Pr,,,g z~-,w~,~ (‘o,,,h,,ti. 3, Vol. 72. pp ?Y IX.

1996
Pergamon Copyrightc 1996 Elsebw Sc~rncc Ltd
Prmtrd ,n Great Brltaln. All rl@hta rewvrd
0360 ,lXS 96 S39 011

0360-1285(95)00012-7

FIRESIDE SLAGGING, FOULING, AND HIGH-TEMPERATURE

CORROSION OF HEAT-TRANSFER SURFACE DUE TO
IMPURITIES IN STEAM-RAISING FUELS

Richard W. Bryers

Abstract-The process of steam raising as a source of heat or means of generating electricity using
combustible fuels began with the turn of the century. From the very beginning. impurities in the fuels were
responsible for added maintenance, a reduction in rate of heat transfer and corrosion due to fireside
deposits of sintered or molten ash. The nature and severity of deposit formation. i.e. slagging and fouling,
changed as the fuels and their impurities changed, the steam raising process evolved and the steam
generators increased in size and efficiency. With the introduction of computer science. the empirical art of
ash deposition from impurities in combustion gases is rapidly being transformed into the science of mineral
transformation and ash deposition. This manuscript presents in chronological order an overview of the art
of ash deposition while firing coal, the mechanistic approach to the problem, the recent introduction of
sophisticated analytical procedures, and modeling of mineral transformations. and ash deposition
underway. Adaptation of fuels such as ash oil, petroleum coke, municipal waste, wood and biomass to the
steam raising process are presented individually in the order in which they were introduced. Empirical
indices presently used to characterize the slagging or fouling potentials of impurities in fuels are present.
Fundamental data are provided where necessary to illustrate mechanisms for ash deposition. An extensive
list of key references is offered for those wishing to investigate details of any particular aspect of fireside
slagging, fouling or corrosion. Copyright ‘(? 1996 Elsevier Science Ltd.

CONTENTS

I. Introduction 30
2. Fireside Problems with Coal 30
2.1. Introduction 30
3. Background for Development of an Empirical Approach 32
3. I. Ash Fusibility 32
3.2. Viscosity 37
3.3. High-Temperature Corrosion Due to Sulfur 42
3.4. High-Temperature Corrosion Due to Chlorine 45
3.5. Fouling of Convective Heat Recovery Surface 49
3.6. Sintering Tests 55
3.7. Pilot Plant 58
3.8. Summary of Empirical Approach 62
4. Mechanistic Approach 62
4.1. Mineral Matter in Coal 63
4.2. Mineral Analysis 66
4.3. Mineral Matter Analysis 6X
4.4. Mineral Distribution 6X
4.5. Thermal Behavior of Minerals 71
4.5. I. Quartz 73
4.5.2. Kaolinite 73
4.5.3. Clays and Shale 73
4.5.4. Pyrite 74
4.5.5. Siderite/ankerite 75
4.5.6. Calcite 76
4.6. Thermal Behavior of Mineral Matter 76
4.7. Fate of Mineral Matter During Combustion 77
4.8. Slagging 80
4.9. Fouling 83
4.9. I. Alkali-bonded deposits 84
4.9.2. Calcium-sulfate-bonded deposits 85
4. IO. Modeling the Mechanistic Approach 87
5. Fireside Problems with Heavy Oil 90
5.1. Introduction and Background 90
5.2. Occurrence of Minerals in Oil 90
5.3. Combustion of Heavy Oil 90
5.4. Deposition on Heat-Transfer Surfaces 92
5.5. Vanadium Corrosion 93

29
30 R. W. Bryers

5.6. Additives 94
5.7. Low Excess Air 96
6. Fireside Problems with Petroleum Coke 97
6.1. Fireside Behavior of Mineral Matter in Petroleum Cokes 99
7. Fireside Behavior of Inorganic Impurities in Municipal Solid Waste 101
7.1. Technical Background 101
8. Combustion of Wood 105
9. Combustion of Biomass 107
9.1. Introduction 107
9.2. Fuel Characterization 107
9.3. Mineral Matter 109
9.4. Fireside Behavior of Minerals 110
9.5. Steam Generator Design and Field Experience 112
10. Summary 113
References 114

1. INTRODUCTION source of troublesome fireside problems occurring in

The impurities found in steam-raising fuels have
had a major impact on steam generator size and its
availability ever since coal was introduced as a means
of generating electricity at the turn of the century.
Although there have been major changes in combus-
tion system design (i.e., fixed bed, cyclone, suspension
firing, and fluid bed combustors with the correspond-
ing changes in combustion kinetics, flame tempera-
tures, and residence times), the fireside behavior of
impurities in coal has managed to be a continuous
source of slagging, fouling, or corrosion in one form
or another. Despite these major changes in combus-
tion system design, the means for characterizing the
slagging and fouling potential of ash has changed very
little. Changes in design to accommodate increase in
capacity, new fuel sources, and new combustion
systems have evolved by empirical extrapolation of
past experience, regardless of changes in the char-
acteristics of the included minerals. Alternative fuels
including oil, petroleum coke, refuse, wood, and
biomass containing impurities of slightly different
composition and proportion have also been the
slightly different ways depending upon variations in
mineral composition.
This paper presents an overview of slagging,
fouling and fireside corrosion associated with all the
steam raising fuels. Each fuel is treated separately and
presented in the order of its present economic
importance. The presentation of the fireside behavior
of impurities in coal has been subdivided into
empirical and mechanistic approaches. The former
is developed as it historically evolved to gain
perspective on the limitations of the relationships
presently needed to assess slagging, fouling and
corrosion and the parameters they employ as applied
to present combustion systems. This approach also
serves to point out two approaches presently
employed to diagnose and predict slagging and
fouling potential. The empirical approach is used
primarily by operating and design engineers, whereas
a more mechanistic approach has been taken by
the fuel technologist. Some repetition will appear in
discussing specific types of slagging and fouling in
order to maintain continuity in developing the
approach.

Table 1. Major elements found in fuel impurities contributing to slagging, fouling, and corrosion

Element Bituminous Subbituminous Lignite Oil and Pet Refuse

Si S S
Al S S
--------------------------- Contribute
Fe S S to Fouling

Corrosive elements

Zn _ C, F
Lz Ni _ _ F C, F
V _ _ C, F C, F
2
VI
Cl C C, F
S C S, F F C, F C, F
C = corrosion-by Cl or S of metal surfaces in excess of 600°F under reducing conditions and 830°F under oxidizing;
conditions, by V above 950°F.
S = slagging-by partial or fully formed melts due to fluxing of quartz by heavy metals at flue gas temperature >1065”F.
F = fouling-fused or sintered ash due to condensation of volatile species, solid-gas reactions with SOs or Cl, solid-state
reaction at flue gas temperatures from 648-1037°C between sulfates and oxides, and molten sulfates.
 Steam-raising fuels 31

Fused Deposits-Sodium. Calcium

Silicates fMrllilites~ Formed
From Na,SO.. CaSO,, and Quartz
Alkali Trisulfate or clays, M.T. -1TBToC
and Cl Corrosion
by Molten Salts

QQQ Q’

CaSO,-Bonded Deposits
High Calcium/Low Sodium
Fluxing of Alumino-
silicates by FeO. Fe203

Deposition of Sticky FeS

Calcium Silicates
Initiated by CaSO, or
Na,SO,

Fluxing of Silicates
by Lime

Cl-Enhanced CO
Corrosion Under
Reducing Conditions

Fig. 1. Typical slagging, fouling, and corrosion found at various locations in the steam generators

The paper is an overview. Although it is lengthy, it ash formed in liberally sized, low-pressure steam
does not include details of the technology, which is generator furnaces, or in furnaces fired with coals
reported in over 4000 individual publications. Key containing high moisture and alkaline earth ash.
references are cited for those wishing to explore the Fouling is defined as deposition in the heat-recovery
technology in greater depth. These include thirteen section of the steam generator subject to convective
major international conferences, two literature sur- heat exchange by fly ash quenched to a temperature
veys, and an index of abstracts which include a large below its predicted melting point, condensation by
portion of the fundamental information. volatiles, or sulfidation by SOs, as shown in Fig. 1.
These deposits may vary from light sintering to
complete fusion. The latter is due to the formation of
2. FIRESIDE PROBLEMS WITH COAL
lower melting sulfates.
2.1. Introduction Fouling and slagging are very complex phenomena
depending upon the transformation of the inorganic
Although the impurities found in steam-raising components found in the impurities in fuels upon
fuels include most of the known elements, only 14 heating and cooling; the juxtaposition of individual
occur in significant concentrations to contribute to inorganic or carbonaceous species during communi-
fireside problems. Table 1 shows how these elements tion, combustion, and quenching while recovering
are distributed in various steam-raising fuels and heat; the chemical reactions between gas, liquid, and
summarizes their contribution to slagging, fouling, solid phases in motion and at rest; the kinetics of
and corrosion. Slagging is defined as deposition of fly transformation of minerals and fly ash; the existence
ash on heat-transfer surface and refractory in the of non-equilibrium conditions frequently associated
furnace volume primarily subjected to radiant heat with supercooling; and, the attachment of impurities
transfer, illustrated in Fig. 1. Although the name to surfaces and the detachment or reentrainment of
‘slag’ suggests a fused or semi-fused ash, the term deposited liquids and solids.’
‘slagging’ may also apply to sintered deposits and dry The complexity of the problem is compounded by
32 R. W. Bryers
the fact that fireside problems cannot be simply
represented by a single rate of deposition on a target
by ash characterized by a single elemental analysis.
The inorganic components (i.e., minerals and
organically-associated carbons) in coal and the fly
ash they generate are heterogeneous with regard to
size and composition. Therefore, individual species
behave differently during combustion and their
subsequent flight through the steam generator. The
degree of fouling and slagging varies throughout the
steam generator depending on the impact of the local
gas temperatures, tube temperatures, temperature
differentials, gas velocities, tube orientation, and
local heat flux on each particle. Furthermore, fireside
problems manifest themselves in a variety of ways,
some of which include:
0 Plugging of slag taps.
?? Formation of agglomerates and clinkers.
?? Loss in furnace heat absorption due to excessive
accumulation-be it molten or sintered deposit, or
due to a change in the thermal properties of the
slag.
. Damage due to excessive slag fall from a specific
location or type of heat exchange surface and its
orientation.
?? Undersized furnace hopper due to a weak slag-to-
tube bond causing excessive sloughing of sintered
ash.
?? Freezing of slag on hopper slopes.
?? Slagging of the heat recovery zone due to
unpredictable low-melting phases in the ash.
?? Slag accumulations about the periphery of burners.
. Fouling of convective heat recovery surface via
condensation of volatile fumes or the sulfidation of
submicron vulnerable species at the tube surface.
?? Tube wastage due to flame impingement.
?? Erosion/corrosion by Ily ash or soot blowers.
?? Tube wastage due to excessive concentrations of
corroding elements.
?? Surface oxidation and exfoliation of inside tube
surfaces due to high gas temperatures created by
excessive fouling.
?? Slagging due to imbalanced air distribution.
. Slagging and/or fouling due to size distribution of
the fuel.
?? Slagging due to poor burner adjustments and coal
size. ’
The wide variation in type, form, and location in
which a deposit may form suggest that slagging and
fouling are very much dependent upon design and
operating parameters. Boilers of identical design
apparently firing identical fuels have often been
reported to be encountering quite different slagging
and fouling problems. In an attempt to maximize
profits by minimizing capital and maintenance costs,
through optimized design, it has made steam
generators sensitive to fluctuations in operating
conditions and fuel ash chemistry. Consequently,
slagging, fouling and corrosion are also dependent
upon design and operating parameters which include:
Design
?? Furnace exit temperature.
?? Furnace absorption.
?? Furnace configuration.
?? Burner arrangement.
?? Burner size.
?? Tube size spacing, orientation, and temperature.
?? Air distribution.
?? Steam conditions.
Operation
0 Coal size.
?? Air distribution between burners.
?? Burner operation.
?? Excess air O2 level.
?? Flame impingement.
?? Soot blower operation.
?? Boiler load.
Historically, steam generators were designed to
operate on a specific fuel. Availability of vast
quantities of coal provided the luxury of selecting
fuels with low slagging, fouling, or corrosion
potential. Troublesome fuels were simply left in
reserve, thereby minimizing the impact of design
and operation on fireside problems. The problems
most frequently encountered were due to opening of
new reserves of untried coals or the use of a new rank
of coal. Empirical indices developed for the new fuels
became the standard for the acceptability of new coals.
Corrective measures such as soot blowing minimized
the attention that must be given to operation and
design.
Unfortunately, reserves are dwindling and changes
in economy dictate that the coals previously con-
sidered difficult to burn be used.
Increased fuel trading activities in the world market
require increased fuel flexibility. Tighter restrictions
on ash disposal and emissions to meet environmental
concerns have resulted in coal blending or switching
to coals with entirely different mineral composition
and slagging or fouling propensity. The option of
selecting an alternate fuel as a means for solving a
fireside problem is rapidly disappearing. All fuels will
ultimately be used interchangeably and the combus-
tion engineer must adapt his design and operation
to deal with variable fuel and ash properties. The
philosophy with which one characterizes fuels must
change from one of predicting its slagging and
fouling potential based on the fluid temperature of a
laboratory-generated ash alone, to one which includes
a selection of a matrix of engineering parameters
which will allow proper location and orientation of
the heat-transfer surface in the combustion chamber
and heat recovery zone for a broad base of fuel types.
Consequently, a more mechanistic approach must be
sought.
Presently, the cost of fireside problems may be as
low as several hundred thousand dollars per installa-
tion for yearly cleaning or as high as millions of
dollars due to a mismatch of design or operation
with the impurities in fuel. It has been estimated
 Steam-raising fuels 33

Table 2. Summary of fusibility correlations’

Nicholls, Selvig, Rickets, 1932 (SiOZ + A1203)/(Fez0s + CaO + MgO + NazO + KzO)

SiOZ + AlzOs
Shaefer, 1933 Rls=$$.
z Fe0 + 0.6(CaO + MgO + NazO + KzO)

Estep, Seltz, Osborn, 1937 CaO = 100% - [SiOz + A1203 + Fe*Os]

Determine S.T.nEM from ternary [SiOz/Al?03/FezO~](~,~,CaO=Conai,

Gauger, 1951 S = SiOz + TiOz + PZOs

A = AlzO,
T = CaO + 0.7MgO + 2.25Naz0 + 1.5K,O
Determine % S, A, T
Obtain S.T. from S, A, T ternary

[3.3Si02 + l.96A1203]
Majum dar, 1955
&’ = [2.5Fez0, + 3.57CaO + 5.OMgO + 3.22(KzO + NazO)]

Garner. 1964 Deposit weight = x

where:
xi = 0.03[Ti02] + 0.09[Fez0s] + O.O6l[CaO] + 0.264[MgO] + 0.423[Naz0] - 10.6
xz = 0.044[Ti02]0 094. [FezOslo 499 . [CaOj” 221 . [MgO]O 226 . [Na20]0,7Z*
and boiler availability =f(x, ,x2)

S,T, =f [Fe201 + CaO + MgO + Na,O + K,O]

Duzy, 1965
[Si02 + AlZ03]

Winegartner, Rhodes, 1974 F.T., ST., I.D. = f (5 I independent variables including various groups of AlzOj. SiOz.
Fe203, CaO, MgO, NazO, K20)

L,R. = [l.74(Naz0 + K20) + 0.73Si02 + 0.39(FezOs)]

Sondreal, 1975
[I .40(CaO) + MgO]
Kovitskii, Karagodina. Marynova. Kr, = (Si02 + A1203)/(FeZ03 + CaO + MgO)
1975 S.T. = 1094 + 42.5Kr,
F.T. = 1139 + 48.6Kr,

Bryers, Taylor, 1975 Western

S.T.,,d = 2863 - 37.X+0.151X2, Si02/A20s > I
S.T.,,d = 2992 - 27.1X+0.27X2, Si02/A120s z 1
Eastern
S.T.,,d = 31 I4 - 38.68 + 0.37X’
where: X = [Fe20, + CaO + MgO + NazO + K20]

that fireside problems collectively cost the electrical evaporating waterwall surface. The sensible heat in
generating industry $4 billion per year.* the non-radiant flue gases was recovered first by
convective heat exchange surface used to generate
steam and later on, convective surface-to-superheat
3. BACKGROUND FOR DEVELOPMENT OF steam. The furnace exit temperature was selected to
AN EMPIRICAL APPROACH
optimize the heat exchanged by radiation and convec-
3.1. Ash Fusibility tion. An adjustment was made to ensure that entrained
ash leaving the furnace was completely dry before
The fireside behavior of minerals in coal was first entering the tightly-spaced convective heat exchange
investigated at the turn of the century. Initially, banks. Furnace configuration was sized to accom-
fireside problems began as soot from coal-fired, modate grates at first and burners later, minimizing
refractory-lined, stoker-fired furnaces.3 Shortly after ash carryover and providing an essential heat-transfer
burning of high-sulfur coals rich in pyrites (FeS2) on surface. The configurations were modified to mini-
grates, it was determined that pyrite was responsible mize deposition by empirically extrapolating the best
for the formation of clinkers-the first problem to be available data from early operating boilers.
associated with a specific mineral species4 It was Although knowledge of the fireside behavior of
recognized that iron occurring in high-sulfur coals minerals in coal evolved after 1900, the fusibility of
acted as a fluxing agent, lowering the melting the constituents comprising the ash had been studied
temperature of quartz and clays found in coal. quite extensively prior to 1900. Prost introduced
These early problems were associated with slagging the concept of fusibility in 1885 and recognized a
as the boilers were small and cycle efficiency was low. relationship between the melting temperature of slag
As steam temperatures and pressures increased, the and the proportional distribution between basic and
furnace cavity was assigned to recovering heat with acidic constituents.4 A. C. Fieldner indicated at least
34 R. W. Bryers

1. Liwtes and Wvommg Subbituminous, SiO,lAI,O,>> I

2. WVOmlng Subbituminous. SiO,/AI,O,>> 1 1600
2900 3. Wvomine Subbitumtnous. SiO,lAI,O, = 1
4. Eastern Bituminous
I

I I I I I I I
2000 I
0 10 20 30 40 50 60 70

Percent Basic [% Z lFe,O, + CaO + MgO + Na,O + K,Ol

Fig. 2. Influence of percentage of basic constituents in ash on ash softening temperatures under reducing
conditions for different ranks of North American coal.

182 other investigators had examined the fusibility
of ash based on eight fundamental oxides most
frequently found in coal ash (i.e., SiO*, A1203,
TiOz, FezOs, CaO, MgO, NazO, and K20) prior to
1981.’ Since that time at least 17 additional correla-
tions have been developed between ash chemistry
and the ASTM ash fusion temperatures in order to
improve the reliability of predicting the melting
temperature of coal ash.3 The 11 most frequently
used are reported in Table 2.3%6 Figure 2 illustrates the
ash fusibility expressed in terms of the ash chemistry.
The procedure for the ASTM ash fusion temperatures
used in the fusibility correlations was accepted as
early as 1924.6 The procedure simply requires
generating ash from a composite sample of coal in
the laboratory, forming cones and monitoring various
stages of deformation of these cones as they are
heated to a temperature at which they completely
melt. Since then, eight different international pro-
cedures have been adopted. The diversity among the
terms and practices is substantial, making it impos-
sible to interchange results. Details of the terms,
procedures, and accuracies have been described in a
recent ASME publication.’ Table 3 compares the
criteria for determining the various stages of melting
used in the various international procedures.
In addition to clinkers, operators of stoker-fired
boilers also reported loss of metal from the lower-side
waterwalls due to CO and FeS attack. Under reducing
conditions in the presence of carbon within the
deposit, the pyrite (Fe&) is reduced to pyrrhotite
and free sulfur. The latter reacts with tube metal iron
to reduce additional FeS. Experiments with FeS have
shown that pyrrhotite by itself contributes little to the
attack. At the time no mention was made of the role
of Cl as a means of enhancing CO attack. The impact
of Cl on CO attack was not discovered until much
later. The detection of Cl in tube wasted areas is
difficult and thus sometimes overlooked. The plug-
ging of convective passes by deposits initiated by a
white layer of alkali sulfates was common, suggesting
Cl may have been present. The source of the sodium
in English coals responsible for fouling was believed
to be sodium chloride.’ This initial attack may have
been aggravated by Cl.
Pulverized coal was introduced in 1920. With the
emergence of full furnace-wall cooling and increase in
volumetric heat release, fireside corrosion due to
flame impingement of partially combusted pyrites on
heat-transfer surface worsened. Two types of corro-
sion occurred: wall wastage due primarily to FeS and/
or CO where the scale was enriched with carbon and
FeS. In those instances where a highly water-soluble,
bluish-white, glassy enamel-type deposit formed, the
 Table 3. Characteristic temperatures for all ash fusibility standards’

Temperature IS0 BS ASMT DIN USSR Australia PRC South Africa

Specimen molds Pyramid, cube, Pyramid, cube, Pyramid Cube, cylinder Pyramid, cylinder Pyramid Pyramid
cylinder cylinder
Initial First sign of First sign of First sign of First sign of First sign of First sign of First sign of
deformation rounding of tip or rounding of top or founding of apex founding of tip or rounding of top or rounding curving rounding of tip
temperature i
edges edges edges (L) edges oftip(T )
(IDT/DT)
Softening _ Spherical mass First sign of _ Cone bends so
temperature (ST) where height = rounding of edges that (a) tip
base touches support;
(b) height 5 base
CT21

Spherical Height = base

temperature (ST)

Hemispherical Height = I/2 Height = l/2 Height = l/2 Height = l/2 Height = l/2 Height = l/2 Height: l/2
temperature (HT) base base base base base or pyramid base base
tip bends to touch
base (tb)
Flow/fluid Height = l/3 Height = l/3 Height = cl.6 Height = l/3 Height = l/3 Height = l/3 Height = < 1.5 Height = l/3
temperature (FT) base at HT base at HT mm (1/16in.) original height height at HT; or height at HT mm (T3) height at HT
(microscope onlv)

NOfe: Preparation, support title, ash binder, particle size, heating rate. and reducing gas vary from one procedure to another.
36 R. W. Bryers

930

920

910

900
890

880

670

060

650
8”
g 040

E 630
$ *
E 82Q
F 810

800 425
790

760

770

760
400
750
740

730
20 100 1000 IO,000
SO, Concentration, ppm

Fig. 3. Melting points in systems Na2S04-SO3 and KzS04-S03.8~9

Table 4. A comparison of slag from a coal with homogeneous-dispersed minerals with a coal of heterogeneously-dispersed
minerals

Puentes heterogeneously-dispersed minerals Kriel homogeneously-dispersed minerals

Coal 1.60 Gr. Furnace Coal 1.80 Sink Furnace

ash fraction slag ash fraction slag

SiOz 47.9 5.5 6.9 48.4 48.2 46.4

A1Z03 30.6 3.6 8.9 25.2 25.3 27.8
TiOz 1.0 0.3 0.2 1.5 1.6 1.7
Fez03 8.3 90.2 79.2 1.8 6.9 4.1
CaO 3.4 0.6 1.3 14.2 5.9 12.2
MgO 1.5 0.4 1.0 2.1 1.4 2.4
Na20 0.2 _ 1.8 3.2 2.3 1.9
K2O 1.9 0.2 0.2 0.5 0.4 0.5
3.5 _ 4.6 4.8 <o. 1
so3
p205 <o. 1 0.7 _ 0.8
Ash fusion temp.
Reducing
I.D. 1237 1248 1315 1282 1243
ST. 1282 1260 1404 1310 1293
S.T. 1437 1271 1537 1337 1304
F.T. 1537 1293 1537 1360 1360
Oxidizing
I.D. 1104 1326 1471 1293 1271
S.T. 1537 1526 1537 1343 1304
S.T. 1537 1537 1537 1371 1315
F.T. 1537 1537 1537 1393 1393

corrosion was due to alkali pyrosulfates of sodium Coast et al. showed that KzSz07 and Na&O, was
and potassium. The pyrosulfates form under reducing molten above 404°C and 393”C, respectively, at levels
conditions. Corrosion depends on a molten phase. of SO3 exceeding 200 and 2000ppm, respectively.
 Steam-raising fuels 37

Their stability depends upon the SO3 level and Temperature, OC

generally they decompose at temperatures above 1100 1200 1300 1400 1500
SlO”C, as shown in Fig. 3.8.9 40,000 1 I I I
I I I I
The importance of fuel-bearing iron on furnace
wall wastage, slag, and clinkers prompted Moody and 50, 56.9 -
Langan,‘” as early as 1933, to examine the occurrence AI,O, 18.8
of iron in coal and they discovered that fusion Equ’valent Fe,O, 12.9 _
10,000
Co0 8 9 _
characteristics of ash varied from one fraction to the ENlOO
6WO
MgO 12 _
other according to the distribution of mineral species Alk I 3
and their juxtaposition with each other and the
carbonaceous portion of coal. Gould and Brunjes”
established the ‘free fusible material in coal (extra-
neous pyrites) as an ash index of clinker and slag
formation’ in 1944. In 1963, Littlejohn and Watt”
examined the distribution of mineral matter in
pulverized coal. It was not until 1968 that Watt, - ??Vlscoslty measured
Reid, Borio, and Bryers13-” seriously focused after cool’ng cycle
their attention on the individual minerals and their + Vlscoslty meosured
after heatmg Cycle
juxtaposition in the ‘coal as a cause for fireside \’
slagging and fouling. Borio and Narcisco13 identified I I I I I I
I00
a correlation of slagging with respect to the highest 2ooO 2’00 2200 2300 2400 2500 2600 2700

gravity fraction, which is usually iron enriched. Bryers

and TaylorIs developed a regression analysis for the Fig. 4. ViscosityPtemperature plot of a typical glassy coal!
ash fusion temperatures vs ash chemistry on size and ash slag.*,19
gravity fractionated coal, indicating the variation in
homogeneity of the distribution of mineral species in
coal had an impact on ash melting temperatures
and hence, slagging potential. Watt” provided the
industry with the most comprehensive document on
the physicochemical behavior of individual minerals
in a combustion environment to-date. As a result of
the works cited above, it became quite apparent that
substantial partitioning of mineral species could be
taking place during combustion, resulting in depos-
ited ash with decidedly different compositions from
the coal. Table 4 illustrates the difference in slag
composition formed by minerals homogeneously and
heterogeneously dispersed throughout the coal.
Despite the evidence indicating the juxtaposition of
pyrites in coal with regard to carbon and other
mineral species has a strong influence on the slagging
potential of coal, only a few have attempted to include
mineral fractionation in their slagging indices.

3.2. Viscosity
I I I
Interest in cyclone and wet-bottom furnaces in 20 30 40 x) 60 70 80 90
the late 1930s prompted numerous investigators to S’O* , Penent
abandon ASTM ash fusion temperatures as a
Fig. 5. Viscosity of coal/ash slags at 1426°C in air (plotted
measure of the high-temperature fusibility of ash
against SiOZ content on the basis of omitting Al203 and
and focused their attention on viscosity. Nichols, making SiOZ + equivalent FezOX + CaO + MgO = 1OO).8
Reid, Cohen, Watt, and others18-2’ developed
viscometers and performed viscosity measurements Newtonian range is the same for all coal slags. By
on coal ash and slags at temperatures as high as making an appropriate parametric correction for
1621°C in oxidizing and neutral atmospheres. They composition, the viscosity curves for all slags could be
found that completely liquid slags behaved as represented by a single curve.” Figure 4 illustrates a
Newtonian fluids and that the rate of change in typical viscosity--temperature relationship for coal
viscosity with a change in temperature at a given ash.
viscosity was essentially constant. Consequently, the As early as 1925, Fulcher proposed the following
functional relation of viscosity vs temperature in the relationship for viscosity in terms of temperature for
 R. W. Bryers

Temperature, OC
1300 1400

1000

8
._
Lf

f
8
s
._
>

100

-‘.d I ,\,
1c I I
2200 2400 2600 2800
Temperature, OF

Fig. 6. Viscosity of Illinois no. 6 coal for various gravity fractions using the Watt-Fereday and Urbain
correlation.

glasses: the compositional parameter, E, affecting viscosity

77 = A,eEjRT
and
loglo~=A*+~
0
where A is a constant, and B is the temperature
coefficient (‘Energy of Activation’), and To is a
temperature correction required to fit the data in a
straight line plot of log of the viscosity against the
inverse of the temperature difference.8,22’23
Corey and Reid reported the following relationship
between viscosity and temperature developed from
North American bituminous coal ash data:
was not influenced by the aluminum level but
was governed by the major basic constituents (i.e.,
Fe203 + CaO + MgO) when treated as a sum.‘.*’
Hence, they developed the silica ratio defined as the
percent silica in an ash normalized to include only
Si02, Fe203, CaO, and Mg0.8S24The impact of silica
ratio on viscosity is illustrated in Fig. 5 at a constant
temperature.’
Investigations performed at BCURA,8.‘4 applying
the same silica ratio to a wider range of coal ash
compositions, produced the following relationship:

n-o.1614= (0,000452)(t) - B (3) Watt and Fereday, also using BCURA data,
derived an expression for viscosity in terms of
They found that within the Newtonian fluid range, temperature from the Arrhenius equation, identical
 Steam-raising fuels 39

terms of temperature, knowing the five major

‘ooon-- constituents of coal ash, all claiming to be accurate

over a given range of slag composition. None of these
expressions include modest amounts of the alkalis
believed to be influencing the surface fusibility of fly
ash and certainly furnace wall slag formed by high-
sodium-bearing lignites. A plot of viscosity using the
Urbain and Watt-Fereday equations on gravity-
fractionated coal in Fig. 6 indicates substantial
disagreement between correlations as iron concen-
i tration increases. This suggests that correlations
2 developed to reduce time and cost of determining
f; viscosity should be verified for slags whose composi-
je tion fall out of the range used to derive the
correlations. Figure 6 indicates heterogeneously-
dispersed mineral matter produces fly ash with a
wide range of viscosities.
Important differences between slags develop as they
are cooled below the crystallization point. Some slags
rich in silica remain glassy over their entire viscous
range.s.‘4 No divitrification occurs and viscosity
depends only on temperature, not the previous
thermal history of the slag.x,‘4 In a second larger
1100 1200 IXCJ 1400 1500 IO group of slags, a solid phase precipitates out abruptly
Temperature. ‘C at some given temperature, forming a pseudoplastic
fluid. Upon reheating, the solid phase is gradually
Fig. 7. Flow characteristics of three typical coal ash slags.”
redissolved but at a temperature level much higher
to the relationship proposed by Fulcher.“3 than that at which the crystals were formed. The
temperature difference between crystal formation and
crystal melt depends on cooling rate. Reid defines a
Arrhenius Eq. (5) third group in which the temperature at which crystals
IO’WI
~- precipitate upon cooling is the same as the tempera-
LNq = ct _ 150)? + c
ture at which the crystals dissolve upon heating.‘K
Figure 7 illustrates the three types, along with their
where m and C are constants dependent on
chemistry.z8 Freezing is not always as abrupt, as
composition:
illustrated by Reid.s Some slags reveal a substantial
m = 0.00835Si02 + O.OO6OlAl203 = 0.109 (6) difference in temperature level between the tempera-
c = 0.0415Si02 + 0.0192A1203 + 0.0276Eq. FezOs ture at which crystallization begins and solidification
is complete. The crystallizing temperature is impor-
+ 0.0160CaO - 3 92. (7) tant to those designing gasifiers, wet-bottom furnaces,
These three original expressions for viscosity of and slag taps, as well as to those modeling slag flow in
silicate melts have been recently modified to extend dry-bottom furnaces. and has become commonly
their range of applicability. Whereas Watt and known as the critical viscosity temperature. r,,.
Fereday used the Arrhenius relationship (Eqs (1) The relationship between the beginning of crystal-
and (4)) Riboud and Urbain have found the lization (or the critical viscosity temperature) and
Frankel equation (Eq. (8)) to give the best fit, and composition is much more complex than predicting
McCauley and Apelian propose the Clausius the fluidity of the slag. Crystal formation depends on
Clapeyron equation (Eq. (9)).25-27 The latter has phase equilibria within a complex multi-component
been used to successfully relate pressure with tempera- system, the presence of catalyst for formation of
ture, enthalpy, and volume. McCauley and Apehan” crystals, and cooling rates of the slag systems.”
indicate ‘many properties including viscosity can be Despite the complexity of the system, researchers at
related to an energy barrier, free volume, and BCURA have developed the following empirical
temperature’. expression for T,., in terms of the composition alone.
based on measured values of 63 coal ash slags.x,‘8
n = ATpBIRT Frenkel Eq. (8)
T,,=2990- 1470(203) +360(20,)?
Clausius Clapeyron
LNq = Cl + C,/T f C3LnT
Eq. (9) - 14.7(FezO, + CaO + MgO)

Presently, there are five expressions for viscosity in + 0.15(Fez03 + CaO + MgO)‘. (10)
40 R. W. Bryers

Temperature, OC
1100 1200 1300 1400 1500
I I I I I -1500
1 I I
0 In air
. Under reducing
conditions - 1400

.
-1300

- 1200

.llOO
2ooo’
2CCO 2200 2400 2600 28Ccl
Temperature of Critlcal ViscosHy, T,,, F

Fig. 8. Relationship between cone-softening temperature and temperature of critical viscosity.sX’9

Ta.F

X Fa IN GLASS

1_1 .(GT 1
w-=
RED
-- OX
0,. CRATT 13EI

0,. nvm.r 13s6 .lsm

*,. ILL I 117s

0,. m-f., ,,M WE3

---- OXIDIZING
- REDUCING

TEM?. F

Fig. 9. Schematic illustration of the approximate abundances of the mineral-derived phases in an eastern
ash and iron in glass as a function of quenching temperature for a reducing atmosphere.34
 Steam-raising fuels 41

There appear to be some parallels between ASTM

ash fusion temperatures and viscous properties of slag
as the initial deformation temperature is an indication I o PYRITE
of the formation of a melt and the softening A IRON POWDER
temperature, the complete dissolution of the solid o MARCASITE
phase. The fluid temperature which exceeds the
softening temperature by 27.7”C or more, is believed
to be a viscous effect impeding the flow of molten
slag.” To minimize the cost and timely process of
determining the r,, by means of a viscometer, Sage
and McIlroy3’ proposed calculating the T,, by simply
adding 117°C to the hemispherical temperature. They
reported that for approximately 70 ash compositions
studied, the T,,was within 111°C of their measured
value, except one. This method of determination is
reportedly applicable to slags in which 20% of the
iron present is in the ferric state.6 The conceptual
relationship between the ASTM softening tempera-
ture and the critical viscosity has led others to modify
earlier regression analyses of ash softening tempera-
ture vs basicity of the coal ash by simply substituting
critical viscosity for ash softening temperature.30.3’
Corey” showed the relationship between the soft-
ening temperature and critical viscosity over a limited
range of coals in Fig. 8.
As the slag is cooled below the crystallization
temperature, the fluxing agents such as calcium and SUBSTRATE TEMPERATURE (‘CI
iron begin to precipitate in crystalline form. Crystals
Fig. 10. Sticking behavior of iron-containiy,g minerals on
of mullite, anorthite. crystobalite, gehlenite, her- oxidized medium carbon steel.
cynite, moscovite, and fayalite have been identi-
fied.32,‘3 Kalmanovitch and Williamson33 examined the tube surface or the increased residence time at
the divitrification of Eastern and Western, North deposit surface temperature on crystallization.
American coal-type ashes quenched over a period of Once cooled below T,,, partial crystallization of the
several hours. Their results show that the crystal- slag alters the composition of the glassy phase and
lization is well represented by the CaO-FeO-Alz03- hence, its viscosity. Lower temperatures and increased
SiOZ quaternary. Huffman et 01.~~ examined the crystalline concentration account for a rapid increase
high-temperature behavior of coal ashes using in viscosity. Hough32 showed that a phase equilibria
Mossbauer analysis, SEM-AIA analysis, and X-ray computer code, employing the Fereday-Watt corre-
diffraction. Huffman’s samples were heated in a lation, could be used to predict the measured viscosity
modified ash fusion apparatus and quenched for of the slag below T,,, for four slag samples. Hoy et
5510s from temperatures ranging from several al. 24 indicate the effect on viscosity of change in
hundred degrees Centigrade below the initial defor- chemical composition of the liquid slag, resulting
mation temperature, to the fluid temperature. They from fully buoyant crystals, is larger than the effect of
found partial melts as low as 200-400°C below their presence as inert solids dispersed throughout the
the initial deformation temperature. Under reducing liquid. However, when the crystal concentration is
conditions, melting was greatly accelerated and sufficiently large to permit contact between individual
controlled by the iron-rich corner of the phase crystals, slag behavior may no longer be Newtonian
diagram. The iron in the ferrous glass below 900°C and may be both quasi-viscous and thixotropic.
was reported to originate from the mineral illite in the Plastic behavior is not normally experienced unless
coal. Under oxidizing conditions, potassium appeared the solids content of the slag is greater than 50%.24
to be the most important low-temperature fluxing Moza and Austin35 recognized discrepancies in
agent as the percentage of glass in samples quenched conventional techniques for measuring ash fluidity
from temperatures below 1100°C was proportional to and therefore, developed a drop-tube quenching test
the potassium-bearing mineral illite. Figure 9 illus- to elucidate precise mechanisms for initiation and
trates the percentage of total iron contained in the growth of slag masses formed by molten slag
glass as a function of quenching temperature under subjected to cooling. Synthetic ash, mineral matter,
oxidizing and reducing conditions. Unfortunately, and low-temperature ash were subjected to the
the data do not treat the percent glass formed quenching tests. The mineral matter was heated
parametrically with quenching rate to illustrate the until it fused, melted, and eventually dropped freely
impact of reduced rates of migration of the fly ash to through a hole in the top of a furnace containing a
42 R. W. Bryers
Temperature,
600 650
0 II00 1200
Temperature, F
Fig. 11. Corrosion of chrome-nickel alloy (TP-321) by molten trisulfates.39.40
target, representing different substrates. The tempera-
ture of the furnace was controlled between ambient
and 600°C. The substrate temperature was controlled
independently. Adherence to the substrate was
observed and the contact angle and adhering force
measured. Pyrites and mixtures of pyrites and quartz,
and pyrites and illite, were found to have sticking
temperatures as low as 250-300°C. The adhesion
force for pyrite is illustrated in Fig. 10. The sink 2.85
gravity fractions of three bituminous coals showed a
drop in sticking temperature of almost lOO”C,
compared to ash from the parent coal. The quench-
ing tests indicate sticky substances deposit at
temperatures much below the initial deformation
temperature. High-speed photography showed that
the molten drop adhered with rapid freezing of the
contact area, followed by a zone of freezing moving
up into the drop. The material next to the interface
was glassy and supercooled. Crystalline nucleation
occurred higher in the drop.35 Consequently, coal-
ash-slag viscosity based on composite ash chemistry is
not necessarily a good index for the slagging potential
of a coal. One must deal with specific chemistry of an
ash particle, the chemistry of the ash deposited, the
temperature and location within the slag, super-
cooling of glassy phases, crystallization, and cooling
rates to avoid significant error.
Correlations for viscosity were originally developed
to predict the flow of molten ash in high-temperature
cyclones and wet-bottom furnaces where the ash was
100% molten. Although interest in slagging-type
combustors has diminished because of high main-
tenance cost and high NO, levels generated at the
very high operating temperatures, viscosity remains
as an indicator of slagging in dry-bottom furnaces by
virtue of a relationship between the softening
temperature of the coal ash and the critical viscosity
of slag. Consequently, T,, has been used as an
indicator of the fluidity of deposited ash or the
plasticity of particulate impacting on tube surfaces.
Slag formed in dry-bottom furnaces is initiated by a
sintering process which accounts for the greatest loss
OC
700 76
1300 1400
in absorption. The sintering process, however, may
be due to viscous flow of surface layers, solid-state
diffusion or contacting particles, or chemical reac-
tions between gas and solid. The plastic or fluid layer
of a deposit includes only the fireside portion of the
deposit. Deposits formed by high-moisture coals may
be entirely sintered. The fluid properties of greatest
interest in dry-bottom furnaces fall within the plastic
range and are dependent upon quenching rates of
crystallization, crystal concentration, and changes in
fluid chemical composition. Consequently, the use of
viscosity-a measure of slag fluidity-as an index for
slagging in dry-bottom, low-heat release furnaces can
produce misleading results.
3.3. High-Temperature Corrosion Due to Sulfur
With the increase in demand for electricity in the
1940s and 195Os, thermal efficiency climbed from
27% in 1948 to 38% in 1963, with a project increase to
40% in 1965. To meet the higher efficiencies, the
steam temperature increased from 454°C in 1948 to
565°C in 1963. Materials of construction of tubes
went from mild steel (i.e., 1% Cr-4% MO) to 2$% Cr-
1% MO. Steam generator design had approached the
threshold for design for some fuels with enriched
concentrations of minor elements of sodium, chlorine,
and sulfur, while exceeding the limits in some
instances3’
The increased consumption of Illinois Basin coals,
known to be enriched with sulfur, chlorine, and
sodium as organically-bound chlorine and sodium
chloride, resulted in wastage of furnace walls and
finishing superheater tubes as well as fouling of the
finishing superheater at the entrance to the heat
recovery zone. Corrosion by alkali trisulfates quickly
became a problem.
As early as 1945, Corey et aL3’ identified the
presence of alkali pyrosulfates in furnace wall
deposits and alkali-iron trisulfates on the leading
edge of the final superheater tube surface as being
responsible for tube wastage. In both cases the deposit
 Steam-raising fuels 43

+ Fe, 0, ( 50 wt. % )

600

“0 I .o 2.0 3.0 4.0 5.0

Probe Distance Above Surface, mm

Fig. 12. SO1 profiles above mixtures containing FezOi at 593°C in 5.8% S02_‘x~44

consisted of a hard, white enamel-like material and generator. The difference is due to insufficient
corrosion was dependent on the existence of a molten residence time for the reaction to occur. Krause et
phase.37.3* Pyrosulfates were found to be molten at al.43 recognized such levels of SO3 would be
temperatures exceeding 398°C for sodium pyrosulfate insufficient for the alkali trisulfates to form. They
(Na2S207) and 454°C for potassium pyrosulfate. also found that conversion of SO? to SO3 within the
Coats et al9 showed in Fig. 3 that K2SZ07 could be boundary layer can be 10 times that occurring in the
formed with as little as 150 ppm SO3 at 404”C, bulk stream due to the catalytic activity of Fe203 and
whereas NazSz07 required at least 2000ppm SO3 to sufficient residence time.43 These data appear in Fig.
form at temperatures of 398°C. Maintenance of their 12. Levy and MerrimanM indicated the catalytic
stability on furnace wall tubes whose surfaces reached behavior of Fe203 was substantially greater than that
482°C requires at least 1OOOppm SO3 for K&O,, of Fe304.
and at least 2% SO3 for NazS207.8 Consequently, the Two observations made of full-scale deposits led to
formation of pyrosulfates would be confined to two diametrically opposed conclusions. ln one case.
furnace walls and economizer tubes. They would Reid’ and others observed the formation of a white.
not be expected to form on superheater tubes. thin layer enriched with alkali-bearing compounds
Corey et d.37~38, Nelson3’ and Cain” reported the shortly after immersing the heat-transfer surface into
alkali-iron trisulfates require at least 250 ppm SO3 to a hot flue gas stream, suggesting direct formation 01
form. The alkali-iron trisulfates are molten at 894°K alkali sulfates on the tube surface. Anderson,
and decompose above 525°C. The bell-shaped curve Jackson, Crossley. and Rayner45-49 all observed on
reported by Cain in Fig. 11 illustrates the range in occasions the absence of inner layers of deposit
which they are molten, stable in the presence of S03, beneath thin accumulations of alkali-sulfate-
and corrosive.40 Cain and Nelson39s40 found that enriched fly ash accumulations, suggesting that the
mixtures of sodium and potassium alkali trisulfates inner layer was formed as a result of migration of the
could lower the melting point of the pure constituents alkali metals to the cooler surface. Jackson474x
to 477°C. presented a very comprehensive summary of vapor
Sulfur trioxide in flue gas can be attributed to and decomposition pressures, shown in Fig. 13, that
reactions within the flame, oxidation of SOZ, and are essential to the understanding of the formation
decomposition of sulfates. The latter makes a very and stability of alkali compounds as they migrate to
minimum contribution as the quantity of sulfate the cooler heat-transfer surface. Assuming a per-
found in coal is insignificant. Hedly explained that meable deposit experiencing a marked temperature
although SO3 can form in the flame, the reaction rates gradient under equilibrium SO3 concentrations, it was
are too slow and the residence time much too slow proposed that the volatilized sodium hydroxide and
for significant SO3 to form.4’ Manning42 reported potassium hydroxide released during combustion
that equilibrium conversion of SO2 increased rapidly reacted with aluminosilicate, which migrate to the
below 982°C and reached 100% by 426°C. At reduced cooler surface and react with SO3 to form sulfates.
levels of 02, as found in flue gas, the conversion is The sulfates interact with Fez03 in the ash and SO3
substantially reduced at the higher temperatures, present at the tube surface to form alkali trisulfates.
However, it has very little impact on achieving as shown by Eq. (11). Between 565 and 676°C the
100% conversion by 426°C. Hedly4’ found the trisulfates are molten. Tube iron goes into solution
conversion of SO3 rarely exceeds l&2% in a steam breaking down the trisulfates and forming iron
44 R. W. Bryers

6 7 IO II I2
‘1’ .’

LI0UID.90LI0 _ 1.1 ’ I

-s
lo’

>
L

IQ%CO*_
4
\ IO2
\ \\ \

EC

TEMPERATLIIE;C
FLUE GAS c-- DEWSIT- ;;;;;ACE
Tenpcraturc Range

- VAWUR PRESSME
..----. OECOMKlSl7l0N PfiESSuRE FcSO4 Deconporl tton 537’C
- - PARTIAL PRESSURE OF SO3
__-_ znso4 Decolposi t Ion 646’C
TENTATIVE OATA
-..- EFFECTIVE VAaA ?RESSLWE
-‘- S03FORMED CdT~LYTICALLY

Fig. 13. Vapor and decomposition pressures of sodium, potassium, iron, zinc, and lead compounds and
partial pressures of sulfur trioxide.47,48

blue gistme* Into silica10 mmrrrl r@rldLlO SWf8C~

cl0 to 10% -s;

Diffusion SWhC8 Alkali
pWlOd phase capture
at 1.000 ( rhOed )
-1,200 ??
c

Fig. 14. Reaction of alkali metals at surface of fused silicate particles!s

 Steam-raising fuels 45

sulfide, which migrates to the deposit corrosion during combustion, which ultimately affects the
product interface and reforms alkali trisulfates to fireside behavior of the species. The forms in which
complete the cycle, as shown below. chlorine occur also determine their potential for
removal during the fuel preparation as a remedial
*ni”a’FeSz(coal) measure for fireside problems. Three major forms
Source
1 for the occurrence of chlorine in coal have been
Fe+K3Fe(S04)3-(Fe20i+K2S04)+FeS proposed: inorganic chlorides, organo-chlorine com-
1 + 02 pounds, and chloride ions in brines and other waters
‘L SO, P SO, + Fe,O, associated with coa1.s0-54 For a good many years it
was believed that chlorine was present as a chloride
(11) of sodium, potassium, and calcium due to the
They assumed that the alkalis arrived at the tube intrusion of saline water-a position initially
surface as a result of a chemical reaction of sodium supported by Gluskoter of the Illinois Geological
hydroxide with the surface of aluminosilicates, Survey with regard to Central Illinois coals.52,53
forming a sticky surface and permitting attachment Aqueous leaching tests generally gave a good
to other deposits on the tube surface. Figure 14 correlation between the chloride and alkali ions
illustrates the counter-diffusion of sodium and with which they were associated as an organic
potassium through the illite fly ash particle and their alkali compound.5’
effect on the melting temperature of the particle Recent aqueous leaching experiments by Gluskoter
surface. In the absence of aluminosilicates and pyritic et al. and Chen et a1.53-s8 have led these investi-
iron but in the presence of high SO3 levels, as in the gators to change their original thinking about Cl in
case of oil, sodium sulfate will form a molten deposit North American coals from chlorine occurring
at the tube surface by passing the first step and predominantly as inorganic alkali chlorides, to a
causing severe fouling while avoiding corrosion. mixture of soluble chlorides and unspecified ‘organic’
Research on alkali trisulfates has taught us that chlorides. Electron probe analysis of an Upper
high-temperature corrosion of furnace wall and Freeport bituminous showed chlorine to be homog-
superheater surface can be avoided by ensuring an eneously distributed throughout a given maceral. No
oxidizing environment and avoiding flame impinge- correlation existed with other inorganic species
ment on furnace walls using ‘air belting’ in the flame presents8 X-ray Absorption Fine Structure (XAFS)
basket, limiting steam temperature to approximately spectroscopy performed by Huggins and Huffman
537°C using shielding to raise exposed surfaces to on various rank coals whose chlorine ran between
temperatures exceeding the melting temperature of 0.04 and 0.84% indicated the chlorine in a majority of
the alkali trisulfates and restricting the sulfur (i.e., coals investigated was present as a chloride anion in
iron level) and alkali level (i.e., KzO, NazO) of high the moisture associated with the microcracks and
alkali bituminous coal:s. pores in the coal. A second form of occurrence was
identified as crystalline NaCl, which presumably
precipitated from the chloride-rich solution as the
3.4. High-Temperature Corrosion Due to Chlorine coal dried.54 Chou59 of the Illinois Geological Survey
reported similar results. With the chlorine occurring
Chlorine became a problem for furnace walls and primarily as anions of moisture in fine cracks and
superheaters while firing pulverized coal. In the U.K. pores, it is not difficult to rationalize the differences in
during the late 1950s where the Cl content ran high as results reported earlier using various analytical
0.8% with an average of 0.25%, experience taught procedures.54 It would also appear that a high level
operators they could operate corrosion-free if they of removal could be achieved by fine grinding and
did not allow the Cl concentration in the coal to aqueous removal.
exceed 0.3% on a dry-coal basis.5’ Most coals in Gibb” recently demonstrated that extremely rapid
North America contain less than 0.3% Cl on a dry- dechlorination of coal occurs in the early stages of
coal basis. However, there are substantial reserves of devolatilization releasing chlorine as Cl or HCl, which
coal in North America that contain high levels of Cl he attributed to the presence of chlorine as weakly
(i.e., >0.3% on a dry-coal basis). These reserves bonded ions in the coal matter. Equilibria for Cl and
consist of deep mines confined to the Illinois Basin. HCl favors the formation of HCl at the low-
Until recently, the abundance of high-sulfur/low- temperature oxidizing conditions to which furnace
chlorine coals provided an economic alternative to wall deposits are normally exposed. Engdahl et aL6’
using a coal with a corrosion potential. Although the and Krause et aL6* indicate Cl has never been detected
abundance of high-chlorine fuel is localized, the in incinerating steam generating flue gases, thereby
increase in restrictions on the use of high-sulfur coal substantiating equilibria predictions-at least as
has created an incentive is developing for exploiting applied to incinerators. The accuracy of equilibria
these reserves. calculations depends, of course, on the reaction
The forms in which the chlorine occur are import- kinetics and the system residence time. It appears
ant as they determine the mineral transformation that system residence times are sufficient in the
46 R. W. Bryers

2oa

I
NO CONDENSATION /
IS00 : : ; :, ,

800

600
so 90 100 110 120 130
PER CENT OF THEORETICAL AIR
PEP CENT OF THEORETICAL AIR

hno Sal, sodlvm compounds, 510s prw8nl

Fig. 15. Thermodynamic equilibrium for sodium compounds in flue gas for off-stoichiometric conditions
and varying SiOz levels while burning a low Cl coal.63

Temperature, “C
100 200 300 400 500 600
I I I I I I

200 300 400 500 9QO 700 900 900 000 1100
Metal Temperature, OF

Fig. 16. Corrosion rates of carbon steel in chlorine and HCl as a function of temperature.68

immediate environs of the tube surface for the
reactions to go to completion. Crystals of sodium
chloride present within the coal structure should not
volatilize until significant decomposition of the char
has taken place. At temperatures in excess of 648”C,
the alkali chlorides would be expected to volatilize.
Depending on the composition of the local environ-
ment, the chlorides would decompose at somewhat
higher temperatures, as illustrated earlier in Fig. 13
prepared by Jackson4’ The potential for direct
deposition of NaCl by passing the combustion
process would then exist as well.
English and North American coals rich in chlorides
also contain high levels of sulfur. Cutler et a1.,64 Boll
and Pate1,63 Wibberley and Wa11,65 Halstead and
Hart,66 and Wal?’ examined the thermodynamic
equilibria of chlorides and sulfates at levels normally
encountered in the high-chlorine coals, as well as
alkali partitioning under reducing conditions, in an
attempt to understand the formation of alkali
chlorides or sulfates on tube surfaces. An example
of Boll’s results appearing in Fig. 15 indicates that
chlorides will deposit on tube surfaces under
reducing conditions in the absence of a ‘getter’
such as quartz. Under oxidizing conditions, sulfates
should form preferentially. Cycling environmental
 Steam-raising fuels
TIME.
Fig. 17. Metal loss data for mild steel in NzO-10%C0-10%N~0~0.5%S0~
400, and 2000ppm at 500”C.76
conditions should provide the worst conditions as Cl
would be released periodically.
Chlorine has a secondary effect on potassium
normally found in coal as a stable silicate such as a
feldspar or illite. The potassium may be displaced by
sodium or chlorine at high temperatures, forming a
chloride or sulfate and thereby producing a second
alkali capable of engaging in the fireside corrosion
problem. Cutler et a,!.64 and Raask” propose the
following reactions:
mK20 - XSi02 e YA1203 (Condensed) + 2NaCl (gas)
+ (m - 1)K20 - K20. Na20XSiOz
x YA120s (Condensed) + 2KCl (gas) (12)
2KCl+ SO3 + O2 Fr! K2S04 (gas) + HCl. (13)
Illite is known to be sticky down to temperatures as
low as 950-1000°C and hence, provides the mecha-
nism for transporting potassium from the flue gas to
the leading edge of convective bank tubes where it is
retained as a semi-molten deposit providing a source
for K,S04 or KCl.
Investigations by Brown et al.,68 as well as by
Battelle, indicate chlorine attack begins at 204°C
whereas hydrogen chloride attack does not start until
426°C as shown in Fig. 16.68-70 Since equilibria
does not favor the formation of Cl* in the flue gas
at furnace walls under oxidizing conditions, any
attack by Cl2 must occur beneath a deposit or under
reducing conditions.
The first step of high-temperature corrosion begins
with the formation of a protective film on the tube
surface. In the second step, the Cl2 released by the
coal, generated from the decomposition of HCl under
reducing conditions or the release of HCl from alkali
salts in the presence of SO2 and 02, penetrates the
oxide scale and reacts with the elemental iron to form
41
.w...-. 400 pwn HCI
--A- - 2000pprnHCI
h
with HCI concentration of 0.
FeCl,, physically separating the protective coating
and corrosion product from the tube surface. Thus,
Cl* + Fe + FeCl?. (14)
The FeC12 vapor diffuses outward through the
oxide scale and on its way is oxidized to Fe304 and
FezO,, releasing fresh Cl1 for attack of base
meta1.72-74 The process can be cyclic. Thus,
4FeClz + 302 = 2Fe20A + 4C12
T (15)
4Fe 2.
Reducing conditions are essential to releasing the
initial Cl,; oxidizing conditions are required for the
corrosion to proceed. Consequently, cycling oxidizing
conditions promoted by flame impingement produce
the worst conditions.
Lee reports that FeC12 has a specific volume of 11
times that of the reacted metal. Its formation will
induce non-protective porous scales. Linear corrosion
rates could result from repeated scale spalding.”
Krause et ~1.” found FeClz as a corrosion product in
the metal temperature range of 148-260°C. Although
FeC12 is somewhat volatile, Krause74 reports cata-
strophic corrosion does not occur until its melting
temperature is reached at 508°C. The volatility and
melting temperatures of FeC12 and FeCl, appear in
the extended version of Jackson’s48 curves for vapor
pressure of alkali metal salts.
On low-temperature surfaces, HCl may react with
the protective coating of Fe203 to form FeC13. Thus,
1/3Fe20s + 2HCl= 2/3FeCls + H20. (16)
Experiments by Mayer and Manulesco” indicated
0.2 volume percent can make an Fe20s layer porous
while 0.8 volume percent will completely disintegrate
it. The FeCls is extremely volatile and will not remain
on tube surfaces in most steam generators.”
 48 R. W. Bryers

Fig. 18. Analysis of gaseous and solid species samples on the rear wall of a 120-MW boiler. Reducing
conditions are found in areas of high corrosion. Excess oxygen is found in areas of low corrosion. Chlorine
content of coal is 0.5-0.6%.”

Brooks and Meadowcroft and Clarke and The saturation effect may have been due to a limit
Morris” investigated the combined effect of CO and imposed on scale porosity formation by the rate of
HCl in the laboratory and compared the results to volatilization of Fez03. The laboratory-scale mor-
field experience. The addition of HCl to the simulated phology and corrosion rates were comparable to that
combustion gases caused a transition from protective of full-scale operation. In all cases, the scales were
parabolic oxidation curve to linear kinetics, which multi-layered, consisting of a loosely adherent, large
increase by a factor of three as the temperature grained, porous outer layer of FeS on top of inner
increases from 400 to 5Oo”C, as illustrated in Fig. bands of FeS and Fe304. The occasional evidence of
17.76 At the higher temperature, the corrosion rate intergranular penetrations in full-scale furnace wall
appeared to be independent of HCl above 400ppm. tubes was missing in the laboratory. There was no
 Steam-raising
INFLUENCE OF COMBUSTlON AT
A FIXED CHLORINE CONCENTRATION
WEIGHTED MEAN CHLORINE
CONCENTRATION DURING TIME ‘1’
Fig. 19. Rationalization of plant corrosion rate data with respect to chlorine concentration and flame
proximity. The degree of attack at a given chlorine level increases as the reducing conditions at the wall
become more severe. Each number represents a different power station.”
evidence of chlorides at the scale metal interface. Lee
illustrates the impact of reducing environment on
sulfidation-chloride enhanced attack in full-scale
furnaces in Fig. 18.” Lee and Whitehead’s” plot of
corrosion rate with respect to mean chlorine concen-
tration (shown in Fig. 19) provides an empirical
quantification of the chloride-enhanced attack of
furnace walls. The role of chlorine is simply believed
to be one of destroying the protective oxide layers of
the tube.7’X72
Experiments simulating superheater surface indi-
cate that under oxidizing conditions, chlorine does
not engage directly in the metal wastage mechanism.
In sodium-free fuels, it was found that chlorine
released potassium, which then engaged in the more
traditional sulfidation corrosion.” From these and
other experiments by Gibb and Angus,” it was
concluded that chlorine, not sodium, was the con-
trolling factor in releasing volatile potassium essential
for alkali sulfate attack. Quantitative data appearing
in Fig. 17 indicate superheater attack is a linear
function of the chlorine content of the coal containing
fuels 49
INFLUENCE OF CHLORINE IN THE ABSENCE
OF SIGNIFICANT VARIATION IN
COMBUSTION OR BOILER OPERATION
more than 0.15% chlorine. Since the role of chlorine
is one of making potassium available in a corrosive
form rather than engaging directly in the corrosion
mechanism, it is unfortunate potassium was not
considered a parameter in the empirical correlation.
Despite the demonstrated dependency of corrosion
associated with chlorine on the presence of CO, the
empirical index of 0.3% Cl in coal is still used as a
means of selecting alternate coals to avoid chloride
attack.
3.5. Fouling of Convective Heat Recovery Surface
Corrosion-free fouling of convective heat-transfer
surfaces did not become a problem until the late 1960s
when low-sulfur/high-sodium lignite became a viable
fuel for generating electricity from steam.
The cooling surfaces of a steam generator are
designed such that the flue gases leaving the radiant
heat exchange portion of the combustion zone are
cooled to a temperature slightly below the initial
deformation temperature of the coal ash. In this
50 R. W. Bryers

, A
8
30
15
1148
1062
31
31
C 7 985 38
D 7.5 876 39
E 5 806 43
F 5 755 44
G 5 562 37

’ S, is the- centerline space between tubes

in the lane perpendicular to gas flow

Fig. 20. A typical convection bank design for subbituminous coals.‘*

Table 5. A comparison of boiler design for variously ranked coals and evolutionary changes to mitigate fouling and
slagging”’

Plant Public Service Commanche Belle River Colestrip 3, 4 Antelope Valley

Indiana

Fuel Bituminous Subbituminous Subbituminous Subbituminous Lignite

Start-up/capacity (gross) 1982/- 1973/360 l984-85/678 1984-851776 1984/440

Furnace dimensions, ft:

width 68 45 82 97 65
depth 41 40 51 46 54
height _ IO 184 217 273
volume 519,600 238,000 678,000 745,000 858,000

Design heat release

furnace volume 12,000 12,540 9,480 9,500 9,500
plant area 2.07 2.10 1.70 1.83 1.83

Design furnace exit, “C 1315 _ II21 1037 1065

Tube spacing: side-to-side, in.

Radiant panels and/or
platens
first 119 54 125 None
second 35 I7 24 25 _
Conventional bank
first 17 8.5 24.0 10.0 24.5
second 8 6.4 12.6 5.0 11.0
third 4.375 4.0 9.0 4.5 9.0
fourth 4.375 4.0 4.5 4.5 6.0
fifth 5.375 4.5 6.0
sixth _ _ 4.5 _
seventh 5.8 _

Slagging limits load Occasional Occasional Occasional Never Never

Fouling limits load Occasional Occasional Never Never Never

 Steam-raising fuels
Formation of White Layer:
- Vapor Phase and Small
Particle Diiusion,
possibly by van der Waals
and electrostatic forces.
Tg= 1360 K (1093
Vg = 10 Mlsec
Fig. 21. Formation of initial deposit in fouling deposits79 (courtesy of Dr. S. Benson. University of North
Dakota).
manner the designer tries to generate dry, innocuous
fly ash before it enters the convective heat recovery
zone employing tightly-spaced tube bundles immersed
in the flue gas perpendicular to the direction of flow.
To further minimize the potential for deposition,
the convection bank is preceded by a screen section of
cooled water which acts as a barrier to radiant heat
exchange and cools the passing flue gas laden with
particles-an additional 50°F. The first rows of
tubes are generally arranged on wide tube spaces to
minimize the collection efficiency. As the flue gas is
cooled and the potential for deposition diminished,
the spacing between tubes is reduced to improve
heat transfer, as shown in Fig. 20 and tabulated in
Table 5.‘,“’
During the early stages of pulverized-coal firing
when steam pressures were low, a large portion of the
enthalpy extracted from the flue gas was used to
generate steam. Consequently, the duty of the
convective heat recovery zones was low and all
economizer superheater and reheat surfaces could be
installed at flue gas temperatures below the initial
deformation of the coal ash. With an increase in
steam pressures, the energy required to superheat and
reheat steam became a much larger portion of the
total duty of the steam generator. The surface-to-
volume ratio of the furnaces also decreased. This
made it necessary to immerse some convective heating
surface in the furnace cavity where it would be subject
to radiant heat exchange if the ash melting tempera-
tures were to be maintained as the criteria for the
furnace exit temperature. Consequently, very widely-
spaced pendant superheated surface was hung in the
Difksion
EERC 5807307
upper furnace as boiler capacity and steam pressure
increased. Deposition of ash, no matter what its
physical state on convection heat-transfer surfaces
shielded from furnace radiation, became known as
fouling and the ash accumulations were referred to as
bonded deposits.
Bonded deposits are characterized as having an
inner layer, composed primarily of sulfate, conform-
ing to the profile of the tube and an outer layer
contoured by the flowing gas and having a composi-
tion approaching that of the entrained fly ash. as
shown in Figs 21-23.79 The transitional layer may be
composed of a fused molten ash or lightly sintered
particles an order of magnitude larger, usually
enriched with one of the minor basic constituents in
the coal ash, as shown in Fig. 22.79 The outer layer
may be semi-fused or sintered, as illustrated in Fig. 23.
Frequently the bonding material wetting the fly ash
trapped in the outer layer is composed of the same
material found in the initiating layer. Bonded deposits
are most frequently formed by the alkalis, calcium,
potassium, and silica-each creating its own type of
deposit peculiar to a specific temperature regime in
the heat recovery section.
Fouling by bonded deposits was first observed in
low-pressure stokers. Silica, the only acidic constitu-
ent in coal ash, deposited as the result of a fume
formed by the volatilization of SiO? under high-
temperature reducing conditions found on the grate
of stokers.“,” Padia et al.” have shown in drop
tube experiments that as much as 4% of the silica
may be released at temperatures of 1557°C as SiO:
and 25530% may be released in the presence of
52 R. W. Bryers

Transitionfrom White to Sinter Layer:

- Inertial Impaction
- Vapor Phase Deposition of
- Adherence of Particles -C
of Particle Stickiness and Formation
of Liquid in the Deposit
- Surface Tension Forces

Fly Ash and

Products of
Combustion

Rebounding Particles

Liquid in Deposit Due to

Temperature increase

Fig. 22. Formation of transitional deposit layers in fouling deposits79 (courtesy of Dr. S. Benson, University
of North Dakota).

Formationof the Outer Sinter Layer:,

- Inertial Impaction Prime Mode of Transport
- Vapor Phase Deposition Decrease Due to
Higher Temperature
- CarWe Surface Collects All
lipacting Particles

Liquid Phase -I I
I

Fig. 23. Formation of outer layers in a fouling deposit79 (courtesy of Dr. S. Benson, University of North
Dakota).

graphite at temperatures of 1694”C.s2,s3 Makowskyx5 mineral constituent fluorapatite [Ca,oFl(PO)4)6], has

demonstrated similar results in crucible tests in which on occasion been responsible for deposits in super-
she reported a white fume of submicron particles.84X85 heaters and economizers of stoker-fired boilers.
In a laboratory pilot plant, Ulrich et al.86 indicated Under reducing conditions at temperature exceeding
that submicron fly ash formed by vaporization of 1593°C. such as may exist in deep fuel beds found in
fly ash may account for 1% of the fly ash but may stokers, the fluorapatite decomposes releasing ele-
represent 99.5% of the total number of ash particles. mentary phosphorous. Oxidation of the phosphorous
However, silicon has not been associated with fouling in the presence of moisture downstream of the
problems in pulverized-coal-fired boilers, possibly due combustion process produces phosphoric acid,
to the improved access of combustibles to combustion which may condense on heat recovery surfaces and
air. react with fly ash to form hard, insoluble crystalline
Phosphorous, found primarily as the minor phosphate.snSx4 Phosphate-bonded deposits have not
 Steam-raising fuels 53

Although the deposits were observed in stoker-fired

boilers, they first became a nuisance while firing high-
sodium bituminous in Central Illinois, the U.K., and
Australia. They became a major problem when the
North American lignite reserves opened in the late
1960s.
The older bituminous coals responsible for alkali-
trisulfate deposits generally contain high levels of
potassium (1.553% by weight K20 in the ash) and
sulfur (l&4% in the coal) in addition to sodium
chloride and organically-bound chloride. The depos-
its were initiated by a thin layer of alkali sulfates or
trisulfates, depending upon the SO3 level at the
tube surface. During the process of combustion, the
volatile sodium released from the decomposition of
sodium chloride and feldspars interacting with
chlorine formed several volatile species (i.e., Na,
NaOH, Na,O), which subsequently reacted with SO3
Fig. 24. SEM photomicrograph illustrating heterogeneous concentrated in the flue gas boundary layer at the tube
condensation of CaO on silaceous fly ash spheres in the surface and condensed as Na2S04. Chlorine occur-
vicinity of the tube surface and subsequent CaS04 bonding. ring in significant concentrations, released potassium
from the mineral feldspar, creating a second alkali
been a problem in pulverized-coal-fired boilers due to species that also formed a sulfate at the tube surface.
the rarity of a significant concentration of fluorapatite With continued growth of the deposit and retention of
in coal, lower flame temperatures, and improved fly ash on the stick alkali-sulfate surfaces, the deposit
distribution of air. fireside surface temperature increased and equilib-
Calcium-sulfate-bonded deposits generally form in rium once again favored the formation of silicates
the cooler portion of the heat recovery zone dedicated with the release of S03. The molten, viscous surface of
to heat exchange between the flue gas and the primary the fly ash particles enriched with alkalis wetting
superheater, reheater, and economizer. The deposits contacting surfaces of adjacent particles and froze as
are associated with coals high in calcium and low in the local temperature dropped with an increase in
alkalis. Bonding of the fly ash is accomplished by deposit thickness and a reduction in heat flux. This
crystals of calcium sulfate, commonly attached to left a sintered or bonded deposit and confirmed the
sites on adjacent fly ash particles as shown in Fig. Reid et al. theory of direct deposition of alkali sulfates
24.x7X88The calcium-sulfate crystals grow as the result on tube surfaces.’
of sulfidation of a calcium fume formed by submicron Utilization of Australian and North American
particles scavenged by fly ash particles. Sulfidation is lignites in the 1960s for generating steam introduced
Ii- .ited to those particles depositing on the tube severe-to-catastrophic fouling also due to sodium-
surface where the residence time is sufficient and the sulfate-bonded deposits. Unlike bituminous, the
S02/S03 levels are high enough for the sulfidation lignites contain very little sulfur, chlorine or potas-
reaction to go to completion. Calcium-sulfate-bonded sium; however, they are rich in calcium and sodium
deposits are frequently initiated by a molten phase appearing as organically-bound mineral matter.
separated from the tube surface by a minute layer of Calcium and sodium in this form volatilize during
submicron particles of CaS04. The fused layer is combustion forming a fume at some point in the post-
probably due to sulfidation of the submicron calcium combustion process composed of NaOH vapor andi
particles in a zone where convective heat transfer ‘is or submicron particles of CaO, which condense on
insufficient to dissipate the heat of reaction.88X89 With heat-transfer surfaces making it receptive to further
continued growth of the deposit, fireside layers deposition. Benson et al. 79 illustrate in Table 6 how
may become fused as the CaS04 decomposes in the composition of the deposit changes with growth.
the presence of quartz and clays at temperatures Numerous empirical approaches were taken to
exceeding 9544982”C.88-93 quantify alkali-bonded deposit fouling. It was
Generally, calcium-sulfate deposits are associated recognized that the initiating mechanism was depend-
with coals rich in organically-bound calcium and low ent upon condensation of a volatile species and
in sulfur, which most frequently include the low-rank consequently was also dependent upon concentration
coals. Details of the formation of CaS04-bonded of the alkali in the flue gas and thus level of
deposits will be deferred to the section on mechanistic concentration of the alkali in the fuel. Michel and
approach. Wilcoxson reported fouling became a problem once
Alkali-bonded deposits occur at high flue gas the alkali content of the coal exceeded 0.8% by
temperatures in the vicinity of the entrance to the weight. Attig and Duz~~~ introduced a range of
convective heat-transfer pass (i.e., 982-1260°C). concentrations of sodium reflecting different levels of
54 R. W. Bryers

Table 6. Crystalline phases found in deposits and fly ash of beulah lignite79

Deposit Fly ash

Inner sintered layer Outer sintered layer

CaS04 CaS04 Quartz

Na$04/NazCa(S04)2 Melilite Fe203/Fe304/MgO
FezOJFe304/MgO Hauyne Na2S04
Akennanite Fe203/Fe304/MgO CaSOI
Hauyne Quartz Na2Ca(S04)2
Quartz Plagioclase CaO
Na2S04 AlzSiOS
Na&a(SO& KSO,
Amorphous phases

Table 7. Summary of key empirical correlations for slagging’02

Test/fuel/index Values

1. Ash fusion temperature Used to select maximum furnace exit temperature

Application: all fuels
Index: initial deformation softening
(Sph.) Softening (hem.) fluid
2. T Temperature at which viscosity changes from Bingham Plastic to
Aiplication: all fuels Newtonian
Index: T,, x Tsocten
3. T250 Dry bottom T250 Wet bottom
Application: all fuels low >2325 T Tzso < 2600°F
Index: temperature at 250 poise-the medium 2250-2100
critical limit for slag tapping high 2275-2050
severe <2200
0.5 max. for dry bottom
>0.27 min. for wet bottom
4. Base-to-acid ratio (B/A)
Application: all fuels
Index: C %(Fe203 + CaO + MgO
+ Naz + &O)
C %(Si02 + A1203 + TiOz)
5. RS-slagging 4 Degree of slagging
Application: eastern bituminous <0.6 low
Index: (B/A) (%S on dry coal) 0.6-2.0 medium
2.0-2.6 high
>2.6 severe
6. Slagging index T, T, Degree of slagging
Application: all fuels 2450-2250 medium
Index--T,: (TFT - Ts.T.) +~/~(TI.D.) 2250-2100 high
<2100 severe
7. Slagging index R,, R”, Degree of slagging
Application: all fuels 0.5-0.99 medium
Index: R,, = [TZso(oxid.)
- T1om(red.)975. 1.o- I .99 high
xfsl >2 severe
where: f, is a correlating factor
corresponding to main temperature
between oxidizing and reducing
viscosity
8. Iron/calcium ratio Eutectics formed between 0.3 and 3.0 increase slagging
Application: all fuels
Index: Fe203/Ca0

fouling by sodium in bituminous coal. They also
made a distinction between volatile and non-volatile
sodium minerals by determining the water-soluble
portion of the total sodium found in the coa1.95 Duzy
and co-workers,95,96 Grondhoud et aL9’ and Sedor et
aL9’ extended the concept to lignites. Borio et aL9’
modified characterization of the alkalis in coal ash to
include the acid-soluble components. This was again
modified at a later date by Miller and Given,loo and
Benson and Helm”’ to include water- and acidic-
soluble ammonium acetate portions as determined by
a chemical fractionation process. Winegartner”’
summarized all of the fouling and slagging indices in
a lexicon and published the results as an ASME
 Steam-raising fuels 55

Table 8. Summary of key empirical correlations for fouling””

Test/fuel/index Values

RF, Rk Degree of
Application: eastern bituminous only G fouling
Index: RF = (B/A) [%Na*O (ASTM ash)]
R; = (B/A) [% water soluble NazO in LTA ash] <0.2 <o.I IOW

020.5 0.110.25 medium

0.5 1.0 0.25--0.7 high
>l.O >0.7 severe

Sodium content of ASTM coal ash Lignitic Bituminous Degree of

Application: all coals % NazO % NazO fouling
Index: % NazO in the ash
<2.0 <0.5 low
226 0.551.0 medium
668 I .O-2.5 high
8 >2.5 severe
Alkali content of ASTM coal ash
Application: all coals Same as 2. above
Index: C (% NazO + 0.6589 % KzO)
Alkali content of coal % Alkali Degree of fouling
Application: eastern bituminous coal
Index: C (% NazO + 0.6589 % KzO) <0.3 low
(% ash/IOO) 0.330.45 medium
0.45-0.6 high
>0.6 severe

Ash sintering strength Strength of fly ash Degree of fouling

Application: all coals at 1700°F
Index: Compression strength of specially IO00 low
prepared fly ash 1000-5000 medium
5000- 16 000 high
>I600 severe
Chlorine % Cl Degree of fouling
Application: all coals
Index: % Cl in coal <0.2 low
0.220.3 medium
0.330.5 high
>os severe

booklet. These indices have been accepted as an
industrial standard and are presently used as a
guideline for characterizing fouling and slagging.
Winegartner’s results are summarized in Tables 7
and 8.“’
The slagging and fouling indices were developed
from field and pilot plant data using specific coals.
Extrapolation of this data to coals from other sources
may be subject to considerable error. An evaluation
of the indices by Barrett of Battelle Institute by means
of a survey of 130 boiler operators in the U.S. and
Europe indicate they were only 50% accurate.‘03”04
One of the main flaws with the indices was that other
than furnace exit temperature, sometimes poorly
defined, they did not include operating or design
parameters. A second survey of design practices by
four major boiler manufacturers for a set of six coals
of varying rank indicated the manufacturers did not
agree on the impact of coal impurities on boiler
design.
An examination of the indices indicates they are
simply based on ash fusion temperatures, viscosity,
and ash chemistry which have already been shown to
be loosely related. In the case of fouling, there are no
corrections to compensate for major concentrations
of other elements such as calcium, and ash concen-
tration is overlooked. The latter should impact on
total surface available for absorption of volatile
species as well as impact on the quantity of ash
impacting on a surface and its collection efficiency. It
has already been shown that slagging and fouling
manifest themselves in a variety of ways depending
upon local environmental conditions, dominating
modes of transport, and local boiler geometry---
giving rise to varying degrees of deposition and
deposit chemistry. The simplified indices do not
address operating and design parameters or variation
in mineral contents.
3.6. Sintering Tests
Subjecting fly ash deposited on tube surfaces to
high temperatures for long periods of time causes
particle-to-particle bonding at temperatures well
below the onset of melting, as defined by the ASTM
initial deformation temperature. This sintering has
been observed to occur over a range of temperatures
as low as 750-1000°C for Eastern bituminous coal,
56 R. W. Bryers
Temperature,
800 900
I I
Sintering Tempercture,F
Fig. 25. Effect of alkali content in coal on strength of sintered fly ash from Illinois coal as determined by
Barnhardt.‘06s’07
producing compressive strengths of 40,000 psi.‘05,‘06
As already noted in the discussion on types of bonded
deposits, the bonding mechanism may be due to a
chemical reaction as in the case of sulfidation or
interparticle wetting by the viscous flow of a multi-
component system. Kuczynski,“’ as early as 1949,
indicated that at least four different mechanisms
could be responsible for particle-to-particle bonding,
including viscous flow, chemical reaction, diffusion,
and surface tension.
Barnhart and co-workers106~‘07introduced a sinter-
ing test as an index of ash fouling tendency of Eastern
bituminous coals as early as 1956. The test was
performed on fly ash generated in a very specific
laboratory combustor simulating residence time and
temperature in full-scale steam generators. The fly ash
was ignited to 490°C to remove carbon and then
crushed to a specific size and pelletized to conform to
a standard. The pellets were heated in a furnace at
sintering temperature for 15 h. The pellets were
dressed and subjected to compression testing in a
standard tensile machine. Figure 25 illustrates the
results for Illinois coals.‘o63’o7The procedure must be
followed precisely, including the generation of the
initial fly ash. The results provide a guideline for
fouling that is restricted to high-alkali Eastern
bituminous coals responsible for sodium- and
potassium-bonded deposits dependent on viscous
flow of complex sodium and potassium silicates and
whose fly ash includes previously formed complex
alkali-silicates. The curves in Fig. 26 indicate the
sintering strength increases exponentially with tem-
perature and can be represented by the Arrhenius
“C
1000 1100
I I
equation:
C = AemEIRT. (17)
Consequently, Barnhart’s data can be illustrated on
a semi-log plot vs the reciprocal of the temperature, as
shown in Fig. 26. In this way, comparisons can be
easily made with those of other investigators.
Barnhart and Williams”06 sintering tests spawned
application of the procedure on new fuels and
development of new techniques involving con-
ductance, ash shrinkage, etc. Other investigators
have found there is a lack of consistence between
measurements performed on field-generated fly ash,
fly ash generated in the laboratory, and ASTM ash.
This stands to reason as the sintering process must
reproduce the precise manner in which the ash is
deposited if the results are to be representative of
fouling in the convection bank. At least two different
types of sintering have already been identified as being
responsible for fouling in the heat-recovery zones of
steam generators. The same sintering test could not
be expected to simulate both types of fouling,
particularly if they occur simultaneously or in series.
Application of Barnhart’s sintering test to lignites
indicated the criteria for fouling established by
Barnhart did not apply.“’ However, the correlation
of sintering strength with temperature appears to
agree reasonably well with correlations of deposit
weight on field probes and pilot plant probes with
temperature. The results appear to be more favorable
from a mechanistic approach than an empirical
approach.
In subsequent investigations, measurements of
 Steam-raising fuels 57

BECOMPOSITION
Decomposition of CaSO, Decomposition of
I ’ --_-----
in the Presence of Illite, etc. ’ Pure CaSO,
I
MELTING TEMPERATURES

Na-Al-Silicates 4

Na,SO,
* ESo4)2

1600°F 1800°F ZOOO'F 2200°F 24OO'F

100,000

Jnvestiqatar Forms of Sodium

Barnhart Silicates

Gibbs Silicates & Chlorides

Walchuk Organic

CClMl organic

Selle Organic

Cunning Silicates & Chlorides

Yilu Silicates

0.75 0.70 0.65 0.60 0.55 0.50 0.45 0.40

Sintering Temperature, l/T x IOOO-‘F

Fig. 26. Summary of sintering test data for various coals compared to Barnhart’s original data

resistivityand ash shrinkage were used as indicators at temperatures exceeding those used by Barnhart
of the formation of a molten phase in a homogeneous, to determine sintering rates for slag applications.
compacted, granulated ash as the temperature was Particle size and alkali concentration had a strong
increased, thus indicating the onset of the viscous flow effect on the rate of sintering.
sintering process. The initial tests were performed The same principles were used to evaluate the
58 R. W. Bryers
impact of temperature on sintering. In most cases,
sintering measured by resistivity was coupled with
tests on shrinkage and compressibility. Conn and
Jones”” test was applied to lignitic ashes rich in
sulfates and calcium. Sintering was observed slightly
below the melting temperature in ASTM ashes
(i.e., @SC) and between 700-800°C for fly ash.“’
The mineral species hauyne nosean [(Na2Ca), .
5AlSi04(S04)], whose melting temperature falls in
this range, was found to be present. The sintering
temperatures defined by Conn and Jones coinci-
dentally agreed very well with melting points defined
by differential thermal analysis endotherms reported
by Bryers8’ for the decomposition of sulfates in the
presence of silicates. The mechanism for sulfatic
bonding, however, is quite different. The compres-
sion test appears to evaluate the fouling tendency
very well and agree with Barnhart and Williams”09
test although the ash composition was different.
The results are somewhat low for predicting actual
fouling in steam generators based on bulk gas-stream
temperatures.
Cummingeral.“O and Yilu”’ investigatingsintering
due to bituminous and anthracite ashes from
England, North America and Chinese, all report
sintering in the ‘non-fouling range’ reported by
Barnhart. Cumming et cd.“’ explained sintering
using the ‘necking’ theory proposed by Raaskz2 in
which the neck formed between adjacent particles was
the source of ash shrinkage and simultaneous change
in resistivity. The neck is driven by surface tension
forces and increased inter-particle content areas
reducing the ash resistance rather than increasing
ionic migration due to the molten phase.“’ Several
investigators evaluated additives synthesized in the
laboratory rather than generated during combustion
and indeed found a reduction in sintering.“2”3
Stallmann and Neave1114 investigated sulfides under
reducing conditions as a means of examining deposits
found in pyrolyzers with melting temperatures well
below the predicted ASTM initial deformation
temperatures. The ashes were found to sinter
between 537-777°C. The data may be applicable to
low-rank coals fired with a deficiency of air.‘14
Sintering via viscous flow is a process dependent
on time and surface tension and inversely pro-
portional to the square root of the viscosity and
particle size. The viscosity decreases exponentially
with temperature. The change in surface tension
with temperature is small. The sintering process in
situ in the steam generator occurs as a result of
condensation of alkalis on silicates. Consequently,
as proposed by Jackson, the alkalis are concentrated
at the particle surface rather than occurring as a
homogeneous spheroid of fly ash.47 As the tempera-
ture increases, the alkalis flow as silicates away from
the sphere forming necks between adjacent spheres
as well as diffusing inwardly. The composition of
the surface changes with time and temperature as
more silica goes into solution and alkali flow away,
unless the alkalis are replaced at a comparable
condensation rate. The latter is not simulated in the
laboratory testing, nor is the difference in composi-
tion between fly ash and deposited ash. Fly ash, be it
generated in the laboratory or the field, has a
decidedly different composition from deposited ash,
particularly in regard to the surface concentrations of
sulfur and alkalis, as the latter react with the silicates
in the immediate environs of the tube surface where
residence time is long.
Rindt et ~l.,“~ Benson,‘15 Bryers,87 etc., have
reported that the mellites form at the tube surface as
a result of decomposition of sulfates in the presence
of silicates. Furthermore, Rindt et ~1.“~ reported a
significant change in composition of sodium silicates
as one proceeds from the tube surface to the fireside
surface of the deposit. The lower melting hauyne
noseans are found near the cooler tube surface along
with sulfates, whereas the higher melting gehlenites
are concentrated in the outer layers. Finally, not
only does the composition of fly ash change with
rank, but so does the sintering mechanisms. It may
be that viscous flow sintering only applies to the
outer portion of deposits formed by higher rank
coals. The sintering tests are highly empirical and
should not be extrapolated from one fuel type to
another unless the mechanisms of fouling are
clearly understood, the local environmental condi-
tions under which fouling occurs are well defined, and
the sintering procedures are upgraded to properly
represent the sintering mechanism taking place in the
steam generator.
3.7. Pilot Plant
In the early 196Os, investigators began to use pilot
plants firing coal at a rate of about l,OOO,OOO B.t.u./h
to evaluate the fireside behavior of coal ash. Presently,
there are 60 or more combustors owned and operated
by industry, government, and academia dedicated to
the examination of fouling and slagging. Most of
the combustors have been catalogued in a register
organized by Higgins and Morley”’ as a project
sponsored by the ASME Research Committee on
Ash Deposits and Corrosion Due to Impurities in
Combustion Gases. Although the thrust of the
combustor work is directed at evaluating fouling,
some investigators have been successful at evaluation
of slagging.
The combustors have been fired vertically up,
down, and sideways. Most use a refractory-lined
chamber with and without supplemental cooling. As
one reduces the size to fit the economic constraints of
the laboratory, the surface-to-volume ratio increases
to a level that prohibits water cooling if the desired
furnace exit temperature is to be met in a reasonable
residence time. Slagging must be evaluated on a semi-
quantitative basis. To match absorption rates, gas
temperature, and surface temperatures, it is desirable
to immerse more than one probe in the furnace.
 Steam-raising fuels 59

8000
YALLOURN COAL

BOILER PERFORMANCE-COAL QUALITY RELATIONSHIP

700 - A YALLOURN ‘C’ STATION

- 40 weeks
MORWELL SOILERS

s
4 6000 -
s
V

5ooo _30 weeks

F
Y
In
9

p 4ooo-

f
I - 20 weeks

9 3000 -
a
z
B

$!j 2000 -
- 10 weeks

1000 -

YALLOURN X MORWELL A
MORWELL
0 I I I I I COAL
0 0.1 0.2 0.3 0.4 0.5 0.6

FOULING INDEX

Fig. 27. Fouling index vs boiler availability.“9

Probes oriented parallel and perpendicular to the
direction of flow should be included to monitor the
difference in slag formation by coarse particulate
depositing by inertial impact and fine particulate
depositing by thermophoresis or diffusivity. Fouling
probes are usually installed in the convection pass at
the furnace exit where they are shielded from direct
flame radiation.
Characterizing the fouling potential of a coal ash is
the primary objective of each pilot plant. Although
fouling probe tube size, spacing and orientation as a
bundle should simulate thermal and fluid simultude to
full-scale bundles, the arrangements vary consider-
ably from facility to facility. Few fouling probes
are shielded from refractory sidewall radiation. All
probes should be monitored for axial and circum-
ferential temperature and have access to continual
visual inspection. Rates of deposition are difficult to
evaluate on a continuously operating facility except
by continuous recording of heat flux. Changes in
deposit composition with temperature or time can
only be monitored by using multiple probes or
performing numerous tests using time as a param-
eter. Since mineral species vary with rank and
geological origin of the coal and each rank of coal
has its own rate of deposit accumulation. Hence, the
testing interval must be geared to specific fuels. In
essence, each combustor is an empirically calibrated
instrument for evaluating slagging and fouling of a
specific fuel type and must have a substantial data
base to be of value. Deposits should be analyzed in
depth to understand the mechanism involved in
depositing ash in the combustor. By so doing, there
is some hope for translating the deposition to other
operating conditions beyond the scope of the
combustor.
The combustor built by the State Electricity
Commission of Victoria is an example of the ultimate
empirical use of a combustor for evaluating fouling of
coal from a dedicated source.“8.“9 Garner ‘I8 per-
formed a statistical analysis on the rate of deposit
formation as a function of ash chemistry.
Two ways of expressing the relation sought were
explored--the first took the form of a linear
expression:
“i’ = a[A] + h[B] + c[C] + d [D] + I + K (18)
where y is the weight of deposit, [A], [B], [Cl, [D],
etc. are the various inorganic constituents in the
coal, and a, h, c, d, etc. are coefficients to which the
60 R. W. Bryers

System Temperatures
1. Primary Combustion Air 10. Combustor Bottom Refractory
2. Secondary Combustion Air 11. Combustor Middle Refractory
3. Tertiary Combustion Air 12. Combustor Top Refractory
4. Tertiary Combustion Air 13. Probe Bank 2 Exit Refractory
5. Comb&or Exit Stack
6. Probe Bank 1 Exit
7.
8.
9.
Probe Bank 2 Exit
Probe Bank 3 Inlet
ESP Inlet
Sample PI
Cyclone v Draft
Fan

> Bypass
/I Cyclone
Pulverized
Electrostatic
Coal Feeder
Precipitator
and Control

u Combustor EERCJGl1331.CDR

Fig. 28. University of North Dakota upfired furnace.‘*’

multiple linear regression analysis describes a level
of significance; the value K is a constant.
The second form was related more closely to the
way in which chemical reaction rates may be
expressed:
y’ = K[A] : [B] b [D] ‘!
This form could be evaluated by the multiple linear
regression analysis when expressed in the form:
logy’ = log K + a log [A] + b log [B]
+ clog [C] + d log [D]
The coefficients a, b, c, d, etc. in this equation being
the exponents in Eq. (19).
The equations developed by this statistical analysis
give excellent correlation between calculated values
for the weight of ash deposited and the actual weights
measured in the furnace. The equations developed are
as follows:
y = 0.030 [TiO*] + 0.99 [Fez03] + 0.061 [CaO]
+ 0.264 [MgO] + 0.423 [Na20] - 10.6
and
y’ = 0.044 [TiOz] “op4[FezOx] o“?99[CaO]
“?*’ [Mg()] ‘? [Na20]0.728~
Sodium was found to be the most significant
constituent. Magnesium was surprisingly high on
the list of significant constituents; its role, however,
appeared to depend upon the presence of CaO and
Na2Q118,119
The double salt MgS04. Na2S04 melting at 680°C
was identified in the deposits from the Morwel coal.
(19) Magnesium sulfate was also reported but in small
proportions compared to the MgO.
The utility of Gardner’s correlation is illustrated in
Fig. 27, showing how the expression was used to
predict operating time between outages. The fouling
index was also used to flag core samples in the mine
(20)
field to permit blending of the coal and to maintain a
low sodium level.“’ The correlations, however, are
empirical and do not apply to any other coals.
The University of North Dakota has probably
accumulated the largest data base on firing low-rank
coals. Their tests also included an assortment of other
rank fuels and petroleum coke. Over 750 tests have
been performed in this facility, backed up by extensive
analytical capabilities for characterizing coal and
deposits including CCSEM, chemical fractionation,
(21) SEMPC, X-ray fluorescence and X-ray diffraction.12’
The facility, illustrated in Fig. 28, has been used to
quantitatively compare the fouling potentials of
Western coals due to organically-bound sodium.12’
Careful, detailed analysis of ash deposits from the
(22) pilot plant as well as from the field have identified the
role of sodium in high-temperature fouling. They
 Steam-raising fuels 61

Percent Ash ln the ioal

1 2 3 4 5 6789
1 2 3 4 5 6 789 : ,I(
_ -
9- _---_
.LSW
a._--__

Fig. 29. The impact of ash and sodium level on western coals on fouling determined empirically in a
laboratory combustor.

have shown, in Fig. 29, that the rate of deposit after bonding, but includes viscous flow. Ultimately,
5 h increases parabolically with total sodium in the gehlenite is formed at a level of which viscous
coal, and exponentially with total ash at a constant flow becomes the bonding mechanism. Numerous
sodium level.“’ Unfortunately, the time in all tests is investigators have shown that the alkali-bearing
limited to 5 h-a serious limitation in all pilot plant silicates formed as a result of the decomposition of
testing. Examination of the deposit indicated an CaS04 and/or Na2S04 in the presence of quartz
initial layer was formed consisting of NazS04 - and clays.86.“‘.‘23 Honea’ showed how an increase
CaS04. Subsequent crystallization gives the deposit in deposit temperature implemented by an increase
its strength. With increased growth in the deposit, the in tube surface temperature results in a decrease in
sodium and calcium mellilites and gehlenite form.‘2’ concentration of the inner white alkali-sulfate layer
Sintering is not purely condensation or gas-to-solid while increasing the formation of gehlenite. Benson rf
62 R. W. Bryers

al.” reported the mineral composition of the inner Table 9. Minerals occurring in coa1’7~48
layer as well as identified some low-melting minerals
Shale group
in intermediate layers in Table 6. Species: muscovite, illite, bravaisite, montmorillonite
Bryers and Walchuk ‘24 found in experiments with General formula: (K, Na, H30, Ca), (Al, Mg, Fe, Ti)4
bituminous coals that the initial layer laid down on (Al, SiOsOz@H, I%)
slagging probes was enriched with potassium origi- Kaolin group
nating as the mineral illite in the coal. Surfaces Species: kaolinite, livesite, metahalloysite
Formula: Alz(Si205)(OH),
subjected to direct impingement of flue gases or high Sulphide group
levels of turbulence were highly enriched with iron Species: pyrites, marcasite
originating as coarse liberated pyrites. Thin films of Formula: Fe&
iron were laid down by an iron fume on surfaces Carbonate group
Species: ankerite, ankeritic calcite, ankeritic dolomite,
subjected to zones of highest heat release, suggesting ankeritic chalybite
fluxing of silicates by iron took place at the slag General formula: (Ca, Mg, Fe, Mn)C03
surface. He also found pilot plants are not always Chloride group
successful in simulating full-scale fouling or slagging. Species: sylvite, halite
Pilot plants did not always accurately portray the Formula: KCI, NaCl
fouling potential of the coal ash on heat-transfer Accessory minerals group
surfaces. In the case of Texas lignites, high-
temperature surfaces such as the refractory in pilot Quartz SiOz
plants were prone to severe fouling, obscuring the Felspar (K, Na)zO-A1203 -6Si02
Garnet 3CaO - Al,O, - 3SiOz
fouling behavior of cooler probe surfaces and Hornblende CaO .3FeO -4Si02
producing misleading results. Fouling was due to Gypsum CaS04. 2Hz0
the formation of a low-melting silicate entrained in Apatite 9CaO. 3PzOs - CaFz
the flue gas, which was prone to deposit on heated Zircon ZrSi04
Epidote 4CaO. 3A1203. 6Si02. Hz0
surfaces. Cooler heat-transfer surfaces in full-scale Biotite K20 - MgO - AllO . 3Si02. Hz0
boilers were not subject to fouling. Consequently, Augite CaO . MgO . 2Si02
one must understand mechanisms by which ash Prochlorite 2FeO. 2MgO. Al,03 - 2Si02. 2H2
deposits and differences in simultude between full- Diaspore A1203. Hz0
scale operation and pilot plants to effectively and Lepidocrocite FezOx - Hz0
Magnetite Fe304
accurately interpret results. Hyanite A1,03 - SiOz
Drop tubes have been used to examine the Staurolite 2FeO. 5A1203 - 4SiO2 . Hz0
transformation of minerals during combustion and Topaz (AlF)$i04
to study the impact of an isolated low-melting species Tourmaline H9A13(BOH)2%019
Hematite Fe203
in the fly ash on fouling. Moza and Austin3’ used a Penninite 5MgO - A1203 ’3Si02 - 2H20
drop tube to examine the sticking potential and
adherence of various mineral species on a substrate at
temperatures and surface conditions simulating heat-
transfer surfaces in a steam generator. The apparent the case. The results are generated in the laboratory
contact angle and adhesion force of the deposited under heating conditions, whereas slagging and
particle to the substrate surface for various substrate fouling occur under quenching conditions. In the
temperatures and surface conditions was examined case of sintering, more than one mode of sintering
by Moza and Austin.35 They found that iron-rich may be taking place simultaneously or in series as the
glass, probably originating as the 2.95 pyritic-rich deposit develops. Consequently, one must know
gravity fraction, and illite melt more thoroughly and which sintering process dominates so that the
remain fluid longer as a super-cooled glass contrib- operating conditions may be duplicated. Deposited
uting to greater adhesion. Partially decomposed ash or fly ash identical to that generated in a full-scale
pyrites gave good wetting and high adhesion strength facility must be used.
at a substrate temperature as low as 3OO”C,as shown Despite numerous innovations in combustion
earlier in Fig. 10. system technology and substantial increases in
combustion system capacity over the past 70 years,
3.8. Summary of Empirical Approach steam generators are still designed and coal is still
traded on the basis of fusibility generated by
Empirical procedures used to evaluate slagging techniques developed outside the technology and
or fouling are usually limited to a small range of applied to stoker-fired boilers. Over 4000 individual
fuels. Consequently, they work best for captive coal investigations have been made to extend the range of
situations where variations in mineral matter are applicability of the fusibility data, develop highly
small, mechanisms of deposition are consistent, and empirical indices, or examine the fundamentals of
design and operating variables remain constant. Most deposition and corrosion to obtain a better, more
empirical indices assume a homogeneous mineral accurate procedure for characterizing the behavior of
composition and distribution, which is not always coal ash. The fundamental studies, although directed
 Steam-raising fuels
MAG. 15X
MAG. 15X
A - Finely Dispersed Pyrite Crystals
6 - Undefined Aluminosilicate Clay Inclusion
C - Quartz Inclusion
D - lllite Inclusion
Fig. 30. SEM photomicrographs of various
at very specific situations, have made it possible to
place limitations on gas or metal temperatures for
specific categories of coal. All the research efforts,
however, have been directed at establishing the
potential for coal to create a fouling, slagging or
corrosive situation. During this period of time, steam
generators were designed for specific fuels and, for the
most part, operated on a captive fuel source or long-
term contract. Since the early 1980s the situation has
changed drastically. Steam generators are expected to
operate on a variable fuel supply, including coals of
different rank containing decidedly different mineral
composition. Fuels from new reserves with decidedly
different mineral compositions are being introduced
to the marketplace. In addition, fuels are being traded
on the international market which contain mineral
compositions whose fireside behavior is unproven. To
meet these new demands, fuels must be characterized
in greater depth and the fundamentals of mineral
transformation, mineral composition, and mineral
deposition must be more clearly understood by
operators and designers.
MAG. 150X MAG. 3000x
E - Pyrite Veins
F -- Pyrite Fracture Filling
S - Calcite
forms of pyrites, quartz. and calcite in Illinois no. 5. coal
4. MECHANISTIC APPROACH
The empirical approaches to fireside behavior of
impurities in coal frequently fall short of satis-
factorily predicting fouling and slagging because they
do not adequately characterize the fuel and its
impurities, and they do not properly model the
chemical processes taking place during combustion
and post-combustion quenching. Coal is a hetero-
geneous substance composed of an array of mineral
and coal components whose individual thermal and
chemical behavior may be quite different upon
heating. In the previous discussion, it was observed
that partitioning of the elements due to volatilization
occurs in the combustion process. In addition, there is
a difference in the way minerals occur and are
associated with carbon and other minerals within the
total coal mass, which affect the true melting and
solidifying temperature of each fly ash species entering
the steam generator, as well as the quantity of mineral
volatilized. Consequently, coals must be characterized
to account for variations in mineral occurrence and
64 R. W. Bryers

COMBUSTION TRENDS

Moisture w Decreases >

Flame Temperature > Increases )

X Ash ) Increases c

Volatility of Inorganic 4 Decreases _

. Slagging Potential Increases )

Fouling Potential c Decreases c

GENESIS OF COAL

PEAT SWAMP LIGNITE SUBBITUMINOUS BITUMINOUS

A PORTION OF Ca LEAVES SYSTEM

Greatest

ORGANO-METALLIC
COMPOUNDS COMPOUNDS MINERALS
I
Ca,Na,Fe Na,Fe,Cad * Silicates
Si,Al,K.Na,Fe

MINERALS ?? F$;i!j'
SOLUBLE SALTS

Si.Al,Ca,Fe.K,Ba. Na,Ca * Silicates * Carbonates

S,Al.K Ca,Mg,Fe

SURFACE AND * Carbonates

GROUND WATER Ca,Mg,Fe,Ba

Na,Fe,Ca,Ba,S,Cl * Silicates
r * :::xv

* Carbonates * Sulfates
Ca,Ba

SOLUBLE SALTS

Least Na,Ca

'"'"""l'4~~1~"~~~~ WATERS-

= Major source of elements

(T; = Traces

Fig. 3 1. Transformation of mineral matter during coalification.

potentialpartitioningofmineralspeciestosuccessfully Nodules including lenticular and spherical concre-

predict slagging, fouling, and/or corrosion.
4.1. Mineral Matter in Coal
Mineral matter in coal is generally considered to be
the sum of all the discrete inorganic mineral phases
and the organically-bound inorganic elements found
in coa1.‘25V’26 There are over 125 different minerals
found in coal. However, only the 25 reported in Table
9 have been recognized as occurring in significant
amounts.‘7~48~‘27The minerals in coal occur as discrete
grains, flakes, or aggregates in one of five modes:
?? Microscopically-disseminated inclusions with mac-
erals.
?? Layers or partings wherein fine-grained clay
minerals usually predominate.
tions.
Fissures including cleat and other fractures or void
fillings.
Rock fragments, megascopic masses of rock
material found within the coal bed as a result of
faulting, slumping, or related disturbances.”
Figure 30 illustrates some of these mineral forms.
Harvey and Ruch’26 explain an understanding of
the genetic classification of mineral matter inclusions
in coal during the coalification process, provides a
means for predicting the quality of coal in areas
ahead of mining and exploration, as well as the
degree to which the coal can be altered by beneficia-
tion and mineral transformations predicted during
combustion.
The ancient coal seams comprising our present coal
reserves were formed from vast peat swamps. The
 Steam-raising fuels

MAG. 3000x MAG. 4000X MAG. 3200X

Fig. 32. Various types of pyrite crystals found in different bituminous.

SiO,

\ Number of
Sample Locations

Appalachian Basin

Western Interior

Northern Great Plains

Rocky Mountains

L-- ”

50 Fe,O,
\

+ CaO + MgO
AP,

Fig. 33. Variation of principal inorganic constituents in coal ash from various U.S. coal basins and
regions.“’

swamps were located on coastal plains often adjacent reduction of aqueous sulfates resulting in crystal
to river deltas. Over periods of many centuries, the growth in microscopic pores within plant remains.
swamps subsided while layer upon layer of fallen The second genetic group includes mineralization
vegetation covered the peat. This vegetation con- around nuclei or other centers forming nodules. These
tained minerals in its tissues that had been drawn into include coal balls and other plant replacement
the plant life during its growing stage. The fallen forms. The third group, epigenesis, includes miner-
vegetation introduced the first genetic group of als formed after the peat was identified as fillings in
minerals into the swamp: detrital-deposited minerals fissures and voids and as products of weathering or
formed by crystallization of inorganic elements oxidation.‘26-‘30
incorporated into the tissues of living plants The process of coalification is a slow, complex
(inherent mineral matter > 1% of the coal ash). process involving increasing pressure and heat with
Detrital deposition also includes minerals introduced time, driving moisture out. Methane and CO1 are
into the swamp as silt from discharging rivers, dust generated and trapped within the pores. Several
from wind storms, or volcanic eruptions. Ultimately, chemical processes take place, described as petri-
the swamps were drowned by discharging rivers or sea fication, humidification, gelification, and vitrification.
water; coastal swamps invaded by sea water were resulting in the transformation of vegetation into
injected with sulfate. The life of the swamp repeated vitrinite-the primary maceral group. Partial oxida-
itself numerous times., each contributing to a new tion creates char or fusinized debris classified as
layer of residue. inertinite. With increased coalification, all macerals
The second generic: group, syngenetic minerals, become enriched with carbon, eventually forming
were formed during the peat stage by bacterial anthracite.‘26m I30
66 R. W. Bryers
During coalification, mineral matter undergoes
transformation. The concentration of silicates and
clays increases due to an increase in coal density. As
the chemical bonds are destroyed, the alkali metals
are transformed from organo-metallic compounds
to dissolved salts and eventually silicates, as shown
in Fig. 31.‘29,‘30 Organically-bound iron and iron
carbonates are precipitated as a sulfide in voids,
fissures and fractures, particularly in coal beds
invaded at some point in time by sea water.
Calcium precipitates as a carbonate or sulfate and
in time, form calcite or react with silicates to form
feldspars.
Iron, which exists in some instances as carbonate in
Iignites, is precipitated as a sulfide in bituminous coals
in voids, fissures, and fractures. Consequently, the
ratio of pyritic iron to total iron in the ash increases to
nearly 100% as coal is aged from the lower ranks to
bituminous. Figure 30 shows how iron and calcium
are transformed from inherent ash and organo-
metallic compounds at location A to precipitates in
coal fissures at locations E, F and S within a
bituminous coal. Figure 32 is an example of pyrites
existing in a crystalline form, possibly generated
during the syngenetic stage. The characteristics of the
mineral composition varies decidedly with coal rank
and with its original exposure to either fresh or sea
water intrusion producing decidedly different fireside
behavior. Glick and Davis13’ show the expected
variability of the five key elements by geological
basin and region in Fig. 33.
Minerals occurring in aged coal may be classified
into five main groups. These include shale, clay,
sulfur, and carbonates. The fifth group includes
accessory minerals such as quartz and minor
constituents such as feldspar.16
Shale, usually the result of the consolidation of mud,
silt and clay, consists of many minerals including illite
and muscovite-these are forms of mica. Kaolinite is
the most common clay minerals.‘4”6
The sulfur minerals include pyrites with some
marcasite. Marcasite has the same chemical compo-
sition as pyrites but a different mineralogical
structure. Sulfur is also present as organic matter
and occasionally as sulfate. The latter usually
occurs in weathered coal such as in outcrops. The
amount of sulfate-sulfur in coal is generally less than
0.01%.
Generally, 60% of the sulfur in coal is pyritic,
particularly when the sulfur concentration is low. At
higher concentrations, it may run as high as 70-90%.
Pyrite occurs in coal in discrete particles in a wide
variety of shapes and sizes. The principal forms are:‘4,‘32
?? Rounded masses called sulfur balls or nodules an
inch or more in size.
?? Lens-shaped masses which are thought to be
flattened sulfur balls.
?? Vertical, inclined veins, or fissures filled with pyrite
ranging in thickness from thin flakes up to several
inches.
?? Small, discontinuous veinlets or pyrite, a number of
which may sometimes radiate from a common
center.
?? Small particles, greater than 2~, or veinlets
disseminated in the coal. Microscopic pyrite
occurs in five basic morphological types:
-framboids;
-isolated, well-defined crystals;
-non-spherical aggregates of euhedral crystals;
-irregular shapes; and
-fracture fillings.
The term ‘framboid’ is derived from the French
word for raspberry and thus refers to naturally
occurring spheroidal clusters of hundreds of cubic
or octahedronal crystals.133Y135
All coals contain some of the third and fifth forms
of pyrites, and some coals contain all five of the
principal forms.125,134~‘40
The carbonates are mainly calcite, dolomite, or
siderite. The occurrence of calcite is frequently
bimodal. Some calcite occurs as inherent ash, while
other calcite appears as thin layers in cleats and
fissures. Iron can be present in small quantities as
hematite, ankorite, and in some of the clay minerals
such as illite. In addition to the more common
minerals, silica is present sometimes as sand particles
or quartz. The alkalis are sometimes found as
chlorides or as sulfates, but probably most often as
feldspars, typically orthoclase, and albite. In the case
of lignites, unlike bituminous and sub-bituminous,
sodium is not present as a mineral but is probably
distributed throughout the lignite as the sodium salt
of a hydroxyl group or a carboxylic acid group in
humic acid. Calcium, like sodium, is bound organi-
cally to humic acid. Therefore, it too is uniformly
distributed in the sample.101,‘36
The mineral composition of Australian coals differ
substantially from that of North American and
European coals. The Black coals contain from 10 to
17% ash and are low in moisture. The Victorian
Brown coals contain less than 5% ash and more
than 60% moisture. Virtually all Australian coals
contain less than 1.3% sulfur and very little
chlorine. Unlike Northern Hemisphere coals in
which iron appears primarily as pyrites and
marcasite, the iron in Australian coals occurs as
siderite and ankerite. In the low-rank Brown coals,
iron is also found as organically-bound mineral
matter and frequently occurs in concentrations
exceeding that of aluminum-not a trend usually
found in Northern Hemisphere coals. Calcium is
generally low and usually appears as a carbonate in
the older coals and organically bound in the low-rank
Brown coals. Magnesium, sodium, and significant
portions of the potassium present also appear as
organically-bound mineral matter. The highest
concentration of sodium is found in the low-rank
coals.‘4’
Despite the apparent order in mineral formation by
geological origin, anomalies do occur. Some lignites
 Steam-raising fuels 67

Table 10. Chemical fraction results”’

Initial % Removed % Removed % Removed % Remaining

(pg/g dry coat) by Ha0 by NH_,OAc by HCI

Beulah lignite
Na 5700 42 57 1 0
Mg 2600 I 97 2 0
Al 5180 0 I 22 77
Si 7230 1 4 2 93
K 0 * * * *
Ca 11,500 0 74 26 0
Fe 10,650 0 I 27 72

San Miguel lignite

Na 19,700 28 72 0 0
Mg 6200 0 16 0 84
Al 11,030 0 7 89
Si 348.800 2 0 98
K 0 * * * *
Ca 26,300 0 65 25 10
Fe 12,700 0 0 49 45

Eagle Butte subbituminous

Na 1000 60 40 0 0
Mg 3300 9 55 30 6
Al 6700 0 0 37 63
Si 10,500 0 0 0 100
K 400 75 25 0 0
Ca 17.700 7 34 58 2
Fe 4000 8 0 78 I5

have been found enriched with pyrites, which could be
responsible for otherwise unpredicted slagging. In
some instances, minerals are reported that are
peculiar to a particular coal source. Zeolites are
the leading sodium source in Texas lignites.
Finkelman’42”43 reports high sodium levels in Utah,
Wasatch Plateau coals as the mineral anaclime
(NaA1Si0206 . H20), which has no record of fouling.
4.2. Mineral Anal,vsis
Characterization of minerals in coal has been
summarized for combustion engineers by Harvey
and Ruch,‘26 and Finkelman and Gluskoter.‘43 They
indicate sample preparation is crucial in charac-
terizing the mineral content of coal. Physical separa-
tion, leaching, thin and polished sectioning, and
low-temperature ashing are the four procedures
commonly used in preparing coal for mineral
characterization. Physical separation is a long,
laborious procedure that is inefficient in releasing
minerals from the coal, particularly in the small size
ranges. In the interest of time and cost, partitioning of
minerals and coal are performed on a very small size
and gravity matrix producing results subjected to
considerable error. Numerous solvents have been
used to dissolve either the organics or inorganics in
leaching processes. Problems have been encountered
with destruction of minerals by organic solvents and
significant hide-out of inorganics in the coal such as
clays, pyrites, quartz and carbonates due to encapsu-
lation of carbonaceous species. Thin polishing has
been used for mineral identification using petro-
graphic techniques. The low reflectivity of most
minerals in coal makes them difficult to recognize
and identify. Low-temperature ashing by passing a
stream of oxygen through an electromagnetic field
produced by a radio frequency oscillator at tempera-
tures less than 150°C which completely oxidizes the
carbon leaving an unaltered residue of minerals.
Unfortunately, artifacts such as bassinite are
generated from the mineral matter comprised of
organically-bound calcium. Similar artifacts are
generated from organically-bound sodium, magne-
sium, and iron. They must be recognized as artifacts
and not minerals indigenous to the coal.
Numerous techniques are now available for
characterizing minerals in the prepared samples.
X-ray diffraction performed on low-temperature ash
is a powerful tool and the most widely used technique
for qualitatively identifying the presence of minerals
in their crystalline form in concentrations of a few
weight percent or greater. Samples as small as
individual particles a few microns in diameter, to
samples as large as several grains can be analyzed.
The X-ray diffraction pattern is a signature analysis of
the minerals, permitting positive identification of the
minerals present. Although quantitative analysis of
mineral concentrations in LTA is frequently reported,
the technique requires further perfection.‘43
Thermal techniques such as different thermal
analysis (DTA) and thermogravimetric analysis
(TGA) have also been used as a signature analysis
based on changes in physical properties with
temperature. The properties monitored include
temperature weight and energy. Although the
system may work well pure mineral species, the
signatures generated may be altered or masked
68 R. W. Bryers

substantially if the mixtures exist and minerals cannot Table I I. CCSEM mineral
be isolated. ‘43 categories’50
Microanalytical techniques including scanning Quartz
electron microscopy (SEM) equipped with energy Aluminosihcate
dispersive X-ray (EDX), electron probe microanalysis K-aluminosilicate
equipped with EDX, transmission electron micro- Ca-aluminosilicate
Fe-aluminosihcate
scopy (TEM), and scanning transmission electron
Iron oxide
microscopy (STEM) have very good resolution to Spine1
very small particle sizes. SEM can magnify from 10x Aluminium oxide
to 20 000 x with a great depth of Focus and secondary Calcium oxide
electron image resolution to 150 A. STEM has spatial Dolomite
Ankerite
resolution in the order of Angstroms (lop4 pm). The Rutile
techniques can be applied to raw coal samples as well Calcium silicate
as low-temperature ash, and provide visual images of Apatite
the morphology of the mineral structure. The Pyrite
Gypsum
techniques are particularly useful in examining very
Barite
fine particulate. These techniques only provide partial Gypsum/barite
analysis for elements with atomic numbers 11 or Aluminosilicate/gypsum
greater. They are somewhat insensitive to sodium in Calcium aluminate
low concentrations-a key element in the fouling/ Iron suIfate/pyrrhotite
Calcium-rich
slagging process. Prediction of the minerals present is Silicon-rich
strictly by inference. Several groups of minerals have Periclase
very similar or even identical elemental composition, Unknown
but decidedly different physical properties (i.e., pyrite
and marcasite are both described chemically as FeSz).
It is also difficult to predict quantitative mineral fractionation to several ranks of coal to illustrate the
composition of a bulk coal sample from a micro- expected variation in organically-bound or water-
analysis. This is partially being overcome by using a soluble mineral species.‘50 It is important to note that
computer-controlled scan of a sample by SEM a comparison of the elemental analysis performed by
(CCSEM). One should understand, however, that ASTM ashing and chemical fractionation reveals a
the final mineral analysis is still by inference.143 deficiency in sodium level of the ashed coal. The
Extended X-ray analyses (fine structure) [XANE] is levels of sodium in the chemically fractionated coal
another signature analytical technique most recently may range from 40% to several orders of magnitude
applied to coal and cokes for specific identification of higher than found in ASTM ash, possibly accounting
the crystalline forms of minerals present.54 for some discrepancies in the empirical fouling
Mossbauer spectroscopy has been widely used for indices.lU
characterizing the mineral forms of iron in coal as well
as in slags and deposits.‘43 4.4. Mineral Distribution

4.3. Mineral Matter Analysis Complete characterization of the mineral content

The inorganic elements occurring in coals as
coordination complexes and ion-exchangeable
cations rather than discrete mineral phases are
determined by chemical fractionation-a process
whereby the inorganic constituents are selectively
extracted based on their bonding in the coal. The coal
is first extracted with water to determine the quantity
of water-soluble species. The residue from the water
extraction is then mixed with 1 M ammonium acetate
(NH40Ac). The ammonium acetate extracts the
elements associated with coal as ion-exchangeable
cations present, primarily as the salts of organic acids.
The remaining residue from the ammonium acetate
extraction is then stirred with 1 M hydrochloric acid to
remove the elements as acid-soluble minerals such as
carbonates and oxides. The elements remaining in the
coal after the extractions are associated with coal as
silicates, aluminosilicates, sulfates and oxides. Table
10 is an example of the application of chemical
of coal requires some understanding of how the
minerals are associated in the coal with each other as
well as the carbonaceous fraction. Mineral associa-
tions will determine the chemistry and physical state
of the individual coal fly ash particles during
combustion and post-combustion quenching. Their
association with carbon will influence partitioning
during combustion by forming more volatile species
as a result of their reduced oxide state as well as the
maximum temperature they will achieve. The distrib-
ution of minerals between inherent and extraneous
ash will also influence the extent to which coal can be
beneficiated as well as the impact of beneficiation on
the fireside characteristics of the deposited ash.
Several investigators have used simple size and
gravity partitioning techniques to examine the
mineral distribution in coa1.“,‘3-‘5 The procedures
are extremely laborious and full of pitfalls when
dealing with pulverized coal, particularly in the
fine size range. Samples are contaminated by the
 Steam-raising fuels 69

Table 12. CCSEM analysis of coals, results expressed as weight percent on a mineral basis15’

Size range, km

I .o--2.2 2.2-4.6 4.6- 10.0 10.0-22.0 22.0-46.0 46.0&100 Totals

Be&h
Quartz 1.2 2.1 2.8 3.8 4.2 3.3 17.4
Iron oxide 0.0 0.0 0.0 0.0 0.5 0.8 1.4
Rutile 0.1 0.1 0.4 0.0 0.0 0.0 0.2
Kaolin&e 0.0 0.0 6.4 0.1 0.0 0.0 0.4
Alumina 9.7 13.2 0.0 2.5 3.0 0.3 35.1
Montmorillonite 2.1 1.4 0.2 0.5 0.2 0.3 4.6
K Al-silicate 0.0 0.5 0.2 0.0 0.0 0.0 0.8
Fe Al-silicate 0.0 0.0 0.0 0.0 0.0 0.0 0.2
Ca Al-silicate 0.3 0.1 0.0 0.0 0.0 0.0 0.4
Aluminosilicate 0.3 0.1 0.0 0.0 0.1 0.0 0.6
Mixed Al-silica 0.4 0.1 0.0 0.0 0.0 0.0 0.5
Fe silicate 0.0 0.2 1.7 0.0 0.0 0.0 0.2
Pyrite 0.2 0.3 0.0 3.8 13.7 5.3 25.1
Pyrrhotite 0.0 0.1 0.0 0.0 0.4 0.0 0.5
Oxid. pyrrhotite 0.0 0.0 0.8 0.4 0.0 0.0 0.1
Gypsum 0.1 0.2 0.8 0.5 0.4 0.0 1.9
Barite 0.5 0.3 0.0 0.0 0.0 0.0 1.7
Gypsum/barite 0.1 0.1 0.0 0.0 0.0 0.0 0.2
Gypsum/Al-silica 0.1 0.0 0.0 0.0 0.0 0.0 0.1
Si-rich 0.2 0.0 0.0 0.3 0.1 0.0 0.7
Ca-rich 0.0 0.1 0.0 0.0 0.0 0.0 0. I
Unknown 3.0 1.9 1.2 I .o 0.4 0.0 7.5
Totals* 18.7 20.9 14.5 12.7 23.1 10.1 100.0

*Totals may not be correct due to rounding errors.

partitioning fluid. Separation of the gravity range of
the partitioning fluid is extremely poor. Separation of
small particles is interferred with by many extraneous
body forces approaching or exceeding that of gravity.
The scanning electron microscope and energy
dispersive X-ray, coupled with the computer (i.e.,
CCSEM) are presently being examined as a means of
determining the distribution of minerals in coal by
size. The micro-analyzer can examine many epoxy-
mounted particles in a reasonably short time. A direct
comparison can be made between raw coal, char and
fly ash samples using the same technique and set of
assumptions.
Computer automation of the scanning electron
microscope (SEM) and energy dispersive X-ray
(EDAX)-commonly referred to as computer-
controlled scanning electron microscopy (CCSEM)-
is being developed to locate dispersed inorganic
particles in coal and quantify their size, shape, and
composition. When coupled with automated digital
image analysis, morphological data can be stored,
examined, and used to determine differences between
the included and excluded mineral matter as well as
species sharing partially common boundaries (i.e.,
juxtaposition of minerals with coal). The two
systems may be applied to raw coal, partially spent
char, and fly ash or deposited ash, in effect revealing
changes in mineral chemistry at various stages of
combustion.145-‘48
SEM and EDAX analyses can be applied manually,
directly on raw coal samples, deposited ash, or fly ash.
The results are limited to exposed surfaces and hence
the subjective surface selection and interpretation by
the investigator: Secondary electron emission is
limited to 100 A penetration while back-scattered
electron emission is limited to 300A penetration,
limiting EDAX analysis to surface composition.
Automation of the SEM/EDAX analysis requires
the pulverized coal, ash deposit or fly ash specimen to
be mounted in epoxy and polished to obtain a more
objective quantitative analysis. Automated methods
employ SEM and the electron microprobe analyzer
(EMPC) equipped with an energy dispersive X-ray
spectrometer (EDS or EDAX), to which are applied
the CCSEM and scanning electron point count
techniques (SEMPC). With the addition of auto-
mated image analysis technique, morphological data
can be collected, stored, and analyzed as well.‘45
The CCSEM analysis employs back-scattered
electron imaging as the back-scattered electrons
provide a significant contrast in the image as their
intensity varies with average atomic number. The
differences in contrast can be used to distinguish
between epoxy, coal, and mineral as the electron
beam scans the surface. In the beginning of the
procedure a scan is made and the image stored in the
computer for future image analysis. The electron
beam is programmed to scan the field of view. Upon
finding a bright inclusion, defined as a mineral
inclusion, the beam performs eight diameter measure-
ments in order to locate the center. An EDAX scan is
performed at the center for twelve elements including;
Na, Mg, Al, Si, P, S, Cl, K, Ca, Fe, Ba, and T.‘45.‘46
An associate computer then analyzes the data for
size area perimeter and chemical composition. Empi-
rical correlations for area-to-volume relationships
 70 R. W. Bryers

EAGLE BUTTE SUBBITUMINOUS

Ca Al
0.0 0.1 0.2 0.3 0.4 OS 0.6 0.7 0.6 0.9 1.0
B3m7a

(A) 0.2 5 Dp < 10 I(M, 869/1092

Si
A

Al
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.6 0.9 1.0
eso3?b

(8) 10 s D,, ( 40 PM, 295/344 PARTICLES

CA-AL-~ ASH COMPOSITIONFOR CROSS-SECTIONEAGLE BUTTE ASH

BY CCSEM AT UND (1500 K, 21% 02)

Fig. 34. Ca-AI-Si ash composition ternary diagrams for CCSEM of Beulah lignite and Eagle Butte
subbituminous at 1500K 21% Oz. Each point represents ash particles with CA + Al + Si >80moIe percent
(courtesy of Dr. J. J. Helble).

developed from standards permits particle size
identification. The elements defined in the EDAX
spectra and the individual elemental count is
compared to those of an extensive list of mineral
categories appearing in Table 11 for identification of
the minerals in the particle. Unidentifiable minerals,
by virtue of unrecognizable elemental composition
or complexity of association (as in the case of a
mixture of aluminosilicates of similar composition)
are listed as K-aluminosilicates, Ca-aluminosilicates,
or unknown. The density of the identified mineral is
used to calculate the weight percent from the volume.
A subsequent program counts the identified mineral
species by area and/or weight and composition, and
summarizes the results in weight distribution form
illustrated in Table 12. Once the data is stored. the
 Steam-raising
45-07 CCSEM Data
particles 14.6 microns
Si
Ca
Fig. 35. CCSEM #data presented on a ternary diagram using a third dimension to express concentration
specific size range (courtesy
computer becomes a powerful tool for analyzing,
characterizing, and displaying the mineral composi-
tion of the coal. As an example, the data can be
illustrated on a ternary diagram that can be used to
visually examine pertinent physicochemical proper-
ties, as shown in Fig. 34.1M
To unmask overlaid data points in congested areas
encompassing large concentrations of data, a third
dimension may be used to illustrate the frequency of
occurrence of a specific mineral species, as shown in
Fig. 35.‘48 Such a diagram quickly identifies levels
of concentrations of low-melting species formed by
association of one or more minerals within the coal.
The technique also permits direct comparison of the
mineral composition of fly ash and deposits with that
of the raw minerals in coal, revealing transformations
during combustion and identifying species respon-
sible for fouling as illustrated in Table 13.“’ Possibly
the oldest application of CCSEM is identifying
particle size. With CCSEM one can make a direct
comparison of fly ash size distribution to mineral size
distribution, providing the first step in predicting char
and mineral fracturing and agglomeration during
combustion.
The procedure is not without flaws or weaknesses.
fuels 71
for a
of Dr. J. J. Helble).
Prediction of particle size and shape from a plane
intersecting the particle, which may or may not
include the particles true center, introduces potential
error. The magnitude of the error might be reduced
by expanding the data base. Assuming mineral
composition from percentage elemental X-ray count
is extremely difficult for particles composed of more
than one clay species, creating large concentrations of
unclassified or possibly mislabeled species. The
technology is developing rapidly and these problems
will no doubt be overcome.
The SEMPC technique is primarily applied to fly
ash and deposits as a means of quantifying the
chemistry of various phases. In the SEMPC tech-
nique, the computer-controlled stage is moved in a
raster pattern over the area of sample to be examined.
The stage is programmed to move in regular intervals
so as to collect a grid of data encompassing the area of
concern. At each interval (i.e., lOOpm), the stage is
halted and an EDAX spectrum is collected. A total
count is taken over a very short span of time to
identify the presence of sample. If a large count is
recorded, then ash has been detected and the count
is resumed and EDAX data collected. The process is
repeated over a minimum of 230 points. The collected
72 R. W. Bryers

Table 13. CCSEM analysis of coals, results expressed as weight percent on a mineral basis15’ (Con/.)

Size range, pm

1.o-2.2 2.2-4.6 4.6-10.0 10.0-22.0 22.0-46.0 46.0-100 Totals

Eagle Butte
Quartz 4.5 8.0 6.2 10.0 10.5 2.2 41.1
Iron oxide 0.1 0.0 0.0 0.0 0.0 0.0 0.1
Rutile 0.2 0.2 0.0 0.9 0.0 0.0 1.3
Calcite 0.5 1.4 0.0 0.3 0.0 0.0 2.2
Kaolinite 2.4 3.8 8.0 4.1 0.6 0.0 19.4
Montmorillonite 0.3 0.3 0.0 0.0 0.0 0.0 0.6
K Al-silicate 0.2 0.2 0.5 0.0 0.0 0.0 0.9
Fe Al-silicate 0.1 0.0 0.0 0.0 0.0 0.0 0.1
Ca Al-silicate 0.4 0.5 0.0 0.3 0.0 0.0 1.1
Na Al-silicate 0.2 0.1 0.3 0.0 0.0 0.0 0.3
Aluminosihcate 0.2 0.3 0.8 0.3 0.0 0.0 1.3
Mixed Al-silica 0.2 0.1 0.0 0.0 0.0 0.0 0.2
Ca silica 0.1 0.0 0.0 0.0 0.0 0.0 0.1
Pyrite 0.2 0.2 0.0 0.9 0.0 0.0 1.2
Pyrrhotite 0.0 0.0 0.0 0.4 0.0 0.0 0.7
Oxid. pyrrhotite 0.0 0.2 0.0 0.0 0.0 0.0 0.2
Gypsum 0.1 0.0 0.0 0.0 0.0 0.0 0.1
Barite 0.6 0.6 0.0 0.0 0.0 0.0 1.2
Apatite 0.0 0.2 0.3 0.0 0.0 0.0 0.5
Ca-AI-P 1.3 3.8 1.2 0.1 0.0 0.0 6.4
Gypsum/barite 0.2 0.2 0.0 0.0 0.0 0.0 0.1
Gypsum/Al-silica 0.1 0.0 0.0 0.0 0.0 0.0 0.6
Si-rich 0.3 0.0 0.0 0.3 0.0 0.0 1.0
Ca-rich 0.7 0.4 0.0 0.0 0.0 0.0 0.1
Ca-Si rich 0.0 0.1 0.0 0.0 0.0 0.0 17.8
Unknown 3.8 3.9 4.9 1.9 3.2 0.0
Total* 16.5 24.5 22.2 20.4 14.3 2.2 100.0
*Totals may not be correct due to rounding errors.

data is converted to quantitative chemical analysis.
Oxygen is calculated by difference restricting analysis
to completely oxidized deposits. The composition at
each point is compared to the chemical composition
of 43 phases commonly found in deposits as well as
X-ray diffraction patterns for the deposit. Those
compositions not appearing in the standard list are
identified as amorphic phases. The procedure appears
to be limited by the standard list and accuracy of the
X-ray diffraction and may not be able to identify
glassy forms or crystalline phases not reported in the
standards. However, once incorporated with an
automated image analysis procedure, differences in
chemistry between amorphic and crystalline phases
may become readily apparent, improving diagnostics
for the sintering process.‘4g,‘50
4.5. Thermal Behavior of Minerals
Minerals analyzed by gravity and size fractionated
coal, as well as CCSEM, have indicated the ash
generated during combustion of pulverized coal is
heterogeneous. Consequently, the physicochemical
properties of the individual particles influencing their
thermal behavior during combustion do not necessarily
conform to the values determined by analysis of a
composite sample but are related to the individual
pure mineral species in the coal. These properties may
be further altered by association with carbon or other
mineral associations. Consequently, the combustion
engineer must be concerned about the thermal
behavior of the pure mineral species as well as its
occurrence as inherent or extraneous mineral matter.
The thermal behavior of minerals commonly found
in coal has been examined by mineralogists for years
using differential thermal analyzers under air at slow
heating rates.” A large portion of these investigations
were summarized in an extensive survey of thermal
behavior of coal minerals by Watt.” The transforma-
tions experienced by several minerals most commonly
found in coal have been summarized by Jackson4’
and Bryers and Walchuk’24 in Fig. 36. The results
must be used only as a guideline for predicting the
thermal behavior, as thermal shocking during
combustion in the presence of carbon and other
mineral forms will alter some of these transforma-
tions and may defer others until post-combustion
deposition on heat-transfer surfaces. More recently,
Mitchell and Gluskoter”’ examined minerals released
from coal by means of low-temperature ashing (LTA)
(i.e., oxidizing carbon at temperatures of 150°C under
an oxygen plasma without disturbing the mineral
structure) by slow heating the released minerals on a
hot stage quenching and analyzing. The analyses were
performed at temperature, and after quenching the
results were summarized in Fig. 37.15’
Most transformations have been examined at a
slow heating rate. Consequently, there remained some
uncertainty as to whether they were chemically or
kinetically driven, Stinespring et a1.‘52 repeated the

3
P
950%
allmdwa
9bd.
Cakik
T
r’
FsS, Fep(SO&,FeO
IOOP to lloooc (partial melt)
525-Z’ ---c
F%Os
liquid
1600%
Fig. 36. Phase transformation of minerals commonly found in coal.
experiments with low-temperature ash in a combustor
at high heating rates. With the exception of pyrites,
he confirmed the transformation proposed by
Gluskoter and others, indicating the transformations
were thermodynamically controlled for all minerals
except pyrite. The decomposition of pyrite was
kinetically controlled and thus time dependent. The
investigations did not include phase separation due to
volatilization of mineral species reduced to a low
oxide state by included carbon.
Ulrich et ~1.~~ examined the transformation of
volatile species generated during combustion under
reducing conditions using JANAF tables to predict
vapor equilibrium compositions at high temperatures
under varying degrees of oxygen. Their data shows
that substantial amounts of silicon, aluminum, iron,
calcium, magnesium, sodium, and potassium can be
expected to volatilize under reducing conditions.
Aluminum, iron, calcium, and magnesium evaporate
as pure metals, whereas sodium and potassium
appear as pure metal cyanides depending upon
oxygen levels. The volatile species are formed at the
carbon flue gas interface. The degree to which they
are released is diffusion controlled. The vapors are
oxidized and precipitated during the migration process
forming submicron particles. Nucleation generally
occurs rapidly, forming a cloud of active particles that
Steam-raising fuels 73
quart3
(sol)
S, SO, 970% 1--s, HIS
III FI
coagulate at a decreasing rate. Brownian collision and
coalescence appear to be a major growth phenomena.
Growth ceases in the cases of oxides and metals when
the temperature drops below the fusion point.
Impaction caused by turbulence and fluid motion is
generally insignificant for submicron particles.86
4.5.1. Quartz
Quartz is the most abundant mineral found in coal.
It melts at 1723°C and boils at 2230°C. Under
reducing conditions, silica monoxide forms which
melts at 1420°C and boils at 2600°C while releasing an
SiO vapor. The vapor pressure of silicon is low in the
range of temperatures experienced during combus-
tion. Honig153 reports values ranging from 0.1 mHg
at 1157°C to 1 mHg pressure at 1852°C (see also Ref.
84). In the presence of carbon and other mineral
species, the vapor pressure is altered substantially.
When a mixture of aluminosilicate and graphite is
heated, the volatilization of silicon monoxide begins
at about 1150°C and reaches a maximum at 1400°C.
Mackowsky’54 reports that volatilization of silicon
monoxide starts at about 1649°C in the presence of
carbonates and clays, and reaches a maximum at
1704°C. In the presence of pyrites or metallic iron,
volatilization begins at about 1560°C and continues at
 R. W. Bryers
14
K(Si,AI)AI,O,,(OH)
Pyrite
t
’ FeS,
Calcite
’ CaCO,
Kaolinite Metakaolinite
Al2Si0,2Hr,O
Gypsum
4 b
%aSO;2H,O
Quartz
4 b
SiO,
Note: Analysis performed at temperature
Fig. 37. Summary of mineral transformations due to heating low-temperature ashed coal by Gluskoter and
Mitchell.“’
a rapid rate as the temperature rises until practically
all the silica in the mineral is volatilized. The melting
temperature of quartz and its volatility are very
important aspects of the thermal behavior of quartz.
However, it is the solidification temperature and the
impact of other mineral contaminants on it that affect
the sticking potential of quartz. It is quite apparent
that the role of quartz in fouling is multi-faceted
(i.e., condensed vapor, an absorbent of alkalis, and
captured aggregate), and consequently, it may con-
tribute to deposition within a given combustor in
several different ways.
4.52. Kaolinite
Kaolinite is the second major source of silica found
in coal. It is most frequently found in the partings of
the seam and as a finely-dispersed particle in the coal
(i.e., <l pm). It has a gravity of 2.60. Although it
experiences several transformations during its decom-
position, resulting in the loss of water, it does not melt
until 2343°C. Its role in fouling is that of a captured
aggregate or possibly an absorbent for alkalis.
45.3. Clays and Shale
The melting temperatures of most pure minerals
are in the vicinity or greatly exceed the maximum
Amorphous
b
Hematite
Fe,O,
Anorthite
b
CaAI,Si,O,
Mullite
4 +
AI,Si,O,,
Anhydrite
- CaO
Gehlenite
b
C%AI,SiO,
: Amorphous
4
flame temperature encountered during combustion.
Therefore, the fused spheroidal fly ash generated from
the mineral matter in coal primarily forms as a result
of the fluxing action between pure minerals
contained in a given particle. Illite and biotite
appear to be an exception. Both minerals contain
small concentrations of iron and potassium and form
a glassy phase at 950°C and llOO”C, respectively.
Depending upon its fluidity, this glassy phase could be
responsible for surface deformation at a relatively low
temperature and provide the necessary sticking
potential to prevent reentrainment on hot surfaces.
These minerals are stable to high temperatures;
however, Cl in the environment will release the
potassium as a volatile species.
45.4. Pyrite
Pyrite is the primary source of iron in Northern
Hemisphere coals. It has a specific gravity of 5.00.
Once liberated from coal or other minerals, it should
be easily separated from non-pyritic matter by gravity
separation at a Sp.Gr. of 2.85. Except for calcite and
illite, few minerals commonly found in coal have
gravities in excess of 2.70. Calcite has a gravity of
3.00, as does illite. Heavier gravity fractions generally
include large concentrations of pyrites with varying
degrees of contamination by illite, quartz, or calcite.
 Steam-raising fuels 75

Table 14. Potential reactions during oxidation of FeS2’56

Primary reactions
Reaction AH AH AH
FeS FeSz 02
KCal KCal/Mol KCal/Mol

1. 4FeSz + I SO2 + 8Hz0 = 2Fe203 + H2S04 1309.20 327.30 87.28

2. 2FeS2 + 702 + 2H20 = 2Fe203 + HzS04 629.78 314.89 89.96
3. 2FeS, + 702 + 2Hz0 = 2Fez03 + H,SO, 608.76 304.38 86.96
4. 2FeSz + 702 + 2H20 = 2Fez03 + 2Hz + 2SOx 546.46 273.23 78.06
5. FeSz + 302 = 2FezS04 t SO2 248.94 248.94 82.98
6. 4FeS2 + 1302 = 2Fe203 + 4SO2 + 4SOj 882.00 220.50 67.85
7. 6FeSz + 1902 = 2Fe20d + 6S02 + 6S0, 1271.30 211.88 66.91
8. 4FeSz + I IO2 = 2Fe201 + 8SOl 799.73 197.66 71.88
9. 2FeSz + SO2 = Fe304 575.14 191.71 71.89
IO. Fe& + 202 = 2FeO $- 4SO? 326.20 163.10 65.24
II. FeS2+302=Fe+2SOz 99.40 99.40 49.70
12. 4FeSz + 302 = 2Fez01 + 8S~a 222.92 55.73 74.32
13. 2FeSz + 202 = 2FeS -t 2S02 102.32 51.16 51.16

Secondary reactions
Reaction AH
KCal/Mol

I. 2FeS03 = FezO1 + SO2 + SO, -71.88

2. 4FeS04 = 2Fe203 + 4S02 + O2 -211.04
3. 3FeS0, = Fe304 + 3S02 + O2 -254.34
4. Fe& + 5Fe203 = 11 Fe0 + 2S02 -172.18
5. FeS2 + 16Fe20, = 11 FexOp + 2S02 - 107.58
6. 10FezOi + FeS = 7Fe304 + SO? -47.93
7. 5FeS04 + FeS = 2Fe304 + 6S02 -169.58
8. 3FeS + 2S02 = Fe304 + 5s -21.24
9. FeS+3S03 =FeO+4S02 +41.64
10. 2FeS04 + 3H20 = 2Fe(OH)3 + 2S02 + 1/202 -78.46
Il. FeS04 = Fe0 + SO3 -62.40
12. 3FeS04 + 1/202 = FexOp + 3S03 -111.50
13. 2FeS04 + 1/202 = Fe20s + 2S03 -56.00
14. 3FeS2 + SO2 + O2 = Fe304 + 7s +68.47
15. 2FeSz + SO2 + 1/202 = Fe201 + 5s f40.49

Pyrite is a combustible mineral with a heating value encapsulated in a molten layer of pyrrhotite can be
of 3000 B.t.u./lb, whose decomposition is kinetically responsible for the formation of very high melting
dependent. The rate of decomposition is governed slag (i.e., containing as much as 85% Fe203, as shown
by reaction rates, pore diffusion, and bulk or stream earlier in Table 4). Srinivasachar et al.‘60 and Wa1l’59
diffusion, as well as the presence of adventitious report the oxidation of pyrrhotite and magnetite
impurities.l7.'55-160
Although the bulk of the particle crystallization, during which time a melt may exist,
does not shrink during combustion, some frag- accounts for more than 80% of the total decomposi-
mentation occurs altering the mineral size dis- tion time, as shown in Fig. 39. Extraneous pyrites
tribution.“’ The combustion process is extremely extracted from coal ignites at temperatures as low as
complex and consequently has been investigated 450°C and proceeds to decompose at a rate slightly
extensively.‘7”55-‘60 FeO, FeS, Fez03, Fe2(S04)3, S, better than anthracite.“’ Carbon and/or other
SOZ, and SO3 are listed as some of the products of mineral species tend to lower the rate of combus-
combustion. Schmukls6 considered thirteen reactions tion. The presence of a reducing condition, by virtue
between FeS2 and 02, listed in Table 14. Several of the of carbon, or deficiency of O2 lowers the ignition
components in the Fe-O-S system may coexist as an temperature and slows down the rate of combustion
intermediate step in the combustion process pro- by promoting the formation of pyrrhotite. Although
ducing a low-melting phase illustrated by the phase decomposition of inherent pyrite has been investi-
diagram in Fig. 38.‘.15’ The melting temperature of gated, the process is not clearly understood and
Fe304 or Fe203, the final product of combustion, is requires further understanding.
1540°C and is of little consequence in ash deposition At least a portion of the extraneous particles of
except as aggregate or a fluxing agent to other pyrites fracture and disintegrate when thermally
deposited species. The intermediate phase is of shocked, yielding a fume of 0. l-l pm diameter
particles.'2.'59""
particular interest as temperatures as low as 590°C Inherent pyrites were found to
have been reported. Coarse, slow-burning pyrites generate an iron fume according to the following
76
I I
2eooC
2600-
2400-
1600- FeO-
I I
14006
20
FeO, weight percent
Fig. 38. Phase diagram of system FeO-FeS.‘57
reaction:
FeS(1) = Fe(g) + 1/2$(g).
The extent to which the iron fume originates as
inherent and extraneous ash is not entirely resolved.
However, the total fume is estimated at 4-7% of the
iron in the coal. This portion of the original iron is
likely to be responsible for fluxing of silicates in the
gas stream or at the surface of the slag.
4.55. SideritelAnkerite
Siderite is more commonly found as the mineral
form of iron in Southern Hemisphere coals. Nelson et
a1.84 report siderite present as nodules and as impure
lenses and bands in coal. As in kaolinite and calcite,
siderite may occur as fillings in the cavities of fusain
and as small veinlets within the coal mass. Siderite has
a gravity of 3.6. When liberated from coal, it should
report to the heaviest gravity fraction. Decomposition
of siderite begins at 1085°F with the release of CO2
and the formation of Fe, FeO, of Fe304 depending
upon the partial pressure of Oz, CO, and COz.
Inherent siderite most likely acts as a flux for silaceous
minerals, while extraneous siderite is innocuous
unless in contact with other silaceous mineral species
on a hot surface.
Ankerite is found in coal on occasions and behaves
similarly to siderite.
4.56. Calcite
Calcite is one of several carbonaceous minerals
R. W. Bryers
I I I
I
-I
FeO+melt - -
900
FeS eutectic
800
I I
40 60 80 100
found in coal. It has a gravity of 2.7 and is found as
veins in coal, particularly in the cleats and fractures.
(23) Like siderite, it decomposes at a low temperature
@lo-920°C) releasing Ca or CO depending upon the
partial pressure of Oz, CO, and CO*. Inherent calcite
more than likely is a fluxing agent for other inherent
silaceous minerals. Extraneous calcite, found as a free
species, may become sulfated at lower gas tem-
peratures contributing to calcium-sulfate-bonded
deposits. Although Graham et al.‘62 and others have
reported calcium fumes, it is uncertain to what extent
or which species (i.e., extraneous or inherent calcite) is
responsible for the fume generation.
4.6. Thermal Behavior of Mineral Matter
Mineral matter includes organically-bound sodium,
calcium, magnesium, and trace amounts of aluminum
and iron found in low-rank coals. One might also
want to include the organically-bound sulfur and
most ofchlorine found in coal in this group. Although
sodium chloride (strictly speaking) is a mineral, it too
might be considered mineral matter on the basis of its
thermal behavior. Mineral matter is all volatilized
during combustion.
Lindner et al.‘63 investigated the release of
organically-bound sodium and sodium chloride
from coal. The transport of sodium from its original
site to the surrounding atmosphere is very complex.
Organically-bound sodium is released under reducing
conditions as metallic sodium. The rate of release
must be dependent upon total surface, pore size, pore
diffusivity, and bulk diffusivity. Linder et al. report
 Steam-raising fuels 71

1800 , , , , , , , , /L , #

51600 -

(a)
Tg .14SOK

kL/kG= -

, I I I 1 I
200 ! ! ! ! ! ! ! ! /L
0 10 20 30 35 40 40 120 200

Residence Time (ms)

(b)

10.20 30 40 40 120 200

Residence Time (ms)

(cl

Fractlonal Time for Each Stage

Fig. 39. Calculated (a) particle temperature and (b) iron-bearing phase distribution profiles as a function of
residence time, (c) fractional time spent in each stage: l-pyrite heatup; 2-decomposition to pyrrhotite;
3-pyrrhotite heating to melting point; 4-pyrrhotite melting; 5-oxidation to molten iron oxide; 6-
cooling of iron oxide to crystallization temperature; ‘I-magnetite crystallization.‘60

the organically-bound sodium is evaporated as the
volatiles are released, intimating that the char is
depleted of sodium once the volatiles have escaped.
Formation of Na(OH) is completed in the gas
stream.‘63
Sodium chlorine melts at 801°C and begins to
volatilize at about 750°C. Above 750°C the rate
increases significantly. Its rate of escape, as in the case
of organically-bound sodium, is dependent upon pore
and bulk diffusivity and instant properties of the
char affecting either. Lindner et ~21.‘~~found that
evaporation of crystals <O. 1 pm in diameter was bulk
diffusion controlled, while particles >0.3 pm were
pore diffusion controlled. Evaporation rates were
comparable to those of devolatilization. Once
released, the dominant sodium-bearing gas species is
Na(OH). It is free to react with the extraneous
silicates present as well as the char and inherent
silicates to form NazSiOs and Na*SOs, as concep-
tually illustrated by Lindner et al.163in Fig. 40. The
reaction rates of the sodium with silica to form
silicates takes place in five stages:
1. Transportation of gaseous reactants and
products in the char/boundary.
2. Diffusion of gaseous reactants and products
through the pores of the char.
3. Reactions at the sodium silicate melt surface.
4. Diffusion through the silicate melt.
5. Sodium silicate forming reactions at the silicate/
silica interface.
Experiments by Lindner et ~1.‘~~indicate that the
controlling stage changes as the reaction proceeds.
Boundary layer transport controls the process
initially, followed by diffusion of the sodium within
the melt and gaseous hydroxide within the char.
Sodium hydroxide servicing the char burnout will
78 R. W. Bryers

Ash Gas
Reactants Devolatilisation Burnout Spheridisation Cooling

Hot (2O%XS 1 N2,02,H20.C02

air S02,NaCI. NaOH
GASES
Na , NaZCIZ
SO2 I

75um coal part+, Char, . Spherical k$e;;ed

co;l:amlng Partially fused
containing 10°~0S102
ash ash
and NaCl crystals Na CI, Na2S04
[-500msl ( 30pm I
(-100 msl
[O.lpml

Fig. 40. Mechanisms of Na ash reactions.‘63

HEAT TRANSFER SURFACES

///I/ /////I////

VAPORS

CHAR PARTICLE / -1
F MO,V,k
--

.a.

‘MINERAL -1
INCLUSIONS

EXTRANEOUS ASH
SP. Gil. > 2.0 A/

RE-ENTRANMENT
“‘=USION AND

__ -..
HEAT TRANSFER SURFACES
A.un -APrnP”

Fig. 41. Fate of mineral matter in coal during combustion.

form chlorides or silicates depending upon level of
concentration of Cl and 02/CO present. At lower
temperatures the salts of NaCl and Na2S04 will form a
submicron fume.‘633’64Consequently, sodium occur-
ring as mineral matter may contribute to fireside
deposits in several ways: as a low-melting silicate
responsible primarily for very high-temperature
slagging and fouling (i.e., >954”C), and as an
initiator of fouling by forming low-melting sodium
sulfate just above convection bank superheater/
reheater tube temperature.
Organically-bound calcium occurs in substantial
quantities in low-rank coals. Although organically-
bound calcium is known to form a fume of reactive
submicron CaO as well as calcium silicate ceno-
spheres, its release from the coal has not been
examined as sodium has. Organically-bound calcium
may also contribute to fireside deposits in several
ways. The fume initiates furnace wall deposits as well
as low-temperature convection bank heat-transfer
surfaces by forming calcium-sulfate-bonded deposits.
Calcium silicate may perpetuate the growth of
partially developed slag as semi-molten anorthite or
gehlenite.
 Steam-raising
Fig. 42. Mode of slag growth
4.1. Fate of Mineral Matter During Combustion
Dr. Sarofim and others at MIT identified the
interaction of the inherent minerals during combus-
tion conceptually.‘62 The diagram was modified by
the author to include extraneous and inherent ash as
well as including types of deposits formed and mode
of transport to the surface, as shown in Fig. 41.
The extraneous ash, in this case, is defined as the
particulate whose gravity exceed ~2.0 and therefore
is virtually free of carbon. The extraneous ash is
primarily associated with the older coals (i.e.,
bituminous and anthracite). It is generally composed
of quartz, pyrites, and some of the heavier clays.
During combustion this material is heated to
temperatures slightly below the flame temperature.
The actual temperature level achieved by each
individual particle depends upon its particle size and
flight path relative to the combustible matter. The
minerals melt and form cenospheres. The size and
number depend upon the size distribution of the
pulverized minerals in the fuel and agglomeration
fuels
,110o $
3
Fu)W ! I r
.lOOO 6
E
FLAME’ . 900 g
I TEMPERATURE
hOVING LAYER
. 600
on furnace wall
during combustion. Depending upon size and local
flow patterns, the fly ash migrates to the surface via
eddy diffusivity, thermophoresis, or inertial impact.
The fly ash is quenched to a temperature substantially
below the melting temperature of the constituents
comprising the individual fly ash particles as they
move through the boundary layers of flue gas to the
bare tube surface. Only those very small particles
subjected to very small gravitational forces approach-
ing the surface with little kinetic energy are retained.
The retaining force is not clearly understood. Large
particles impact and become reentrained. Once a thin
layer of dust is formed by particle fl pm in size, the
surface of the tube becomes irregular and its
temperature increases. Eventually the surface tem-
perature reaches the solidification temperatures of
specific fly ash species originating as a mineral in coal
and specific particles begin to stick. Melts also begin
to form between two high-melting species that share a
common low-melting eutectic such as quartz and
completely oxidized pyrites. At this point the rate of
furnace deposit growth increases and its thickness,
80
MAG. 3001 600X
North Dakota Montana
Lignite Subbituminous Subbituminous
Fig. 43. Initial layers of ash deposited on a slagging surface while firing a lignite, subbituminous, and
as illustrated by the model in Fig. 42, increases
significantly. The thickness of the initial layer depends
upon the initial tube temperature, the local heat flux,
and the thermal properties of the deposited ash (i.e.,
thermal conductivity). Particles passing through the
boundary layer may also scavenge volatilized mineral
matter formed by inherent ash, including SiO, Ca, Fe,
Na20, and K20. Eventually the entire slag layer
becomes molten. Continued growth may be sustained
by direct impact of solid or liquid fly ash and direct
condensation of volatilized mineral matter. Equilib-
rium is achieved when the rate of flow of plastic ash
down the tube wall is equivalent to the rate of capture
of fly ash.
At low flame temperatures and low heat flux,
voluminous quantities of sintered slag may form.
Thickness approaches an equilibrium as a result of
shedding of ‘slag’ when the deposit weight exceeds the
bonding strength at the deposit/tube or deposit/
refractory interface.
Extraneous ash will not cause fouling unless the
furnace exit temperature exceeds the melting tem-
perature of the lowest melting species of fly ash
entrained in the flue gas, a reaction takes place with
SO3 formed at the tube surface to cause bonding by
sulfidation, or a low-melting sulfate deposited on the
tube surface increases the stickiness of the tube
surface, thus retaining the otherwise innocuous
silicates. Partially-spent pure pyrites can also cause
severe slagging of the inlet to the convection pass due
to a transitory melt formed between FeS and S, or
FeS and FeO.
Inherent ash includes finely divided, uniformly
disseminated particles or crystals of various mineral
types and organically-bound mineral matter. Inherent
ash is primarily found in low-rank coal. During
R. W. Bryers
300x 300x
- ._._- ..- ._-
Utah Bituminous Bituminous
Upper Freeport Kentucky No. 9
bituminous.
combustion these mineral forms are subjected to the
highest possible flame temperatures, as well as a
reducing environment. Thus quartz, calcite, dolomite,
or pyrites are partially reduced to their lower oxidized
states. During char burnout the char and solid
mineral matter are subjected to fragmentation
resulting in size reduction. Minerals retained in the
char particle are subjected to melting coalescence
and partial vaporization-further altering their size,
chemistry, and physical state. Thus quantifying the
distribution of mineral matter between volatilized
species and the residual solidified or molten particles
is extremely difficult. The residual solid and molten
particulates are also subject to agglomeration-
further altering their size. At this point, they might
be treated as ‘extraneous’ fly ash. The volatilized
mineral matter from the reduced mineral species will
condense homogeneously via the process of nuclea-
tion, or heterogeneously on fly ash on tube surfaces.
The temperature at which condensation takes place
depends upon whether or not the vapor has been
chemically altered (i.e., oxidized or sulfated), its
concentration, and its vapor pressure. Nucleation
and scavenging may take place in the gas stream or
within the tube boundary layer, depending upon the
residence time and temperature level required for the
phase transformation to take place. Either process
may require substantial subcooling for the condensa-
tion to occur at a reasonable rate. The volatile
contribution from inherent ash may be small as the
inherent mineral matter in pulverized coal is generally
small.
4.8. Slagging
Slagging is defined as the formation of fused or
 Steam-raising fuels
sintered deposits on heat-transfer surfaces and
refractory in the furnace cavity subjected to radiant
heat exchange. The nature, degree, and composition
of slags may vary significantly throughout the furnace
depending upon surface temperature, flame tempera-
ture, absorption rates, direction of gas flow, mineral
composition (i.e., coal rank), mineral and coal size
distribution, concentration of mineral matter, and
oxygen level of the flue gas in contact with the
heat-transfer surface. Therefore, an understanding of
slagging and where it might occur requires knowledge
of a complete temperature and compositional flue gas
profile for the furnace. Changes in composition and
temperature profile at the tube surface are especially
important.
Slagging may be the result of direct impingement of
unspent flue gas and entrained molten particles on
heat-transfer surfaces within the combustion zone due
to an excessively high heat release, poor air distribu-
tion, poor burner management, or on heat-transfer
surfaces immersed perpendicular to the direction in
flow of flue gases as in the case of divisions walls and
pendant superheaters located upstream of the classic
furnace ‘nose’.
Under these circumstances, coarse molten particles
simply impact on the surface, freeze, and stick until a
layer with sufficient thermal resistance develops to
form a molten ash. ln most cases the slag will
resemble the extraneous coal ash and its slagging
potential will depend upon the fluxing capabilities of
the basic elements found in the extraneous ash or the
combustibility of pyrites when the pyrites are not
associated with other mineral species. The latter
frequently results in a slag consisting of 85% Fe203,
In low-rank coals whose minerals exist primarily as
inherent ash, the slag may be rich in silica, which is
frequently the dominant coarse species. The deposi-
tion may coincide with or be preceded by a layer of
calcite laid down as a fume by organically-bound
calcium. Quartz enrichment of a completely fused
deposit has been found on leading edges of pendant
superheaters subjected to direct radiant heat from the
flame, while 90” from the stagnation point on
cylindrical tube surfaces, the deposit consists of
sintered calcium sulfate.
Under good combustion conditions where surfaces
designed for dry-bottom operation are subject to
parallel flow under oxidizing conditions, slagging is
initiated by the finer mineral species with the lowest
melting potential or fumes formed by organically-
bound mineral matter and volatiles released during
combustion from the inherent minerals. As illus-
trated in Fig. 43, the morphology and composition
of the initial layers change significantly with coal
rank. The initial layer of low-rank coal consists of
submicron particles of calcite, calcium sulfate, and
clays originating as inherent mineral matter and
organically-bound calcium. Particulate found in the
innermost layers of slag from older coals are enriched
with potassium-bearing silicates originating as illite in
81
the coal, free quartz, and submicron iron scavenged
by quartz particles from an iron fume.
The inner layer is also sensitive to the size
distribution of the minerals in the coal. The size of
the particles occupying the inner layers are decidedly
smaller for coals containing extremely fine minerals
primarily occurring as inherent ash. It is believed
there is a substantial reduction in heat absorption as a
result of deposition of the initial layer due to its
porosity. The total reduction in absorption differs
significantly between low- and high-rank coals due
to differences in chemistry responsible for major
differences in reflectivity and thermal conductivity.
Continued development of low- and high-rank
coals is also decidedly different. Subsequent layers of
high-rank coal develop from random sites on the tube
surface, very much like drop-wise condensation. The
site probably develops as a result of the deposit of a
relatively large particle whose outer half penetrates
a thermal boundary layer where the temperature
exceeds the melting temperature of any eutectic
formed by fluxing agents depositing on the particle.
The individual ‘droplets’ grow; new sites develop.
Eventually the voids between sites fill in and a molten
layer forms. On a macro basis, slag on a full furnace
wall develops from patches, also in a ‘drop-wise
condensing’ fashion. At elevated surface tempera-
tures, particles deposit as dry fly ash, subcooled glassy
phases, and a condensed fume. Fluxing of the dryer
material takes place at the slag surface between ~8 15
and 1300°C (lowest eutectic in the SiOz-Al@-Fe0
system). The fused slag is composed of rapidly
quenched, subcooled glassy silicates. The material is
in the plastic range and flows as a non-Newtonian
fluid. Its thermal conductivity is several times higher
than the initial layer. Above 1300°C thickness of the
deposit will depend primarily upon composition. Slag
composed of eutectic mixtures will melt forming a
fluid whose thickness will depend on the viscosity of
the fluid and equilibrium between the mass deposited
and the mass flowing down the wall. Off-eutectic
mixtures may grow substantially as the viscosity
will depend upon the percent of solid component
precipitating from solution. Large concentrations of
precipitated material (i.e., large differences between
initial deformation or solidification temperature and
fluid temperature or melting temperature), extends
the permissible temperature range during which the
deposit is extremely viscous, thus allowing it to grow.
The mixture consists of crystals suspended in a liquid
and consequently behaves as a non-Newtonian fluid.
The concentration of crystals depends on composi-
tion and quenching rate. A slow quenching rate (i.e..
thick deposit with high surface temperature) permits
crystallization of the precipitating phase. Figure 44
shows the glassy substrate, precipitation of iron near
the slag surface, and deposition of condensed iron
fume originating as fragmented pyrites on the surface.
Crystals of iron also appear to congregate about gas
pockets just below the slag surface. It is believed the
82 R. W. Bryers
Fig. 44. SEM photomicrographs and EDAX scan profiles of the cross section of slag formed on furnace
probes after firing a bituminous coal.
gas pockets were formed by the decomposition of
pyrrhotite with the release of SO*.
If partitioning of minerals occurs during com-
bustion, an iron-rich slag can be formed by
preferential deposition of partially-combusted pure
pyrites (probably as pyrrhotite) in a semi-molten
state. Oxidation of the pyrrhotite occurs at the tube
surface, leaving a solid deposit consisting of 85%
FezOX with a melting temperature in excess of 2800°F.
Increasing the surface temperature of the furnace
wall, as in the case of refractory or a burner throat,
reduces the heat flux substantially-see Fig. 42. A
combination of low heat flux and off-eutectic
mixtures of high-melting and low-melting substances
can result in very thick slag deposits. Morphological
examination of eyebrow deposits frequently reveal
submicron crystals of iron and/or silica, suggesting
at least a portion of the deposit arrives as a fume
possibly with recirculated gases. This may be due to
the excess of carbon in the early stages of combustion
and the willingness of small particulate to follow the
stream lines of recirculating gas. Coarser material
tends to congregate in the high velocity portion of
the flowing stream. Uncooled surfaces (as in the
case of many refractory-lined burner throats) will
readily collect recirculated ash whose temperatures
exceed about two-thirds the melting temperature
of the lowest melting species (i.e., the Tamman
incipient sticking or solidification temperature of
glass). Consequently, burner eyebrows are strongly
dependent upon the quartz temperature and the
composition of the lowest melting species in the coal
ash. This could be illite in high-rank coals.
The steps for forming slag with low-rank coals
differ slightly from bituminous coal due to the lower
inherent flame temperature (i.e., three times as much
coal moisture), the presence of calcium and sodium as
organically-bound mineral matter instead of iron, the
reduced ash level, and the smaller mineral particle
size. Calcium fume deposits on virtually all surfaces
in the steam generator. At high concentrations of
sodium, the initial layer may be contaminated with
sodium sulfate. The CaO reacts with the SO3 present
to form bonded CaS04. Sintering begins at tem-
peratures as low as 500°C and the strength steadily
increases.
In the presence of COZ, a carbonate may form, in
which case Skrifvars et al.165 report severe sintering
between 600 and 750”C.165 Add sodium sulfate and
a known melt will occur at ~900°C. Submicron
aluminosilicate found as clay in low-rank coals
migrate to the surface at 1600-1750°C. They react
with the sulfates between 750 and 950°C to form
calcium aluminosilicates as gehlenite in the absence of
sodium and mellilites in the presence of sodium.
They have a melting temperature in the vicinity of
1780- 13OO”C, respectively. A white layer develops
that adheres tenaciously to the tube. It appears to be
 Steam-raising fuels

1 1 I 1 L c 11 1 1 I

300 1250 1500 1750 2000 2250 1000 1250 I500 1750 2000

J
1000
1

1250
I

1500
1
1750 2000
, I
2250
II-
1000 1250 I500 1750 2000 2250 1000 I250 1500 1750 2000

Temperature (OK) Temperature (OK) Temperature (“K)

Fig. 45. Calculated partitioning of sodium under P.F. combustion conditions. Top plots represent oxidizing
conditions in the furnace gases; bottom plots represent the extreme reducing conditions probable with the
burning char. (a) Lowell; (b) Leigh Creek; and (c) high chlorine-sulfur coa1.65

of uniform thickness, has a low thermal conductivity,
and high reflectivity reducing the local absorption
rate. A subsequent layer develops randomly over the
furnace wall. The rate of developments appears to be
greatest at the crown of the membrane wall tubes
where the surface temperatures are the highest.
At low heat flux and local flame temperatures, a
sintered deposit is formed at cenospheres, originating
either as clay and quartz in the coal, scavenge CaO or
CaS04 from the local flue gas and stick to the surface.
Outer layers of slag have been found to be enriched
with silica reaching concentrations about twice that
found in the coal ash. The surface temperatures of the
particulate must be very high as the lowest melting
eutectic in the CaO-Als0s-Si02 system is about
1250-1300°C. At high heat flux, the entire particle
goes into solution with the CaO at the tube surface
forming a mixture of pseudo-wollanstonite and
either anorthite or gehlenite. Polished cross sections
reveal precipitates of CaO * SiOZ in a matrix of CaO .
A1203 - 2Si02, which agrees with predicted mineral
composition on a phase diagram. Slag removed from
burner throat areas include iron selectively deposited
at the burner despite low concentrations of pyrites in
the coal.
The melting temperatures of fused low-rank coal
ash are about 100°C lower than fused ash formed by
minerals in high-rank coals due to the presence of
calcium rather than iron. The increased resistance of
low-rank coal ash to heat exchange results in thinner
fused layers with higher surface temperatures. Since
the composition of the ash impacting the wall very
closely matches the composition of eutectic mixtures
of anorthite, gehlenite and pseudo-wollanstonite, the
ash simply melts once the deposit surface temperature
reaches the fluid temperature of the slag and runs
like water. There appears to be a very limited plastic
range. Slag equilibrium is reached rapidly.
A third category of coals includes bituminous coals
that are low in iron but ‘rich’ in calcium and contain
less than 1% potassium as a feldspar. The calcium, in
this case, exists as a calcite rather than organically-
bound calcium. Both of the minerals identified as being
responsible for initiating slag growth are missing.
Consequently, the bond for deposits mechanically
attached to the wall is weak and the furnace
84
E
5
NON AOHERENT
POWOER
UPSTREAM
MOST
TUBE
ADHERENT
DEPOSIT
j 20
L
0 L
I II
DEPOSITION
Fig. 46. Various stages of ash deposition including I--thermophoresis,
condensation, and III-inertial impact.‘68
periodically sloughs a sintered slag creating
unusually high proportion of bottom ash.
4.9. Fouling
Fouling is the deposition of ash in the non-radiant
convective heat-transfer portion of the steam gen-
erator immersed in flue gases at temperatures below
the melting temperatures of the bulk coal ash. If there
is a large particle-to-particle variation in composition
of fly ash particles resulting in a significant variation
in melting temperature of individual particles,
some slagging may be experienced at the inlet to the
convection pass. Slagging may also be caused by
unspent pyrites if they appear in the coal as coarse,
liberated minerals and the residence time in the
furnace is too short. Fouling, however, is most
frequently caused by the condensation and chemical
reaction of volatile alkali mineral matter with fly
ash either in the gas stream or at the tube surface
creating a deposit and making the surface receptive
to collection of other species normally found to be
innocuous.
As discussed in a previous section on empirical
approaches, the constituents primarily responsible
for fouling include volatile sodium and calcium,
chlorine, sulfur, and phosphorous. Potassium may
also be included in this group even though it exists as
a stable silicate such as illite. Potassium may
contribute to fouling in either one of two ways. As a
low-melting silicate, unassociated with other miner-
als, it may be directly responsible for deposition on
surfaces immersed in gas streams exceeding ~2000°F.
R. W. Bryers
GAS FLOW
-I
FACE
;
t
I UPSTREAY
TUBE FiCE
MASSIVE DEPOSIT
m
STAGES
II--thermophoresis and
an It may also become very troublesome in the presence
of Cl and Na, which will displace it from the silicates
forming KC1 or K(OH)--the first step in forming
low-melting sulfates in the presence of sufficient levels
of S03. Silica has also been identified as a source of
fouling due to the volatilization of SiO in stoker-fired
steam generators under localized reducing conditions.
Its occurrence, however, is rare.‘66 Phosphorous has
also been reported to be a source of low-temperature
phosphate-bonded deposits due to the formation of
phosphoric acid (H4P207), which condenses on cooler
surfaces capturing impacting fly ash. The unique
conditions under which the phosphoric acid forms
and the very low concentrations in which it normally
occurs make phosphate-bonded deposits a rare
experience.84 The bulk of fouling, however, is due to
alkali-bonded deposits and calcium-sulfate-bonded
deposits.
4.9.1. Alkali-bonded deposits
Equilibrium calculations performed by several
investigators using existing thermodynamic data
based on the minimum free energy of formation
concept have predicted that sodium exists at flame
temperatures as NaCl, Na(OH), and Na. The
weighted distribution of the sodium compounds for
a specific case is illustrated in Fig. 45 by Wibberly
and Wa11.65Wa11’63reports a qualitative agreement
with measurements made using analytical techniques
such as flame photometry, mass spectrometry, laser-
induced fluorescence, and laser-induced photodisso-
ciation. The predictions assume the absence of
 Steam-raising fuels
elements such as alumina and silica which in reality
are not the case. However, compensation can be
partially made by assuming a surface availability
factor. The parametric analysis should be completed
by including the impact of O2 level or reducing
conditions on the reactions.‘63
The equilibrium calculations as well as morpho-
logical studies of deposited ash indicate fouling may
proceed in two slightly different ways: deposition of
sodium silicates formed in the gas stream; or sodium,
potassium, and calcium sulfate formed at the tube
surface. Above 950°C equilibrium favors the forma-
tion of sodium silicates as a result of a surface reaction
of Na(OH) with quartz and aluminosilicates, creating
a slightly sticky surface on fly ash particles. The
absence of SOs, except within the tube boundary
layer at these temperatures, dismisses the presence
of NazS04 as an intermediate phase. The melting
temperature of the silicates formed by sodium with
free silica may be as low as 8OO”C, whereas the
addition of alumina in the presence of clays raises
the melting temperatures to that of a feldspar (i.e.,
llOOC+). As the flue gas temperatures increase
above these levels, the quantity of molten phase
increases significantly until the initial deformation
temperature of the bulk ash is reached.‘67
To avoid catastrophic fouling of the flue gas
entering the convection bank, heat-transfer surfaces
are limited to a temperature in the immediate vicinity
of the initial deformation temperature of the ash. To
minimize fouling by the fly ash with sticky surfaces.
the initial banks of convective heat transfer are
constructed with exceptionally wide tube spacing to
minimize ash collection, efficient without completely
sacrificing heat-transfer rates according to the
schedule appearing in Fig. 20. Within this tempera-
ture range, the particle size will play an important role
in whether or not the fly ash will deposit. The reaction
rates of alkali with large quartz particles is limited
by diffusion through the gas boundary layer to the
particle surface and ultimately, diffusion through the
outer layer to the core. The molten phase is limited to
a surface effect illustrated in Fig. 14. Reaction rates
for smaller particles are greater. Consequently,
equilibrium is reached and the entire particle is
molten. The smaller particles are more likely to
form a sticky surface at high temperatures. Although
the collection efficiency of the larger particles is
greater, the ratio of kinetic energy to retaining force
will also be greater, encouraging re-entrainment.
Small particles, 1 pm or less, deposit at a slow rate
by either thermophoresis or Brownian motion and
are subject to rapid cooling to temperatures below
their melting temperature as they penetrate the
boundary layer. Consequently, it is the mid-range
sized particles which appear to be most vulnerable
to deposition. Fouling also depends upon the
receptiveness of the impacted surface. Frozen
deposit is not nearly as receptive to trapping
impinging solid particles,
85
Although empirical fouling data appears to
support deposition by inertial impact by virtue of an
exponential increase in fouling rate with time, it
may also be indicative of the change in stickiness of
deposit surface as the deposit develops and the
surface temperature increases. Field experience
indicates a period of immunity during which
fouling does not proceed exponentially, suggesting
deposits are initiated by means other than impac-
tion of sticky particle-see Fig. 46.16’ Morpholo-
gical as well as chemical analysis of initiating layers
indicate the first particles to stick are submicron
particles of calcium and sodium originating as a
fume in the gas stream, which condense in the
vicinity of the tube surface and migrate to the tube
surface via thermophoresis. Potassium associated
with a low-melting silicate is not found in these
layers except in systems containing Cl and substan-
tial quantities of sulfur. Bituminous coals are
generally enriched with potassium chlorine and
sulfur. Low rank coals contain little potassium or
sulfur but are enriched with calcium and sodium. The
latter are more prone to fouling.
An examination of the high-temperature surface
immersed in the flue gas stream between 926 and
1093°C indicates the ash was formed as the result
of the chemical reaction of SO3 with NaOH and
submicron calcium particulate within the tube
boundary layer. Levy et al. have shown that SOsU
at the tube surface may be several orders of
magnitude of that in the flue gas stream, permitting
sulfidation to occur at locations where the bulk gas
stream favors the formation of SO1. Analysis of fly
ash leaving the steam generator indicates the kinetics
of the sulfidation reaction is too slow for sulfation of
the calcium in the bulk gas stream. In low-rank coals,
submicron CaO provides sites for preferential
deposition of Na7SOI over the tube surface--raising
the melting temperature of the deposit ash signifi-
cantly. The tight radius of the smaller particle
reduces the subcooling required of the sodium
sulfate to deposit on the surface. In the absence of
calcium and presence of potassium, as in the case
of bituminous, a corrosive layer is formed by direct
condensation of supercooled Na2S04 on the tube
surface. Deposition of KzS04 lowers the melting
temperature further. The surface temperature of the
deposit having been elevated above that of the
tube, mid-range sized particles of silicates (some of
which may already have surfaces enriched with
sodium) deposit and remain. The SOs reacts with
NOH present in the gas or the sodium at the
particle surface to form sulfates and contacting
adjacent particles are bound by the crystals of
Na2S04 and CaSO+
At a temperature between 750 and 950°C. the
CaS04 and sodium sulfate decompose in the
presence of silicates forming a mellilite with melting
temperatures as low as 752°C depending upon
other minerals present. According to the following
86
reaction,
[xNazS04 + yCaSOd] + A1203 .zSiOz
-+ xNazO - yCa0. A1203 - zSiO*
+ (x + y)SOs
bonding shifts from a chemical reaction to viscous
flow as the surface melts wet adjacent particles. One
might expect the rate of deposit to increase as
equilibria favors the transformation of sodium
sulfate to silicates.
To avoid fouling, one must use liberal tube spacing
and limit temperatures to the convection bank based
on equilibria of conversion of sodium sulfate to
silicate and melting temperatures of the mellilites,
rather than bulk ash fusion. Dead gas spaces and
horizontal tube arrangements above 750°C must be
minimized to avoid collection of fly ash that may
proceed to sinter as a result of extended residence time
at elevated temperatures. Sootblowing must proceed
at sufficient intervals to avoid the transition from
the weaker sulfate-bonded deposit to the stronger
mellilite-bonded deposits. The gas temperature to the
convection bank should be based on the melting
temperature of mellilites rather than ash fusion
temperatures and the quantity of molten phase
expected from equilibria calculations.
4.9.2. Calcium-sulfate-bonded deposits
Calcium-sulfate-bonded deposits were first reported
back in the 1960s by Grant and Weymouth.‘69 They
have recurred on and off since then.‘6g-‘75 They have
become increasingly more important in recent years
with burning coals rich in organically-bound calcium
and in systems using finely ground limestone for
sulfur capture.
Grant and Weymouth’69 described calcium-
bonded deposits as containing fine crystals of the heat of formation may raise the temperature
calcium sulfate intimately associated with the ash
particles in aggregates and effectively binding them
together. Crumley”’ proposed a mechanism for the
formation of bonded deposits based on the condensa-
tion of calcium chloride. Grant and Weymouth,‘69
Jakisch,“’ Zinzen,“* and Lenkewitz’73 all proposed
+L” ,....,*,11:.., ~al~llllll
1116~lyaralllllr; nn,?.:..... “..,C”tn “” l.&..”
DuI,aLea?i ueu,g *L, ,“A ..,‘
L11e=111l
of oxidation of calcium sulfide at the tube surface.
They also acknowledged the formation of a melt at
830°C in the calcium-sulfide/calcium-sulfate
Hein’ reported that calcium sulfates formed by before the decomposition of CaCO,. The process
Rheinish Brown coals are not troublesome except in
the presence of sodium sulfate, which forms a low-
melting eutectic with the calcium sulfate, and causes
sulfatic bridging. Under locally 02-lean conditions,
sulfides will form which also create low-melting
eutectics and bonding.
Gibb’75 reported that calcium promotes the initia-
tion of deposit growth. He also showed that the initial
layer of deposit is anhydrite-rich, whereas the fused
R. W Bryers
(24)
500 700 900 1100 1301
DEPOSIT TEMPERATURE
The basic sketch for the sintering of CaO as a function
of the deposit temperature. Four casas are illustrated:
(1 I Sintaring in an inert-gase phase: 100% NI
(2) Sintering with 1000 ppm SO, in tha gas phase
(3) Sintaring with 10% CO, in the gas phase
(4) Total sintering tendency, when both SO, and CO,
would be present in the gase phase
Fig. 47. Sintering due to CO* and SO3 at various deposit
outer layer is rich in plagiocase, which he defined as a
solid solution series between anorthite and albite.”
In the absence of sodium, it would appear that
depletion of O2 or the presence of sulfur was required
to form a low-melting eutectic with either CaO or
CaS04 essential to bonding fly ash particles to each
other or the tube surface.
As early as 1959, Nelson et al.84 summarized
Sulzer’s89 work on CaS04-bonded deposits formed
when firing oil. He proposed a mechanism as follows:
‘CaO forms during combustion and collects on metal
surfaces where it reacts exothermally with the SO3 in
the gas stream to form CaS04. Sulfur dioxide in the
gases may be oxidized catalytically to SO3 by V2O5
from the oil combustion. Although CaS04 has a
reported melting point of 1448°C Sulzer feels that
sufficiently to cause a sticky surface. It should be
pointed out, however, that the dissociation of CaS04
begins at about lOlO”C, which is significantly below
this melting point’.84s9
Recently, Skrifvars et al.‘65 indicated sintering of
calcium-bonded deposits depends on the SO2 and
...,t 1 CO* present. ~~‘
IGJU‘ A....orPnt’
J,alr‘lrl~., tr.,
LL,G..__,._0” ;0 a t.,rr\
‘J’“CbJJ 1J “+a..l
rrrv-orti’
procedure beginning with sintering by CO2 at
temperatures as low as 300°C due to the formation
system. of carbonates and reaching a maximum of 750°C just
begins once again with the formation of CaS04,
reaches a maximum at x954-1037°C as the CaSO
reacts with quartz or aluminosilicates to form
calcium-see Fig. 47.‘65
Micro-analysis of a calcium-sulfate-bonded deposit
using SEM reveals an inner layer composed of
submicron calcium and sodium sulfate upon which
develops a completely molten or fused layer of Ca
and S, as shown in Fig. 48. The second layer is
 Steam-raising fuels

Mag. 3000X Mag. 6000X

s c NASS CT F
a ALI Al E
CURSOR (KEY) = 65.166 EOAX CURSOR (KEY) = 65.166 EDAX

First Fused I_,ayer ot the Deposit

Fig. 48. SEM photomicrographs and EDAX scans of the finishing superheater deposit surface showing the
tube deposit interface.

generally of uniform thickness and may contain calcium deposited on fly ash particles, as shown in
submicron aluminosilicate spheroidal inclusions. Fig. 48. The calcium sulfate begins as a submicron
Sulfated barium has also been frequently identified particle from which large crystals of CaS04 form. The
as an immiscible fused inclusion. The melting tem- sphere eventually becomes completely encapsulated
perature of this portion of the deposit is probably in with the crystals. Ultimately, the bond is achieved as
the temperature range Iof 590&65O”C. crystals begin to share adjacent particles, illustrated in
A number of theories have been postulated to Fig. 24. As the deposits grow, the temperature rises.
explain the existence of a molten layer. A definite At 950°C the CaS04 decomposes in the presence of
answer has not yet been developed. It has been silica and aluminosilicates forming a fused calcium
observed that the deposit is frequently associated with aluminosilicate, frequently identified as gehlenite or
low oxygen levels (i.e., <2.5%) and excess carbon. anorthite. The precise temperature of decomposition
Consequently, the molten phase could be attributed has been determined by TGA using artificial as well as
to a CaSO, - CaS complex; however, CaS has never real deposit ash, as shown in Fig. 49.87 This has also
been identified in the laboratory. The melt could also been observed by many other investigators dating
be caused by sulfidation of submicron CaO in a zone back to the 195O~.s’~‘~~-‘~~
where there is inadequate ventilation for dissipation Fly ash initiating deposit formation in the
of the heat of reaction causing temporary local temperature range of 510P704”C consisted of sub-
excursions in temperatures to very high levels. micron particulate of CaO. Above 704”C, crystals of
Subsequent layers are formed by the sulfidation of CaS04 appear which are the result of homogeneous
88 R. W. Bryers

Temperalure (‘C)

Fig. 49. Thermal analysis of tubeside layer and cross section of primary superheater showing low-
temperature melts at ~600°C below the initial deformation temperature of the ash and decomposition of
CaS04 in the presence of silicates at ~800°C.

condensation of CaO reacting with S03. The fly ash
discharged from the steam generator in the flue gas
shows little to no signs of sulfidation, indicating
CaS04 is formed at the deposit/tube surface interface
where residence time is many orders of magnitude
higher than in the gas stream. Microanalysis of a
number of fly ash samples indicates that in some
instances calcium is scavenged by fly ash during
combustion or post-combustion as particles of CaO
adhering to the surface of aluminosilicates. In other
cases, the calcium has gone into solution forming a
single sphere. The availability of CaO at the fly ash
surface varies with some yet-to-be-determined param-
eter (possibly flame temperature) which may have an
impact on the degree of fouling.
Calcium-sulfate-bonded deposits are associated
with organically-bound calcium. They are prone to
form at O2 levels below 2.5% and on horizontal
surfaces in the heat recovery section between 750
and 954°C. Dead gas space and horizontal surfaces
should be avoided as much as possible above 750°C.
The fouling is coupled to a furnace slagging problem
resulting in a loss in absorption and high furnace exit
temperatures created by a highly reflective ash.
4.10. Modeling the Mechanistic Approach
The mechanistic approach to an understanding
of how and why slagging and fouling occurs has
prompted the use of models and computers to seek
a solution to fireside problems. An explosion in
availability of analytical equipment in the 1970s and
1980s has supported this approach as well as provided
the capability to identify minerals present in coal,
their size, and association. CCSEM, in particular, has
permitted examination of coal mineralogy and the fly
ash it generates on a particle-to-particle basis. Thus
coals with ash of similar elemental composition, but
decidedly different mineral composition or distribu-
tion and association, can be examined in light of
the differences and variations in ash deposition
behavior between steam generators or locations
within a given steam generator and can be accounted
for or evaluated. Prediction of fly ash size distribution
permits evaluation of differences in ash deposition
and deposition rates throughout the boiler. For the
first time, engineering parameters other than furnace
exit may be incorporated into a slagging, fouling and
corrosion index. It is reported that several utilities are
requiring CCSEM as a routine characterization of
fuels.
New restrictions on emissions and the availability
of the computer has facilitated and promoted detailed
analysis and modeling of steam generator furnace
fluidynamics and thermodynamics. Add to this the
ability to examine mineral matter on a particle-to-
particle basis and the availability of fundamentals of
mineral transformations; the next logical step would
be to attempt modeling of the slagging and fouling
process.
The bulk of the modeling thus far has been carried
out in the U.S. by Brigham Young University (BYU),
the Energy and Environmental Research Center
(EERC) of the University of North Dakota, PSI
 Steam-raising fuels 89

Table 15. Principal ash-forming elements in crude oil”’

Element Type Solubility in oil Probable chemical form

Aluminum Inorganic Insoluble Complex aluminosilicates in suspension

Calcium Organic Soluble Not identified

1norganic Insoluble Calcium minerals in suspension; calcium salts in
suspension or dissolved in emulsified water

Iron Organic Soluble Possible iron porphyrin complexes

Inorganic Insoluble Finely-sized iron oxides in suspension
Magnesium Organic Soluble Not identified
Inorganic Insoluble Magnesium salts dissolved in emulsified water or
in suspension in microcrystalline state

Nickel Organic Soluble Probably porphyrin complexes

Silicon Ilnorganic Insoluble Complex silicates and sand in suspension
Sodium !lnorganic Insoluble Largely sodium chloride dissolved in emulsified
water or in suspension in microcrystalline state
Vanadium Organic Soluble Vanadium porphyrin complexes
Zinc Organic Soluble Not identified

Table 16. Analyses of ash from crude oils (wt%)’

Element California Mid-continent Texas Pennsylvania Kansas Iran No. I Iran No. 2

SiOz 38.8 31.7 I.6 0.8 I.0 52.8 12.1

Fez03
Al203 17.3 31.8 8.9 97.5 19.1 13.1 IX.1
TiO. i

CaO 8.7 12.6 5.3 0.7 4.8 6.1 12.7

MgO 1.8 4.2 2.5 0.2 1.3 9.1 0.2
MnO 0.3 0.4 0.3 0.2 Tr Tr Tr
v2°5 5.1 Tr 1.4 0.4 14.0 38.5
NiO 4.4 0.5 I.5 0.6 I .4 10.7
Na20 9.5 6.9 30.8 0.1 23.6
_ I.0 0.9
K2O _

so3 15.0 10.8 42.1 0.9 36.4 2.6 7.0

Chloride _ _ 4.6 _ 0.1 _

Technologies, Sandia National Laboratory, MIT, first step to evaluation of mineral transformation. The
and Reaction Engineering International. The pro- model has been validated on small boilers. Measured
grams presently being developed are directed at and predicted temperatures and species concentra-
specific aspects of the fouling and slagging rather tions were in good agreement in most regions of the
than a comprehensive model. furnace. The largest discrepancies between measured
A comprehensive three-dimensional model for and predicted values generally occurred near the
simulating combustion systems is being developed at furnace walls. This is the zone most critical to the
BYU. This program simulates large-scale, steady- understanding of slag deposit formation and growth.
state, gaseous and particle laden, reacting and non- PSI Technology uses CCSEM data combined with
reacting systems. It uses advanced numerics which traditional characterization data to predict slagging
are capable of solving very large computational potential of a coal in specific zones. A fly ash
meshes that are required to simulate temperature formation model predicts size and composition of
and flow fields in large steam generator furnaces. Both ash particles, allowing for char fragmentation and
convective and radiant heat transfer are modeled. The mineral coalescence. A viscosity model is used to
codes assume equilibrium gas-phase chemistry and calculate particle viscosity. Simplified boiler flow
couples the turbulent flow field with the chemical modeling predicts particle transport to the walls.
reactions by integrating the equation over a prob- Although it is claimed that deposit amounts and
ability density function. The program is an essential locations can be predicted, no claim is made to predict
90 R. W. Bryers

the impact of a coal on boiler performance. The D-

model is limited to furnace slagging.
MIT is currently attempting to integrate a
number of computational codes that characterize
the coal minerals by CCSEM, predict fly ash size D-
and composition, and the probability of particle
impaction and retention.
Sandia has developed a reasonably simple model
whose objective is to predict the elemental composi- D-
tion of deposited ash. The model is based on first-
principle derivations and a series of experimental
results. Attempts have been made to validate the
program on large-scale steam generators. It has been
O-
indicated there is a need for rates of condensation
and heterogeneous chemical reaction, and deposit
properties such as emissivity, thermal conductivity
and viscosity.
I-
EERC has developed two models known as
ATRANI (Ash Transformation Version 1) which
predicts size and composition, and LEADER (Low-
Temperature Engineering Algorithm of Deposition
Risk), designed to predict low-temperature fouling. 11-

The first is stoichiastic based on random variables. I

The second is an expert system derived from a

knowledge base together with some inferential rules
related to ash formation.
The modeling is in its infancy. Each is directed at
solving only a portion of the total program. There are
some who feel a totally mechanistic approach will
never be achieved due to the overwhelming com-
plexity of the chemical processes involved. However,
when fully developed and applied piecemeal, they
may be a valuable tool for diagnosing problems. The
largest thrust in the fundamental arena has been
directed at understanding mineral transformations
and transport mechanisms. Very little attention has
been given to deposit formation and growth. As
pointed out earlier, the mechanism of deposit
formation has not yet been identified in some cases.
The mechanistic approach has identified a need
for fundamental understanding in several areas as
applied to fly ash:
. Fragmentation.
. Agglomeration.
. Coalescence.
. Heterogeneous condensation.
. Scavenging.
. Nucleation.
. Crystallization.
. Sintering.
. Bonding or adhesion (ash to ash, ash to metal).
. Re-entrainment.
. Deposit properties such as emissivity, thermal
conductivity.
5. FIRESIDE PROBLEMS WITH HEAVY OIL
5.1. Introduction and Background
Fireside fouling and corrosion due to impurities
11_
7( ,/_L lo
Temperature (“C)
Fig. 50. Vapor pressures of fuel oil ash constituents.*“**-‘93
in oil became a problem in the late 1940s/early
1950s as steam temperatures increased and heavy
oils from crudes rich in vanadium were introduced
to the marketplace. The most thorough study of the
problem was performed by Miller et al.179 for the
Bureau of Yards and Docks of the Navy in 1963. The
survey was based upon many fine surveys previously
reported, as well as the Marchwood Conference of
1963 which was organized, in part, to resolve the
problem.8‘t>ts0-‘s3 The mineral matter in oil primary
responsible for fireside fouling and corrosion is
vanadium and sulfur. Sodium is also a major
contributor; however, it is a substance that is
basically foreign to oil and is introduced during
handling as NaCl found in seawater.
High-temperature catastrophic corrosion by VzOs
is the most important fireside problem associated with
heavy oil. Fouling by addition of impurities such as
sodium and additives to inhibit corrosion are the
secondary problem. Although numerous approaches
have been taken to inhibit the corrosion and minimize
fouling, limitation of the surface temperature of heat
transfer to the threshold level of V205 attack (i.e.,
melting temperature of VzOs-bearing ash) and the use
of 50Cr-50Ni for uncooled metal supports have been
the most successful. The use of magnesium as an
additive has been successful in inhibiting corrosion of
surfaces where neither of the two alternatives are
applicable.
 Steam-raising fuels 91

Table 17. Melting points of possible deposit constituent?

Compound Melting, ‘C

Silica, Si02 1720

Alumina, AlzO, 2050
Alummum sulfate, FezO, Decomposes at 770 to AlJO
Ferric oxide, Fe*O, 1565
Ferric sulfate, Fe,(S04)3 Decomposes at 480 to Fe?03
Ferrosoferric oxide, FelOd 1538
Nickel oxide, NiO 2090
Nickel sulfate, NiS04 Decomposes at 840 to NiO
Nickel vanadate, NiO . V20, 900
Magnesium oxide, MgO 2500
Magnesium sulfate, MgS04 Decomposes at 1125to MgO
Calcium oxide, CaO 2572
Calcium sulfate, CaSO, 1450
Sodium sulfate, Na2S04 880
Sodium pyrosulfate, NazSzO Decomposes at about 400
Vanadium trioxide, VzO, 1970
Vanadium tetroxide, V,O1 1970
Vanadium pentoxide, V205 675
Sodium metavanadate, NaV03 630
Sodium pyrovanadate, 2Naz0. Vz05 640
Sodium orthovanadate, Na3V04 850
Sodium vanadyl vanadates
NazO. Vz04. 5V205 625
5Naz0. V,O, . I lV>O, 535

-ECON.-- ---&Ii -

Fig. 5 1. Typical distribution of deposits in oil-fired boilers.‘95.‘96

92 R. W. Bryers

MAG 1500X - CROSS-SECTION CRYSTALSOF V

--h_

Si K

Fig. 52. Typical oil ash deposition superheater surface illustrating inner crystalline deposit due to
condensation of Na2S04 and VzOs reacting to form Na,O - V204 - 5Vz05.

5.2. Occurrence of Minerals in Oil
Thomas’84 identified, by spectrographic analysis,
as many as 25 elements intrinsic to the crude. The
principle ash-forming constituents in crude oil were
reduced and tabulated by Bowden’ in Table 15.
Both inorganic and organically-bound oil-soluble
forms have been observed for each element. The
mineral matter is not destroyed during processing and
thus appears in the heavy oil in the same form.
Sodium is not intrinsically found in crudes; conse-
quently, its concentration may increase substantially
during shipment. However, it should not exceed
60 ppm if properly desalted at the refinery. Asphaltic
base crudes are generally rich in vanadium, par-
ticularly those from Venezuela, which often contain
as much as 900 ppm reported as V205 .ls6 Some crudes
from the Middle East and California also contain
appreciable amounts of vanadium. Paraffinic base
crudes are usually free of vanadium.‘79”81 Typical
analyses of crude ash appear in Table 16.8 Iron is the
second-most abundant element in crude oil. In more
recent years, nickel has replaced iron as a leading
second element in some crudes.
5.3. Combustion of Heavy Oil
During combustion of oil, vanadium is volatilized
and oxidized to V,O, in the presence of excess air,
exceeding 3%. Unlike sulfur, the kinetics of the
oxidation process are fast enough to insure complete
oxidation at temperatures encountered in oil flames.
VzOs has a high vapor pressure, as illustrated in Fig.
50, and remains in a gaseous state to temperatures
in excess of its melting temperature (i.e., 675°C) at
concentrations in the oil equivalent to ~80ppm.’
Below 3% excess air, the oxidation of vanadium is not
complete and V203 and/or VZ04 are formed.‘87-194
The latter have low vapor pressures and very high
melting temperatures (i.e., 1970°C). Table 17 lists
 Steam-raising fuels 93

600

0 IO 20 30 40 50 60 70 80 90
No,O.mol percent

L I I I I I I I I 1
100 SO SO 70 60 50 40 30 20 10
V, 0, ,mol percent

Fig. 53. Phase diagram for Na?O-V,OS system.*

Table 18. Melting temperatures of various magnesium and tension is very low permitting it to wet all surfaces in
vanadium compounds deposited in steam generators’98 the immediate vicinity. The deposit is formed as a result
of condensation of pure V205 on the tube surface.
Compound Melting characteristics Na/V
mole Oils containing sodium in excess of 40ppm, but
Sinter Initial Final ratio little to no vanadium, will produce voluminous
point, ‘C melt melt deposits. The NaCl volatilizes and decomposes
point, “C point, “C during combustion forming Na(OH), which is
Na2S04 _ 885* subsequently sulfated at the tube surface, forming
I/O
NaV03 528 590 621 l/l Na2S04 with a melting temperature of 855°C.
NazO. 3V205 554 621 668 113 Although the bisulfate may not form, pyrosulfates
Naz0.6VzOct 590 657 701.6 116 can form since generally sufficient sulfur is available
_ 798*
v205 O/l to create the equilibrium condition for forming
2MgO. VZ05 704 835 1073
3MgO. V205 976 1190 1243 _ Na2SZ07 (i.e., 1200ppm). In the presence of other
compounds such as CaS04 and MgS04, low-melting
* Reported in ‘Handbook of Chemistry’, Lang, 7th Edition.
eutectics will form. Mixtures of high-melting sulfates
t Melting point of Na$. VZ04 reported, which is slightly
higher than freezing point of NazO - 6V205; 620°C. such as CaS04 and MgS04 with low-melting eutectics
produce thick deposits as the temperature differential
the melting temperatures of constituents frequently between a completely dry ash and a totally liquid slag
found in oil ash.8 Consequently, VZOj and VZ04 are is large. The intermediate state is a plastic phase with
innocuous, leaving the combustor as dry suspended a high viscosity.
matter. Oils containing sodium in excess of 40ppm and
5.4. Deposition on Heat-Transflr Surfaces
exceeding 0.3 times the weight percent of vanadium
will lower the melting temperature of V205, forming
Vanadium, sodium, and sulfur are the elements in eutectic mixtures with extremely low melting points,
heavy oil primary responsible for ash deposition. The as shown in Fig. 53.8 When introduced in sufficient
deposition rate is greatest in the superheater and quantities, additives used to inhibit vanadate attack
furnace.‘79 Vanadium is the dominant element will increase the fusion temperature of the ash
present in ash responsible for ash deposition when significantly creating a fouling problem. Refractory
firing oil not contaminated with sodium or addi- oxides can raise the melting temperature of the ash to
tives, as illustrated by Jacklin et a1.,‘95 and Kirsh and well over 1243°C depending upon the formation of
Pross,‘96 in Fig. 51. The deposit usually consists of a intermediate compounds with higher solidification
few very thin layers of yellow-red submicron particu- temperatures---see Table 18.197,198
late, upon which develops a thin black crystalline
scale, illustrated in Fig. 52. The scale is thin, as VZOs 5.5. Vanadium Corrosion
melts at a very precise temperature only 100°C above
maximum tube metal surface temperature. Its surface Attack by VZ05 has been associated with the
94
. of all of the elements in search of an additive to
0 , 20; , I
400 500
loo 300
Vanadium in Oil, ppm
Fig. 54. Oil ash corrosion.“’
formation of a melt. The molten V205 acts as a
fluxing agent for protective oxide coatings of most
metals leaving the surface in an exposed, reactive
state. Metal wastage is further enhanced by the release
of O2 and Na2S04 and V&s react at the surface of
the tube to form beta-sodium vanadyl vanadate
according to the following reaction:
NaO - V204 - 5V205 + 1/202 + NaO - 6VlOs
and
Na20 - 6V20, + Fe + NazO. V204 - 5VzOs + FeO.
O2 formed by this reaction is augmented by 02
absorbed at the surface of the molten slag from the
surrounding and diffuses through the molten film to
the unprotected surface sustaining the high rate of
oxidation. Phillips and Wagoner’99 found the greatest
oxygen-absorbing capacity, most severe corrosion,
and greatest differences between melting and freezing
temperature all occur at approximately the same ash
mixture that is at Na20 * v204. 5v205.
Experiments by Niles and Sanders19* showed
that three intermediate compounds could be formed
between V205 and Na2S04, depending upon the ratio
of Na2S0 to V20s present. Thus,
Na2S04 + V,Os + Na20 * V20s + SO3
Na2S04 -I- 3V205 + Na20 e3v205 f so3
NazS04 + 6V2O4 + Na20 +6V20s + SOs.
Off-stoichiometric ratios produced mixtures of
the bracketing compounds. Field experience has
indicated, however, that regardless of the sodium-
to-vanadium ratio in the oil, only NazO. 5V2Os has
been found in ash deposited in steam generators, and
either Na2S04 or V205 depending upon which side
of stoichiometry the concentration fe1l.2ooThis seems
to imply that only a portion of the total vanadium
is completely oxidized, maintaining a low level of
V205/Na2S04 in the flue gas.
R. W. Bryers
Hansen and Kessler”’ provided the empirical
correlation illustrated in Fig. 54, indicating corrosion
became significant once the concentration in the oil
exceeded ~SOppm. Babcock Atlantique showed an
increase in corrosivity with gas temperature for a
given metal temperature.*02
5.6. Additives
Buckland et a1.*03performed an exhaustive study
inhibit corrosion and found magnesium to be by
600
far the only choice. Young and Hersey,19’ and
numerous others, confirmed the selection of mag-
nesium. Alumina was found to be a good comple-
mentary additive for minimizing the impact of
fouling, which would inevitably occur with the
addition of magnesium to the oil.
Niles and Sanders’98 investigated the behavior of
the magnesium-vanadium-sulfur system. The results
showed that the equilibrium compounds formed in
the reactions depended upon whether the sulfur or the
oxide was used as a reactant. When magnesium oxide
was reacted with vanadium pentoxide, the equilib-
(25) rium compound identified in the reaction was
magnesium orthovanadate (3MgO - V20s):
3MgO + V205 + 3MgO. V205. (30)
(26) It was further shown that the formation of this
compound is not a function of magnesium concentra-
tion. When the mole ratio of MgO to V205 was less
than 3: 1, the reaction products were 3Mg0.V20S
and V2Os. When the ratio was greater than 3 : 1, the
3MgO - V2Os and MgO were found after heating.
At equilibrium, the compound identified in the
reaction of magnesium sulfate with V205 was
magnesium pyrovanadate, 2MgO. V205:
2MgS0 + V20, + 2MgO - V205 + V20, + 2SOs.
(31)
When magnesium sulfate was increased to four
times the molar ratio of V20s, the products showed
(27) the pyrovanadate and excess magnesium sulfate:
(28) 4MgS04 + V 20 5 + 2MgO * V20s + 2MgS04 + 2S03.
(29) (32)
The ash fusion data for the magnesium ortho-
vanadate and pyrovanadate appears in Table 18.
The pyrovanadate has a low softening temperature
and would appear to cause fouling in most steam
generators. The orthovanadate has a somewhat
higher softening and fluid temperature and might be
expected to cause fouling in boilers with high furnace
exit temperatures.
In a more complex situation where sodium and
magnesium are present in the oil along with the
 Steam-raising fuels 95

0 1 2 3 4 5 6 7 8
Excers Air

Fig. 58. SO? formation as a function of excess air (2.5% S

Corrected to 13OO’F heavy oil).*”
Metal Temperature

II
0 5 10 15
Excess Alr
38 -
Fig. 55. Critical excess air for high-temperature corrosion.“”

140

0 2 4 6 8 10
Excess Air
20
Fig. 59. Stack-solids acidity as a function of excess air.“”
Excess Air

Fig. 56. Critical exces’s air vs deposit formation.*”

* 4.0-
‘0
:
u)
ul
= 3.0 -
s
E
_
g 2.0-

2
(D
I!
8 l.O-
2.5 S tiowy Futi
% %
Q Acidity Up to pH 7.5
z
1100 1200 1200 1400
Tube MOW Tompemtura, OF
0 1 2345670
Excess Alr
Fig. 57. Effect of excess air and metal temperatures on
corrosion due to V20,.2’o Fig. 60. Stack-solids formation as a function of excess air.“’
96 R. W. Bryers

Table 19. Ash analysis of various types of cokes

Elemental composition Delayed coke Shot coke Fluid coke Flexicoke

Si02 10.1 13.8 23.6 28.2

A12O3 6.9 5.9 9.4 2.9
TiO 0.2 0.3 0.4 0.6
Fe203 5.2 4.5 31.6 2.7
CaO 2.2 3.6 8.9 10.3
MgO 0.3 0.6 0.4 0.8
Na20 1.8 0.4 0.1 0.5
!A0 0.8
0.3 0.3
1.6 2.0
1.2 10.0
0.0

Ni 6 12.0 10.2 2.9 4.5

v2os 58.2 57.0 19.7 39.9
ASTM ash fusion
Reducing
I.D. 1598 1436 1378 1216
ST. (Sph.) 1598 1598 1386 1322
S.T. (Hem.) 1598 1598 1439 1314
F.T. 1598 1598 1473 1537
Oxidizing
I.D. 1373 1259 1095 1281
S.T. (Sph.) 1425 1429 1155 1386
S.T. (Hem.) 1431 1471 1183 1473
F.T. 1432 1471 1224 1431

2.4

2.2

1.6

1.4

1.2

0.8 - Porphyrm (‘VTPP)

0.6

04

02

0
20 44-I 60

Energy (eV)

Fig. 61. A comparison of the forms of vanadium in delayed and fluid coke with the porphyrins found in oil
using X-ray absorption near edge structure (XANES) analysis by Huffman at the University of Kentucky.

vanadium, all the constituents will be found as
principal components in the ash deposit. When
sodium and vanadium are the major components of
an ash, the compound formed will depend upon
the ratio of sodium to vanadium. When magnesium
is used, SO3 partial pressure will control which
vanadium/magnesium compound will form. There-
fore, in a boiler where the SO3 partial pressure is
above equilibrium for the formation of MgS04 and
magnesium is used as an additive, one would expect
to find MgS04, NaS04, and 2MgO - V205 in the
deposits. Although the corrosion problem might be
resolved depending upon the properties of sodium
sulfate, magnesium sulfate, and vanadium pentoxide
present, a deposit problem could occur as a result of
the formation of mixtures of sodium sulfate and the
 Steam-raising fuels 97

pyrovanadates in the deposit that have low ash-

fusion temperatures. In the presence of MgSO, the
Na2S04 ash-fusion temperatures can be lowered
substantially.
Again, not all investigators are in agreement as to
the chemical reactions taking place. Elsmout and
Kema204 disagree with Niles and Sanders.‘98 Their
investigations showed that upon heating MgO - V205
mixtures, three well-defined magnesium vanadates
are formed as expected, rather than the ortho-
vanadate with an excess of MgO or V20s. They also
conclude that, ‘in oil-fired boilers, compounds such as
3MgO. V205 and 2MgO - V20s are normally formed
only in exceptional cases. even when an excess of
MgO is present. The causes of heavy fouling are
mostly due to the formation of compounds within the
system Na2S04-MgS04 and Na2S04-Fe2(S04)s-
MgS04.‘04
It seems reasonable to conclude that if magnesium
is to be used successfully with a high-vanadium oil,
the sodium concentrations of the oil should be
restricted or the oil should be washed free of the alkalis.

5.7. Low E.xcess Air

UTILIM STYLE STEAM GENERATOR
SIDE ELEVATION
During the process of combustion, vanadium is
oxidized to one of three compounds depending upon
the availability of 02--V203, Vz04, or V20s. The
compounds V203 and V204 have melting points in
excess of 1648°C and therefore, if formed, remain dry
in their flight through the steam generator. Conse-
quently, reducing O? levels is one means of reducing
fouling and corrosion.
The approach was first introduced by Glaubitz.205,206
Since then it has been studied and successfully applied
by Cardinal and Clevarec;z07,‘08 Tipler;*09 Seigmund
and Chaikivsky;*‘” Hedley et al.;*” Brown;“’ Reese
et 01.;~‘~ and Lovejoy et ~1.“~
Seigmund and Chaikivsky’s”” experiments indi-
cated the critical level for high-temperature corrosion
and deposit formation was 3% excess air, as
illustrated in Figs 55 and 56. The effect of metal
temperature and a reduction in excess air on tube
metal wastage are illustrated in Fig. 57.“’ The impact
of low excess air on SO3 is shown in Fig. 58,“’ and the
reductions in slack solids acidity illustrated in Fig.
59.“O Total slack solids increase slightly with a
STAGED ADOITION OF
reduction in excess air as shown in Fig. 60.“” COMBUSTION AIR
With the reduction in SO3 level, the cold-end dew
point for sulfuric acid drops, permitting a slight Fig. 62. A typical steam generator design for firing petroleum
coke and other solid fuels containing less than 10% volatile.
increase in boiler efficiency. O’Neal”’ indicates a 1%
change in excess air results in a 0.05% change in
efficiency. Therefore, a decrease in excess air from 20 a refining operation as a fuel for steam generators
to 5% means a 1% increase in boiler efficiency. producing steam and electricity. The increased
demands for oil products necessitated taking deeper
cuts in refining crude, leaving a residual solid coke
6. FIRESIDE PROBLEMS WITH PETROLEUM COKE high in vanadium (i.e., lOOO-lO.OOOppm), iron, and
nickel. Table 19 shows a typical analysis of coke
Since the late 1950s. an excess of petroleum coke for the various types of coking operation. The total
has created an interest in using this byproduct from concentration and the relative composition are
 R. W. Bryers
Fig. 63. Gas recirculation in a coke-fired boiler.
Mag. 1200X
Fig. 64. SEM photomicrograph at 600x of crystalline nickel
vanadate formed on the superheater of a petroleum coke-
fired steam generator.
dependent upon the source of crude and, to a lesser
extent, the cooking operation. XANE analysis of
the coke from various operations performed by
Huffman and illustrated in Fig. 61, shows that the
vanadium remains as a porphyrin in the coke despite
refining process temperature. There are essentially
four different types of coke being considered for
steam raising: delayed coke, shot coke, Auid coke, and
flexicoke.
Delayed coking is an endothermic process in which
the crude is rapidly heated in a furnace batch-wise and
then confined to a reaction zone or coke drum under
proper conditions of temperature and pressure until
the unvaporized portion of the furnace effluent is
converted to vapor and coke. Products of the coke are
gas, gasoline, gas oil, and coke. Although the exact
mechanism of delayed coking is extremely complex, it
can conceptually be broken down into three distinct
steps:
?? Partial vaporization and mild cracking of the feed
as it passes through the furnace.
?? Cracking of the vapor.
?? Successive cracking and polymerization of the
 Steam-raising fuels 99

OF PURE MOLTEN V20s

2
I=: -
5”
ig OUTSIDE LAYER OF DEPOSIT

kt
=w -
1
W
aa
?f -AT= l°C

$ -
if
ri_ INSIDE LAYER OF DEPOSIT
t-m -

L_ 1 I I I I I I I I
low
,

200 400 600 800

TEMPERATURE, ‘C

Fig. 65. Differential thermal analysis thermogram of pure VzO, compared to vanadium- and nickel-rich ash
deposit thermograms.

liquid trapped in the drum until it is converted to The resultant fluid coke withdrawn from the burner is
vapor and coke.“6.2’.’ a solid spherical particulate smaller than 8 mesh (i.e.,
The coke produced from the normal feeds is <2380pm). The coke is very abrasive and can have a
hard, porous, irregular in shape, and occurs as lumps Hardgrove Index as low as 17.
ranging in size from 20 inches down to fine dust. This The flexicoke is essentially a fluid coke that
type of coke is called ‘sponge coke’ because of its includes a gasifier loop for gasifying and heating
appearance. Delayed cokes are literally mined from the coke leaving the fluidized bed burner in the
the coking drum in a roding operation as large fluid coke system. The latter functions as an
chunks, which must be ground and pulverized to 10% intermediate heat exchanger between the reactor
<200 mesh for combustion in suspension.“’ and gasifier. Adding the gasifier to the system
When charging the coke with highly aromatic increases the yield. Flexicoker yields can be 2240%
feedstocks at high pressures (i.e., lOOpsig), a coke higher than that of delayed coker. At the higher
with needle-like structure can be produced. The yields, one might expect higher concentrations of
needle coke has high strength and a low coefficient ash. The yields may also be limited by the initial
of expansion. It is preferred over sponge coke for use concentration of minerals in the feedstock.
in electrode manufacturing because of its lower
electrical resistivity and lower coefficient of thermal 6. I. Fireside Behavior qf’hfineral Matter in
expansion.“’ Petroleum Cokes
A third type of coke is produced unintentionally
during operational upsets. probably as a result of low Petroleum cokes containing vanadium in concen-
coke drum pressures or temperatures or low API feed trations as high as 4000ppm have been fired since
gravities. This type of coke is called ‘shot coke’ as it 1957 in full-scale steam generators, illustrated in Figs
occurs as clusters of shot size pellets. Strangely. shot 62 and 63, free of corrosion or fouling except for
coke is peculiar to California crudes.“’ occasional deposits attributed to either an excursion
Fluid coke, as the name implies, is generated in a in nickel or sodium concentration or operation
fluidized bed reactor operating at 1000°F. Feedstock resulting in total char burnout. The arch-type
is sprayed onto a bed of fluidized coke. The thin film furnace is used to ensure flame stability and provides
of feedstock is vaporized and cracked by steam additional flame length for the low volatile, less
introduced to the bottom of the reactor as the coke reactive petroleum coke. The furnace box is partially
laden with feedstock flows downward and is with- lined with refractory to increase flame temperature.
drawn from the bed. The coke is removed from the Air is introduced along the flame path and hot gas is
reactor where it is fed to the fluidized bed burner. recirculated to permit ignition and flame stability. The
Approximately 25% of the coke is spent to raise the deposits, when formed, consisted of nickel vanadates
temperature of the reactor coke back to 1000°F formed as a result of condensation of a nickel
and thus provide for the endothermic losses due to compound and VZ05. Their occurrence is usually
feedstock vaporization and cracking yields form fluid limited to a narrow flue gas temperature range. Figure
cokes which are about 75-80% that of delayed coke. 64 illustrates the crystalline nature of the deposit
loo R. W. Bryers
fly
,::!
G
Fig. 66. A typical low-pressure refuse-fired steam generator.
formed. A DTA thermogram of the petroleum coke
deposit, illustrated in Fig. 65, indicates that two
endotherms were encountered during heating-one
coincident with the liquidous line for V20s +
Ni(V03)r, and the other coincident with the
liquidous line of Ni2V207-suggesting the presence
of Ni(V03)2 + Ni2V207. The deposits were formed
by condensible species on nickel and vanadium that
occurred during operating conditions which pro-
moted complete oxidation of the vanadium to VzOs.
Slagging has also been encountered on occasion in
recent years. Careful analysis of the deposit attributes
the deposition to dirt inclusions pickup during
handling of the petroleum coke.2’8-22’
When properly handled and fired, petroleum coke
can tolerate vanadium levels several orders of
magnitude higher than oil due to suppression of the
oxidation of vanadium to its highest oxide state. V203
and V204 have very high melting temperatures
and are innocuous with regard to the formation of
fireside problems. Recent combustion tests have
demonstrated that near-complete char burnout
resulted in generation of very little V20s.2’o The
reduction in rate of oxidation must then be attributed
to differences in the way vanadium is released from
liquid and solid fuels. In the case of oil, the oxidation
of the carbon and vanadium occurs directly at the
surface of the droplet at very high temperatures.
Solid fuels burn slowly at lower temperatures. In
addition, the vanadium must migrate through an
atmosphere enriched with CO and CO2 counter-
current to the flow of oxygen. Exposure to the maxi-
mum level of oxygen occurs at lower temperatures in
a flame front removed from the surface of the particle.
The rate of cooling is faster than the rate of oxidation
of vanadium to V205.
Recent combustion tests of fluid cokes containing
10,OOOppm for 1OOh in a pilot plant indicated the
cokes could be burned free of fouling, slagging and
corrosion, despite very high levels of vanadium.
Corrosion by vanadium pentoxide is catastrophic
and 1OOh is more than adequate to identify its
occurrence with carbon steels or super-alloys. The
pilot plant on which the tests were performed is
designed to reveal moderate to severe fouling in 5 h of
operation. Consequently 1000 h provides a good
measure for demonstrating extended operation, free
of fireside problems.
One of the cokes was clean and contained very little
accessory mineral species. The second coke was
contaminated with dirt, reducing the vanadium
concentration to 39% in the ash. The tests indicated,
 Steam-raising fuels

Metal Temperature. C
200 400 600

o.6-
x 1400 F Gas Temperature
0.5 o 1550 F Gas Temperature 13

t A
11

9;
2
3i
X ti
X 7%
X
:
*X 5;
X’
X

OG'
0 200 400 600 a00 1000 1200
Metal Temperature. F

Fig. 67. Effect of metal and gas temperature on the corrosion rate of carbon steel.7J

in addition to a low ra1.e of fouling, the nature of the surface temperature to levels below the melting
deposits formed were altered by the presence of dirt or temperature of VZ05, the formation of the lower
accessory mineral species (i.e., SiO, A1?03. CaO, oxide states of vanadium, and the high-temperature
MgO, etc.). Deposits formed by cokes enriched with absorption of available V205 by calcium and nickel.
accessory minerals developed as a result of inertial It would then be expected that blending of
impact of fly ash composed of accessory mineral petroleum cokes with coal in an environmentally-
species including calcium, iron and nickel which sound manner would indeed provide sufficient
absorbed the small portion of vanadium converted absorbing mineral species to minimize a fouling,
to VZOs as an intermediate phase. Scanning electron slagging and corrosion situation. Indeed, this has
microscope (SEM) photomicrographs, energy disper- been the case for those few reporting operating
sive X-ray (EDAX) diagrams, and dot maps indicate experience with petroleum coke/coal blends.
the fly ash was reasonably coarse and the primary Formation of vanadium pentoxide during the
absorbents were calcium, iron and nickel. Silica combustion of vanadium-rich petroleum cokes is
was present but did not appear to be responsible inhibited by excess carbon in the fly ash, a reduction
for absorbing vanadium. The heavy metals and in the rate of oxidation of vanadium and/or the
alkaline earths behaved as an additive absorbing what presence of additional mineral species such as SiO? or
little VZOs formed. CaO in the ash. Petroleum cokes containing as much
Deposits formed by coke ash void of accessory as 10.000 ppm VZOs have been fired free of corrosion
minerals developed as a result of condensation of with minimal fouling. There appears to be sufficient
volatile vanadium and nickel compounds. The ash absorbing minerals in coal ash to inhibit fouling,
was uniformly dispersed about the entire periphery slagging or corrosion when petroleum cokes are blended
of the tube and consisted of a l/64 inches thick with coal in an environmentally-sound manner.
crystalline scale. X-ray analysis indicated the
material was primarily a solid solution of nickel
vanadate (Ni3(V04)2) and vanadium pentoxide as
VZOs. Again, less than 2% of the total vanadium 7. FIRESIDE BEHAVIOR OF INORGANIC IMPURITIES IN
MUNICIPAL SOLID WASTE
fired deposited on the tube. The fly ash captured
was composed of vanadyl hydrogen sulfate I. 1. Tecllnicnl Bmkground
(V02)H2(S04) and some vanadium pentoxide. The
SEM photomicrographs indicate the fly ash con- The rapid increase in affluence after World War II
tained superfine material. probably generated by in North America and Europe led to an increase in
nucleation of a fume composed of a sulfate both the quantity and quality of refuse. The shortage
vanadate. Corrosion and serious fouling were of landfills and the cost gave rise to increased use of
avoided as a result of the controlling heat-transfer incinerators. In Europe where fuel costs were higher
102 R. W. Bryers

than in the U.S., and because of the administrative Table 20. Eutectic compositions with low melting points”’
organization in the cities, waste-to-energy plants
Eutectic mixture, mole % Melting point
began to emerge in the mid-1960s. Initially they
were coupled with steam turbines in power plants. F C
The upper plateau of steam conditions was in the
range of 925-2750 psia with saturated temperatures 25 NaCI-75 FeCb 313 I56
37 PbCL-63 F&I, 347 I75
in the range of 280-365°C. Superheat temperatures
60 SnCI,-40 KCI 349 176
were as high as 538°C. At the same time, waste- 70 SnCIl-30 NaCl 361 I83
to-energy units began to appear in the U.S. but 70 ZnCl2-30 FeC13 392 200
with steam conditions at lower pressures and 20 ZnCl?-80 SnClz 400 204
55 ZnCIz-45 KCI 446 230
temperatures.“” zs4
70 ZnCl2-30 NaCl 504 262
Shortly after startup, tube wastage was encoun- 60 KClL42 FeClz 671 355
tered on waterwalls in the furnace and superheater 58 NaClL42 FeCl? 698 370
surface of several European unitsZZ4 A close 70 PbC12-30 NaCl 770 410
examination of the problem by researchers in the 52 PbCl?p48 KCI 772 411
72 PbCI-28 FeCI? 790 421
U.S. and Europe indicated that tube metal wastage
90 PbClzp10 MgC& 860 460
was caused by chlorine acting independently or in 80 PbCl>-20 CaClz 887 475
conjunction with heavy metals of lead, zinc, sodium, 49 NaCI-5 I CaCI? 932 500
and potassium. Chlorine, as HCI, was believed to be
the primary source of wastage of surfaces when they
were exposed to reducing conditions or when erosion were reduced to about 650 psig and 246°C saturation
appeared to be a secondary source of tube wastage. It temperature.‘22
was also established that chlorides of the heavy metals During the mid-1970s interest in waste-to-energy
could produce melting eutectics that could act as a plants in North America increased dramatically. Tube
fluxing agent on the protective deposit on the tube wastage also appeared in some of these units. Some
surface, subjecting the tubes to excessive rates of North American designers followed the European
oxidation or chlorination.z23,“4 concept of protecting the superheater with a double-
New designs evolved out of the first decade of pass radiant heat exchanger surface discharging at
operating experience. They involved major changes approximately 648°C. Others chose to use a single tall
in furnace chamber geometry to insure complete furnace with liberal use of alloy steel with furnace exit
combustion of the refuse and to establish the temperatures limited to 8 15°C. Superheater outlet
following empirical process design parameter to temperatures and pressures were limited to 454°C
avoid fireside wastage.‘24.2’s and 650 psig, respectively. As in Europe, the geometry
All surfaces in the combustion zone were completely of the lower furnace, in most cases, was designed
protected with refractory. Extensive baffling of one to promote turbulence and to ensure complete
form or another was installed in the combustion combustion.
chamber to promote turbulence and to insure Although there was a significant improvement
complete combustion. Combustion zone exit tem- in availability (in some cases in excess of 90% over
peratures were limited to 954°C. Radiant furnace exit 3 years for the new systems installed for power
temperatures of 760°C were recommended. Flue gas production at steam conditions as high as 86Opsig,
temperatures were limited in new installations to 443°C and some even higher), the problem of metal
about 704°C in a parallel flow chamber prior to being wastage still persisted.
introduced to the heat recovery zone containing the Novel remedial measures were undertaken to cope,
superheater, as illustrated in Fig. 66. Recommended including an array of tube covering materials and
superheat temperatures were reduced to about 443°C. application methods; less vigorous slag/soot removal
Krause has shown, as illustrated in Fig. 67, that the methods; avoiding radiant superheaters downstream
corrosion rate increases significantly at higher tube of some or all of the boiler bank surface; and lowering
metal temperatures for gas temperatures exceeding the gas temperature to which the superheater was
760”C.74 Superheaters were redesigned to minimize exposed. These measures further improve system
erosion and to reduce the differential temperature availability but at significant cost. However, these
between the flue gas and the metal temperature. A were reactions to the problem and did not address the
combination of parallel/counterflow heat exchanger cause or its mitigation.
surface was used to maximize protection of the As a result of the Sheraton Palm Coast Conference
high-temperature surface at the superheater outlet. on Incineration of Municipal and Industrial waste, it
Mechanical wrappers were employed rather than soot was learned that the root cause of the metal wastage
blowers to minimize erosion/corrosion problems. remained uncertain.“3 Furnace wall wastage could be
While tube wastage appeared in high-pressure/high- due to HCI or Cl reacting with the tube surface under
temperature units, there were a number of units both reducing conditions, or it could be due to reducing
in Europe and the U.S. which successfully operated at conditions alone. It has not been clearly established
lower pressures and temperatures. Process pressures whether the corrosion is a gas phase HCI attack in
 Steam-raising fuels

Whlte(NoK),SO,.K,Pb(f SO+& PbSO. --

p No,SO,.KOH.SIO,.M~,BO,
Fe,O,.Fe,O, ,(NoK&SO, Whlte(NoK1,SO,
____ C&O, 4PbO’PbSO,
Fe,O,,Fep,.(NaK),SO, Amber PbO.PbSO,

Fe,O,.Fe,O,,(NaK),SO, adherent to deposit

Scale-DeposerSeporol~on Interlace

Mlxed oxide
layer adherent
I
to substrate
a Fe,O.. Fe.0. 3 Fe,O,.Fe,Q h

Red a Fe, 0, powder I Red Q Fe,O, powder Red Q Fe,O, powder

Fe CI,.FeS
FeClz FeCI,
Dtscontmws white and
Cotmnwus white layer Contmuous gold layer
blue-block layer

900-l IOOT 600 - 000°F 300- 5009

Fig. 68. Schematic diagram showing location of phases identified by X-ray diffraction.7J”‘

the absence of deposits or Cl generated within the continuous basis, as well as the distribution of air.
deposits in the absence of Oz. There is some introduce new technical dimensions directly respon-
uncertainty as to whether the reducing conditions sible for the elimination of the corrosion problem and
are created by CO or unspent polyvinyl chlorides. minimizing its economic role in refuse incineration.
There is also uncertainty as to how the chlorides The process parameters (i.e.. time, temperature, and
arrive at the tube surface (i.e.. polyvinyl chlorides or mixing) are intimately woven into parameters
salts of sodium, potassium, zinc, or lead). Some feel affecting emissions.
the corrosion could be caused by the fluxing action of Mechanistically, on-line corrosion due to chlorine
low-melting eutectics. Some observers have witnessed in fuels can be broken down into several categories
corrosion in the absence of deposits, while others (i.e., molten salt attack, high-temperature corrosion
claim deposits are the source of the problem. The one due to Cl or HCI under oxidizing and reducing
common denominator is the presence of reducing conditions, and low-temperature corrosion due to
conditions in one form or another when surface condensation of HCI). Bryers and Kereke? were the
temperatures exceed ~246°C. Good mixing, sufficient first investigators to recognize heavy metal molten
residence time, and combustion temperature all salt attack may occur on high-temperature incinera-
influence the furnace wall corrosion. In stoker-fired tion heat-transfer surfaces exceeding temperatures of
boilers where a heterogeneous wet fuel such as -443°C. The attack will occur if low-melting eutectics
refuse is fed on a grate cross flow or perpendicular to formed by sulfates and chlorides in the heavy metal
the direction of the flow of air and flue gas, thereby cations-Pb, Zn, Na, and K-deposit on the tube
placing extraordinary local demands on precise surfaces. Typical melting temperatures are shown in
metering of air to meet the local stoichiometry Table 20.“’ As shown earlier in Fig. 13. the chlorides
requirements of the fuel. Measures such as the of the heavy metals have relatively high vapor
introduction of 40% or more excess overfire air and pressures.47.4” Lead appears to be the most likely
modifications in chamber geometry to ensure sufti- candidate for deposition on the tube surface. The
cient turbulence must be taken to minimize CO presence of the heavy metal chlorides. of course, will
levels and carbon loss. Development of a means of depend upon the temperature level of the flue gas at
monitoring temperature and CO in situ on a the tube gas interface, the partial pressure of the trace
104 R. W. Bryers

Corrosion Rate Normalized to

Metal Temp 640°C,
Gas Temp. 1050°C

O-
0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55

CHLORINE CONTENT OF COAL (% as received)

Fig. 69. The linear dependence of corrosion rate on coal chlorine content for austenitic steek.76

NOTES o ConcmtrrI8ons
O\

\o
0
Sulplm~o 10n
cNorla0 Ion
I lrom 0~os11s
surlaca
doIwmMd
on metal

_ 14

c
f.

40 80 100 120 140

METAL 1EMPERATUAE Oc

Fig. 70. Plant rates of sulphate and chloride ion deposition measured after the precipitator.‘-‘”

elements, and the existence of oxidizing or reducing
conditions. Sommerlad et al.*‘* and Krause74 have
identified the presence of chlorides in layers of deposit
adjacent to the corrosion product, as illustrated in
Fig. 68. The molten salts, when present, act as a flux
for protective oxides on the tube, thus exposing
the surface to continued high-temperature oxidation
and/or chlorination.
Krause74 also identified the presence of the least
volatile iron compound, FeC12, between the corrosion
product and the raw metal surface. The corrosion
product suppresses volatilization, Its presence in
deposits on waterwalls makes Cl or HCl rather
than chlorinated salts-the most likely candidates
responsible for tube metal wastage.
In most cases the attack of heat-transfer surfaces
by chlorine in fuels is dependent upon the interaction
of Cl or HCl with the metallic components, their
protective film. or their corrosion product. The
aggressiveness of the attack depends upon the partial
pressure of Cl in the gas and the equilibria between
HCl and Cl under reducing and oxidizing conditions.
At low temperatures, equilibria favors HCl; at high
temperatures, it favors Cl.”
Under oxidizing conditions in the temperature
regimes encountered within the tubeside layers of
 Steam-raising fuels

BoilerBank

, Cyclone

Fig. 71. Typical elevation view of a stoker wood-fired steam generator.

deposited ash, equilibria favors the formation of lower temperatures, one must conclude that Cl, which
sulfates with the release of HC1.74 forms preferentially over HCl under reducing con-
ditions, was present at some point in time. Brown
2MC1+ SO2 + l/20? -+ 2HCI + MzS04. (33) et al.“” clearly show that Cl corrodes steel rapidly at
The corrosion rate of bare iron or mild steel surface the lower temperature.68
in pure HCl typically occurs at a low parabolic Krause74 indicates cyclic reactions can occur
reaction rate up to llOO”F, as shown by Brown et beneath the deposit with the chlorine attacking the
u/.,~’ in Fig. 16, because the FeCl? reaction product tube metal to form more FeCI1:
forms a stable surface layer:
2/3FeC13 + l/20? -+ 1/3Fe203 + Cl?
Fe + HCl ---t FeClz + H,. (34) (37)
I Fe 2
Although, as shown previously, Fe& is somewhat
volatile, catastrophic corrosion will not occur until Under reducing conditions, Brooks and Meadow-
the melting temperature is reached at 675°C. How- croft76 have shown that the corrosion rate due to CO
ever, in the presence of sufficient oxygen, the very is enhanced by the presence of chlorine. At concen-
volatile FeCls will form: trations of HCl exceeding 200ppm, there is a
transition from parabolic to linear kinetics with
FeCI, + HCl + 1/407 + FeCls + 1/2Hz0 (35) little further increase in rate for higher concentra-
FeCls will also be formed by the action of HCl on tions of HCI-see Fig. 17. The increase in
the oxide scale which develops on the steel: corrosion resulting from the presence of HCI in the
reducing atmosphere was attributed to oxidation/
1/3Fez0, + 2HCl -+ 2/3FeCls + HZ0 (36) sulfidation promoted by scale disruption through
FeCl? formation and volatilization.“5 They show a
Krause,74 Grabke,” and Mayer and Manolesco75 linear dependency of corrosion rate on coal chloride
report disruption of protective oxide layer by HCI. content for austenitic steels in Fig. 69.76
The porosity increases with an increase in HCI The cold-end corrosion is due to condensation of
concentration.” At 2 volume percent, the layers are aqueous acidic condensates on low-temperatures
completely destroyed. surfaces. The rates of deposition on cold surfaces
Since FeClz is found in the corrosion product at the of sulfate and chloride ions are shown in Fig. 70 as
 Table 2 1. Fuel properties of eastern Canadian bark

Balsam Black White Red Jack Poplar Birch Birch Maple Maple Elm Beech Tamarack Hemlock
spruce spruce spruce pine white yellow hard soft

Proximate analysis
Volatile 17.4 14.7 72.5 72.9 74.3 78.9 80.3 76.5 75.1 78.1 73.1 75.2 69.5 72.0
Fixed carbon 20.0 22.5 24.0 23.7 23.6 17.2 18.0 21.0 19.9 18.9 18.8 18.9 26.3 25.5
Ash 2.6 2.8 3.5 3.3 2.1 2.2 1.7 2.5 5.0 3.0 0.1 7.9 4.2 2.5
Ultimate analysis
Carbon 52.8 52.0 52.4 52.1 53.4 51.8 57.4 54.5 50.4 50.1 46.9 47.5 55.2 53.6
Hydrogen 6.1 5.8 6.4 5.9 5.9 6.5 6.7 6.4 5.9 5.9 5.3 5.5 9.9 5.8
Sulfur 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Nitrogen 0.2 0.1 0.1 0.1 0.2 0.3 0.3 0.6 0.5 0.3 0.6 0.6 0.7 0.2
Oxygen 38.6 39.7 38.4 38.6 38.9 38.0 33.8 26.2 39.1 40.7 39.1 38.5 31.0 37.9
Ash 2.3 2.4 3.0 2.0 3.1 3.4 1.8 2.3 4.1 3.0 8.1 7.9 4.2
2.5 9
Ash analysis
SiO, 24.6 6.4 2.0 7.6 16.0 1.5 3.0 4.1 39.5 6.1 3.6 12.4 7.3 10.0 5
A&t% 1.8 1.1 0.6 0.0 6.3 0.5 0.6 0.3 3.8 3.1 0.0 0.0 8.4 2.1 5
Ti02 0.2 * * 0.1 0.2 * * * * 0.1 OFI * 0.1 *
Fe:% 2.5 1.1 0.7 3.1 5.0 0.6 2.9 0.8 1.7 0.8 0.3 1.1 3.6 1.3
cao 43.2 67.6 62.9 58.4 51.6 62.3 58.2 54.2 55.5 60.4 67.1 68.3 50.3 53.6
taco, 7.8 11.2 13.6 11.3 4.9 14.6 13.0 17.8 1.4 16.7 16.3 2.2 4. I 9.7
MgO 2.2 1.7 6.4 4.7 5.5 1.9 4.2 5.4 19.4 2.3 2.0 11.5 8.5 13.1
MnO 2.6 2.2 1.2 2.0 1.6 0.3 4.6 1.3 1.0 0.4 0.1 0.4 3.4 1.2
P@s 4.6 2.2 2.6 2.2 2.8 2.0 2.9 3.8 1.1 0.3 1.3 2.3 4.7 2.1
K?O 10.1 6.2 7.3 5.3 4.1 7.2 6.6 8.0 5.8 6.3 4.4 2.6 5.3 4.6
Na,O 2.5 2.5 0.8 2.0 3.1 3.9 1.3 1.7 2.2 0.9 0.7 0.9 3.2 I.1
so3 2.7 1.4 2.2 1.3 2.6 0.6 3.2 1.3 1.4 2.0 0.8 0.8 2.6 1.9
Fusion temperatures, -K
’
Initial 1838 1760 1755 1627 1616 1744 1760 _ 1727 1660 _ 1633 1505 1788
Softening 1844 1784 1755 1821 1783 1810 1766 1777 1821 1738 _ 1811 1533 1744
Fluid 1849 _ 1760 1827 1805 1816 1771 1777 1827 1744 _ 1816 1560 I799
 Steam-raising fuels 107

Table 22. Chemical composition of biomass ash”’ “’

Si02 Fe?0~ MgO cao ZnO KJO Na20 SO, P,O, Total

Bean straw (I) 29.9 2.7 0.9 4.67 0.03 22.34 0.52 4.7 2.29 68.05
Safflower 20.46 1.2 6. I 10.84 0.03 30.0 I 0.91 8.36 3.64 Xl.65
Rice hulls 94.6 0.03 0.02 0.25 0.00 2.4 0.135 2.24 0.46 lO0.l’
AlfAlfa 7.96 0.51 2.87 I I.2 0.125 33.97 3.64 4.64 10.46 75.46
Cotton gin trash 23.2 1.93 2.87 7.18 0.187 I3 00 1.59 4.24 IO.00 64.20
Barley straw 44.7 2.6 4.84 3.22 0.125 8.01 5.25 I.8 Il.56 XI.11
Corn stalks 50.7 3.14 3.08 3.9 0.95 10.3 0.53 I I .08 10.00 93.68
Rice straw 75.2 0.58 0.83 0.72 0.00 1 I.9 0.28 I.51 X.87 99.x9
Bean straw (II) 32.7 3.93 3.65 6.3 0.15 25.3 0.82 2.28 7.3 x2.43
Wood chips 8.3 10.0 6.22 18.61 0. I93 I I.8 I .32 9.0 6.X7 71.61
Corn fodder 55.3 2.4 3.32 I .05 0.087 9.59 0.73 3.4X 2.YX 78.Y5
Paper pellets 57.2 4.29 0.83 0.15 0.31 I 85 5.09 4.0 4.46 7x. IY
Corn stalks (ex.) 63.3 4.72 4.78 0.56 0.00 X 37 0.47 7.2 2.06 Yl.46
Almond shell 22.6 3.77 2.49 12.27 0.05 I4 14 5.08 X.0 5.5 73.90
Corn cobs 40.3 4.06 2.49 I.27 0.22 2.04 1.19 8.74 6.87 X5.53
Manzanita chips 5.97 2.86 4.94 24.49 0.25 10.96 2.85 6.74 x.2 67. I6
Tree pruning 9.95 I .94 8.29 19.87 0.06 12.66 I .48 19.72 4.Yh x5.93
Walnut shell 13.6 2.44 3.65 7.0 0.44 21 50 I .0X 8.48 4 58 62.92
Olive pits 10.5 2.2 3.48 25.89 0.12 3.13 7.60 17.2 7 56 77 74
Almond shells 18.6 3.83 1.99 16.0 0.23 14.7 5.86 17.4X 7.79 X6.48
Corn stalks 71.7 7.1 2.7 0.46 0.02 10.2X 0.33 2.2 0.66 95.45
Cotton stalks 33.0 2.8 6.05 3.56 0.07 2 I .40 1.374 6.55 6.4 x3.57
Rice mix 75.0 0.47 2.5 1.1 0.00 15.85 0.54 I .o I.1 97.56
Wheat + corn (I : 3) 71.7 3.3 8.3 0.95 0.619 14.76 0.54 2.96 I.1 103.64
Rice straw (good bales) 78.3 0.36 2.0 0.7 0.00 13.0 0.43 1.6’) 08 ‘)7.7x
Rice straw (decayed bales) 78.6 0.44 2.0 0.88 0.00 14.50 0.44 I .x3 0.9 09.59

a function of temperature. Latham rr a/.“’ indicate inclusions containing quartz partitioned from the
condensation corrosion can be avoided by good thermal calcium-rich wood ash during combustion may
design and diligent housekeeping to avoid cold regions. react independently with any potassium present as a
volatile species. The potassium absorbed as K(OH)
on the surface of the quartz produces a low-melting
8. COMBUSTION OF WOOD
eutectic (i.e., 800 C), which will stick to hot surfaces
or heat-transfer surfaces where the shear force
Wood wastes were uniformly disposed of in tepee produced by flowing gas is less than the adhering
incinerators. Growth of the paper and wood products force to the tube surface.
industry and a need for process steam provided the The presence of NaCI may not present a problem
incentive for adapting wood waste to stoker-fired for pure wood bark. However, in the presence of
steam generators, as illustrated in Fig. 7 I. In practice. sand particles. the slagging may be compounded by
bark waste is usually fired in combination with other the increased level of alkali concentration and the
fuels which sometimes leads to some unexpected enhanced volatilization of potassium in the presence
fireside problems.“’ of Cl.
The ash in wood is generally very low (running Blending of wood with any of the sulfur-bearing
about l&3%) as shown in Table 21. The ash is very fuels almost ensures fouling due to calcium-sulfate-
rich in calcium as calcite or carbonate (i.e., 50-60%). bonded deposits as the sulfur reacts with the
with minor amounts of quartz (i.e., 10% or less). Clay submicron calcite particles at the tube surface. By
exists in trace amounts. Although potassium is found itself. wood does not appear to be a problem. Blended
in minor concentrations, its level of concentration is 4 with fuel containing other minerals or mineral matter
or 5 times that found in coal. The analysis of the ash, species, particularly sulfur-laden gases. may create
however, may be slightly altered during transporta- serious fouling in the form of CaSO?/K,SO,-bonded
tion of the log by sand inclusions or the intrusion of deposits.
NaCI found in seawater. Ash fusion temperatures are
generally very high due to the extremely high
concentration of calcium.
9. COMBUSTION OF BIOMASS
Wood contains no measurable level of sulfur.
Consequently, during combustion the minerals
commonly found in ,wood form a high-melting.
calcite-rich ash slightly contaminated with potassium The genesis of the biomass power industry is in
and silica. Consequently, the combustion of pure the paper and wood products industry, where wood
bark should not present a problem. However, sand is used to cogenerate heat and power for process
108 R. W. Bryers

Table 23. Deformation and fusion temperatures of biomass ash’3’.2”

I.D. # Fuel name Deformation Fusion

temperature, temperature,
“C “C

1. Bean straw I 900 1150

2. Safflower 700 1430
0. Rice hulls 1439 >I65
3. Alfalfa 700 1550
4. Cotton gin trash 1010 1380
5. Barley straw 925 1100
6. Corn stalks 820 1091
7. Rice straw 823 1190
8. Bean straw II 940 1260
9. Wood chips 1050 II90
10. Corn fodder 1010 1180
I 1. Paper pellets 890 1130
12. Corn stalks (ex.) 1120 1235
13. Almond shell (ex.) 790 1440
14. Corn cobs 900 1020
15. Manzanita chips 1080 1400
16. Tree prunings 770 1550
17. Walnut shell 820 1225
18. Olive pits 850 1480
19. Almond shell 860 1350
20. Corn stalks (8 1) 980 1140
21. Cotton stalks (81) 1110 1275
22. Rice straw mix 985 1200
23. Corn stalks + wheat (I : 3) 985 1260
24. Good rice straw 1060 1250
25. Partially decomposed rise straw 850 1280

m: Solid Data - Osman’s Data I233.2341

@ Biomass - Bryrrs II I

Ic I n 1600
03
A

1500

0
1400 ._

%
‘fii
5
E
1300 e

1200

1100
I I rod I I I I I I
2000
0 10 20 a 30 40 go 60 70
Percent Bask I% E ( 203 + Co0 + MgO + No20 + KS01
0
Fig. 72. Regression analysis of ash softening temperature vs percent basic in the ash for three different types
of biomass compared directly with various ranks of coal.
 Steam-raising fuels 109

Table 24. Summary of percent ash determined by various techniques

Low-temp. ash TGA on LTA Proximate ash TGA on biomass

<25O”C 1000”c -950°C 1ooo”c

80% wood/20% wheat straw 9.20 7.6 7.67 4.0

Almond hulls 9.03 3.79 4.87 5.0
Almond shells 3.57 2.07 2.25 2.0
Rice straw 22.58 17.1 19.09 17.5
Wheat straw 9.44 6.6 7.35 5.0
Olive pits 2.26 1.28 1.53 1.0
Wood waste/almond shells 8.32 6.6 6.23 2.5
Waste paper 8.70 6.96 8.56 7.0

Table 25. Chemical fractionation-olive pits

Chemical Water IM IM Remaining

fraction Ammonium Hydrochloric residue
acetate acid
pg/g IJg/g

Sodium 650 240 420 2400

Potassium 610 1400 150 245
Calcium 170 910 197 940
Magnesium 70 450 66 400
Iron 10 <IO 750 112
Aluminum 40 10 400 270

uses. Wood has been used as a fuel for generating
stream over 40 years. By 1989 approximately
6 GWe of biomass energy-based generating capacity
was available in the United States-primarily
owned and operated by industrial entities. Disposal
of wood waste and availability of a cheaper source
of fuel were the main reasons for using biomass as
a source of energy. In the United States, biomass
electric power generation experienced dramatic
growth after the Public Utilities Regulatory Policies
Act (PURPA) of 1977, which guaranteed small
electric producers that utilities would purchase their
surplus electricity at a price based on the cost of
producing electricity that was avoided by the utilities.
From less than 200MWe in 1979, biomass energy-
based generating capacity in the U.S. grew to
approximately 66GWe by 1989. It is estimated that
there are 1000 wood-fired plants in the United States,
typically in the range of lo-25 MW.230
9.2. Fuel Characterization
Wood represents about 80% of the biomass
consumed for raising steam. Agricultural waste (i.e.,
straw, manure, shells, etc.) constitute the remaining
20%. Wood presents very little fireside problems
when burned in a steam generator by itself, despite the
fact that S-10% of the ash is composed of potassium.
The bulk of the ash is composed of calcium, and silica
appears to constitute less than 10%. The ash is highly
basic with high melting temperatures. Although
potassium appears to be present as an organically-
bound constituent which is highly volatile during
combustion, in the absence of sulfur, it presents little
trouble as it remains suspended in the gas stream as
K20 or K(OH) to very low temperatures. A typical
wood-fired steam generator is illustrated in Fig. 7 1.
Agricultural wastes, on the other hand, are rich in
silica and high in potassium. Occasionally sodium
occurs in substantial amounts. Calcium occurs in
modest concentrations. The solid ash has very high
melting temperatures; however, once the silica
absorbs the alkalis present, the fly ash particulate
surface becomes molten at very low temperatures.
Agricultural wastes are generally low sulfur (i.e.,
~0.05%) but contain chlorine between 400 and
4000 ppm.
Osman and Gross23’.232presents the ash chemistry
for an extensive list of agricultural wastes in Table 22.
The ash fusion temperatures for the fuels appears in
Table 23. To gain a better perspective for the fusibility
of the ash as compared to coal, the physicochemical
properties have been plotted on a regression analysis
for softening temperature vs percent basic for coal
in Fig. 72. From the regression analysis, it is quite
apparent that there are three different systems: a high-
silica/high-potassium/low-calcium ash as found in
grasses; a low-silica/high-potassium/high-calcium ash
found in wood derivatives, pits and shells; and a high-
calcium/high-phosphorus ash found in manure. All,
except for wood derivatives, have unusually low
melting temperatures. Blending of various groups
may produce ash with somewhat unpredictable
melting temperatures, particularly when one recog-
nizes a good deal of the mineral matter volatilizes
during combustion.
An examination of Osman and Gross’23’.232data,
as well as undisclosed data by others, reveals a high
degree unaccounted for when the fuel is traditionally
ashed at 750°C. Ashing via various techniques such
110 R. W. Bryers

Ho&gonoouo
InorganIc Vapor
IY DF- PI\ Condonoatlon,
Combuatlon Sulfldatlon Nucloatlon,
\ K,C.KWCy’W Coal*aonco

SIo&aO,MgO i 2. &SO.

CI,K,S /’ -4

oontralnmont Inwilal
L
viscous Sla
-
Molton Lw*

_ _
ltlgh S;rt&o- - - - - -
Radhnt
-Low sutfao. 1High Tamp.
hmporaturo Tompemture
nod ?i-•lsfw Convmt/vo Ho& ?hn*fof Surface

Fig. 73. Transformation of mineral matter in biomass.

as low-temperature ashing (LTA) at <25O”C, thermo- Chlorine in biomass appears as a chloride ion and
gravimetric analysis on LTA at variable tem- serves the role of balancing charge. Its concen-
peratures, and high-temperature ashing at lOOO”C, tration is closely related to the nutrient composition
summarized in Table 24, has taught us that certain of the soils. The levels of chlorine required for
components are lost continuously as the temperature optimal plant growth are usually far less than the
increases and are responsible for the unaccounted for. levels made available by nutrients. Therefore,
Below ~750”C, the mineral matter components such variations in chlorine levels are usually indicative
as potassium form nitrates and perchlorates as of soil conditions rather than plant physiology.234,235
artifacts of the low-temperature oxidation process. Phosphorus exists in its most oxidized form in
These compounds decompose between 200-7OO”C, biomass fuels and is not reduced during plant
releasing nitrogen and chlorine above 750°C. metabolism. It is primarily introduced in the form
Livingston233 has shown a significant loss in the of dihydrogen phosphate ions (HzPO4) and either
alkalis. Consequently, care must be taken in the remains in the inorganic form or is incorporated in
procedures used to quantify the elements present. A organic structures by forming esters or pyrophos-
typical analysis by chemical fractionation of olive phates.236s237
pits in Table 25 at room temperature indicates Silicon is introduced by plant by absorption of
potassium is organically bound, whereas sodium is silicic acid from the soil solution. It is present in most
predominantly tied up as a silicate. Ash fusion plants at macro-nutrient levels (O.l-10% dry basis).
temperatures mean very little since too much of the Silicon is deposited as a hydrated oxide (Si02 . nH20),
alkali is lost during the ashing process. Evaluation usually in an amorphous form but occasionally in
of the fireside behavior of mineral matter in biomass crystalline forms.234,235
then depends on an understanding of the minerals Potassium is the second most prevalent element
present and how they behave during combustion. found in straws and grasses. Potassium occurs as a
univalent ion (K+) that is highly mobile with little
9.3. Mineral Matter structural function. It is not associated with the silica.
Potassium uptake is highly selective and correlates
Sulfur can be incorporated into plants both by with plant metabolic activity. Osmotic potentials
absorption and assimilation of atmospheric SO2 and across membranes and in the cytoplasm are regu-
by absorption through the roots. The two principal lated to a large degree by potassium. It plays an
forms of sulfur in plants are as sulfates and organic important role in enzyme activation, membrane
sulfur. The former increases with increasing sulfate in transport, and stomata1 regulation. Because of these
the nutrient supply. The latter is far less sensitive to metabolic and transport roles, potassium is often
sulfate supply in most plants.234,235 found in regions where plant growth is most
 Steam-raising fuels Ill

Mag. 3000X Calcium occurs almost exclusively in the axoplasm.

It forms exchangeable bonds with the ceil walls and
has significant function in cell wall stiffening and the
structural integrity of plants. It helps regulate plant
growth.234.235
Aluminum is toxic to most plants and occurs in
small quantities. Aluminum concentrations rarely
exceed 300ppm on a dry basis. When it does, it is
usually considered a marker for contamination via
dust, dirt, or other soil inclusions.‘“4,‘35
Iron has two principal roles in plants: formation of
chelates that are active in transport, and participation
in reversible oxidation/reduction reactions. Iron is
concentrated in leaves.236,‘37

9.4. Fireside Behavior c~j’Mineral~

During combustion, the mineral matter, generally

referred to as ionically or organically-bound inor-
ganic species (i.e., K, Ca, P, Fe, S and Cl), is released
Fig. 74. SEM photomicrographs at 3000x of calcium as a vapor phase. Depending upon how they are
phosphate fly ash upon which potassium sulfate has released and during which phase of combustion (i.e..
deposited forming a voluminous deposit on screen tubes devolatilization or char), a portion may be absorbed
between radiant and convective heat-transfer surfaces. by the minerals present [Le., SiOZ or included
extraneous clay (dirt)]. As shown in Fig. 73, the K,
P, Ca, and Cl are oxidized, chlorated or sulfated, as
Mag. 3000X the case may be, to form oxides, hydroxides and
chlorides. These compounds all have high vapor
pressures and remain in a gaseous state until cooled to
very low temperatures. Equilibria in the presence of
silica, chlorine and sulfur dioxide favors the forma-
tion of chlorides at high temperatures, silicates at
intermediate temperatures, and sulfates at the lower
temperatures, say 1000°C and lower.
The compounds formed and their level of concen-
tration depends on the level of concentration of Cl, S,
and O2 in the gas stream. Being that Cl concentration
is generally low, potassium will be absorbed by the
silicates, creating a particle encapsulated by a viscous
potassium silicate enriched with potassium. The level
at the surface and hence its melting temperature and
viscosity depend on the rate of absorption of
potassium and counter-diffusion of potassium and
silica to and from the core. Potassium may also be
absorbed on high-temperature surfaces of well-
developed deposits or it may homogeneously
Fig. 75. SEM photomicrograph at 1500x of thin scale in condense in the presence of SO, or SO3 at lower
convective furnace formed by deposition of K2S04. temperatures as potassium sulfate. If this occurs in the
gas stream, nucleation produces submicron particles
that are subsequently agglomerated or scavenged by
vigorous. Tree branches and forest wood slash are larger fly ash, shown in Fig. 14, deposited on cooler
generally enriched with potassium compared to core tube surfaces by thermophoresis. or leaves the boiler
,,,d,234-236
as a fume. Depending upon time and temperature, the
Sodium is not considered an essential element to potassium sulfate may also deposit directly on a tube
plant. In low concentrations (<2%), it may be surface, creating a low-melting sticky surface, shown
beneficial to some plants vis substitution for potas- in Fig. 75. Such a deposit will continue to grow until it
sium. At higher concentrations, it is generally reaches the dewpoint for sulfate, at which time
considered toxic. High sodium concentrations are equilibria is reached and growth ceases. If, during
frequently an indication of intrusion of salt water or a the course of the formation of the deposits, discrete
process additive.234,235 particles impinge upon the surface. they may become
112 R. W. Bryers

,Y- Economizer

<Air Heater

LPrimary Superheater

Secondary Superheater

654°C
Water-cooled Grate

\/
Ash Hopper ’

Fig. 76. Typical biomass stoker-fired steam generator.

Table 26. Composition of fuel and deposits-stoker-fired boilers

SiOz Al203 TiOz FezOx CaO MgO Na20 KzO P205 SO3 Cl CO* Undet

Stoker-l: Wood/20% wheat straw blend, fuel ash = 8.14%

Fuel 57.58 1.16 0.48 3.98 11.29 2.96 3.4 6.89 1.07 2.26 0.16 0.13
Superheater 33.77 9.47 0.50 3.57 14.68 3.79 4.09 11.80 1.12 16.30 0.91
Upper wall 5.41 1.63 0.07 2.74 4.97 1.26 9.05 27.90 0.76 41.90 4.31
Grate slag 60.75 10.72 0.56 3.79 11.25 3.23 2.32 6.01 1.28 0.13 -0.04

Stoker-2: Wheat straw, fuel ash = 7.95%

Fuel 63.42 1.95 0.02 0.66 4.20 0.46 0.83 13.10 4.96 1.95 2.40 6.05
Superheater 18.62 1.12 0.02 0.32 14.41 2.45 0.47 33.40 3.46 8.67 15.20 0.30 1.56
Grate slag 62.26 1.94 0.07 0.48 10.59 2.15 0.47 17.7 3.74 0.04 0.04 0.12 0.40

Stoker-3
Superheater 10.64 0.99 0.02 8.73 4.80 0.80 0.97 43.50 1.29 3.90 26.00 0.05 -1.69
Upper wall 7.54 1.55 0.02 0.52 3.79 0.08 1.12 51.20 1.06 5.99 29.20 0.16 -2.23
Front nosewall 49.51 2.16 0.05 0.66 15.09 2.71 1.58 18.70 3.94 0.20 4.89 0.06 0.45

Undet = Undetermined.

entrapped, permitting interaction of the potassium the silicates may absorb potassium, forming a low-
sulfate with the aggregate and allowing it to grow melting compound. Whether or not the low-melting
thicker. fly ash sticks and forms a deposit depends on the
Chlorides may form in a similar manner. However, surface temperature, local temperature gradient, the
their high vapor pressures, lower concentrations, level of local kinetic energy, and degree of super-
and equilibria with other contaminants present cooling of the depositing fly ash. Surface tempera-
produce a very narrow window for their deposition tures in excess of ~850”C, such as exposed refractory,
and collection. They may be confined to the external will certainly be good collectors of impacting fly ash,
surfaces of low-temperature deposits (i.e., in the particularly if the refractory is exposed to gases with a
temperature range of 750-800°C). low level of turbulence. Deposits may grow to great
The minerals in the biomass (i.e., SiOz and thicknesses on such surfaces due to low heat flux and
Si07(NaCa)(AlSi)40s) melt and agglomerate during flat temperature profiles, particularly if the deposit is
combustion. They may be subject to some fragmenta- viscous or in a semi-crystalline state over a wide
tion of the mineral or biomass char. Upon cooling, temperature range.
they solidify. Some SiO vapor may be released during Molten and supercooled fly ash depositing on
reducing conditions at high temperatures. The dry, cool surfaces stick and form either a frozen fused
pure species impact on heat-transfer surfaces and layer or sintered deposit. At high absorption rates
reentrain unless captured mechanically or in a (i.e., high flame temperatures), the ash experiences a
viscous layer. At very high temperatures, some of steep temperature gradient due to the low thermal
 Steam-raising fuels
conductivity of dry sintered ash. Once the surface
temperature reaches the initial deformation tempera-
ture of the lowest melting phase or the plastic range of
the deposited ash, the thermal conductivity increases
and the temperature gradients flatten, allowing the
deposit to grow. Growth continues through the
plastic range until the fluid temperature is reached.
Equilibrium is reached once the fluid temperature is
achieved at the surface and the flow away from the
surface of molten slag equals the rate of ash
deposition. The initial layer of dry sintered ash is
primarily responsible for loss in heat transfer. The
thickness of the deposit is primarily governed by the
temperature range and viscosity of the plastic slag
(i.e., the range over which the crystalline phase melts
and goes into solution) and the viscosity of the final
molten phase.
9.5. Steam Generator Design and Field Experience
To overcome slagging and fouling by low-melting
fly ash and large concentrations of volatile alkalis in
the presence of SOS and Cl, a folded furnace design is
used consisting of a radiant chamber in series with a
convective chamber, illustrated in Fig. 76. The exit
temperature from the radiant chamber is 898°C and
the entrance to the convective heat-transfer surface
immersed perpendicular to the flow of flue gases is
between 654-732°C depending upon cycle efficiency
and steam conditions. Surface parallel to the direction
of flow may be immersed in the convective furnace.
This type of surface will be subjected to scale
formation by K2S04 and allowance must be made
for a reduction in absorption.
Jenkins et al.236 report that a white, reflective,
porous scale, similar to that shown in Fig. 75, is laid
down on furnace wall tubes and high-temperature
convective surfaces composed primarily of sulfates.
Slag formed in the lower grates and furnace walls are
enriched with silica and depleted of S03. Heavier
deposits in the superheater contain silicates but are
enriched with sulfates and chlorides, as illustrated in
Table 26.236 Some corrosion has been reported;
however, the mechanisms remain undefined.
10. SUMMARY
Fireside problems are extremely complex. Dis-
position of mineral impurities from the fuel as fly
ash or deposited ash on heat-transfer surfaces and
refractory throughout a combustion system depends
on mineral origin not elemental composition, mineral
size, mineral association, juxtaposition of minerals
with regard to combustibles, availability of oxygen,
gas temperature, surface temperature, and orientation
of heat transfer with the gas stream. Transformations
that take place during combustion and post-
combustion quenching may be thermodynamically
controlled or kinetically driven depending upon the
113
mineral species and gaseous environment. Once the
fuel is combusted, changes in state of the transformed
minerals and mineral matter occur under a quenching
mode and consequently, are subject to supercooling
from a meta-stable state. The degree of cooling
depends upon available sites to precipitate the
change and the size of the site. Modes of transport
include inertial impact and diffusivity in various
forms. Dramatic partitioning of mineral species and
hence individual elements occurs once the process
of combustion begins. Consequently, the elements of
iron, calcium, sodium, potassium, and magnesium
found in two coals containing ash of the same
composition may behave quite differently during the
combustion process. The individual elements found
in the impurities within a given fuel may also be
divided in their behavior since portions of each follow
different process paths through the steam generator as
a vapor, solid, or liquid depending upon mineral form
and subsequent transformations encountered. The
deposition of vulnerable species varies throughout the
steam generator as the mechanism for deposition
varies due to local environmental conditions (i.e., O2
level), gas and surface temperatures, and local flow
patterns.
Several elements such as calcium and chlorine
may play multiple roles in the fireside fouling or
corrosion process. Submicron calcium may be
providing sites for condensation of alkalis aggravat-
ing the fouling problem, while coarse calcium may
act as an absorbent and thereby inhibit fouling or
minimizing its severity. Chlorine tends to enhance
corrosion by CO. It also releases potassium from
otherwise stable silicates to form low-melting,
potentially corrosive sulfates. Consequently, it is no
wonder that simple elemental analysis of fuel ash and
the corresponding fusibility based on heating a
composite sample of coal ashed to 750°C is only
50% effective in predicting fireside problems.
An understanding of the process of fouling,
slagging, and corrosion from a mechanistic or
phenomenologic point of view is by no means
complete. To achieve these objectives, considerable
information must be developed on areas such as
fragmentation, volatilization, agglomeration, nuclea-
tion, etc., to predict fly ash size and composition, and
vapor composition of heavy metal species. It may be
that the total process is too complex to ever hope to
predict explicitly the degree of fouling from a detailed
fuel analysis. However, it is very important that we
understand the phenomena taking place as best we
can so that a correct diagnosis can be made on a
fireside problem when it occurs. Too many deposit
problems have been studied in the laboratory under
conditions not representative of the actual case in the
field, resulting in inadequate or erroneous solutions.
The technology of fireside slagging, fouling, and
corrosion has progressed substantially over the last
100 years. Much has been learned about very specific
systems of minerals, their thermal behavior, and the
114 R. W. Bryers
threshold limits beyond which they will cause serious,
unmanageable problems. In recent years, analytical
and diagnostic capabilities have exploded to a level
much beyond their utilization. However, today, steam
generators are still constructed based on proprietary
extrapolation of the best available prior experience
and fuels are still evaluated on the simple elemental
analysis of ash and ash fusion temperatures developed
for an outdated combustion system. There is a need
for bridging the gap between fundamental research
and applied engineering-transforming technology
from an art into a science. There is a need to apply our
advanced analytical diagnostics to real-time fireside
problems to determine the source of the problem.
Some of the more specific areas requiring attention
include:
On-line monitoring of both slagging and fouling
in order to effectively and efficiently carry out
management of slagging and fouling.
Continuous on-line monitoring of furnace exit
temperatures to control slagging and avoid the
creation of a fouling problem.
Upgrading of fuel characterization by employing
the more advanced analytical techniques and
modifying indices to reflect design and operating
conditions.
An understanding of the impact of slag chemistry
on furnace absorption.
*,A better understanding of the operating and
maintenance cost of slagging and fouling so that
alternatives can be realistically assessed.
Exploration of the impact fuel variability, blending,
switching, and opening of new reserves on fuel
characterization fouling, slagging, and corrosion.
Establish the role of Cl in fireside problems.
Standardize characterization of fuels on an
international basis.
Improve upon on-line management of deposits and
develop new techniques for deposit removal.
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