2.2 1.3 2.3 0.7 0.1 0.2 0.5

Reversal 267 0.1 98.6 46.3 27.8 7.6 5.5 2.0 2.3 3.3 0.9 0.1 0.3 2.6
chamber fines

| Smoke box fines 16 0.4 88.6 37.9 20.0 8.2 6.2 1.8 2.7 4.9 0.9 0.1 0.6 6.1

1 Cyclone fines 85 0.4 83.7 39.5 22.0 6.5 5.0 1.6 2.3 3.3 0.8 0.1 0.3 2.0

TABLE XXXXVI 00
U1

ANALYSES OF COMBUSTION PRODUCTS FROM THE CHAINGRATE STOKER TRIAL 7 »INJECTION OF ADDITIVE PI

I Combustion Mass H20 Ash %ad

i Product kg %ad %ad
Si0 2 Al 2 0, Fe 2 0, CaO MgO Na 2 0 K20 TiO, Mn,0 4 P*0, SO,

Grate ash 4498 0.2 92.5 50.6 24.9 10.7 4.7 2.1 1.4 3.1 1.0 0.2 0.3 0.3

165 0.2 99.6 45.0 29.2 11.0 6.6 1.8 1.9 2.6 1.0 0.1 0.6 3.6
Reversal
chamber fines

22 0.4 91.1 31.2 20.4 6.4 3.5 0.8 2.2 3.4 0.6 0.1 1.0 8.4
Smoke box fines

7 0.9 78.6 28.6 21.7 10.5 7.1 1.6 2.2 2.5 0.9 0.1 1.1 6.9
Cyclone fines
 TABLE XXXXVII

ANALYSES OF THE DEPOSITS FROM THE CHAINGRATE STOKER - TRIAL 1 (CONTROL1

Mass %ad
Deposits kg
Ash Si0 2 Al 7 0, Fe,0, CaO MgO Na,0 KjO TiO, Mn 3 0 4 P,0, SO,
Tube plate deposit 8.4 99.8 36.4 18.6 10.3 7.3 1.7 4.3 6.3 1.1 0.1 2.4 10.4

Tube plate base <0.1 ND 9.9 4.6 4.6 1.2 0.4 13.5 19.5 0.2 <0.1 3.4 41.0

Inside smoke tubes 47.8 87.5 18.9 9.7 7.5 4.5 0.9 6.4 10.4 0.7 0.1 4.0 31.8

Powder in furnace tube 0.8 91.3 21.6 12.1 12.0 4.3 1.0 5.7 9.7 0.7 0.1 3.0 25.5

Side walls 12.0 99.9 44.4 25.0 12.6 6.5 1.8 3.1 3.3 1.2 0.1 1.5 1.4

Rear wall 21.0 99.8 42.7 23.2 15.8 6.9 2.0 2.8 2.9 1.1 0.1 1.2 1.0
00
an
Top of rear arch 10.1 99.9 44.9 24.4 11.1 6.3 2.0 2.4 3.9 1.0 0.1 0.7 3.3

| Inside of rear arch 5.3 99.8 36.1 22.4 19.9 7.5 1.9 3.4 3.1 1.1 0.2 1.9 3.8

| Furnace tube roof 0.9 99.6 38.1 19.3 14.8 6.8 2.1 4.0 5.7 0.9 0.2 2.2 5.4

ND Not determined
 TABLE XXXXVIII

ANALYSES OF THE DEPOSITS FROM THE CHAINGRATE STOKER - TRIAL 2 ADDITIVE C

%ad
DEPOSITS Mass
Ash Si0 2 Al2O3 Fe 2 0, CaO MgO Na 2 0 K20 TiO, Mn,0 4 P2O5 SO,
kg

Tube plate deposit 14.4 98.1 27.5 13.7 7.5 4.4 9.3 3.6 5.6 0.8 0.1 1.1 24.6

Tube plate base 0.1 98.7 6.9 3.4 5.8 2.3 20.3 4.2 8.9 0.3 <0.1 1.0 45.3

| Inside smoke tubes 65.8 88.7 18.4 10.9 8.3 4.4 7.2 4.9 6.4 0.7 0.1 1.8 28.0

H Powder in furnace tube 0.7 92.7 23.0 10.6 11.4 3.9 1.2 6.0 8.6 0.6 0.1 1.7 23.0

H Side walls 6.3 99.7 48.3 23.5 10.4 5.6 1.9 3.4 3.7 1.2 0.1 1.0 2.6

R Rear wall 10.3 99.8 45.4 21.9 14.1 6.3 2.0 3.2 3.4 1.2 0.2 0.9 2.0

Top of rear arch 3.6 99.7 48.1 22.9 9.8 6.0 2.8 3.1 3.3 1.1 0.1 0.8 2.6 00

Inside of rear arch 3.1 99.6 40.1 19.6 15.7 5.9 1.9 4.2 4.2 1.0 0.1 1.4 5.2 87

Furnace tube roof 1.5 97.1 41.1 18.1 12.7 6.1 2.3 4.2 4.9 0.9 0.2 1.0 6.8

1 Roof 4.6 99.5 45.2 20.8 10.6 6.1 2.4 4.2 4.2 1.1 0.1 1.3 4.5
 TABLE XXXXIX

ANALYSES OF THE DEPOSITS FROM THE CHAINGRATE STOKER - TRIAL 3 ADDITIVE B

1 %ad
I DEPOSITS Mass
Ash SiO, Al 2 0, Fe 2 0, CaO MgO Na 2 0 K20 TÍO, Mn,0 4 P 2 0, SO,
kg
1 Tube plate deposit 15.0 97.1 30.1 15.0 8.6 5.6 1.5 5.6 8.5 0.9 0.1 1.3 19.9

Tube plate base <0.1 74.5 14.0 14.0 11.8 3.0 0.7 5.4 8.4 0.5 0.1 1.8 41.2

Inside smoke tubes 39.7 80.9 15.5 6.9 8.4 3.9 0.9 5.5 9.7 0.6 0.1 3.6 36.2

Powder in furnace tube 0.8 90.5 17.0 8.6 15.1 3.2 0.8 6.2 10.2 0.5 0.2 1.9 25.9

Side walls 5.3 99.9 40.5 21.6 11.4 5.7 1.7 4.5 5.1 . 1.1 0.2 1.0 5.9

Rear wall 7.1 99.9 38.5 19.7 16.6 6.1 1.7 4.3 4.4 1.1 0.2 1.7 4.9

Top of rear arch 10.3 99.5 42.3 21.8 11.8 6.2 2.0 3.0 4.2 1.1 0.2 0.7 6.1 00
00
Inside of rear arch 3.9 99.9 34.6 18.5 17.1 5.9 1.7 4.3 5.4 1.0 0.2 1.1 9.0

Furnace tube roof 1.4 98.9 33.3 16.7 14.5 5.5 1.8 5.5 6.8 0.8 0.2 1.0 10.8

Roof 7.8 99.7 38.4 19.5 10.7 5.9 1.8 5.0 6.3 1.0 0.2 1.0 9.4
 TABLE L

ANALYSES OF THE DEPOSITS FROM THE CHAINGRATE STOKER - TRIAL 5 »CONTROL!

1
I DEPOSITS Mass
%ad

kg Ash Si0 3 Al,0, Fe 2 0, CaO MgO Na 2 0 K,0 TiO, Mn,0 4 P,0 8 SO,

Tube plate deposit 10.9 97.5 32.4 16.8 7.8 6.5 1.7 4.7 7.9 1.0 0.1 0.9 18.8
Tube plate base <0.1 94.2 9.4 4.8 9.7 2.5 0.6 7.2 16.8 0.3 0.1 1.8 41.1
Inside smoke tubes 20.0 75.8 12.5 6.3 10.3 3.7 0.8 6.0 7.1 0.5 0.1 2.1 34.2
Powder in furnace tube 0.8 90.9 20.7 11.1 11.3 4.1 1.0 5.9 5.2 0.6 0.1 1.6 24.1
Side walls 3.9 99.7 39.5 20.9 9.3 6.4 1.8 3.4 5.6 1.1 0.1 0.8 9.9
Rear wall 4.1 99.8 38.4 20.0 10.0 6.3 1.8 4.2 6.0 1.1 0.1 0.8 10.7
| Top of rear arch 12.7 99.3 44.1 22.8 8.2 6.2 2.0 2.6 4.2 1.1 0.1 0.6 7.4
00
Inside of rear arch 2.3 99.6 38.6 20.1 8.1 6.1 1.7 4.4 6.4 1.0 0.1 0.9 10.9 10

Roof 8.3 99.7 37.1 20.4 8.8 6.5 1.8 4.6 6.9 1.0 0.1 0.9 13.1
 TABLE LI

ANALYSES OF THE DEPOSITS FROM THE CHAINGRATE STOKER - TRIAL 6 ADDITIVE P

1 %ad
1 DEPOSITS Mass
kg Ash S¡0 2 Al 2 0, Fe 2 0, CaO MgO Na 2 0 K20 TiO, Mn,0 4 P 2 0, SO,

Tube plate deposit 8.9 96.5 26.5 15.4 10.0 6.8 1.7 7.2 9.5 0.9 0.1 1.9 16.3
Inside smoke tubes 24.0 75.6 15.3 8.0 12.7 3.8 0.9 5.3 11.1 0.5 0.1 2.6 15.3
Powder in furnace tube 1.0 94.0 21.5 11.7 9.8 3.9 0.9 7.2 14.4 0.5 0.1 1.3 22.5
Side walls 2.2 99.6 .38.8 23.4 7.6 5.9 1.7 5.0 6.0 1.0 0.1 0,6 9.4
Rear wall 2.7 99.8 36.2 19.9 12.7 5.1 1.4 5.1 8.6 0.8 0.1 0.7 9.2
| Top of rear arch 6.5 99.6 44.2 24.9 7.2 5.3 1.7 3.0 6.2 0.9 0.1 0.5 5.8
N Inside of rear arch 1.5 99.6 39.8 23.1 8.0 6.3 1.8 5.2 6.9 1.0 0.1 0.7 7.0
o
Q Roof 5.6 99.8 40.4 21.7 7.9 5.8 1.6 5.8 7.2 0.9 0.1 0.6 8.0
 TABLE LII

ANALYSES OF THE DEPOSITS FROM THE CHAINGRATE STOKER - TRIAL 7 ADDITIVE P INJECTED

%ad
I DEPOSITS Mass
kg Ash SiO, Al 2 0, FeaO, CaO MgO Na 2 0 K,0 TiO, Mn,0 4 PA SO,
1 Tube plate deposit 11.0 92.9 34.5 24.1 6.6 3.1 0.8 4.6 7.2 0.5 <0.1 1.0 17.9
H Tube plate base <0.1 67.8 3.0 2.1 19.1 0.6 0.1 4.4 11.9 <0.1 <0.1 1.1 49.2
Inside smoke tubes 34.2 87.9 42.3 31.0 4.4 2.1 0.6 2.0 4.3 0.4 <0.1 1.0 12.1
Powder in furnace tube 2.0 91.9 30.0 21.1 13.5 4.2 1.0 4.4 5.4 0.6 <0.1 1.0 16.8
Side walls 3.6 99.1 43.3 30.1 8.0 4.1 1.2 2.8 4.5 0.7 <0.1 0.6 5.1
Rear wall 3.8 99.2 40.0 27.1 12.0 3.9 1.1 3.2 4.5 0.6 <0.1 0.7 6.4
Top of rear arch 6.8 99.3 44.0 30.6 8.1 4.3 1.2 2.3 4.0 0.7 <0.1 0.6 4.6
I Inside of rear arch 1.6 99.4 41.7 29.0 7.8 4.1 1.1 3.2 4.7 0.7 <0.1 0.7 5.0
1 Roof 4.9 99.4 40.7 28.0 7.8 4.2 1.1 3.8 5.0 0.7 <0.1 0.7 6.5
 TABLE LIII

X-RAY DIFFRACTION ANALYSIS OF DEPOSITS FROM THE CHAINGRATE STOKER

Deposit Control Additive C Additive B Additive P

Tube plate deposit Hematite Hematite Hematite Calciati albite

Anorthite Langbeinite Sanedine Anhydrite
Anhydrite Quartz * Microcline Hematite
Hauyne Anhydrite Anhydrite Quartz
Anorthite Hauyne Thenardite
Aphthitalite

Tube plate (basel Potassium sodium sulphate Langbeinite YavapaHte Anorthite

Sodium sulphate Magnesium sulphate Anhydrite Hematite
Microcline Anorthite Anhydrite
Unknown Yavapaiite
Sodium sulphate
Quartz

Inside smoke tubes Albite Anorthite Anorthite (sodian) Anhydrite

Anhydrite Mullite Yavapaiite Anorthite/aibite
«o
Hematite Hematite Microcline Quartz N>
AphthitaHte Hauyne Anhydrite Boron phosphate
Quartz Aphthitalite
Anhydrite
Langbeinite

Powder in furnace tub« Potassium sodium sulphate Potassium sodium sulphate Potassium sodium sulphate Cetcian albita
Aphthitafite Hematite Hematite Aphthitalite
Albite Anorthite Anorthite Hematite
Anhydrite Anhydrite Anhydrite
Hematite Lenbeinite Calcium aluminium oxide
I
Side walls Sodian anorthite Anorthoclase Hauyne Albite I
Hematite Anorthite Anorthite Quartz 1
Hematite Hematite Mullite 1
Anhydrite Anhydrite Hematite
| Quartz Anhydrite

| Rear waN Albit« Quartz Hauyne Anorthoclase

1 Hematite Hematite Hematite Hematite

1 Albite
Anhydrite
Albite
S anadine
Quartz
Anhydrit«
| Anhydrite
TABLE LIII CONT'D

Deposit Control Additive C Additive B Additive P

Top of rear arch Sodian anorthita Anhydrite Anhydrite Hematite
Hematite Albite Anorthita Albita
Hematite ' Hematite Anhydrite
Quartz Quartz Muffite
Quartz
Insida rear arch Sodian anorthite Albite

I << z
Anorthite
Hematite Hematite Hematite

• • •
Anhydrite Hauyne
Quarti Muffite
Muffile

Furnace tuba roof Insufficient Hematite Hematite Sodian anorthite

Anorthite Anorthite Hematite 0
Quartz Quartz Sodium sulphate I
Potassium sodium sulphate Potassium sodium sulphate

Albite NaAISi,0,
Anhydrite CaS04
Anorthite CaAI2Si20,
Anorthoclase (Na,K) AISi,Oa
Aphthitalite K,Na(S04)2
Calcium aluminium oxide CaOAIjO,
Hauyne (Na.Ca)1(Si.AI)12024(S04)2
Hematite Fe2Oa
Langbeinite K 2 Mg 2 (S0 4 ),
Microcline KAISi,Oa
Mullite AI,Si 2 0„
Potassium sodium sulphate KNaS04
Quartz Si0 2
Sanadine KNaAISijO,
Thenardite Na 2 S0 4
Yavapaiite KFe(S04)2
 TABLE LIV

ELEMENTAL SOLUBILITIES OF COMBUSTION PRODUCTS FROM THE CHAINGRATE STOKER

TRIAL 1 TRIAL 2 TRIAL 3

(CONTROL) • ADDITIVE C ADDITIVE B

SAMPLE LOCATION % SOLUBILITY |

Na K Ca Mg Na K Ca Mg Na K Ca Mg I
Grate ash 2.7 1.2 3.6 <0.5 3.5 1.8 5.3 <0.5 2.9 1.3 5.8 <0.5 [
Cyclone fines 57 55 23 14 25 20 20 5.0 35 25 26 11
Reversal chamber fines 6.2 2.8 25 2.0 4.5 2.7 23 <0.5 4.6 2.0 27 <0.5
Smoke box fines 80 72 37 22 68 61 28 72 71 63 49 29

Deposits
Side walls 7.3 7 7.8 2.0 5.3 4.3 19 4.7 18 8 17 11
Roof ND ND ND ND 15 11 14 22 39 15 25 23
Rear wall 4.3 0.5 8.0 1.5 4.2 3.7 19 <0.5 15 6 16 7.0

Top of rear arch 18 4.5 21 6.5 4.1 2.7 17 5.6 18 8 25 7.7

Inside of rear arch 12 10 14 6.8 28 10 17 9.7 35 14 22 16
Tube plate (outer) 69 38 31 18 72 61 36 102 107 67 40 40

Tube plate (inner) ND ND ND ND 110 97 26 91 108 74 63 83

Furnace tube roof 45 49 12 5.3 53 41 17 15 68 58 17 7.6

U Powder in furnace tube 10 81 71 44 102 83 58 41 104 87 53 38

| Inside smoke tubes 83 107 84 58 100 84 43 113 96 78 50 65

ND - Not Determined
 TABLE LIV cont'd

TRIAL 5 TRIAL 6 TRIAL 7

(CONTROL) ADDITIVE P PREMIXED ADDITIVE P INJECTED
, % SOLUBILITY
SAMPLE LOCATION
Na K Ca Mg Na K Ca Mg Na K Ca Mg

Grate ash <0.4 <0.3 4.6 <0.4 <0.5 <0.3 5.1 <0.4 <0.1 1.0 2.8 <0.1
Cyclone fines 41 36 40 21 21 19 21 11 49 39 15 30

Reversal chamber fines 3.0 1.9 19 <0.4 4.3 4.6 19 2.5 4.8 2.0 9.3 <0.1
Smoke box fines 63 44 35 27 56 36 39 30 73 38 35 53

Deposits .

Side walls 29 7.7 22 23 21 9.3 18 19 8.6 1.6 20 15

Roof 39 12 25 30 12 5.5 19 16 19 5.4 29 31 «0

in
Rear wall 30 8.0 26 28 47 11 46 2.6 15 4.7 27 29

Top of rear arch 10 4.3 21 10 8.4 2.3 28 8.9 6.4 1.3 35 10

Inside of rear arch 44 17 22 26 39 17 28 24 12 3.2 37 13.0

Tube plate (outer) 76 39 48 39 20 18 23 19 62 32 60 53

Tube plate (inner) 93 62 82 79 ND ND ND ND 57 42 93 85

Furnace tube roof ND ND ND ND ND ND ND ND ND ND ND ND

Powder in furnace tube 75 97 48 37 70 44 43 30 57 33 45 34

| Inside smoke tubes 102 66 72 79 47 27 64 46 43 16 40 28

ND « Not Determined
 TABLE LV

RESULTS FROM THE CHAINGRATE STOKER

MINERALOGICA!. INDEX ASH DEPOSITED TOTAL RECOVERY OF

(% TOTAL THROUGHPUT) SOLUBLE SODIUM (%)
Trial 1 (Control) 0.7 1.1 4.1
Trial 2 (Additive C) 0.6 1.4 5.4
Trial 3 (Additive B) 0.7 1.3 4.3
Trial 5 (Control) 0.5 1.7 4.8
Trial 6 (Additive P, premixed) 0.8 1.2 2.9
Trial 7 (Additive P, injected) 1.0 1.4 1.9

Mineralogical index includes contribution from additive and is calculated from kaolinite/(Na2O + 0.67CaO + 0.54MgO) (molar concentrations)

Kaolinite content of coal determined by normative analysis

 97

TABLE LV)

ANALYSES OF COMBUSTION PRODUCTS FROM THE MINI-COKING STOKER

%on ash
Moisture Ash Mass
%ad %ad Na20 KaO CaO MgO 'Q

Control Test
Grate ash 0.2 45.0 2.4 0.9 5.8 1.0
Reversal chamber fines 0.4 49.0 3.2 0.9 5.2 1.2
Cyclone fines 2.0 41.8 3.9 1.0 4.3 1.0 •
Tube deposit 0.9 74.0 8.3 2.0 4.2 1.0 200

Additive P Test
Grate ash 0.2 40.6 1.8 1.3 3.5 1.0
Reversal chamber fines 0.3 66.3 2.8 1.4 3.7 0.9
Cyclone fines 1.2 51.0 3.0 1.6 2.9 0.7
Tube deposit 1.0 85.3 13.2 4.3 2.2 0.5 130

TABLE LVII

SODIUM SOLUBILITIES IN THE COMBUSTION PRODUCTS FROM THE MINI-COKING STOKER

Product Sodium Solubility (%)

Control Trial Additive E Trial
Grate ash 1.7 1.2
Reversal chamber fines 9.4 6.5
Cyclone fines 4.7 5.7
Tube deposit 26.4 33.2
 98

ŢABLg tvin

XRD RESULTS FOR THE DOPED SAMPLES

Sample Glassy? Major Phases Minor Phases Trace Phases

U1 Metal Y Mullite Magnetite (0%) Quartz

Hematite
Hercynite (100%)

U1 Mullite Y Mullite Magnetite (0%) Quartz

Hematite

U2 Metal Y Mullite Magnetite (0%) Quartz

Hematite Hercynite (100%)

U2 Mullite Y Mullite Magnetite (50%) Quartz

Hematite

U3 Metal Y Mullite Magnetite (0%) Quartz

(FeCr204) Hematite
Hercynite (100%)

U3 Mullite Y Mullite Magnetite (100%) Quartz

Hematite

U4 Metal Y Mullite Magnetite (0%) Quartz

(FeCr204) Hematite Hercynite (75%)

U3 Metal Y Mullite Magnetite (0%) Quartz

(FeCrA) Hematite Hercynite (100%)
 99

TAPIE LVIX
XRD RESULTS FOR THE DOPED SAMPLES

Sample Glassy? Major Phases Minor Phases Trace Phases |

T1 Metal Y Mullite Magnetite (0%) Quartz
(FeCra04) Hematite

T1 Mullite Y Mullite Hercynite (75%) Quartz

Hematite
T2 Metal Y Mullite Magnetite (25%) Quartz
(FeCr204) Hematite
T2 Mullite Y Mullite Magnetite (0%) Quartz
Hematite
T3 Metal Y Mullite Magnetite (0%) Quartz
Hematite

T3 Mullite Y Mullite Quartz

Hematite Magnetite
Hercynite (75%) (0%)
T4 Metal Y Mullite Quartz
(FeCr204) Hematite
Hercynite (100%)

T4 Mullite Y Mullite Quartz

Hematite
Hercynite (100%)
T5 Metal Y Mullite Magnetite (0%) Quartz
(FeCr204) Hematite Hercynite (100%)
T5 Mullite Y Mullite Magnetite (25%) Quartz
Hematite
 100

TAPLE LX
XRD ANALYSIS OF DEPOSITS FROM THE 150 kW PF COMBUSTOR
WITH AND WITHOUT ADDITIVE P

ADDITIVE COUPON MATERIAL MAJOR PHASES MINOR PHASES

NONE METAL QUARTZ MULLITE
ANHYDRITE
HEMATITE
1% P METAL MULLITE ANHYRITE
QUARTZ HEMATITE
ANORTHITE
NONE MULLITE QUARTZ MULLITE
HEMATITE
ANHYDRITE
1%P MULLITE QUARTZ MULLITE
HEMATITE
ANHYDRITE

ANORTHITE CaAljSljO,
HEMATITE
QUARTZ SiO,
MULLITE AI,S¡ 2 0„
ANHYDRITE CaSO«
 101

10 20 30 . 40 50 60 70 80
BASIC OXIDES, WEIGHT PERCENT

FIGURE 1 ASH FUSIBILITY AS A FUNCTION OF THE

BASIC CONSTITUENTS OF AN ASH
 COAL
EXHAUST HOPPER
CAS

VIBRATORY
FEEDER

EXHAUST
GAS
COA I. FEEDER TUBE
o
to
TWO SECTIONAL
SILICA GLASS REACTOR

SILICA GLASS
PROBES

FLUIDISING SAND
BED

SINTERED SILICA
GLASS DISC

FIGURE 2 SCHEMATIC DIAGRAM OF THE 70mm FBC

 103

COAL FEED TUBE

COMBUSTION
PRODUCTS

REACTOR
CONNECTING
RING

SINTERED QUARTZ
GLASS SUPPORT

FIGURE 3 DIAGRAM OF THE 70mm FBC REACTOR

 VENI

Chem.lum.
NO . N 0 2

IR.
CO,

FI »IMAC E
WAIL
MS.
THERMO-
COUPLE 0 2 . C 0 2 . H2,
CH4 . H2.

FRU

GLC / ECD.
N20
TEMPERATURE
CUM I ROI 1ER

PREI iE A l ER FURNACE

VZZZZZZZZZZZZZZZZZTFZZZZZZn COMBUSTION I FlINOISING

—• GAS
--* SIH'IHICS
'¿¿/¿¿¿¿zzzza * *

FIGURE 4 SCHEMATIC DIAGRAM OF THE FBC USED FOR THE EMISSIONS TESTS
 105

HOPPER LID

HE VT EXCHANGER*
INTEGRAL COAL
HOPPER

FAN

COAL FEEL)
DRIVE

SHEAR UN

FIGURE 5 SCHEMATIC DIAGRAM OF THE 9kW UNDERFEED STOKER

 106

OPTIONAL LIMESTONE FEED

SIGHT PORT
i
FLUE GAS

WATER FLOW

HEAT EXCHANGER TUBES

COAL FEED
UNDERFEED RETORT

ACCESS DOOR

AUTOMATIC ASH REMOVAL

ALTERNATIVE BATCH ASH REMOVAL

F I G U R E 6 S C H E M A T I C D I A G R A M O F
T H E 1 5 0 K W U N D E R F E E D S T O K E R
 FI UE GAS
OUII.EÏ
ITO CYCIONE ANO'
riiiiNAcu neniACiíMíY AUCH
STACK) STEAM

SMOK E UOX
REAR TUUE
KAIE
COAL HOPPER ►
SMOKE TUOES
GU|t LOTINE DOOR
o
»J

GRATE ASH
OUTPUT ' '

A-FURNACE ROOT OEPOSIT

B-TUBE PL ATE INNER OEPOSIT
C-TUBE PL ATE OUTER OEPOSIT
REVERSAL D-REAR WAL L OEPOSIT
FURNACE TllfiE CIIAMUER
E-DEPOSIT FROM BASE OF REAR
EN» OF FURNACE TUUE

FIGURE 7 SCHEMATIC DIAGRAM OF THE 2MW CHAINGRATE STOKER

 r. estove
AMO ÌTACK

f\ - C-R/)rc o
00
6 - n/gß tcñxt

FIGURE 8 SCHEMATIC DIAGRAM OF THE 1.12MW MINI-COKING STOKER

 BURNER

o
IO

SIDE ELEVATION

FIGURE 9 SCHEMATIC DIAGRAM OF THE 150kW ASH DEPOSITION RIG

(PILOT SCALE PF COMBUSTOR)
 MFOUTMN COUPON*

SSSSS3 l±3^//////i^\\\\\\*¿¿¿¿¿L<y¡& 213

V^I4
AM OUT

c o o i n g AW
S SS S S A I S S V ;
//////
;
æ%æp=z Z3m
j ; ; / s s~rz
H»
m ©

/ s / / 7~-n i / / / / ; j s s s ; s 7—> / / / / / y T Jdrß-Xt\j 1 \ \ \ \ T

w w w w v /// y/¿z=2
Amour
SSSSX3KS
THUMUOCOUHA CO*WM«A*X«T THKNMOCOUM.1
»OCXfTt WCIWTi

FIGURE 10 DIAGRAM OF THE ASH DEPOSITION PROBE

 SOLUBLE SODIUM /ppm
300

250
ADDITIVE (COAL)

200 • C (COAL I)
+ D (COAL I)
150
* F (COAL I)

100 ° C (COAL IV)

x P (COAL I)

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

ADDITIVE (%w/w)

FIGURE 11 SOLUBLE SODIUM IN EXTRACTS FROM THE ASHED

COAL/ADDITIVE MIXTURE (ADDITIVES C,D,F AND P)
 SOLUBLE POTASSIUM /ppm

ADDITIVE (COAL)

• C (COAL 1)
+ D (COAL 1)
* F (COAL 1)
D
C (COAL IV)
x
P (COAL 1)

2 2.5 3
ADDITIVE (%w/w)

FIGURE 12 SOLUBLE POTASSIUM IN EXTRACTS FROM THE

ASHED COAL/ADDITIVE MIXTURES (ADDITIVES C,D,F &P)
 SOLUBLE SODIUM /ppm
250

200
ADDITIVE (COAL)

150 ■ B (COAL I)
+ H (COAL I)
100 * L (COAL I)
■ M (COAL I)

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

ADDITIVE (%w/w)

FIGURE 13 SOLUBLE SODIUM IN EXTRACTS FROM THE

ASHED COAL/ADDITIVE MIXTURE (ADDITIVES B,H,L AND M)
 114

PEAK INTENSITY

1213

10% KAQUNI^E

1200 1000 600 600 ¿00 200

B
TEMP. C

FIGURE 14 TA-MS PROFILES OF S02 EVOLUTION FROM THE

LTA OF COAL I, WITH 10% w/w KAOLINITE OR MAGNESIA
 TENSILE STRENGTH kPa

ADDITIVE & COAL

■ P COAL III HTA
J
C COAL lib
x
C COAL V

0 10 20 30 40 50 60 70 80 90 100
ADDITIVE %w/w

FIGURE 15 TENSILE STRENGTHS OF ASH/ADDITIVE PELLETS

 116

SOLUBLE SODIUM (% OF INPUT)

COMBUSTION PRODUCT

ED SAND
S FLY ASH
■AQUEOUS

B C D F H I J K M M N O
ADDITIVE

FIGURE 16 RECOVERIES OF SOLUBLE SODIUM IN

THE COMBUSTION PRODUCTS FROM THE FBC WITH COAL I
 117

SOLUBLE SODIUM (% OF INPUT)

COMBUSTION PRODUCT

□SAND
Q FLY ASH
■AQUEOUS

B C D F H I J K L L M N O Q

ADDITIVE

FIGURE 17 RECOVERIES OF WATER SOLUBLE SODIUM IN

THE COMBUSTION PRODUCTS FROM THE FBC WITH COAL IV
 118

SOLUBLE SODIUM (% OF INPUT)

COMBUSTION PRODUCT

□BEDASH
S FLY ASH
■AQUEOUS

SAND 0 0 1 5 10
KAOLINITE (% ON COAL)

FIGURE 18 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE COMBUSTION PRODUCTS FROM THE FBC
WITH COAL I AND A LIMESTONE BED
 119

SOLUBLE SODIUM (% OF INPUT)

COMBUSTION PRODUCT

D BED ASH
0 FLY ASH
■AQUEOUS

SAND 0 0 1 5 10
KAOLINITE (% ON COAL)

FIGURE 19 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE COMBUSTION PRODUCTS FROM THE FBC
WITH COAL IV AND A LIMESTONE BED
 120

SOLUBLE SODIUM (% OF INPUT)

100

COMBUSTION PRODUCT

O BED ASH
0 FLY ASH
■AQUEOUS

SAND 0 0 1 5 10
KAOLINITE (% ON COAL)

FIGURE 20 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE COMBUSTION PRODUCTS FROM THE FBC
WITH COAL V AND A LIMESTONE BED
 121

SOLUBLE SODIUM (% OF INPUT)

60

50

40

COMBUSTION PRODUCT

D BED ASH
30 D FLY ASH
■AQUEOUS

20

10

SAND 0 0 1 5 5

KAOLINITE (% ON COAL)

FIGURE 21 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE COMBUSTION PRODUCTS FROM THE FBC
WITH COAL IV AND A DOLOMITE BED
 122

SOLUBLE SODIUM (% OF INPUT)

COMBUSTION PRODUCT

D BED ASH
Q FLY ASH
■AQUEOUS

SAND 0 0 5
KAOLINITE (% ON COAL)

FIGURE 22 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE COMBUSTION PRODUCTS FROM THE FBC
WITH COAL I AND A DOLOMITE BED
 123

SOLUBLE SODIUM (% OF INPUT)

25

20

15

□ REACTOR RESIDUE

10

SAND 0 0 1 5 10

KAOLINITE (% ON COAL)

FIGURE 23 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE REACTOR RESIDUES FROM THE FBC
WITH COAL I AND A LIMESTONE BED
 124

SOLUBLE SODIUM (% OF INPUT)

□ REACTOR RESIDUE

SAND 0 0 1 5 10

KAOLINITE (% ON COAL)

FIGURE 24 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE REACTOR RESIDUES FROM THE FBC
WITH COAL IV AND A LIMESTONE BED
 125

SOLUBLE SODIUM (% OF INPUT)

10

□ REACTOR RESIDUE

SAND 0 0 1 5 10

KAOLINITE (% ON COAL)

FIGURE 25 EFFECT OF ADDITIVE P ON SOLUBLE SODIUM

LEVELS IN THE REACTOR RESIDUES FROM THE FBC
WITH COAL V AND A LIMESTONE BED
 CN

>800 C
0H O
HCN—S^NCO - £ £ U NH »N ► NO
O»

<800 C NO NO NO

N20 *N2
H
>1000 C

FIGURE 26 REACTION PATHWAYS FOR THE OXIDATION

OF HCN TO NO, N20 AND N2
 OH
NH3 +-NH2 i-»
K)

►850 c N 2 H NO
>850 C

FIGURE 27 REACTION PATHWAYS FOR THE OXIDATION

OF NH3 TO NO, N20 AND N2
 128

SOLUBLE SODIUM (% RECOVERED)

120

100

COMBUSTION PRODUCTS
BOTTOM ASH E HEAT EXCHANGER ED FLY ASH

FIGURE 28 SOLUBLE SODIUM LEVELS IN

THE COMBUSTION PRODUCTS FROM THE
UNDERFEED STOKER - 1 DAY TESTS
 129

SOLUBLE SODIUM (% RECOVERED)

COMBUSTION PRODUCT
D STACK ASH
D HEAT EXCHANGER DEPOSIT
■BEDASH

FIGURE 29 SOLUBLE SODIUM LEVELS IN

THE COMBUSTION PRODUCTS FROM THE 9 kW
UNDERFEED STOKER - 5 DAY TESTS
 130

SODIUM SOLUBILITY (%)

ADDITIVE
■ NONE
SP
□B

FIGURE 30 SODIUM SOLUBILITIES IN THE HEAT EXCHANGER

DEPOSITS FROM THE 150kW UNDERFEED STOKER
 131

SODIUM SOLUBILITY
25

20

15

COMBUSTION PRODUCT
D HEAT EXCHANGER DEPOSIT

D BOTTOM ASH

10

0 .5 1 2
ADDITIVE P (%w/w)

FIGURE 31 SODIUM SOLUBILITIES IN THE

COMBUSTION PRODUCTS FROM THE 150kW UNDERFEED
STOKER WITH ADDITIVE P AND COAL VI
 133

PLATE 1 SECTION THROUGH UNDOPED SLAG ON A MULLITE COUPON

SHOWING RANDOM NUCLEATION OF Fe RICH SPINEL PHASES
BAR = 100 pm

PLATE 2 SECTION THROUGH A COPPER OXYCHLORIDE DOPED SLAG ON

A MULLITE COUPON SHOWING THE PRESENCE OF AN ALMOST
CONTINUOUS LAYER OF BRIGHT REFLECTING IRON RICH SPINELS ON
THE EXPOSED SURFACE OF THE SLAG
BAR = lOOjJm
 134

r%?"À

PLATE 3 SEM MICROGRAPH OF UNDOPED DEPOSIT FROM THE MULLITE

COUPON SHOWING THE PRESENCE OF BOTH MOLTEN AND FLOCCULANT
MATERIAL
BAR = 10 pit

PLATE 4 SEM MICROGRAPH OF KAOLINITE DOPED DEPOSIT ON THE

MULLITE COUPON SHOWING THE PRESENCE OF LARGE QUANTITIES OF
MOLTEN BONDING MATERIAL AND LITTLE FLOCCULANT MATERIAL
BAR = 10/Ultl
ir

The Communities research and development

information service
CORDIS
A vital part of your programme's
dissemination strategy

CORDIS is the information service set up under the VALUE programme to give quick and easy access
to information on European Community research programmes. It is available free-of-charge online via
the European Commission host organization (ECHO), and now also on a newly released CD-ROM.

CORDIS offers the European R&D community:

— a comprehensive up-to-date view of EC R&TD activities, through a set of databases and related
services,
— quick and easy access to information on EC research programmes and results,
— a continuously evolving Commission service tailored to the needs of the research community and
industry,
— full user support, including documentation, training and the CORDIS help desk.

The CORDIS Databases are:

R&TD-programmes - R&TD-projects - R&TD-partners - R&TD-results
R&TD-publications - R&TD-comdocuments - R&TD-acronyms - R&TD-news

Make sure your programme gains the maximum benefit from CORDIS
— Inform the CORDIS unit of your programme initiatives,
— contribute information regularly to CORDIS databases such as R&TD-news, R&TD-publications and
R&TD-programmes,
— use CORDIS databases, such as R&TD-partners, in the implementation of your programme,
— consult CORDIS for up-to-date information on other programmes relevant to your activities,
— inform your programme participants about CORDIS and the importance of their contribution to the
service as well as the benefits which they will derive from it,
— contribute to the evolution of CORDIS by sending your comments on the service to the CORDIS
Unit.

For more information about contributing to CORDIS,

contact the DG XIII CORDIS Unit
Brussels Luxembourg
Ms I. Vounakis M. B. Niessen
Tel. +(32) 2 299 0464 Tel. +(352) 4301 33638
Fax +(32) 2 299 0467 Fax +(352) 4301 34989

To register for online access to CORDIS, contact:

ECHO Customer Service

BP 2373
L-1023 Luxembourg
Tel.+(352)34981240
Fax+(352) 3498 1248

If you are already an ECHO user, please mention your customer number.
>6" 426709 7Õ9 "410066 "426709 4ÏÖÖ66 426709
11 410061