Minerals Engineering 20 (2007) 496505

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Automated mineralogical analysis of coal and ash

products Challenges and requirements
C. van Alphen

Van Alphen Consultancy, P.O. Box 1648, Jukskei Park 2153, Johannesburg, South Africa
Received 25 September 2006; accepted 13 December 2006
Available online 15 February 2007

Abstract
To ensure accurate and reliable automated mineralogical analysis of a sample, it is a common practise to use chemically derived elemental proportions to validate the mineralogical proportions. Automated mineralogical analysis of coal and corresponding ash is a challenge as a signicant proportion of the phases/minerals are amorphous with variable elemental proportions. In coal, the organic macerals
are the amorphous phases and depending on the rank of the coal have varying carbon, hydrogen, nitrogen, oxygen and inorganic element
compositions. In ash, aluminosilicate glasses and partially transformed minerals are the major amorphous phases. The elemental composition of these glasses is controlled by the mineral deportment in the source coal, operating conditions and conguration of the boiler,
gasier or furnace.
To compound the problem, the traditional chemical analysis of coal (proximate, ultimate and XRF ash elemental analysis) is based on
heating the coal to dierent temperatures and recording mass losses or analysing the ash derived from the coal. These analyses each have
inherent limitations, sampling and analytical errors, which when combined can provide misleading interpretations.
If accurate and precise mineralogical data are to be provided to coal practitioners for optimising processing plant, predicting combustion/gasication performance and for resolving coal quality problems, it is necessary to develop a cost eective and reliable automated coal and ash analytical system.
With the advancement in X-ray detector and scanning electron microscope technology it is potentially feasible to provide a cost eective and quick mineralogical (minerals and macerals) and elemental analysis of raw coal and ash. The new automated systems have the
potential of combining the traditional proximate, ultimate, XRF ash elemental, XRD and petrographic analyses into one analysis, without heating or modifying the existing coal sample.
Detailed coal and ash particle characterisation is now feasible, enabling the development of coal processing, y ash formation, slagging prediction and combustion performance models. Coal and ash analysis is now entering a new and exciting era.
2007 Elsevier Ltd. All rights reserved.
Keywords: Automation; Coal; Fly ash; CCSEM; QEMSCAN; MLA

1. Introduction
Simplistically, coal consists of organic amorphous macerals and inorganic crystalline minerals in varying proportions, whereas ash consist of minerals, char and amorphous
aluminosilicate glasses.

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doi:10.1016/j.mineng.2006.12.013

The element composition (carbon, hydrogen, oxygen,

nitrogen and organically bound inorganic elements) of the
macerals is inuenced by the rank of the coal, whereas
the elemental composition of the glasses is controlled by
the minerals deportment in the source coal and the operating conditions and conguration of the boiler or furnace.
With the high proportion of amorphous phases in coal
and ash, accurately characterising elemental distributions,
elemental proportions and mineralogical characteristics is
dicult for coal and ash, irrespective of the technique used.

C. van Alphen / Minerals Engineering 20 (2007) 496505

Proximate and ultimate and to lesser extent X-ray uorescence (XRF) ash elemental are some of the traditional
and routine analyses undertaken by coal suppliers, users
and buyers to characterise coal (Fig. 1).
Proximate analysis is the inherent moisture, volatile
matter, ash, xed carbon (by dierence) and ultimate analysis is the carbon, hydrogen, nitrogen, total sulphur and
oxygen (by dierence) content of the coal. Ash elemental
is the elemental composition of the ash derived from the
coal. For each analysis, the coal is heated and the mass%
loss, mass% of the reaction products and mass% of the residue (ash) are measured.
Inherent moisture is the mass loss after heating the coal
to 100110 C (SABS Method 925), volatile matter is mass
loss after heating the coal to 900 C (SABS Method 927,
ISO562M and ASTMD3175M) and ash is non-combustible residue after slowly heating the coal to 815 C (SABS
Method 926) or 900 C (ASTM D3174). The volatile matter is derived from organic fraction and from certain minerals, whereas the ash% can include volatile organic
sulphur, which has reacted with CaO and uncombusted
carbon. Ash% is not a direct measure of the total mineral
matter content of the coal. The sum of inherent moisture,
volatile matter and ash% subtracted from 100% is termed
xed carbon. Fixed carbon should represent the proportion
of non-volatile carbon and is the accumulation of any analytical errors.
The ultimate analysis reports the carbon, hydrogen,
nitrogen, total sulphur and oxygen content. Carbon
includes organic carbon and inorganic carbon from carbonates, hydrogen includes organic hydrogen and hydrogen in the water derived from minerals and nally total

COAL

Proximate Analysis
Inherent moisture
Ash-%
Volatile
matter

Fixed carbon (by difference)

XRF Ash elemental

SiO2, Al2O3, Fe2O3,

TiO2, CaO, MgO,
K2O, Na2O, P2O5,
MnO, SO3
LOI

Ultimate Analysis

Carbon
Hydrogen
Nitrogen
Oxygen (by difference)
Other
AFT
CO2 (carbonates)
Total sulphur
HGI
Calorific value (CV)
XRD

Petrography
CCSEM

MINERALS
Fig. 1. The variety of typical coal and ash analyses.

497

sulphur is organically bound sulphur and sulphur derived

from pyrite. Oxygen is a calculated value.
Determining the mineral matter in coal is either calculated using X-ray uorescence (XRF) ash elemental proportions (SEDNORM, Cohen and Ward, 1991) or
determined directly using X-ray diraction (XRD) and by
scanning electron microscope (SEM) based automated
mineralogical systems such as CCSEM, QEMSCAN and
MLA.
Normative programs such as SEDNORM assumes that
specic elements can be assigned to one mineral. Unfortunately, this is not always possible as certain elements occur
in more than one mineral. An example is Fe, which can
occur in pyrite, siderite Fe-chlorite and Fe-oxides, K in
mica/illite and feldspar and nally Si in quartz, clays,
mica/illite and feldspars. In lower rank coal, a proportion
of the elements are organically bound to carbon and not
associated with minerals. Extensive knowledge of the coal
prior to normative analysis is benecial.
An X-ray diraction pattern of raw coal and ash is characterised by high background continuum originating from
the amorphous macerals in coal and amorphous aluminosilicate glass in the ash. This broad background can mask
peaks of crystalline phases. Ashing the coal at low temperature (120150 C) in electronically excited oxygen plasma
can isolate minerals from the organic fraction (LTA).
Unfortunately, LTA can take 34 days and in lower
rank-coals secondary calcium and iron sulphates are
formed during the ashing process (Ward, 2002). A technique was developed to determine the proportion and elemental composition of glass in ash (Ward and French,
2003). The calculated elemental proportion of the glass
relies on the accuracy of XRF ash elemental analysis and
X-ray diraction derived mineral proportions in the ash.
X-ray diraction and normative calculation predicts the
mineral composition of the coal, but does not determine
the morphological features (size, association) of the minerals and particle characteristics.
Petrographic analysis describes the proportion of macerals in coal and to a limited extent the proportion of minerals in coal. Maceral discrimination is visual and based on
texture, morphology and light reectance observed under
a reected light microscope tted with an oil immersion
objective. Since maceral identication is visual and requires
human intervention, it can be subjective, especially for ne
particles. Micrinite, a maceral described by petrographers
was shown by Faraj and Mackinnon to be ne-grained
kaolinite (Faraj and Mackinnon, 1993) and not a carbon
bearing phase. The mineral proportions are reported as
the three main groups quartz/clays, pyrite and carbonates.
It is not possible to accurately distinguish between the different minerals, especially if they are ne grained and
included in coal matrix.
The US Steel Research Laboratories initiated the scanning electron microscope (SEM) based automated mineralogical analysis of coal in the early 1970s with the
development of the particle recognition and characterisation

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C. van Alphen / Minerals Engineering 20 (2007) 496505

(PRC) software (Galbreath et al., 1996). PRC software

located the minerals dispersed in the coal matrix and positioned the electron beam at the centre of the included grain
(Lee et al., 1978; Huggins et al., 1982). Initially, CCSEM
analysis was time consuming and only the minerals were
quantied. It was only in the early 1990s that the organic
coal was analysed (Human et al., 1991; Straszheim and
Markuszewski, 1990, 1992). This was made possible by
mounting the coal sample in either carnauba wax (Straszheim et al., 1988) or iodoform doped epoxy resin (Gomez
et al., 1984) and by the introduction of light element detectors. Since CCSEM mineralogical identication is based
on the elemental proportions derived from X-rays, it can
accurately determine the mineral type and elemental proportions of the minerals in coal (Van Alphen and Falcon, 2000)
and amorphous glass phases (Van Alphen, 2005). In its current form, CCSEM is unable to accurately distinguish
between the dierent macerals and all the macerals are
grouped as coal. This is a limitation.
Each of the chemical and mineralogical analytical techniques described above have limitations and do not provide
the full particle and mineralogical characterisation required
for coal-processing optimisation, coal combustion performance assessment and the impact on boiler/furnace/gasier
performance. For ne (<0.5 mm) coal-processing optimisation it is important to quantify the density, ash deportment
and size distribution of particles. The surface characteristics of particles are important for otation. The liberation
characteristic of the inorganic and organic component in
coal is important for assessing the potential yields and
grade (ash%) of the product and can be used to evaluate
the eciency of separation technique (spirals, cyclones or
otation). The mineral deportment in coal and organically
bound inorganic element distribution inuences the slagging potential of the coal. The proportion of reactive macerals (vitrinite and liptinite) in the particle controls ignition
and combustion rate.
The development of faster X-ray detectors, stable scanning electron microscopes, and high-resolution backscattered electron detectors and good processing software
have improved the analytical capabilities of automated
scanning electron microscopes (CCSEM, QEMSCAN
and MLA). With further research, these systems have the
potential of providing the detailed mineralogical and elemental information required.

2. Coal and ash automated mineralogical systems

There are numerous CCSEMs around the world,
which have dierent congurations, analytical approaches
and data processing software. Each system is however
based on a scanning electron microscope, use X-rays to discriminate minerals and have suitable microanalysis and
image processing systems.
The numerous data processing software programs
include

1. Particle recognition (PRC) and coal mineral analysis

(CMA) developed by the US Steel Research Laboratories (Nissen and Greulich, 1987). The Combustion
Research Facility at Sandia National Laboratories (Nissen and Greulich, 1987; Yang and Baxter, 1991), University of Kentucky (Human et al., 1991) and the
Combustion Research Facility at Massachusetts Institute of Technology (Beer et al., 1991) employ CCSEM
with the basic PRC and CMA routines.
2. The Energy and Environment Research Centre (EERC)
at the University of North Dakota developed the SEM
point-count routine (SEMPC), windows based MINCLASS mineral classication program (Folkedahl
et al., 1993) and particle-by-particle scanning electron
microscope programme (Steadman et al., 1991).
3. Brigham Young University developed the Analysis of
Minerals and Coal Associations (AMCA) program
(Yu et al., 1993).
4. Anglo American Research Laboratory developed the
ASCAN software to initially analyse base metals, but
was modied by Van Alphen Consultancy to analyse
coal and ash (Van Alphen, 2005).
QEM*SEM or QEMSCAN is an integrated system originally designed by CSIRO (Skorupska and Couch, 1993)
for the base and precious metal mining industry, but has
been used to classify mineral matter in coal and y ash
(Creelman et al., 1993; Creelman and Ward, 1996; Gottlieb
et al., 1991).
University of Queenslands JK Centre recently
announced an ACARP funded project to integrate of the
Mineral Liberation Analyser (MLA) and the JenkinsKwan Technology MACE 300 system (MLA Today,
October 2005).
The multitude of possible CCSEM congurations, different analytical conditions and software approaches has
resulted in some concern regarding the reliability and accuracy of the CCSEM. To address this problem an international round robin test involving six laboratories was
undertaken in 1994 (Galbreath et al., 1996). The laboratories that participated were EERC (CCSEM), CSIRO
(QEMSCAN), the R.J. Lee Group (CCSEM), the University of Kentucky (CCSEM), the Sandia National Labs
(CCSEM) and the Netherlands Energy Research Foundation (CCSEM). Each laboratory determined the abundance
of calcite, kaolinite, pyrite and quartz for three North
American coals. The results indicated that QEMSCAN
reported the most precise results. Kaolinite showed the
poorest reproducibility for all three coals. Kaolinite had
the lowest backscattered electron intensity (BSI) of the
minerals and typically occurs as ne disseminated grains
included in a coal particle. These attributes make it dicult
to accurately detect kaolinite and to quantify its morphological and association properties.
X-ray acquisition speeds, electron beam positioning
and mineral characterisation procedures are the main
dierences in the automated systems described above.

C. van Alphen / Minerals Engineering 20 (2007) 496505

499

Further research is required and new techniques need to

be developed to improve quantitative elemental analysis,
maceral discrimination and mineral and particle characterisation.
Fortunately, coal and ash have certain mineralogical
and physical characteristics that can be exploited to achieve
the objectives listed above. These characteristics are outlined in the following sections.
3.1. Quantitative elemental proportions
Fig. 2. Electron beam positioning. Centroidal or raster of closely spaced
points.

QEMSCAN X-ray acquisition speed is 1015 ms, ASCAN

is 100 ms and remaining systems in excess of 400 ms25 s.
Either the electron beam is positioned at the centre of a
phase of similar backscatter electron intensity (centroidal
approach) or a closely spaced raster of points are positioned across the particle (Fig. 2). MLA and the traditional
CCSEM systems use the centroidal approach, whereas
ASCAN, QEMSCAN and EERC CCSEM use the raster
approach. QEMSCAN and the traditional CCSEM systems use a sequential mineral identication program,
ASCAN uses fuzzy logic and MLA compares standard
X-ray spectrum of the unknown to identify the minerals.
The two commercially available automated mineralogical systems, QEMSCAN and MLA have included the
signicant advances in X-ray detector technology, backscatter electron detectors and the modern digital scanning
electron microscopes. The introduction of the liquid nitrogen free silicon drifted detectors (SDD) with counts rates in
excess of 1,000 000 cps are 10 times faster than the traditional Si(Li) detectors.
Increase counting times will ensure better statistics and
rapid analytical times. The introduction of these new technologies will advance the analytical capabilities of these
two systems, especially for analysing coal and ash
products.

In coal, elements can be distributed between organic

(macerals) and the inorganic components (minerals). Low
rank lignites and sub-bituminous coals commonly have a
signicant proportion of organically bound inorganic elements (Fig. 4). The organically bound elements increase
the average backscatter electron intensity of organic coal
particles (Fig. 3).
The mineral free organic phase in a lignite sample had
signicant proportions of Ca, Mg, Fe and S (Fig. 4). It is
perceived that these inorganic elements are bound to the
carboxyl group (COOH). As the rank increases, the proportion of organically bound inorganic elements decrease
(Fig. 4).
The macerals of a South African high volatile bituminous (RoV% random = 0.64) coal, have distinct organically bound elements (Fig. 5). Generally, sulphur and
titanium were elevated in vitrinite and pseudovitrinite, aluminium, silicon, sulphur, and to a lesser extent calcium and
magnesium are elevated in reactive and inert semifusinite,
calcium and sulphur are elevated in sclerotinite and aluminium, silicon, sulphur in liptinite.
Electron microprobe analysis of telecollinite in Australian DM Bando coal with a Rmax varying from 0.68 to
2.20 identied organically bound Al, Si and Fe (Gurba

3. Automated mineralogical system requirements

In the authors opinion, to provide the necessary mineralogical information required by coal practitioners,
researches and users, the new generation automated mineralogical systems must:
1. accurately quantify the elemental proportions and elemental distribution between the organic (macerals) and
inorganic (minerals) fractions;
2. discriminate and quantify the proportion of macerals
and determine the maceralmineral association characteristics on a particle-by-particle basis;
3. accurately determine the mineral/coal proportions and
mineral/coal morphological features;
4. be cost-eective with a minimum turnaround time of
two days for a batch of six sections. The sample must
not be heated or chemically treated prior to the analysis.

Fig. 3. Backscatter electron intensity image of lignite mounted in normal

epoxy resin. The organic component (light grey) has a high BSE intensity
relative to epoxy resin (grey) and the included minerals white. Scale bar is
100 lm.

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C. van Alphen / Minerals Engineering 20 (2007) 496505

0.5
0.45

Counts

0.4
0.35
0.3
0.25

O
Na

0.05
0

Ca

Mg

Fe

4
5
6
Peak Positions

10

Fig. 4. X-ray spectrum obtained from the organic phase in a lignite.

Normalised counts (cts/s)

0.006
Si

0.005

Reactive Semifusinite

Al

Inert Semifusinite
Liptinite
Vitrinite

0.004
S

0.003

ASCAN elemental proportion was within 15% of the standard XRF ash elemental analysis for the major elements.
This provided sucient information for trending and to
conrm the elemental variation between samples.
Increasing the number of counts from 1000 to 10,000
will obviously improve the accuracy, but will unfortunately
will increase the time and cost to analyse a sample using the
existing Si(Li) EDS detectors. However, with the introduction of new liquid nitrogen free SDD detectors this
becomes a feasible option, without signicantly compromising the time required to analyse a sample.
Organic hydrogen will be the only element, which cannot be directly quantied using the existing EDS detector
technology. This however, could be calculated by dierence, analogous to determining the proportion of oxygen
in an ultimate analysis and xed carbon in the proximate
analysis. Since the macerals and glasses are amorphous,
the elemental proportions are not consistent. If the elemental composition of macerals and glasses are to be accurately
quantied the automated mineralogical system should be
based on raster of analytical points across particles and
not on the centroidal positioning method (Fig. 2).
3.2. Maceral discrimination

Mg

0.002

Ca
Ti

0.001

0
0.8 1.3 1.8 2.3 2.8 3.3 3.8 4.3 4.8 5.3 5.8 6.3 6.8
KeV
Fig. 5. Organically bound elements associated with dierent macerals in
high volatile bituminous coal.

and Ward, 2000). Organically bound sulphur is widely

reported (Timmer and van der Burgh, 1984; Straszheim
et al., 1983) in bituminous coals.
Improvement in elemental quantication is important as
the automated mineralogical system must be able to quantify the proportion of organically bound inorganic elements, discriminate between organic and inorganic C, H
and N and the elements associated with minerals.
Elemental quantication using the rapidly acquired 1000
count X-ray spectrum was achieved on the ASCAN system
(Van Alphen, 2005). Two to three second count energy dispersive (EDS) X-ray spectra were acquired from mineral
standards. Using a random number generator, the standard X-ray spectrum was broken down into a 1000 count
spectrum a 100 times and the number of counts for each
element was computed. Good correlations were obtained
between the average elemental count and the known elemental proportion (Fig. 6) for the major elements. The correlation coecient varied from 0.98 to 0.99. The linear
equation was used to determine the oxide proportions of
coal and ash from the ASCAN 1000 count X-ray spectrum.
Compared to the standard XRF ash elemental analysis, the

Accurately discriminating and quantifying macerals in

coal is important as the proportion of reactive macerals
is used to predict combustion behaviour (Su et al., 2001).
Su maceral index is a function of vitrinite, liptinite and
inertinite. Magasiner used the reactive maceral proportions to predict the ratings of chain grate stockers combusting coal and biomass (Magasiner et al., 2001). This index
was based on the proportion of vitrinite, liptinite, reactive
inertodetrinite and reactive inertinite. Following this
research, the automated mineralogical system, should at
best be able to discriminate between reactive macerals (vitrinite and liptinite) and inert macerals (inertinite).
Under the light reectance optical microscope maceral
characterisation is based on texture, association and light
reectance intensity. It is reliant on the interaction of light
with the sample and the ability of the eye and human brain
to discriminate textures. Mineral discrimination in a scanning electron microscopes (SEM) is based on the interaction of a high-energy electron beam and the sample.
Typically, backscatter electron intensity (BSI), secondary
electrons intensity (SEI) and X-rays are produced and used
to acquire images and the elemental composition of the
mineral or phase. Since SEM discrimination is electron
based and the optical microscope is light based, the SEM
is unable to identify all the macerals.
JKTech at University of Queensland has initiated maceral discrimination by integrating the Mineral Liberation
Analyser (MLA) and the MACE 300 system. The MLA
using the centroidal approach will dene the mineral content and the MACE 300 system will dene the macerals.
A composite image of each eld of view will be developed
by combining the MACE 300 maceral image and the

C. van Alphen / Minerals Engineering 20 (2007) 496505

40

0.8

0.7

0.6

80
Ca%=-0.43 + 79.18cts
n=23
r=0.98

30

Fe%=2.78 + 94.93cts
n=36
r=0.98

70
% Elemental Fe

35
25
20
15
10
5

60
50
40
30
20

0.8

0.7

0.6

0.5

0.4

Fe X-Ray Count Fraction (Total Spectra)

0.07

0.06

0.04

0.03

0.02

Mg%=0.11+ 73.87cts
n=19
r=0.98

0.01

5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0

Element % Mg

Ca X-Ray Count Fraction (Total Spectra)

0.3

0.2

0.5

0.45

0.4

0.3

0.35

0.25

0.2

0.15

0.1

0.05

10

Element % Ca

0.5

Si X-Ray Count Fraction (Total Spectra)

Al X-Ray Counts Fraction (Total Spectra)

0.4

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45

0.1

0.3

0.2

10

Si%=0.17 + 60.46cts
n=36
r=0.98

0.1

15

50
45
40
35
30
25
20
15
10
5
0

0.05

Element % Al

20

Element % Si

Alwt%=0.128 + 56.78cts
n=39
r=0.99

25

501

Mg X-Ray Count Fraction (Total Spectra)

Fig. 6. Correlation between element counts and known elemental proportions. Data acquired on the ASCAN system (Van Alphen, 2005).

MLA mineral image, from which the maceral and mineral proportions will be determined (Fandrich et al.,
2006). If liptinite proportions are required the images are
edited manually to separate liptinite from the dark minerals (OBrien et al., 2006). The combined MACE 300
and MLA system will quantify maceral and mineral proportions and will characterise each particle into specied
groups depending on the maceral and mineral associations.
As the electron beam is not positioned on the macerals, it
will not be able to automatically determine the elemental
proportions of the macerals. The expected turnaround time
of a single sample is one day (OBrien et al., 2006, personal
communication).
It is proposed that the macerals can be discriminated
using a combination of backscattered electron intensity
and elemental proportions. This could be the focus of the
new automated mineralogical systems.

The density of vitrinite varies from 1.27 g/ml in high volatile bituminous coals to 1.8 g/ml in anthracites (Falcon
and Snyman, 1986). Liptinite ranges in density from 1.18
to 1.25 g/ml with increasing rank. The density of the individual inertinite macerals vary from 1.35 to 1.7 g/ml, but
do not change signicantly with an increase in rank. Since
backscattered electron images are atomic weight contrast
images, the density variation of macerals will be reected
by a variation in grey levels in backscattered electron
images (Fig. 7). Any low-density phase (vitrinite/liptinite)
will be black and high-density phase will be grey
(inertinite).
For a given rank, liptinite has the highest hydrogen content, vitrinite the highest oxygen content and inertinite the
highest carbon content (Tang et al., 2005; Ward and
Gurba, 1999). Published data on mainly density-separated
fractions in general support the trend observed by Tang

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C. van Alphen / Minerals Engineering 20 (2007) 496505

Fig. 7. Individual high volatile bituminous coal particles highlighting the textural relationship and variation in backscatter electron intensity (<1.5 g/ml
density fraction). Low-density coal is black, higher-density coal is light grey and minerals are white.

90

20
Exinite
Vitrinite
Inertinite

82
80

12

14

10

78

76

74
0.44

Mass-% hydrogen

oxygen

84

16

Mass-%

86

8
7.5
7
6.5
6
5.5
5
4.5
4
3.5
3
0.44

0.5

0.56
0.63
Rank (Romax)

Exinite
Vitrinite
Inertinite

18

0.82

4
0.44

0.91

0.5

0.56
0.63
Rank (Romax)

0.82

0.91

2.4
2.2

Mass-% nitrogen

Mass-% carbon

88

Exinite
Vitrinite
Inertinite

0.5

0.56
0.63
Rank (Romax)

0.82

0.91

2
1.8
1.6
1.4
1.2
1
0.8
0.6
0.44

Exinite
Vitrinite
Inertinite

0.5

0.56
0.63
Rank (Romax)

0.82

0.91

Fig. 8. Carbon, hydrogen, nitrogen and oxygen variation with rank (Burragato et al., 1997; White et al., 1987; Xie et al., 1994; Milligan et al., 1997).

and Ward (Fig. 8). Any variation is attributed to the density fraction not necessary containing 100% of the maceral
of interest.
It is conceivable that a new SEM based maceral classication scheme could be developed based on elemental
proportions and backscattered electron intensity. This

new classication scheme is not subjective and once set

up will not require an experience operator.
If backscatter electron intensity is the main discriminator, then the automated mineralogical system has to be
extremely stable as the BSE variations are a few atomic
mass units. It is imperative to monitor the beam current

C. van Alphen / Minerals Engineering 20 (2007) 496505

during the analysis and if necessary automatically adjust the

beam. The mineral identication software used by the automated mineral identication software must include BSE
intensity as a discriminating factor. Using the raster of analytical points instead of centroidal method is preferable as
the slight changes in BSE intensity and elemental compositions can be recorded and used to dene the maceral. This
ne detail will produce an image texture, which could
be used to classify macerals (Fig. 6). Maceral discrimination
in high rank coals, using BSE based automated mineralogical system will probably not be as successful as in lower
rank coals. From a practical point of view, this is not a
major issue as a signicant proportion of the coal utilised
is high to low volatile bituminous coal. Obviously, if the
rank of the coal is known prior to analysis, the maceral discrimination system can modied to suit this rank of coal.
In ash, the prominent carbon phase is char. Char identication is based on morphological features (Alvarez
et al., 1997). The automated mineralogical system must
rst identify carbon-rich phases in the ash samples and secondly have image analysis capabilities that measure wall
thickness and porosity of the char particles. It is important
to have the necessary o-line processing software, which
can classify the particles into dierent classes based on
the wall thickness and porosity.
3.3. Mineral quantication and particle characterisation
Quantifying and qualifying minerals in coal is routine
for any automated mineralogical system, but not necessary
as routine for ash. In coal, ne clay is nely disseminated in
coal. It is this reason why kaolinite is often over or under
reported (Galbreath et al., 1996). The automated mineralogical system must have the mechanism to quantify the
mineralogical variations of these nely disseminated grains.
A system using a raster of closely spaced analytical points
will provide the best opportunity to record the elemental
and subsequently mineral variations.
Simplistically, ash (y ash, slag and clinkers) consists of
crystalline phases (e.g. anorthite, mullite and spinels),
amorphous Ca- and Fe-bearing aluminosilicate glasses of
varying elemental compositions, amorphous Ca-oxide rich
ash particles, amorphous Fe-oxide rich particles and char.
Quantifying and identifying the crystalline phases
should not propose a problem as by denition these phases
have a dened elemental composition and structure. The
problem is classifying the amorphous phases. Grouping
the dierent amorphous phases based on the elemental
composition is the only feasible route.
In South African y ashes and slag deposits at least six
groups have being identied (Van Alphen, 2005). These
include
1. Aluminosilicate, with a Al/Si ratio similar to the original
kaolinite source and no uxing elements (Ca, Fe, Mg, K
and Na). This phase represents the intermediate to high
temperature transformation products of kaolinite.

503

2. CaFe-bearing aluminosilicate glass, typically occur as

spherical particles and is derived by the coalescence of
pyrite, carbonates and kaolinite. Invariably, these
phases initiate the development of slag deposits.
3. K-bearing aluminosilicate glass is derived from K-bearing illite/mica and feldspar.
4. Quartz and Si-rich glasses with minor proportions of Al,
Ca, Fe and Mg. Quartz is the nal transformation product of quartz and the Si-rich glasses represent the high
temperature coalescence of quartz with kaolinite, calcite/dolomite and pyrite.
5. Ca(Mg)-rich oxides (lime) with minor concentrations of
Al and Si. This y ash phase is transformation product
of extraneous calcite and dolomite.
6. Fe-rich oxides with minor concentrations of Al and Si.
This y ash phase is the transformation product of
extraneous pyrite.
Operating conditions and ash formation processes
within the boiler/furnace can be inferred from the mineralogy and elemental distribution of the ash. Comparing the
elemental distribution of the y ash phases to the elemental
distribution in the source coal provides valuable information, which can be used to trace mineral transformation
and reactions within the combusting coal particles and in
the combustion zone. In eect, the elements are used as
tracers.
Measuring the sulphur content in Fe-oxide rich y ash
particles, C-content in Ca-rich y ash particles and the
Al/Si ratio in aluminosilicate y ash particles are indicative
of the extent of pyrite, carbonate and kaolinite transformation. If the data from an automated mineralogical system
are to be used to model mineral transformation, y ash formation and slag development in any commercial boiler,
gasier or furnace, it is important to accurately characterise the y ash phases and to fully understand mineral and
elemental deportment in the source coal (Van Alphen,
2005). Without this detail, the model will not produce accurate and meaningful results.
Identifying these ash phases and measuring the variation
in elemental proportion is only possible if a raster of points
is used. Since there is a tenuous link between the backscattered electron intensity and elemental composition of
glasses, the centroidal approach is not feasible.
4. Conclusion
To satisfy the mineralogical requirements for coal utilisation, coal-processing optimisation, coal resource assessment and coal combustion performance it is important that
the automated mineralogical system should be able to
quantify and qualify elemental proportions (organic and
inorganic), major maceral groups, mineral deportment
and proportions in coal. This same system must identify
the numerous amorphous phases in glass and accurately
quantify the elemental proportion of these amorphous
glasses.

504

C. van Alphen / Minerals Engineering 20 (2007) 496505

Coal process engineers require the particle size distribution, density distribution and mineral(ash) distribution of
coal particles for optimising the circuit and improving the
quality of the product. The maceral composition and surface characteristics of ne particles are important for
otation.
Reducing the number of ame-outs, unplanned outages
and the proportion of char in the y ash are important for
combustion engineers. Flame-outs are partially a function
of the maceral composition and unplanned outages are
commonly attributed to extensive slagging and fouling.
To resolve these problems, the automated mineralogical
system must accurately determine mineral proportion and
deportment, proportion and deportment of reactive macerals, particle characteristics, size and angularity of abrasive
minerals, distribution of elements and nally the distribution of carbon, hydrogen and oxygen.
The introduction of liquid nitrogen free SDD detectors,
stable digital scanning electron microscopes and high-resolution backscatter electron detectors coupled with unique
mineralogical features will enable the automatic mineralogical analysis of coal and ash samples. In the authors opinion, the raster of closely spaced points is preferable to using
the centroidal method of position the electron beam. Further research is required to substantiate the trends and
observations mentioned in this paper. Coal and ash analysis is now entering a new and exciting era.
Acknowledgements
The original mineral matter transformation, y ash formation and slag development research and setting up the
ASCAN system was funded by Eskom Resources and
Strategy Division. This funding enabled the author to
develop the techniques and to comprehend the complexity
of analysing coal and ash. Eskoms support and funding is
gratefully acknowledged.
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