7

Mineral Matter

7.1 INTRODUCTION
As well as organic matter coal also contains a significant proportion of minerals and other inorganic
contaminants, collectively referred to as mineral matter. Some of these materials may be removed
during coal preparation, but a certain amount is intimately associated with the organic components
and becomes involved in various ways when the coal is finally used.
The inorganic constituents of coal are often expressed in the form of ash yield and sulfur content.
It is, however, often necessary to express an inorganic constituent relative to environmental emissions, such as the amount of sulfur dioxide produced during combustion (Chapters 14 and 15).
Furthermore, many of the elements that may be of environmental concern occur in the fly ash after
coal combustion (Chapter 14) and, in the case of power plants using flue gas desulphurization (FGD)
systems, in the FGD (or scrubber) by-products (Chapter 15).
Coal beneficiation processes prior to utilization (Chapter 6) may also serve as a means of reducing
the levels of at least some mineral elements. Such elements, especially those that occur at significant
levels in the residue from utilization processes, can cause waste disposal or control problems, such
as leaching into the environment (Chapter 25) following ground or surface water infiltration.
Thus, minerals in coal have been, and continue to be, a subject of much interest. Early studies
approached the subject somewhat indirectly by means of chemical analysis of high-temperature
ash and back calculation to obtain estimates of the mineral matter. Others supplemented chemical
studies by handpicking the coarser minerals or performing density separations for chemical tests
and optical microscopic studies. With the introduction of radio frequency ashing at low temperature
(<150C), it became possible to directly investigate all of the mineral constituents (Gluskoter, 1965;
Miller, 1984).
The general term mineral matter as it applies to coal science and technology is a widely used, but
often misrepresented (and even misinterpreted) expression insofar as the terms mineral matter and
ash are often used interchangeably. This is, of course, incorrect since ash is, in reality, the residue
remaining after complete combustion of the organic portion of the coal matrix to carbon dioxide
and water, etc. Thus, the constituents of ash do not occur as such in coal but are formed as a result
of chemical changes which take place in the mineral matter during the combustion (ashing) process.
These changes usually involve the breakdown of complex chemical structures (such as can occur in
clays and many minerals) with the formation of the metal oxides.
Coal is a sedimentary rock composed of three categories of substances: (1) organic carbonaceous
mattermacerals, (2) inorganic (mainly crystalline) minerals, and (3) fluids. The latter occur in
pores within and between the other two solid constituents. The fluids in coal prior to mining are
mainly moisture and methane. Applied to coal, the term mineral matter is an inclusive term that
refers to the mineralogical phases as well as to all other inorganic elements in coal, that is, the
elements that are bonded in various ways to the organic (C, H, O, N, S) components.
The mineral matter content of coal varies considerably and may even be as high as 35% w/w of
the coal. The composition of the mineral matter in the coal (or the composition of the mineral ash
after combustion) is of importance for, as examples, the performance of design of postcombustion
cleanup equipment, such as electrostatic precipitators and FGD units (Kelly and Spottiswood, 1982,
1989; Hjalmarsson, 1992). The alkali metals (sodium, potassium, and lithium) affect (decrease) the
resistivity of the ash and can influence sulfur removal.

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The Chemistry and Technology of Coal

Aluminum, silicon, and iron can influence the size of the electrostatic precipitator. But, moreover, the fly ash can cause degradation of any catalyst used downstream by blocking the pores
as well as causing erosion. This is in addition to any possible detrimental effects of the mineral
matter in a coal conversion plant. Again, catalyst poisoning as well as adverse catalytic effects
of the mineral constituents on the process may occur (Jenkins and Walker, 1978). On the other
hand, any potential beneficial catalytic effects of the mineral constituents of coal (especially
in relation to conversion processes) (Bredenberg et al., 1987) also need evaluation and precise
definition.
Furthermore, ash fusibility can be strongly influenced by differences in calcium, magnesium,
and iron content. Too high a magnesium content can cause clinkering troubles leading to magnesia
swelling (Mackowsky, 1968).
While many environmental issues focus on the discharge of gaseous material such as sulfur
oxides and nitrogen oxides (Chapters 22, 23, and 25), the discharge of mineral slag to the surrounding environment is also cause for concern. The constituents of these slags and their relative toxicity
to the flora and fauna, not only in the immediate vicinity of the plant but also in areas quite remote
from the plant, are also cause for concern. In addition, it is quite possible that the toxic materials
can be transported by surface and ground waters as well as by the prevailing winds (e.g., sulfur
dioxide, fly ash).
Coal may also be recognized as a source of valuable elements and inorganic materials. For
example, coal may provide a supply of uranium or other desired elements while the production of
sulfur from coal (by conventional gas-cleaning methods) is also feasible.
Hence, it is now considered essential that the nature of the mineral constituents of coal
be more thoroughly understood in order to evaluate the nature of the inorganic material, for
example., fly ash and discharge, produced when coal is employed as a fuel or feedstock (Babu,
1975; Braunstein etal., 1977; Given and Yarzab, 1978; Quast and Readett, 1991; Straszheim and
Markuszewski, 1991).

7.2 ORIGIN OF MINERAL MATTER IN COAL

Mineral matter originates from the inorganic constituents of the vegetation which acted as the precursor to coal and from the mineral matter that was transported to the coal bed from a remote site
(Chapters 3 and 4). Thus, mineral matter in coal has often been classified as inherent and extraneous
mineral matter (Francis, 1961; Stach et al., 1982; Spears and Zheng, 1999).
The inherent mineral matter is that mineral matter which had its origin in the organic constituents of the plant giving rise to the coal bed but the extraneous mineral matter was brought into the
coal-forming deposit by mechanical means from outside, for example, as dust by air or as suspended
or dissolved material carried by water. The inherent mineral matter is also sometimes defined as the
inorganic material combined with the organic coal substance, but such material need not be derived
from the coal-forming plants.
The inherent mineral matter is usually much smaller in quantity than the extraneous mineral
matter and can be expected to differ quite markedly in composition from the inorganic residue
of the major coal-forming plant types. This is due to reuse (in no small part) of the inorganic
elements by succeeding vegetation and to leaching of inorganic constituents by the waters percolating and flowing through the peat bog during coalification. The percolating waters may be
presumed to have an increased dissolving action on the inorganic constituents because of their
content of humic acids (Stevenson and Butler, 1969), carbon dioxide, and other products of decay.
Furthermore, the differences in solubility and reactions of the inorganic elements present in the
plants dictate that these elements not contribute to the coal mineral matter in proportion to their
presence in the plant material.
There has been considerable discussion and conjecture about the origin of the so-called inherent and
extraneous mineral matter in coal. Indeed, it is in regard to this particular aspect of coal technology

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Mineral Matter

that many researchers find this terminology not only misleading but also difficult to apply, especially to
those minerals that are contemporaneous with the peat bog in which the coal was formed; such minerals may not have been incorporated into the plant matrix prior to the formation of the coal bed.
The intimate interrelationship between coal and mineral matter can only be adequately
explained if it is accepted that the mineral matter became part of the coal matrix either during
the early stages of coalification in the peat bog or at some early stage of the subsequent maturation process.
Mineral matter that originated within the immediate environs of the peat bog is often referred
to as authentic mineral matter whereas mineral matter which was transported by water or by wind
is often referred to as allogenic mineral matter. The additional term syngenetic mineral matter
(Table7.1) is also applied to mineral matter that may have been transported into future coal deposits
(i.e., this mineral matter was not a part of the plant substance that contributed to the coal precursor
nor was it introduced during the coalification process) by water or wind. On the other hand, epigenetic mineral matter refers to that material which was deposited into the peat bog by descending for
ascending solutions in cracks or fissures or in the bedding planes of the coal; such mineral matter
may often be found as cleat fillings (Spears and Caswell, 1986).
TABLE 7.1
Types of Coal Minerals and Their Origins
Syngenetic Formation
(IntimatelyIntergrown)

Mineral Group
Clay minerals
Carbonates

Transported by
Water or Wind

Newly Formed

Kaolinite, illite, sericite, clay minerals with

mixed-layer structure tonstein

Sideriteankerite
concentrations,
dolomite, calcite,
ankerite

Sulfide ores

Oxide ores

Quartz

Quartz grains

Phosphates
Heavy minerals
and accessory
minerals

Apatite
Zircon, rutile,
tourmaline,
orthoclase, biotite

Epigenetic Formation
Deposited in Fissures,
Cleats, and Cavities
(Coarsely Intergrown)

Transformation of
Syngenetic Minerals
(IntimatelyIntergrown)
Illite, chlorite

Ankerite, calcite,
dolomite

Siderite, calcite, ankerite in fusite

Pyrite concretions,
Pyrite, marcasite, zinc
melnikowite-pyrite,
sulfide (sphalerite),
coarse pyrite
lead sulfide (galena),
(marcasite),
copper sulfide
concretions of
(chalcopyrite)
FeS2CuFeS2ZnS

Pyrite from the

transformation of
syngenetic concretions
of FeCO3

Pyrite in fusite
Goethite, lepidocrocite
(needle iron ore)
Chalcedony and
Quartz
quarts from the
weathering of
feldspar and mica
Phosphorite

Chlorides, sulfates,
nitrates
Hematite

Source: Murchison, D. and Westoll, T.S., Eds., Coal and Coal-Bearing Strata, Elsevier, New York, 1968.

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7.3 OCCURRENCE
Mineral matter is common to all types of coal, and it has been recognized from the time when coal
was first mined for general use that coal contained some material other than the main (organic) coal
substance. The presence of the mineral matter is even more apparent when the coal is examined
in place in the bed, after being mined or finally prepared for market, and, finally, when the residue
from its combustion is examined.
In the bed, extraneous matter is apparent as definite horizontal layers of varying thickness and
extent, as surface deposits or fillings in the vertical cleats, and more unusually as intrusions of claylike (or other) material which occurs irregularly throughout the coal deposit. Furthermore, these
horizontal layers that attain a considerable thickness may serve as a means of separating different
coals or simply separating the different phases of formation of one particular coal. However, bands
of this type are always regarded as being formed during the deposition of the coal precursors.
The most common minerals in coal (e.g., illite clay, pyrite, quartz, and calcite) are made up
of these most common elements (in rough order of decreasing abundance): oxygen, aluminum,
silicon, iron, sulfur, and calcium. These minerals and other less common minerals usually contain
the bulk of the trace elements present in coal (Finkelman, 1982, 1993; Davidson and Clarke, 1996;
Davidson, 2000).
Minerals in coal commonly occur as single crystals or clusters of crystals that are intermixed
with organic matter or that fill void spaces in the coal; sizes of mineral grains range from submicroscopic to a few inches. Some clusters of mineral grains, however, such as fracture fillings or
coal balls, may reach sizes that range from fractions of an inch up to several feet across. Coal balls
result when mineral matter (such as calcite, pyrite, or siderite) infuses peat before it is compressed.
Mineral grains in coal also often occur as discrete particles, such as the blebs of pyrite (framboids),
which may be identified in the photomicrographs of coal. The more finely divided the mineral
grains, the higher the magnification needed for identification.
Although much is known about the minerals in coal, much remains to be learned about their
occurrence, abundance, origin, and composition. For example, the type of clay mineral in a coal,
whether montmorillonite or illite, determines how a coal will react when burned.
Montmorillonite may or may not break down (dissociate) into its constituent parts when coal is
burned; if it does dissociate, then, upon cooling, it may recombine with other elements or minerals to form mineral deposits on the inside surfaces of furnaces and boilers. This process (slagging
or fouling) produces barriers to heat exchange in the affected equipment, which can substantially
reduce its efficiency and require costly repairs. Illite, however, with its simpler composition, does
not cause such problems under normal furnace operating conditions. Where these two clay minerals
and others occur, their relative abundances, relationships to other minerals, and exact compositions
are subjects for continued research in coal quality.
The deposits in the shrinkage cracks or cleats, which may, for example, be kaolinite, calcite, gypsum, or pyrite, are usually thick surface deposits and may not always be present and were presumably
deposited later in the coal-forming process. On the other hand, the larger adventitious bodies of foreign
matter in the coal (clay veins, sandstone intrusions, washouts, and the like) may be the result of rather
unusual geological conditions during and after the time the coal was laid down (Chapters 3 and 4).
However, a large part of the mineral matter in marketed coal arises from the inclusion during
mining of roof (or floor) rock of the impure streaks or of some of the large impurities. Such inclusions may be deliberate insofar as little effort is made to remove them during the mining operation,
or they may be accidental in that their elimination during mining was not complete. Indeed, with
the increasing use of mechanical methods of mining (particularly in large-scale strip operation), it
is becoming the practice to do little exclusion during mining and to subject the coal to a cleaning
process afterward (Chapter 6).
Obviously, the amount and type of minerals found in coal varies widely (Table 7.2) and depends
on the coal history. The most abundant minerals are the clay minerals of which illite, kaolinite, and

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Mineral Matter

TABLE 7.2
Indication of Minerals in Coal Expressed as a Percentage of the Total
Mineral Matter
Classification
Silicates

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Carbonates
Oxides

Sulfates
Sulfides

Mineral Constituents
Kaolinite
Illite
Chlorite
Mixed-layer illite, montmorillonite
Siderite
Quartz
Hematite
Rutile
Gypsum
Thernardite
Pyrite

Elkhorn No. 3
Seam, Kentucky

Hartshorne
Seam, Kentucky

340
Trace
Trace
Trace

110
110
110

4050

3040
110

110
110

110

110

110

Source: Braunstein, H.M. et al. (Eds.), Environmental health and control aspects of coal conversion: An information overview, Report ORNL-EIS-94, Oak Ridge National
Laboratory, Oak Ridge, TN, 1977, pp. 230.

TABLE 7.3
Iron Sulfate Minerals Identified
inWeathered Illinois Coal
Mineral
Szomoluokite
Rozenite
Melanterite
Coquimbite
Rosmerite
Jarosite

Chemical Formula
FeSO4 H2O
FeSO 4H2O
FeSO47H2O
Fe(SO4) 9H2O
Fe2(SO4) Fe2(SO4)3 12H2O
(Na,K)Fe3(SO4)2(OH)6

Source: Gluskoter, H.J., Trace Elements in Fuel,

S.P. Babu (Ed.), Advances in Chemistry
Series No. 141, American Chemical
Society, Washington, DC, Chapter 1, 1975.

montmorillonite occur most frequently. Pyrite is the common sulfide mineral while sulfates are
relatively rare but increase with weathering (Table 7.3). Carbonates form readily in nonacid areas
(dolomite and ankerite are encountered frequently) and quartz (which is found virtually in all coals)
may occur in concentrations as high as 20% w/w of the total mineral matter. Sulfide minerals often
constitute as much as 25% of the coal mineral matter.
There may also be regional variations in the mineral distribution in coal, and even a cursory
examination of the major minerals that occur within the coal matrix presents only a general
indication of the vast number of metals that can occur in coal. Even though less than 12 elements
usually constitute the major portion of coal ash (Table 7.4), there are many individual mineral
elements present which (on the basis that a trace element is a particular element which occurs in

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The Chemistry and Technology of Coal

TABLE 7.4
Major Inorganic Constituents
ofCoal Ash

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Constituents
SiO2
Al2O3
Fe2O3
CaO
MgO
Na2O
K2O
SO3
P2O5
TiO2

Representative Percentage
4090
2060
525
115
0.54
0.53
0.53
0.510
01
02

concentrations of less than 0.1%; <1000 ppm) in the earths crust are classified as trace elements
(Table 7.5) (Finkelman, 1982, 1993).
Extensive chemical analyses on coals have shown that elements with relatively large ranges of
concentrations (e.g., arsenic, As; barium, Ba; cadmium, Cd; iodine, I; lead, Pb; antimony Sb; and
zinc, Zn) include those that are found in coals within sulfate and sulfide minerals. In addition,
many elements appear to be positively correlated in coals such as calcium and manganese, zinc and
cadmium, the chalcophile elements (i.e., those elements which commonly form sulfides, such as
cobalt, Co; nickel, Ni; lead, Pb; and antimony, Sb) and the lithophile elements (i.e., those elements
which commonly occur in silicate phases, such as silicon, Si; titanium, Ti; aluminum, Al; and
potassium, K).

7.4 MINERAL TYPES

A variety of minerals have been reported to be present in coals although many occur infrequently
and are not regularly found in all coals or may be detectable only in trace amounts in various suites
of coals (OGorman and Walker, 1971; Gluskoter, 1975; Gluskoter et al., 1977; Finkelman, 1982,
1993; Roscoe and Hopke, 1982).
The complex environmental conditions which occur at the time the organic detritus is laid down
of and the geological upheaval which may have occurred during the maturation process can play an
important role in determining which minerals survive in coal (Cecil et al., 1982). Nevertheless, the
large majority of minerals found in coal can be classified into several types, such as shale, kaolin
compounds, sulfide derivatives, and carbonate derivatives (Table 7.6).

7.4.1 Clay Minerals (Aluminosilicates)

The name clay is often used in various contexts: (1) to indicate particle size (<2 in. [<0.005 mm]),
(2)to indicate a rock composed predominantly of clay minerals, and (3) to indicate a name for a
group of minerals, the clay minerals.
These minerals are hydrated aluminosilicates which are characterized by a sheetlike structure and can be conveniently divided into three groups: (1) the kaolinite group, (2) the montmorillonite group, and (3) the potash clay (or hydrous mica) group (Table 7.7). In the kaolinite
group, all have the same chemical composition and differ only in individual crystal structures.
The montmorillonite group can be represented by means of ion substitutions in the general
chemical formula. For example, in montmorillonite itself, approximately 16% of the aluminum

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Mineral Matter

TABLE 7.5
Elements and Trace Elements in Coal

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Constituent
Arsenic
Boron
Beryllium
Bromine
Cadmium
Cobalt
Chromium
Copper
Fluorine
Gallium
Germanium
Mercury
Manganese
Molybdenum
Nickel
Phosphorus
Lead
Antimony
Selenium
Tin
Vanadium
Zinc
Zirconium
Aluminum
Calcium
Chlorine
Iron
Potassium
Magnesium
Sodium
Silicon
Titanium
Organic sulfur
Pyritic sulfur
Sulfate sulfur
Total sulfur
Sulfur by x-ray fluorescence

Range
0.5093.00 ppm
5.00224.00 ppm
0.204.00 ppm
4.0052.00 ppm
0.1065.00 ppm
1.0043.00 ppm
4.0054.00 ppm
5.0061.00 ppm
25.00143.00 ppm
1.107.50 ppm
1.0043.00 ppm
0.021.60 ppm
6.00181.00 ppm
1.0030.00 ppm
3.0080.00 ppm
5.00400.00 ppm
4.00218.00 ppm
0.208.90 ppm
0.457.70 ppm
1.0051.00 ppm
11.0078.00 ppm
6.005350.00 ppm
8.00133.00 ppm
0.43%3.04%
0.05%2.67%
0.01%0.54%
0.34%4.32%
0.02%0.43%
0.01%0.25%
0.00%0.20%
0.58%6.09%
0.02%0.15%
0.31%3.09%
0.06%3.78%
0.01%1.06%
0.42%6.47%
0.54%5.40%

Source: Ruch, R.R. et al., Environmental Geology

Note No. 72, Illinois State Geological
Survey, Urbana, IL, 1974, p. 18.

is substituted by magnesium and by other ions such as calcium, sodium, potassium, and hydrogen (as well as some additional magnesium).
Clay minerals are the most commonly occurring inorganic constituents of coals (Gluskoter, 1975)
(aswell as the strata associated with coals) and, therefore, can act as the source of a wide variety of metals
in substantial or trace amounts. The most common clay minerals found in coals are kaolinite and illite
while montmorillonite, chlorite, and sericite have also been regularly reported to occur in various coals.

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The Chemistry and Technology of Coal

TABLE 7.6
Minerals Commonly Associated with Coal
Group

Species

Formula

Shale

Muscovite
Hydromuscovite
Illite
Montmorillonite
Kaolinite
Livesite
Metahalloysite
Pyrite
Marcasite
Ankerite
Calcite
Dolomite
Siderite
Sylvite
Halite
Quartz
Feldspar
Garnet
Hornblende
Gypsum
Apatite
Zircon
Epidote
Biotite
Augite
Prochlorite
Diaspore
Lepidocrocite
Magnetite
Kyanite
Staurolite
Topaz
Tourmaline
Hematite
Penninite
Sphalerite
Chlorite
Barite
Pyrophillite

(K, Na, H2O, Ca)2(Al, Mg, Fe, Ti)4

(Al, Si)8O20(OH, F)4 (general formula)
(HO)4K2(Si6 Al2)Al4O20
Na2(Al Mg)Si4O10(OH)2
Al2(Si2O5)(OH)4
Al2(Si2O5)(OH)4
Al2(Si2O5)(OH)4
FeS2
FeS2
CaCO3 (Mg, Fe, Mn)CO3
CaCO3
CaCO3 MgCO3
FeCO3
KCl
NaCl
SiO2
(K, Na)2O Al2O3 6SiO2
3CaO Al2O3 3SiO2
CaO 3FeO 4SiO2
CaSO4 2H2O
9CaO 3P2O5 CaF2
ZrSiO4
4CaO 3Al2O3 6SiO2 H2O
K2O MgO Al2O3 3SiO2 H2O
CaO MgO 2SiO2
2FeO 2MgO Al2O3 2SiO2 2H2O
Al2O3 H2O
Fe2O3 H2O
Fe3O4
Al2O3 SiO2
2FeO 5Al2O3 4SiO2 H2O
2AlFO SiO2
3Al2O3 4BO(OH) 8SiO2 9H2O
Fe2O3
5MgO Al2O3 3SiO2 2H2O
ZnS
10(Mg, Fe)O 2Al2O3 6SiO2 8H2O
BaSO4
Al2O3 4SiO2 H2O

Kaolin

Sulfide

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Carbonate

Chloride
Accessory minerals

7.4.2 Quartz (Silica)

Quartz is a widely distributed mineral species consisting of silicon dioxide (silica, SiO2) (Table7.6).
It is one of the most common minerals and is found in many varieties with very diverse modes
of occurrence. Quartz is a primary constituent of rocks such as granite, quartz, porphyry, and
rhyolite. It is also a common constituent in many gneisses (laminate rocks) and crystalline schists
(foliated rocks). It is also, in a sense, mobile since by the weathering of silicates, silica passes into
solution and is redeposited in cavities, crevices, and along joints of rocks of all types. Thus, it is not

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Mineral Matter

TABLE 7.7
Subdivision of Clay Minerals
inVarious Groups
Clay Mineral Group

Individual Members

Kaolinite

Kaolinite
Dickite
Nacrite
Halloysite
Montmorillonite
Beidellite
Nontronite
Saponite
Hectorite
Sauconite
Hydromica
Hydrous mica
Illite
Glimmerton
Bravaisite

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Montmorillonite

Potash (hydrous mica)

surprising that quartz also occurs in all coals either by virtue of its proximity to the coal bed or by
deposition at a later stage of coal formation.

7.4.3 Carbonate Minerals

Carbonate minerals are the salts of carbonic acid (H2CO3), and the extensive possibilities for interchanging the more common metals, such as calcium, magnesium iron, and manganese, are realized
in the wide variety of carbonate minerals that occur in nature. Consequently, it is not surprising that
a wide variety of carbonate minerals also occurs in coals (Table 7.6).
Calcite (CaCO3) and siderite (FeCO3) are commonly reported as constituents of the mineral
matter in coals while the more complex carbonates dolomite (CaCO3MgCO3) and ankerite
(2CaCO3MgCO3FeCO3) are also frequently reported.

7.4.4 Sulfur (Sulfide and Sulfate) Minerals

The sulfide minerals of particular importance here are the pyrite group (Table 7.8), which are essentially metal disulfides occurring in widespread locations and different crystalline forms; pyrite itself
is found in large deposits in metamorphic rocks.
The dominant sulfide mineral in coal is pyrite while marcasite has also been reported to be present
in many coals. These minerals are dimorphic in that they are identical in chemical composition (FeS2)
TABLE 7.8
The Pyrite Group of Minerals
Mineral

Formula (Approx.)

Pyrite
Marcasite
Braoite
Laurite

FeS2
FeS2
(Ni Fe)S2
RuS2

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The Chemistry and Technology of Coal

but differ in crystalline formpyrite is cubic whereas marcasite is orthorhombic. Other sulfide minerals which have been found (but to a lesser extent) in coals are galena (lead sulfide, PbS) and sphalerite
(zinc sulfide, ZnS).
The related sulfate minerals (Table 7.3) are not as common as the sulfides and are not usually
present in unweathered fresh coals. Obviously, the anaerobic maturation of (the majority of) coals
are not conducive to the formation of sulfates. For example, pyrite is markedly susceptible to oxidation and will decompose to iron sulfate minerals even under ambient conditions.
Fe 2S3 + O2 FeSO 4

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7.5 CLASSIFICATION
Coal is a sedimentary rock composed of three categories of substances: (1) organic carbonaceous
matter, termed macerals, (2) inorganic (mainly crystalline) minerals, and (3) fluids. The latter occur
in pores within and between the other two solid constituents. The fluids in coal prior to mining are
mainly moisture and methane.
Applied to coal, the term mineral matter is an inclusive term that refers to the mineralogical
phases as well as to all other inorganic elements in the coal; that is, the elements that are bonded in
various ways to the organic (C, H, O, N, S) components. The term mineral refers only to the discrete
mineral phases.
Because coal is a type of sedimentary rock, 100 or so mineral can occur in coal; however, only
about 15 are abundant enough to have high importance. It must be noted that minor impurities
commonly substitute for the major cations as well as some anions which account for a considerable
fraction of the minor and trace elements reported in coals.
More than 125 different minerals have been reported in coal and occur as discrete grains, flakes,
or aggregates in one of five physical modes:

1. As microscopically disseminated inclusions within macerals (distinct organic designations

such as vitrinite, liptinite, and inertinite)
2. As layers of partings wherein fine-grained clay minerals usually predominate
3. As nodules including lenticular and spherical concretions
4. As fissures including cleat and other fracture or void fillings
5. As rock fragments found within the coal bed as a result of faulting, slumping, or related
disturbances

Useful also is a genetic classification of minerals in coal, wherein they are classified as (1) detrital,
(2) syngenetic, or (3) epigenetic.
Detrital grains were introduced into a coal-forming basin (such as swamp land) by rivers,
tidal waves, and wind. Syngenetic minerals were formed during the peat stage of coal formation and include minerals formed by crystallization of inorganic elements in plants (intrinsic
mineral matter). Epigenetic minerals are those found as filling of fissures and voids after the
peat was formed.
More generally, the minerals present in coals are grouped as either detrital or diagenetic. The
detrital minerals undergo diagenetic modifications however, and provide one of the sources for
elements incorporated into diagenetic minerals. The detrital minerals are present either dispersed
or concentrated in the coal seams. The overall composition of the detrital minerals is a function of
grain size and thus of current velocity.
Clay mineral composition varies with the maturity of the sediment, and in particular whether
this is reworked from within the basin or is more representative of the upland source. Dirt partings
(intraseam mudrocks) represent either an increase in detrital sediment input or a reduction in the
rate of organic accumulation, or even loss of organic matter.

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Mineral Matter

Wind-blown sediment in coals are best represented by altered volcanic ashes, tonsteins, providing a means of correlation and minerals for absolute age determinations. The alteration of ash to
kaolinite both in the peat and in the associated sediments demonstrates which clay mineral is stable
in the pore waters. Diagenetic kaolinite, probably formed from elements organically derived, is
also recognized, particularly in low-ash coals. The elements present in diagenetic silicates, sulfides,
and carbonates originated from within the peat and also from mud rocks in the sequence. The
diagenetic sequence of minerals in the cleat is equated with that of other clastic sediments and is
similarly interpreted as a burial depth sequence. The residual, diagenetic pore fluids resulting from
burial diagenesis are the source of economically important, high chlorine concentrations in the coal
(Spears, 2005).

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7.6 EVALUATION OF MINERAL MATTER

The use of coal as a fuel and the varied, often detrimental, effects of the mineral matter on the fuel
properties of coal has been a source of concern for consumers (Alpern et al., 1984). Even the interactions of the mineral constituents themselves (Table 7.9) have directed interest toward the mineral
constituents of coals but with the tendency to an increased use of coal for power generation as well
as for gasification and conversion plants that will enable coal to act as a source of liquid and gaseous
fuels. Therefore, methods by which the mineral matter can be evaluated have been a constant target
for quantitative and qualitative improvement.
Furthermore, the broad definition which defines mineral matter as all elements in coal except
carbon, hydrogen, nitrogen, oxygen, and sulfur needs some modification since four of these five
elements occur in inorganic locations and are, therefore, part of the mineral matter. For example,
(1) carbon occurs in carbonates; (2) hydrogen occurs in water of hydration, as well as in any free
water in the coal; (3) oxygen occurs in carbonates, sulfates, and silicates as well as in water as well
as in water of hydration and free water in the coal; and (4) sulfur occurs in sulfates and sulfides,
predominantly pyrite and marcasite.
Finally, mineral matter in coal is the parent material in coal from which ash is derived and
which comes from minerals present in the original plant materials that formed the coal, or from
extraneous sources such as sediments and precipitates from mineralized water. Mineral matter in coal cannot be analytically determined and is commonly calculated using data on ash
and ash-forming constituents. Coal analyses are calculated to the mineral matterfree basis by
adjusting formulas used in calculations in order to deduct the weight of mineral matter from the
total coal.
TABLE 7.9
General Behavior of Minerals of High Temperatures
Inorganic Species
Clays
Carbonates
Quartz
Pyrite
Metal oxides
Metal carboxylates (lignites and subbituminous only)
Note: VM, volatile matter.

Behavior on Heating
Loose structural OH groups with rearrangements of structure
and release of H2O
Decompose with loss of CO2; residual oxides fix some
organic and pyritic S as sulfate
Possible reaction with iron oxides from pyrite and organically
held Ca in lignites; otherwise no reaction
In air, burns to Fe2O3 and SO2; in VM test, decomposes to FeS
May react with silicates
Decompose; carbon in carboxylate may be retained in residue

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7.6.1 Ashing Techniques

There are many minerals in coal which will produce as ash residue (Table 7.6) and, although the
ash composition varies around wide limits, the ash may appear to be composed of only a few of the
more common elements (Table 7.4). But it is often the trace elements (Table 7.5) that can give ash
some of its more obnoxious properties.
The determination of the mineral matter content of coal (determined as mineral ash after
combustion) has been an essential part of coal evaluation for many years (Shipley, 1962; Rees, 1966;
Given and Yarzab, 1978; Huggins et al., 1982; Nadkarni, 1982) (Chapter 8). For example, when coal is
cleaned by various processes to reduce the sulfur and mineral content, it is an advantage to be aware
of the mineral (ash) content to determine the best cleaning method insofar as the various cleaning
methods have different tolerance levels for the mineral constituents of coal. Furthermore, the ash
content is also a means of assessing the adequacy of the various sampling procedures (Chapter 8),
and it is one of the criteria normally specified in contracts between a purchaser and a supplier of coal.
The amount of mineral matter in coking coal (Chapter 16) is an indication of the amount of ash
that will eventually be part of the coke made from the coal. Thus, the higher the ash content of the
coal, the lower the proportion of usable carbon in the coke and the more the fluxing limestone that
must be added to the furnace to assist in ash (mineral) removal. However, the fouling tendency of a
coal is dependent upon several factors, not the least of which is the nature of the mineral matter and
the resulting ash (Beer et al., 1992).
Similarly, the higher the mineral matter content, the lower the heat of combustion obtainable
from a unit sample of coal, hence the need for removal of mineral matter during cleaning and preparation operations (Chapter 6). A high mineral content also introduces additional problems such as
a loss in the combustion efficiency as well as problems related to handling and disposing of larger
amounts of mineral ash. Obviously, mineral matter in coal will (and often does) cause problems
during utilization and measures to counteract any adverse effects that will arise from the presence
of the mineral matter are necessary.
On the other hand, the potential benefits that could arise from the presence of this same mineral
matter should not be ignored; catalytic effects in processes designed for the liquefaction (Chapters
18 and 19) and the gasification (Chapters 19 and 20) of coal may be cited as examples.
Mineral matter in coal is often determined indirectly with the ash analysis (determined by direct
combustion of the sample) (Chapter 8) forming the basis of the calculation. However, determination
and chemical analysis of the ash content of coal gives the average content of the inorganic elements
in a particular coal but is not an indication of the nature or distribution of the mineral matter in
coal. Nevertheless, ash analysis can provide valuable data which, when used with data from other
sources, may give a representation of the mineral content of coal.
However, it must be emphasized that there has to be some attempt to recognize the limitations
of the method before any projection relating to the mineral composition of coal is possible. For
example, the high temperature required for the ashing may result in the loss of the volatile constituents of the minerals or the mineral constituents will undergo a chemical change. In the former
case, certain of the mineral elements will escape detection while in the latter case the constituents
of clays or shale (to cite an example) will lose water of hydration or the carbonate minerals will lose
carbon dioxide and the oxides so produced may even undergo further reaction with sulfur oxides or
with silica to produce completely different mineral species:

CaCO3 CaO + CO2

CaO + SO3 CaSO 4

CaO + SiO2 CaSiO3

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Mineral Matter

At the same time, pyrite will be converted to ferric oxide and oxides of sulfur:

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4FeS2 + 11O2 2Fe 2O3 + 8SO2

Any organically combined inorganic elements may be converted to the respective oxides and eliminated (e.g., nitrogen and sulfur) or may be retained in the ash (e.g., various metals that may be
combined with an organic fragment).
The pathways of these various reactions can be followed by differential thermal analysis (DTA)
which allows for the identification of the various minerals in more complex mixtures, as might be
found in coal (Warne, 1979).
Several formulae have been proposed for calculating the amount of mineral matter originally in
the coal using the data from ashing techniques as the basis of the calculations. Of these formulae,
two have survived and have been used regularly to assess the proportion of mineral matter in coal
and these are the Parr formula and the KingMaviesCrossley formula.
In the Parr formula, the mineral matter content of coal is derived from the expression:

% Mineral matter = 1.08A + 0.55S

where
A is the percentage of ash in the coal
S is the total sulfur in coal
The KingMaviesCrossley formula is a little more complex:

% Mineral matter = 1.09A + 0.5Spyr + 0.8CO2 1.1SO3ash + SO3coal 0..5Cl

where
A is the percentage of ash in the coal
Spyr is the percentage of pyritic sulfur in the coal
CO2 is the percentage of mineral carbon dioxide in the coal
SO3ash is the percentage of sulfur trioxide in the ash
SO3coal is the percentage of sulfur trioxide in the coal
Cl is the percentage of chlorine in the coal
The Parr formula (which has been widely used in the United States) is obviously considerably
simpler than the KingMaviesCrossley formula (which has been in common use in Great Britain
and Europe) and requires less analytical data. However, the KingMaviesCrossley formula will,
because of the detail, provide more precise mineral matter values. It is, however, a matter of
assessing whether the slight improvement in precision is justifiable on the basis of the additional
analytical effort.
There are, of course, limitations to the use of the data derived from the ashing techniques. For
example, the indefinite amount of sulfur which may be retained in the ash will reduce the reliability
of the ash values. In fact, the ash value is only an approximation of the noncombustible material
in coal, and the relationship of ash composition to clinkering, boiler tube slagging, and other hightemperature behavior of the mineral constituents is complex and can be difficult to interpret. The
disadvantages of using the ashing technique to evaluate the mineral matter in coals are evident
from the earlier text but these disadvantages should not detract from a method that certainly has
some merits.

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7.6.2 Ash Analysis and/or Direct Mineral Analysis

The evaluation of coal mineral matter by the ashing technique can be taken further insofar as
attempts can then be made to determine the individual metal constituents of the ash. On the occasion when the mineral matter has been successfully separated from the coal, it is then possible to
apply any one (or more) of several techniques (such as x-ray diffraction, x-ray fluorescence, scanning electron microscopy, and electron probe microanalysis) not only to investigate the major metallic elements in coal but also to investigate directly the nature (and amount) of the trace elements in
the coal (Jenkins and Walker, 1978; Prather et al., 1979; Raymond and Gooley, 1979; Russell and
Rimmer, 1979; Jones et al., 1992).
However, when coal ash is prepared for complete analysis, it has been considered necessary to
ensure that sulfur is not retained in the ash. If sulfur is retained in the ash, the analysis will most
likely be inaccurate unless corrections to a sulfur dioxidefree basis are made. In addition, attempts
must be made to ensure that important elements are not lost during the ashing procedure by virtue
of the higher temperatures (ca. 850C, 1560F) that are used. In fact, a low-temperature ash sample
can be of the order of 150% w/w of the high-temperature ash sample.
To alleviate the problem of element loss by the use of high temperatures, various low-temperature ashing techniques have been developed. One method involves passage of activated oxygen
(generated by passing commercial grade oxygen through the high-energy electromagnetic field produced by a radio-frequency oscillator) over a dry, finely ground coal sample. Throughout this whole
procedure, the temperature has been observed to remain below 200C (390F) and is usually in the
range of 150C160C (300F320F).
One other technique for the investigation of trace elements in coal applies the float-sink principle
in which comminuted coal can be separated into several specific gravity fractions by flotation in
mixtures of liquids such as perchloroethylene and naphtha; a liquid such as bromoform (CHBr3)
can also be employed for further subfractionation. This procedure can virtually be employed as a
fractionation technique to remove significant proportions of the mineral matter from coal without
resorting to the use of heat.
There are several options available for the choice of an analytical technique, although in practice it may be necessary to use more than one technique because of the limitations of the various
methods with respect to concentrations of the individual elements, or the method may be determined by the amount of available sample. For example, application of any one of the conventional wet analytical methods (such as for the determination of silicates) may require up to 10 g
of sample ash whereas a variety of spectrophotometric techniques may require only micrograms
(110 6 g) of sample.
Spectrophotometric techniques have been the basis of many coal analysis methods. One of the
most widely used techniques for analysis of trace elements is atomic absorption spectrometry, in
which the standards and samples are aspirated into a flame. A hollow cathode lamp provides a
source of radiation that is characteristic of the element of interest and the absorption of characteristic energy by the atoms of a particular element. X-ray fluorescence is also employed as a quantitative
technique for trace element determination and depends on election of orbital electrons from atoms
of the element when the sample is irradiated by an x-ray source.
Another method for trace element determination is neutron activation analysis (Weaver, 1978),
which is a highly sensitive, nondestructive method for the analysis of many elements. Briefly, the
samples are irradiated in a nuclear reactor which produces radioisotopes of the elements and appropriate measurements of the activities of the generated (daughter) species afford a means of calculating the concentrations of the parent isotopes (elements).
Although these three spectrophotometric methods are mentioned here as a means of examining the variety of trace elements which occur in coals, they are by no means the only applicable
methods but are used as examples. Of course, each method has various detection limits for the different elements (Tables 7.10 through 7.12) and it is also essential to recognize the limitations of the

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Mineral Matter

TABLE 7.10
Sensitivity and Detection Limits for Elements by Atomic Absorption Spectroscopy
Detection Limits

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Element

Sensitivity (g/mL)

Range (g/mL)

(g/mL)

(g/m3)

0.036
0.76
0.20
0.017
0.22
0.021
0.011
0.066
0.055
0.040
0.062
0.38
0.010
0.017
0.003
0.026
0.003
0.066
0.11
0.042
0.044
0.28
0.88
0.009

0.55.0
550
110
0.11.0
110
0.11.0
0.11.0
0.55.0
0.55.0
0.55.0
0.55.0
550
0.11.0
0.11.0
0.050.50
0.55.0
0.050.50
0.55.0
110
0.55.0
0.55.0
550
10100
0.11.0

0.003
0.04
0.01
0.002
0.06
0.005
0.006
0.007
0.005
0.003
0.005
0.05
0.003
0.002
0.0003
0.003
0.0003
0.008
0.02
0.003
0.004
0.02
0.1
0.002

0.1
2
0.4
0.08
3
0.02
0.03
0.3
0.2
0.1
0.2
2
0.1
0.08
0.01
0.1
0.01
0.3
0.8
0.1
0.2
0.8
4
0.08

Ag
Al
Ba
Be
Bi
Ca
Cd
Co
Cr
Cu
Fe
In
K
Li
Mg
Mn
Na
Ni
Pb
Rb
Sr
Tl
V
Zn

Source: Kneip, T.J. et al., Health Lab. Sci., 12, 383, 1975.

TABLE 7.11
Detection Limitsa for Various Elements by X-Ray Fluorescence
Ag, 1.2
Al, 5.0
As, 0.11
Au, 0.001 cm2
Ba, 0.12
Bi, 0.61
Ca, 0.100
Cd, 0.40
Ce, 0.17
Co, 0.05
Cr, 0.00006

Cs, 0.15
Cu, 0.00002
Eu, 0.66
Fe, 0.0085
Ga, 0.01
Hg, 0.24
In, 1.1
K, 0.52
La, 0.12
Mn, 0.0015
Mo, 0.072

Nd, 0.30
Ni, 0.06
P, 0.001
Pb, 0.0003
Rb, 0.0075
Rh, 103 mL1
Sc, 0.38
Se, 0.020 cm2
Si, 170 ppm
Sm, 4.1 mL1
Sn, 3.9 ppm

Sr, 0.00007
Tb, 159 mL1
Te, 0.12
Th, 6.5 mL1
Ti, 0.001
U (as UO2), 0.72
U, 0.00002
Y, 0.22
Yb, 6.8 mL1
Zn, 0.00004
Zr, 0.00002

Source: Adapted from Braunstein, H.M. et al., Eds., Environmental health and control
aspects of coal conversion: An information overview, Report ORNL-EIS-94,
Oak Ridge National Laboratory, Oak Ridge, TN, 1977, pp. 513.
a In micrograms except as noted.

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The Chemistry and Technology of Coal

TABLE 7.12
Sensitivity of Various Elements to Neutron Activation Analysis
Sensitivity (g)
10 10
10121011
10111010
1010109
109108
108107
107106
106105

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13

12

Elements
Dy, Eu
Au, In, Mn
Hf, Ho, Ir, La, Re, Rh, Sm, V
Ag, Al, As, Ba, Co, Cu, Er, Ga, Hg, Lu, Na, Pd, Pr, Sb, Sc, U, W, Yb
Cd, Ce, Cs, Gd, Ge, Mo, Nd, Os, Pt, Ru, Sr, Ta, Tb, Th, Tm
Bi, Ca, Cr, Mg, Ni, Rb, Se, Te, Ti, Tl, Zn, Zr
Pb
Fe

Source: Adapted from Braunstein, H.M. et al., Eds., Environmental health and control
aspects of coal conversion: An information overview, Report ORNL-EIS-94,
Oak Ridge National Laboratory, Oak Ridge, TN, 1977, pp. 513.

individual methods before any attempt is made to interpret the data. Nevertheless, the methods have
found considerable use as means by which trace elements in coal can be identified as well as giving
indications of the concentrations of the various elements.

7.7 CHEMISTRY OF ASH FORMATION

Ash-forming elements, that is, Al, Ca, Fe, K, Mg, Na, and Si, occur in fossil fuels or biofuels as internal or external mineral grains or simple salts such as NaCl or KCl, or are associated with the organic
matrix of the fuel (Benson et al., 1993). In pulverized coal combustion, approximately 1% (w/w) of
the inorganic metals is vaporized, while the rest remains in a condensed form as mineral inclusions
(Flagan and Friedlander, 1978). Depending on the gas/particle temperature and local stoichiometry during coal particle heat-up, devolatilization, and char burnout, these mineral inclusions will
undergo phase transformations and approach each other to form a fly ash fraction: the residual ash.
The vaporized metal species may undergo several transformations: nucleation, subsequent coagulation, scavenging, heterogeneous condensation, and/or interactions with mineral inclusions in the
burning char or residual fly ash particles. The extent of transformation depends on the total specific
surface area of the residual fly ash particles, the cooling rate of the flue gas, the local stoichiometry,
and the mixing in the gas phase.
When coal burns in air, as in the determination of ash in proximate analysis, all the organic
material is oxidized or decomposed to give volatile products and the inorganic material associated
with the coal is subjected to the combined effects of thermal decomposition and oxidation. As a
result, the quantity and the composition of the resulting ash differ considerably from those of the
inorganic materials originally associated with the pure coal substance.
It is therefore impossible to determine accurately the composition of the pure coal substance
from the usual ultimate analysis simply by making allowance for the quantity of ash left behind as
a residue when the coal is burned. Results obtained in this fashion are, as a consequence, quoted as
being on the dry, ash-free basis and no claim is therefore made that these results do in fact represent
the composition of the pure coal substance. If, however, it were possible to calculate accurately the
quantity of mineral matter originally present in the coal sample, then by making due allowance for
this material, the composition of the pure coal material could be deduced with reasonable precision
and certainly with a greater accuracy than could be obtained by adopting the analytical figures
calculated to a dry, ash-free basis.

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Mineral Matter

The thermal and oxidation changes in which the mineral matter takes part during the combustion of coal are very complex but, fortunately, the majority of the reactions are fairly clearly understood (Table 7.9) and it has been possible to derive a formula which enables the mineral matter
content of the original coal to be calculated from a knowledge of the quantity of ash produced on
combustion, together with the quantities of pyrite sulfur, chlorine, carbonate present in the coal.
The formula has been deduced from a consideration of the stoichiometric relationships existing
between the reactants and products in reactions of the following types, all of which take place
during combustion of coal and which together account for practically all the inorganic reactions
involved in the process.
It is difficult to determine, either qualitatively or quantitatively, the mineral matter content of
a coal from the high-temperature ash. During high-temperature ashing, as designated by various
standards (usually 750C [1382F]), a series of reactions takes place involving the minerals in the
coals. Of the major mineral groups, only quartz is not significantly altered during high-temperature
ashing.
The clay minerals in coal contain water that is bound within their lattices. Kaolinite contains
13% bound water; illite contains 4.5% bound water; and montmorillonite contains 5% bound water.
In addition, montmorillonite that occurs in mixed-layer clays also contains interlayer or adsorbed
water. All the water is lost during the high-temperature ashing, for example,

A12O3 2SiO2 xH 2O A12O3 2SiO2 + xH 2O

During high-temperature ashing, pyrite and marcasite (FeS2) are oxidized to ferric sulfate
(Fe2(SO4)3) and sulfur dioxide (SO2). Some of the sulfur dioxide may remain in the ash in combination with calcium, but much is lost. If all of the possible sulfur dioxide is emitted during ashing,
there would be a 33% loss in weight with respect to the weight of pyrite or of marcasite in the
original sample:

4FeS2 + 11O2 2Fe 2O3 + 8SO2

Calcium carbonate (calcite, CaCO3) is calcined to lime (CaO) during high-temperature ashing and
carbon dioxide is evolved, resulting in a 44% reduction in weight from the original calcite, for
example,

CaCO3 CaO + CO2

Other metal carbonates behave similarly, that is, the oxides are formed during the ashing procedure.
The stable mineral quartz (silicon dioxide, silica, SiO2) is the only major mineral found in coal
that is inert during high-temperature ashing.
Sulfates in coal ash are derived from two sources: (1) sulfates (generally of calcium or magnesium) present as such in the coal sample and (2) sulfates formed by the absorption of sulfur oxides
by the basic constituents of the ash during incineration of the coal and occurring mainly as calcium
sulfate but also, to some extent, as alkali sulfates. The quantity of sulfates from the first source is
usually very small and, in normal cases, can usually be neglected in comparison with those derived
by absorption. Consequently, a determination of the sulfate in the ash enables a measure of the
quantity formed during incineration to be established.
During combustion of the coal, organic chlorides are decomposed and liberate the chlorine
atom as hydrochloric acid, while inorganic chlorides decompose with evolution of hydrochloric acid and ultimately leave a residue of the metallic oxide. Since approximately half the chlorine in coal occurs as inorganic chloride and the remainder as inorganic chloride, a correction
forthechlorine present originally as inorganic material is easily applied when the total chlorine
is known.

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The Chemistry and Technology of Coal

Except for oxygen and sulfur, elements that normally constitute the ash residues derived from
coal combustion can arbitrarily be grouped as follows: (1) major elements, that is, elements in concentrations greater than 0.5% in the whole coal and these normally include aluminum, calcium,
iron, and silicon; (2) minor elements, that is, those in the range of concentration of about 0.02 in the
whole coal and these usually include potassium, magnesium, sodium, and titanium, and sometimes
phosphorus, barium, strontium, boron, and others, depending on the geological area; and (3) trace
elements, that is, all other inorganic elements usually detected in coal at less than 0.02% (200 ppm)
down to parts per billion and below. Most nonmetallic elements, even though they are more volatile
than metals, leave a detectable residue in coal ash.

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7.8 EFFECT OF MINERAL MATTER IN COAL

Mineral matter in coal is one of the most important sources of problems in coal combustion, including fouling, slagging, corrosion, among others. Mineral matter transformation and slag formation
are specific properties of coal that provide more information on the suitability for coal combustion
or gasification.
The different states of iron (Fe2+ or Fe3+) are the dominant reason for different sintering behaviors under different conditions. The iron-bearing minerals in ash, such as wustite (FeO), almandite
(3FeOAl2O33SiO2) and fayalite (among others), are the most important factors influencing ashsintering behavior because of the initial melting behavior during coal combustion.
Advanced industrial and utility power systems typically use direct fired gas turbine engines.
Using coal to directly power a gas turbine has yet to be accomplished commercially, primarily
because the ash causes erosion of the blades and deposition on the blades. If the combustion products contain a significant fraction of molten ash particles, deposition on the turbine blades occurs
which blocks the flow path and degrades performance. If the ash particles are solid, erosion of the
blades occurs which also degrades performance. In addition, mineral matter can cause corrosion of
the blades. The size distribution, concentration, and composition of the ash, as well as the turbine
design, determine the lifetime of the turbine blades.
Mineral matter in coal, during combustion, transforms into fly ash, and results in the buildup of
ash deposits on heat transfer surfaces in PC-fired boilers. The ash formation process determines the
ash character, that is, its particle size distribution and variation in chemistry. There are two models
that can be used to represent ash formation from mineral matter: (1) coalescence of included mineral grains and (2) fragmentation of excluded mineral grains during combustion.
When coal is burned, most of the mineral matter and trace elements generally form ash; however, some minerals break down into gaseous compounds which go out the furnaces flue. Pyrite,
for example, breaks down into the individual elements: iron and sulfur. Each element then combines with oxygen to become, respectively, iron oxide and sulfur dioxide. Iron oxide, a heavy solid,
becomes part of the ash and sulfur dioxide is emitted as part of the flue gas. Some trace elements
also dissociate from their organic or mineral hosts when coal is burned and follow separate paths.
Most become part of the ash, but a few of the more volatile elements, such as mercury and selenium,
may be emitted in the flue gas.
The mineral content of coal determines what kind of ash will be produced when it is burned. The
fusion temperature (melting point) of the ash dictates the design of furnaces and boilers. In general,
if the fusion temperature is relatively low, then the molten ash is collected at the bottom of the furnace as bottom ash, requiring one design; however, if the fusion temperature is relatively high, then
the part of the ash that does not melt easily (fly ash) is blown through the furnace or boiler with the
flue gas and is collected in giant filter bags, or electrostatic precipitators, at the bottom of the flue
stack, requiring a different design.
Coal that is relatively rich in iron-bearing minerals (such as pyrite or siderite) has a low fusion
temperature while coal relatively rich in aluminum-bearing minerals (such as kaolinite or illite)
tends to have a high fusion temperature. If an electric generating or heating plant is designed to burn

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Mineral Matter

211

one type of coal, then it must continue to be supplied with a similar coal or undergo an extensive
and costly redesign in order to adapt to a different type of coal. Similarly, furnaces designed to use
coal that produces high amounts of heat will suffer severe losses in efficiency if they must accept
coal that burns with substantially less heat.
Ash particulates are formed from mineral matter due to three different mechanisms. First, part
of the mineral matter is found in layers or bands separate from the organic matter. This is called
adventitious mineral matter, and it can be partially separated from the coal after crushing and fine
grinding. The adventitious mineral matter is transformed directly to ash in the combustor, and the
shape is semirounded. Second, mineral matter in coal is contained within the organic matrix in
the form of chemically bound molecules and submicron crystals. Grinding does not liberate this
intrinsic mineral matter. Third, some of the mineral matter is vaporized during combustion and
condenses on cooler surfaces such as turbine blades.
Adventitious mineral matter is transformed directly to ash in the combustion zone. Depending on
the temperaturetime history, the ash particles will be spherical or semirounded. The size distribution of this ash depends on the size distribution of the adventitious mineral matter. Intrinsic mineral
matter forms ash nodules in the pores of the char, and as char burnout proceeds, the ash nodules
coalesce on the surface of the char.
Frequently, cenospheres (hollow glass-like spheres) are formed. The size distribution of this ash
depends on the temperaturetime history in the combustor. In PFBC tests, three hot cyclones yield
an ash size distribution of 98% less than 10 m and 80% less than 4 m.
The ash loading and size distribution depend on (1) the extent of grinding and fuel cleaning and
(2) the combustion timetemperature history. Regardless of the type of combustion system, much
of the ash is in the 120 m size range. Particles down to about 10 m can be efficiently removed by
hot cyclone collectors. Particles in the 110 m range can be removed by other advanced methods;
however, this tends to cause additional pressure drop and heat loss.

REFERENCES
Alpern, B., Nahuys, J., and Martinez, L. 1984. Mineral matter in ashy and non-washable coals: Its influence on
chemical properties. Community Service in Geology Portugal, 70(2): 299317.
Babu, S.P. (Ed.). 1975. Trace Elements in Fuel. Advances in Chemistry Series No. 141. American Chemical
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