Fuel Vol 74 No. 4, pp.

522-529, 1995
Copyright kc 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0016-2361/95/$10.00+0.00

Particle size-density relation and

cenosphere content of coal fly ash
Sarbajit

Ghosal

and Sidney

A. Self

High Temperature Gasdynamics Laboratory, Department

Stanford University, Stanford, CA 94305, USA
(Received
14 February 1994; revised 4 May 1994)

of Mechanical

Engineering,

The results are reported of detailed physical characterization of six ashes from coals representative of those
burned in US power plants. Centrifugal separation was used to classify the ashes into six density categories
in the range < 1.6 to > 3.2 g cm- 3. The size distributions of all density classes were determined in the range
l-200 pm. For most of the density classes, log-normal functions, truncated outside the measurement limits,
described the size distributions quite well. For all six ashes, the median diameter initially decreased and
then increased with increasing particle density. The influence of particle structure on this large variation
(up to sixfold) in size is discussed. Centrifugal separation using a liquid of density 2.2 g cm- 3 was used to
estimate the mass fraction of cenospheres (i.e. particles with trapped interior bubbles) in the ashes. This
fraction varied from < 5 to > 95 wt%. The cenosphere content was apparently uncorrelated with coal rank
but was positively correlated with the total mineral content of the coal. The median diameters of the
cenospheric fractions were found to be two to three times those of the non-cenospheric (solid) fractions.
The density-size data were used to determine the Fe,O, distribution in the ashes.
(Keywords: fly ash; siz.e-density relation; cenospheres)

In pulverized coal boilers, fly ash is produced during char

burnout from the melting of inorganic mineral matter in
the coal by a complex series of processes involving initial
mineral fragmentation followed often by coalescence on
the char surface,. The molten ash particles, entrained
in the combustion gases after char fragmentation,
are rapidly quenched to primarily spherical, glassy
particles as they are swept away from the flame region.
Microanalysis of ash collected in flue gas cleaning plant
shows that it consists primarily of spherical particles of
impure aluminosilicate glass3*4. The particle size varies
from submicrometre to > 100 pm.
Ash particle densities vary significantly, owing to
variation in composition from particle to particle, and
because gas bubbles are trapped within many particles.
The latter class of particles, referred to as cenospheres,
is the more important cause of density variation and is
the subject of this study. The bubbles may occur either
in multiple form within a particle or in single, concentric
form with a diameter that may be nearly as great as that
of the particle. Their occurrence has been widely noted3-*.
Quantitative data on size-density relations for fly ash
are not available in the literature but would be helpful,
for example, in understanding slagging and fouling
mechanisms in combustors, and for improved models of
fly ash formation. This study however is part of an effort
to provide data for reliable prediction of the effects of fly
ash on radiative heat transfer in combustors. Both the
chemical composition and physical structure of fly
ash particles influence their radiative propertiesg. Six
representative ash samples were therefore obtained for
* Current address: Department of Mechanical Engineering,
of Kentucky,

522

Lexington,

Fuel 1995

KY 40506, USA

Volume

74 Number

University

study. Their physical characterization included optical

and scanning electron microscopy, size measurement
using the Coulter Multisizer, and density classification
by centrifugal separation.
Fly ash has a submicrometre component resulting from
condensation of mineral vapours and from extraneous
(submicrometre) fines in the pulverized coal. However,
in radiative transfer, the submicrometre component
makes a negligible contribution
to scattering and
absorption, so that particles of diameter 2 1 pm are
of interest. Submicrometre ash particles can be expected
to be solid (non-cenospheric), since the excess pressure
needed to sustain bubbles within such a small particle is
much greater than that typical of compressed gases
trapped in the porous char or in the mineral particle
itself. In studies of ash sections in the literature the
smallest detected cenosphere was found to be - 4 pm4.
Hence, from the viewpoint of cenospheres, data on
size-density relation are relevant for ash particles of
diameter 2 1 pm.
Insufficient accurate information is available on the
size distribution of fly ash. Size distribution, determined
using cascade impactors in terms of the aerodynamic
diameter, is generally resolved into a few overlapping
ranges. Since the aerodynamic diameter, D,, includes
density (p) information (D,ocD&),
it is not useful for
determining the sizeedensity relation. Current microscopic
techniques can size only relatively small samples (one
to two thousand particles). In contrast, the Coulter
Multisizer reports the geometric diameter and is suitable
for sizing agglomerated powders such as fly ash, using
statistically significant sample sizes12.
This paper presents the results of density classification
of six ashes using centrifugal separation in liquids, and

Physical characterization

size distribution measurements of each of the density

classes with the Coulter Multisizer. The parameters for
the best-fit log-normal functions to the size data are
tabulated for all density classes. An estimate is made of
the total cenosphere content of the ash by density
classification, and the size distributions of the two
components are reported for each ash.

For the Foster-Wheeler ashes, the fractions collected

in the cyclone were also supplied. However, the ashes
could not be reconstituted, because the mass ratios of
baghouse to cyclone ashes were not available. Except for
a slightly different size distribution, the cyclone ash was
found to be quite similar to the baghouse ash for each
coa19, and hence the measurements described here were
made only on the baghouse ashes.
The ashes showed no detectable solubility in water.
Chemical analyses of the coals and the ashes are given
in Tables I and 2 respectively. The average ash
compositions were obtained by electron microprobe
measurements on slags produced by melting 40-50g of
each ash. It is seen that Beulah and Illinois No. 6 ashes
had the highest iron oxide content (16-19 wt%). The silica
contents of the three bituminous coal ashes were - 50 wt%,
and the SiO,/Al,O, ratio was -2:l. The San Miguel
lignite ash was rich in silica (65 wt%). The SiOJAl,O,
ratio for the Beulah lignite slag was close to unity. The
Eagle Butte subbituminous coal ash had an unusually
high calcia content (CaO:SiO,:A1,0,=33:29:17).
This
coal from the Powder River Basin is known to contain
much organically associated calcium.

EXPERIMENTAL
Fly ash samples

The ashes originated from coals typical of those burned

in US power plants. Their properties, including mineral
transformation during combustion, have been studied
extensively13. The coals were Illinois No. 6, Kentucky
No. 9, Upper Freeport, PA (all three bituminous), Beulah,
ND, and San Miguel, TX (both lignites) and Eagle Butte,
WY (subbituminous). The first four samples came from
the baghouse of Foster-Wheelers pilot-scale combustor.
The remaining two composite ashes came from full-scale
power plants in Colorado (Eagle Butte) and San Miguel
(Texas lignite). The combustor conditions, however, were
not available.

Table 1

Analyses

Proximate
Volatile

(wt% as-received)

analysis
matter

of parent

of ashes: S. Ghosal and S. A. Self

coals of fly ashes

Kentucky
No. 9

Illinois
No. 6

Upper
Freeport

Eagle
Butte

Beulah

San
Miguel

29.9

36.9

20.6

32.8

29.3

25.3

Ash

18.4

9.4

23.6

4.9

9.6

40.4

Moisture

12.1

12.2

3.2

31.2

30.2

20.3
23.1

Ultimate analysis
Carbon

58.2

61.3

62.5

41.3

41.3

Hydrogen

3.8

4.3

4.2

3.6

2.9

2.8

Oxygen

1.6

7.8

2.8

12.0

13.8

11.8

1.0

1.2

0.7

0.6

0.8

0.4

4.3

3.8

3.0

0.4

1.3

1.3

2.3

1.2

2.0

1.1

0.3

2.0

2.6

1.0

0.2

1.0

Nitrogen
Sulfur
Forms of sulfur
Pyritic
Organic
R. W. Bryers, personal

communication,

Table 2

(wt%) of slags by electron

Compositions

1987

microprobe

analysis

U. Freeport

Illinois

Kentucky

E. Butte

S. Miguel

Beulah

SiO,

51.36

49.39

47.19

28.53

64.61

30.81

Al@,

27.51

21.09

28.95

17.44

21.49

32.51

Fe@,

13.05

18.96

12.59

6.88

2.75

16.40

CaO

2.59

2.94

5.17

33.00

4.85

7.35

MgO

0.23

0.90

0.15

7.47

0.10

3.27

Na,O

0.53

1.44

2.27

1.76

3.34

6.49

K,O

3.16

2.17

2.24

0.00

1.80

1.45

TiO,

1.08

0.68

1.06

1.11

0.9 1

0.65

P*O,
BaO

0.40

0.19

0.25

0.27

0.03

0.38

0.08

1.58

0.12

2.50

0.12

0.60

Clb

0.02

0.64

0.00

1.04

0.01

0.02

SO,b

0.00

0.02

0.00

0.01

0.00

0.01

From ref. 9
b Most of the S and Cl volatilized

during

slag preparation

Fuel 1995 Volume 74 Number 4

523

Physical characterization

of ashes: S. Ghosal and S. A. Self

Density classljkation

The density classification followed the scheme of

Furuya et al.14. Separation liquids of density 1.6,
2.0, 2.4, 2.8 and 3.2 g cmm3 were created by mixing
carbon tetrachloride, dibromomethane and di-iodomethane
(density 1.594, 2.497 and 3.325 g cme3 respectively)
in appropriate proportionsg. A standard centrifugal
separation procedure l 5 was used, with some modifications
to improve accuracy. Relatively dilute ash suspensions
(-0.8 g in 40 ml of liquid) were initially deagglomerated
by ultrasonic agitation and gravitationally separated for
10min. The centrifuge speed was gradually increased
to - 2000 rev min- , which subjected the ash to an
acceleration of w 10009. These measures minimized the
carryover of smaller particles into the larger-sized and
lighter cenospheric fraction. Because the density of most
of the ash was expected to fall between 2 and 3 g cme3,
the liquid of density 2.4g cmm3 was used for initial
separation. Centrifugal separation was next performed
with the liquids of density 2.0 and 2.8 g cm-3 on the floats
and sinks respectively. Separation was carried out in this
manner for the other density classes. The reproducibility
of the separation process was within 3%.
Size analysis

Fly ash has an unusually broad size distribution, with

diameters spanning more than three orders of magnitude.
Hence it is important to measure the dispersion of
the size distribution (i.e. the standard deviation). In
general, size data available in the literature give only the
median diameters. Furthermore,
for calculations, a
suitable mathematical function is needed to describe the
size distribution.
The Coulter Multisizer is particularly suited for
accurate sizing of agglomerated powders, such as fly ash,
that are spherical and insulating, and whose density varies
from particle to particle. A detailed method for sizing
ashes is described elsewhere.
For each density class, the smallest possible Multisizer
orifice that was not clogged by the larger ash particles
in that class was used for sizing. Orifices of diameter 30,
50, 70, 100, 140 and 280pm were used, allowing
measurement of particle diameters in the range 1.2-180 pm.
For most classes, 100 000-200 000 particles were sampled
by the Multisizer in 334 min. For a few classes the mass
fraction of ash was small and the sample sizes were
restricted to 70 OO&lOO000 particles.
For effective deagglomeration, the ashes in the two
highest-density classes were demagnetized by placing a
coil carrying alternating current around a test tube of
ash and then slowly withdrawing the test tube from the
Table 3

coil. The ash particles were thus subjected to a rapidly

alternating magnetic field that gradually decreased to
zero. As a result the magnetic domains within the particles
were randomly orientated.
Determination of cenosphere content

The presence of cenospheres in fly ash was noted by

Raask5, who assumed that only those ash particles lighter
than water were cenospheric. However, among the oxides
typically present in fly ash, the lowest density (in the
pure state) is that of silica (2.2 and 2.28 gcme3 for
crystalline and fused forms respectively). Consequently,
the minimum density of a solid (non-cenospheric) ash
particle is in the range 2.2-2.28 g cm- 3. In particular,
ash particles with average density 52.2 g cmm3 can
be expected to contain significant voids. Hence the
cenospheric fraction was defined here as that having a
density ~2.2 gcme3. However, it is to be noted that
particles with density >2.2 g cmm3 may also contain
bubbles.
Centrifugal separation was carried out with liquid of
density 2.2 g cm - 3 on the six ashes to determine their
cenosphere contents.
RESULTS

AND DISCUSSION

Density classification

The results of the density classification are shown in

Table 3. All but two ashes have mass fractions of 2 80%

in the density range 2.0-2.8 g cme3, and average densities

in the range 2.1-2.4 gcmP3. Of the two prominent
exceptions, the Texas lignite fly ash from San Miguel has
90% of its mass in the first two classes and a negligible
fraction in the highest-density class. The low density
indicates that the ash is overwhelmingly cenospheric. The
other exception is the Eagle Butte ash, more than
two-thirds of which falls in the class 2.8-3.2 g cmm3. As
seen in Table 2, the reason for its relatively high density
is its high calcia content. (The density of lime is 3.4 g cm- 3,
but the effectivedensity of CaO in aluminosilicate glassi
is N 3.9 g cm- 3.)
Samples of Beulah and Eagle Butte ashes from
each density class, embedded in acrylic, were ground
and polished to expose sections of the ash particles.
Examination by scanning electron microscopy showed
that the first two classes (density < 2.0 g cm- 3, consisted
almost entirely of cenospheres. Small ash particles were
sometimes observed inside the voids of the cenospheres
(such particles are discussed later). Small amounts of char
were present in class 1; the total char content of each ash
was < 1 wt% as determined with a high-temperature

Density classification (wt%) of fly ashes

Class
Density (g cmm3)

1
<1.6

2
1.6-2.0

3
2.0-2.4

4
2.4-2.8

5
2.8-3.2

6
> 3.2

Density of
whole ash
(gcme3)

Kentucky No. 9

1.0

7.6

26.1

59.6

1.4

3.1

2.15

Illinios No. 6

1.2

7.2

42.8

42.0

2.8

4.0

2.12

1.3
0.5
0.2
35.6

6.1
0.2
2.1
52.9

27.0
3.5
10.2
7.0

57.0
21.4
16.3
3.5

2.4
68.5
8.9
1.0

5.6
5.9
2.3
0.0

2.29
2.16
2.31
1.73

Upper Freeport
Eagle Butte
Beulah
San Miguel

524

Fuel 1995 Volume 74 Number 4

Physical characterization

of ashes: S. Ghosal and S. A. Self

elemental analyser. In class 3, all the particles of diameter

> 15 pm are cenospheric. Few cenospheres are seen in
classes 4, 5 and 6.
The ash particles in classes 5 and 6 are darker than
the corresponding unseparated ashes. All the ash in
class 6, and a large fraction in class 5, is magnetic.
Energy-dispersive X-ray spectroscopy (SEM-EDS) of
20-30 particles of the two classes showed that they
contained high proportions of iron. A few particles
composed of >90 wt% iron oxide were noted. These
large, non-glassy particles consist primarily of magnetite
(Fe,O,) or haematite (Fe,O,) produced from combustion
of excluded pyrite grains I7 . However, most of the iron
in the ash (originating from included pyrites and other
iron containing minerals embedded in the coal particle)
is present in a glassy state in the aluminosilicate matrix,
as found in several studies7*8,18.The occurrence of a wide
range of iron fraction in the glassy ash may be predicted
from studies on slags formed under oxidizing and
reducing conditionslg.
For comparison with the density-classified ash, the
average density of the whole (unseparated) ash was
measured using a specific gravity bottle and distilled
water. Bubble formation was minimized by gradually
adding water to ash in the bottle with an eye-dropper.
The suspension was ultrasonically agitated to allow the
bubbles to rise to the surface and escape. Multiple
measurements yielded a precision of 1.5%. The results
are shown in the last column of Table 3. The average
density ranges from 1.73 g crnm3 (the highly cenospheric
San Miguel ash) to 2.76 gcmm3 (the high-calcia Eagle
Butte ash).
Size-density relation

The two-parameter log-normal function is often used

to represent broad particle size distributions.
A
modified form of the function, truncated outside the
measurement limits a and b, is used here, since no size
information is available outside (a, b)l. The differential
volume distribution is the fractional volume contributed
by particles with diameters within d(ln D), and is given by
_2:lna,r.P(

dF:,bD)
(
d(ln D) =

-l(zr]

Inb

s lna ./L

exp[ -kr$y]d(lnx)
In IT,
D

a6Ddb

(1)

In the limit a-+0 and b-+oo, the denominator +l and

the distribution shown in Equation (1) approaches the
standard form of the untruncated distribution.
Half the volume is due to particles with diameters
smaller than the median diameter, D,. The geometric
standard deviation, (TV,is a measure of the breadth of the
distribution. About 68% of the particles have diameters
between D,fo, and ogDv. A value of a,>2 indicates a
very broad distribution, whereas a closely monodisperse
powder has o,+l. Other quantities of interest such as
the number and area median diameters can be obtained
from D, and ggg.
The log-normal function (Equation (1)) was fitted to the
size data of all density classes for the six ashes. The size
parameters are listed in Table 4, but graphs of size
distributions are given here only for the Upper Freeport

Fuel 1995 Volume 74 Number 4

525

Physical characterization

of ashes: S. Ghosal and S. A. Self

0.8
0.6
8
I?

0.4

0.2

810

20

40

60

80 100

D WI

Figure 1 Cumulative volume distribution, F,(D), for all six density

classes of Upper Freeport ash. For clarity, only every twelfth datum
point is plotted. The lines show the best-fit log-normal functions

ash. The data for cumulative distribution by volume,

F,(D), are plotted in Figure 1 for all six size classes, with
the corresponding best-fit log-normal functions. The size
distributions of unseparated fly ashes are known to be
closely log-normal * , but it is interesting to find that the
size distributions of the density classified fractions too
are very well represented by log-normal functions. Classes
1 and 2 have smaller values of og than do the other
classes, indicating that cenospheres have narrower size
distributions than do non-cenospheric particles. The
exception is the San Miguel ash, which is almost entirely
cenospheric. The values of gB for most classes lie in the
range 1.2 c eBc 2.0. The unseparated ash encompasses all
diameter classes and has the highest eB (bottom row of
Table 4).

In the following discussion, a simplified model for a

cenosphere is considered: one consisting of a single
concentric bubble within the particle, and characterized
by the quantity R,, the ratio of the inner to the outer
diameter, which is assumed constant for all particles. In
reality, of course, the situation is far more complex,
with multiple (isolated or interconnected) voids that
may be non-concentric, with variable shell thickness.
Nevertheless, this simple model (after Raask5) can be
useful in characterizing the general nature of the
cenospheric fraction.
From Figure 2, it is seen that for all ashes, D, has a
V-shaped distribution when plotted as a function of
density (class). The lightest class (containing thin-walled
cenospheres with R, closest to unity) also has the
largest median diameter. The median diameter decreases
progressively to classes 2 and 3. Class 4, having the
smallest D, and containing no cenospheres, represents
the largest mass fraction for four of the ashes (although
for the Illinois No. 6 ash, the mass fractions in classes 3
and 4 are almost equal). The two exceptions are Eagle
Butte and San Miguel. The Eagle Butte ash, with its high
calcia content, has the smallest size and largest mass
fraction in class 5. The San Miguel ash, containing
95 wt% cenospheres, has the smallest D, in class 3, the
maximum mass fraction in class 2, and the average density
in class 1.
It is reasonable to expect the average density of each
ash (last column of Table 3) to belong to the class

526

Fuel 1995 Volume 74 Number 4

representing the highest mass fraction. However, it is

observed that the average density of each ash falls in the
class containing the second-highest mass fraction, which
is the density class just below that containing the highest
mass fraction. This skewness probably arises because the
median diameters in classes 1 and 2 are larger than those
in classes 5 and 6.
A possible mechanism of cenosphere formation is a
process similar to glass blowing, either when a molten
ash droplet on a char particle surface blocks a pore
emitting gas under pressure, or when gas is generated
within the ash particle during melting. If two molten ash
particles of comparable diameter are subjected unequally
to the blowing action, the particle that is blown more
will produce a cenosphere with a larger diameter, a
thinner wall (i.e. R,+l)
and a lower density. This
observation is borne out by the first three classes, where
the median diameter increases as the class number
decreases from 3 to 1.
A possible explanation for the relatively large sizes of
denser, iron-rich particles may lie in their formation
processes. Particles that are high in pyrite content do not
decrease in size as much as coal particles of average
mineral content. A larger mass fraction (i.e. the carbon)
of the latter type of coal particles is converted to gaseous
form during combustion, and the former type form more
ash.
For all the ashes except San Miguel, the class with the
largest mass fraction (class 5 for Eagle Butte, class 4 for
the rest) also has the smallest median diameter and is
closest in median diameter to the unseparated ash. The
ash particles in this class contain few bubbles and are
the most representative of the unseparated ash. Class 5
(2.8-3.2 g cm- 3, contains particles that are rich in iron
and other relatively heavy oxides (especially calcia for
the Eagle Butte ash, and alumina for the others). These
oxides are present in ash particles with a broad range of
diameters. Hence this class has the highest value of (r8,
with the exception of the Beulah ash.
It was found that the Fe,O, content obtained by
microanalysis of > 1000 individual ash particles was only
20-50% of that obtained by electron microprobe
measurements on slag made by melting the ash. The
100
80

2
a

ISo
40

0
0

Density Class
Figure 2 Distribution of volume median diameter, D,, of densityclassified ashes, as a function of density class

Physical characterization

reason for this discrepancy is that high-iron ash

particles and magnetite particles belong to density
classes 5 and 6, with significantly higher median
diameters, so they are fewer in number, and a sample
size of a few thousand particles is not statistically large
enough to detect sufficient numbers of such particles.
The location of the iron is especially important for optical
characterization, because iron plays an important role
in radiative transfer through its absorption in the
wavelength range l-4 ~m21,22.
Cenosphere content

The results of the determination of cenosphere contents

are shown in Table 5. The San Miguel ash is almost
entirely cenospheric, whereas the Eagle Butte ash have
very few cenospheres. The three bituminous coal ashes
have cenosphere contents of 14-24 wt%.
There are two sources of uncertainty in the method
used for determining cenosphere content. First, this
method does not encompass cenospheres with particle
density >2.2 g cme3. However, SEM examination of
sections of ash particles showed that only a small
fraction of the heavier ash particles (p>2.2 g cme3)
are cenospheric. Second, some of the smaller, noncenospheric ash particles are carried over into the

Table 5

Characterization

of cenosphere

content

(wt%) of fly ashes

Proportion
(wt%) of ash with
density (g cme3)

Kentucky No. 9
Illinois No. 6
Upper Freeport
Eagle Butte
Beulah
San Miguel
Cenosphere

< 2.2 (A)

2.O<p<2.2

19.3
14.6
23.9
3.6
7.7
96.9

10.7
6.2
15.9
2.9
5.4
8.4

(B)

55.4
42.5
66.5
80.6
70.1
8.7

content

0.012 F 1

B/A
(%)

of ashes: S. Ghosal and S. A. Self

lighter fraction during centrifugal separation, resulting in

overestimation of the cenosphere content and underestimation of D,. However, these two effects may cancel
each other out to some extent. For comparison, Casuccio
et a1.23 estimated the cenosphere content of fly ash
sampled from a coal-fired boiler at 32.6 wt %. Hemmings
and Berry24 noted that at least 50 wt% of the ashes they
studied (generated from coals of different rank) had
true-particle densities (i.e. average densities) less than
expected for solid materials of their composition.
In the simple concentric-sphere model of a cenosphere,
assume that the shell is made of material of the
non-cenospheric fraction (p ,2,2). If the average density
of the cenospheric fraction is pt2,2, it can be shown that
the diameter ratio is given by
Q3

l-Pt2.2
J

P22.2

For example,
measurements

for the Upper Freeport ash, density

show that p < 2,2= 2.01 g cme3 and
p,2.2 =2.36 g cme3. The resulting R,=0.53 shows that
the average wall thickness of a cenosphere is about half
its diameter. From the density classification data
(Tables 3 and 5), it is found that the ash fraction with
~~2.0 g cmm3 forms only 8 wt% of the whole. Thus
- 16 wt% of the ash (two-thirds of the cenospheres) have
a density between 2.0 and 2.2 g cm-j, i.e. with 5 10%
porosity. Similarly, for the other ashes it is seen from
Table 5 that a large fraction of the cenospheres
(-4&80%)
contains such small voids. Again the
prominent exception is the San Miguel ash, most of the
cenospheres in which are thin-walled.
The size distributions of both density fractions (above
and below 2.2 g cmm3) were measured with the Coulter
Multisizer for all the ashes except the San Miguel ash,
which was almost entirely cenospheric. Figure 3 shows
the volume distributions for the two fractions of the
Upper Freeport ash. Distributions for other ashes can
be found elsewhere. The distributions appear to be

I I I III

0.010

s 0.008

A
g 0.006

E!
m
%

0.006

0.004

0.004
0.002
0.002
0

Figure 3 Differential size distributions

of cenospheric
solid lines represent the best-fit lognormal functions

( < 2.2 g cmm3), and non-cenospheric

(>2.2 g cmm3) fractions

of Upper

Freeport

ash. The

Fuel 1995 Volume 74 Number 4

527

Physical characterization

of ashes: S. Ghosal and S. A. Self

Table 6 Size parameters for best-fit log-normal functions for

cenospheric and non-cenospheric (solid) ash fractions; D,, a and b in pm

Illinois No. 6
Kentucky No. 9
Upper Freeport
Eagle Butte
Beulah

>2.2

<2.2

Density (g cm-)

100

9
r
3

SO_

cg

(a, b)

D,

og

(a, b)

60 -

32.5
19.3
24.7
40.0
43.3

1.63
1.88
2.01
1.96
1.61

4.9,88.0
3.563.0
3.5,63.0
9.8J80.0
4.9, 88.0

13.7
8.4
7.7
14.4
13.4

3.40
2.10
2.41
3.21
2.17

1.7,33.0
1.7,33.0
1.7,33.0
1.7,33.0
3.563.0

8
u

Keatucky#9

0 Illinois#6
0

UpperFreeport

0 EagleButte
+ Beulah

011
lo1 I
0
10

20

30

40

I-I
50

Mineral Content (Mass %)

log-normal, and the parameters for the best-fit functions

for all the ashes (except San Miguel) are presented in
Table 6. It is seen that D, for the cenospheric fraction of
an ash is two to three times larger than that for the
non-cenospheric fraction.
A few large cenospheres with broken walls were
observed under the microscope to contain smaller
ash particles. Some investigator&l4 have referred to such
particles as plerospheres (Greek pleres, full). However,
it is difficult to conceive of processes that could
result in their direct formation. A simpler and more
plausible explanation is that the small particles filled the
cenospheres after their thin walls had been ruptured
during collection, storage or sample preparation. The
observations of Carpenter et a1.25 appear to support this
hypothesis. They crushed several large, low-density
ash particles in situ under an optical microscope. All
the particles contained voids, but none contained smaller
particles.
Further useful data (outside the scope of this work)
may be obtained from chemical analysis of the density
classes, and will contribute to better understanding of fly
ash formation. To the authors knowledge, such studies
are currently available for only two ashes7,s (though
without data on coal mineralogy). Some idea of the
chemical composition may however be obtained from
physical properties. For example, since the most dense
ash fractions are rich in oxides that are dense in their
pure states (CaO, Fe,O,, Al,O,), the lightest fractions
(cenospheres) will be poor in these oxides and hence
relatively rich in SiO, 8.
The fact that the cenospheric components contain
lower-than-average Fe,O, is apparent from their lighter
colour compared with the solid fraction for all the ashes.
This observation contradicts an earlier hypothesis that
the cenospheric fraction of an ash is positively correlated
with its iron oxide content. The present data show that
the San Miguel ash, with the lowest Fe,O, content, has
the highest cenosphere content. However, from Figure 4
it is clear that the cenosphere content is positively
correlated with the total ash content of the coal. This
relation suggests a significant role of the mineral matter,
as well as the mineral type (such as zeolites in the
Texas lignite coal, and illite2j in the Upper Freeport
coal), in the formation of cenospheres. The connection
between cenosphere formation and the mineralogy and
association of the minerals within the coal matrix needs
further investigation. Surface tension and viscosity of the
melt, and the transformation of the minerals during
combustion (e.g. gas generation during pyrolysis), are
expected to be important factors in cenosphere formation.

528

Fuel 1995

Volume

74 Number

Figure 4 Dependence of cenosphere content of fly ash on total mineral

content of coal. The line represents the best-fit quadratic polynomial
function

CONCLUSIONS
Density classification of six US coal ashes by centrifugal
separation shows that >80 wt% of four of them lies in
the density range 2.c2.8 g cme3. More than 95 wt% of
the San Miguel ash, which consists almost entirely of
cenospheres, is of density < 2.4 g cmm3, and more than
two-thirds of the high-calcium Eagle Butte ash is of
density 2.8-3.2 g cm - 3.
Truncated log-normal functions describe the size
distributions of the ashes very well. The median diameters
of the low-density (cenospheric) classes and the highdensity (rich in CaO, Fe,O, and Al,O,) classes are
considerably larger than that of the whole (unseparated)
ash.
The cenospheric fraction of the ash, defined as that of
density < 2 g cmm3, varies from < 5 wt% for Eagle Butte
to >95 wt% for San Miguel. The median diameter of
the cenospheric fraction is significantly larger (two- to
threefold) than that of the non-cenospheric fraction.
However, for some of the ashes, a considerable fraction
of the cenospheres contains only small bubbles (i.e. its
average density is 2.s2.2 g cm - 3).
Density classification of an ash is a useful technique
in optical characterization because the optical properties
(more specifically, the complex refractive index) of a fly
ash particle depend on its composition, and since density
and composition are correlated, this technique helps in
detecting the distribution of infrared-active oxides such
as Fe,O,.
The scattering and absorption characteristics of a fly
ash particle also depend on its geometry; hence the need
to quantify the cenospheric fraction. However, from
the standpoint of radiative properties, the effective
cenosphere content is somewhat lower than the measured
value because for particles of low porosity ( < 10 vol.%)
the radiation penetrating the particle will be absorbed
before it detects the presence of the bubble(s).
This study, together with complementary data, shows
that as much as half of the Fe,O, in the ash is
concentrated in large (D > 20 pm) spherical particles that
are relatively few in number and some of which are
non-glassy. Hence the influence of iron in radiative
transfer is less than if it is distributed more uniformly in
the ash.
The cenosphere content of an ash is directly related to
the total ash content of the coal.

Physical characterization

ACKNOWLEDGEMENTS

12

This work was supported by US DOE contract number

DE-AC22-87PC 79903. The authors would like to thank
Rod Leach for his help in centrifugal separation, and
Jon Ebert for several helpful discussions.

13

14

of ashes: S. Ghosal and S. A. Self

Ghosal, S., Ebert, J. L. and Self, S. A. Particle Particle Syst.

Charuct. 1993, 10, 11
PSI Technology Company, Transformation of Inorganic Coal
Constituents in Combustion Systems, Vols 1 and 2, Phase 1,
Final Report to Pittsburgh Energy Technology Research Center,
US DOE, Pittsburgh, 1990
Furuya, K., Miyajima, Y., Chiba, T. and Kikuchi, T. Environ.
Sci. Technol. 1987, 21, 898

15

16

REFERENCES
1

Loehden, D., Walsh, P. M., Sayre, A. N., Beer, J. M. and

Sarofim, A. F. In Mineral Matter and Ash Deposition in Coal
(Eds
R. W. Brvers
K. S. Vorresh Enaineerina Foundation
Conferences,
1990, and
p. 279
I

17

18

10

11

Baxter, L. L. Prog. Energy Cornbust. Sci. 1990, 16, 261

Ramsden, A. R. and Shibaoka, M. Armos. Enuiron. 1982,16,2191
Del Monte, M. and Sabbioni, C. Arch. Meteorol. Geophys.

19

Bioclimatol. 1984, 35, 93

20

Raask, E. J. Inst. Fuel 1968, 43, 339

Fisher, G. L., Prentice, B. A., Silberman, D., Ondov, J. M.,
Biermann. A. H.. Ragaini. R. C. and McFarland. A. R. Environ.
Sci. Technol. 1978, 112,447
Hemmings, R. T. and Berry, E. E. Mater. Res. Sot. Symp. Proc.
1986,65, 91
Hemmings, R. T., Berry, E. E., Cornelius, B. J. and Scheetz B. E.
Mater. Res. Sot. Symp. Proc. 1987,86,81
Ghosal, S. Optical Characterization of Coal Fly Ashes and
Infrared Extinction Measurements on Ash Dispersions, Ph.D.
Dissertation, Stanford University, 1993
Flagan, R. C. and Friedlander, S. K. In Recent Developments
in Aerosol Science (Ed. D. T. Shaw), Wiley, New York. 1978,
p. 25
Holve, D. J. Combust. Sci. Techrrol. 1986. 44, 269

Browning, J. S. Heavy Liquids and Procedures for Laboratory

Separation of Minerals, Information Circular 8007, US Bureau
of Mines, 1961
Volf, M. B. Mathematical Approach to Glass, Elsevier, 1988
(containing data from Appen, A. A. Khimiya Stekla, Izd.
Khimiya, Leningrad, 1970)
Srinivasachar, S., Helble, J. J. and Boni, A. A. Prog. Energy
Combusr. Sci. 1990, 16, 281
Qian, J. C., Lachowski, E. E. and Glasser, F. P. Mater. Res.
Sot. Symp. Proc. 1989, 136, 77

21

Huffman, G. P., Huggins, F. E. and Dunmyre, G. R. Fuel 1981,

60, 585
Crow, E. L. and Shimizu, K. Lognormal Distributions, Dekker,
New York, 1988
Goodwin, D. G. and Mitchner, M. AIAA J. Thermophys. Heat
Transfer 1989, 3, 53

22

23

Ghosal, S. and Self, S. A. In Radiative Transfer-Theory

and
Applications (Eds A. M. Smith and S. H. Chan), HTD Vol. 244,
American Society of Mechanical Engineers, p. 105
Casuccio. G. S.. Janocko. P. B.. Lee. R. J.. Kellv. J. F..
Dattner, S. L. and Mgebroff. J. S. J. Air Pollut. Corlirol Ass:
1983, 33. 937

24
25

Hemmings, R. T. and Berry, E. F. Muter. Res. SW. Symp. Proc.

1988, 113. 3
Carpenter, R. L., Clark, R. D. and Su, Y. F. J. Air Pollut. Control
.4ss. 1980. 30, 679

26

Hubbard, F. H.. McGill, R. J., Dhir, R. K. and Ellis, M. S. Min.

Mtrg. 1984. 48, 251

Fuel 1995 Volume 74 Number 4

529