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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
of Mechanical Engineering,

High Temperature Gasdynamics Laboratory, Department Stanford University, Stanford, CA 94305, USA (Received 14 February 1994; revised 4 May 1994)

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, Lexington, KY 40506, USA 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

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Volume

74 Number

Physical characterization

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

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. 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-Wheeler s 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.

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.

Table 1

Analyses

(wt% as-received)

of parent

coals of fly ashes Illinois No. 6 Upper Freeport Eagle Butte San Miguel

Kentucky No. 9 Proximate Volatile Ash Moisture Ultimate analysis Carbon Hydrogen Oxygen Nitrogen Sulfur Forms of sulfur Pyritic Organic R. W. Bryers, personal analysis matter

Beulah

29.9 18.4 12.1 58.2 3.8 1.6 1.0 4.3 2.3 2.0 communication, 1987

36.9 9.4 12.2 61.3 4.3 7.8 1.2 3.8 1.2 2.6

20.6 23.6 3.2 62.5 4.2 2.8 0.7 3.0 2.0 1.0

32.8 4.9 31.2 41.3 3.6 12.0 0.6 0.4 _ _

29.3 9.6 30.2 41.3 2.9 13.8 0.8 1.3 1.1 0.2

25.3 40.4 20.3 23.1 2.8 11.8 0.4 1.3 0.3 1.0

Table 2

Compositions

(wt%) of slags by electron

microprobe

analysis Kentucky 47.19 28.95 12.59 5.17 0.15 2.27 2.24 1.06 0.25 0.12 0.00 0.00 E. Butte 28.53 17.44 6.88 33.00 7.47 1.76 0.00 1.11 0.27 2.50 1.04 0.01 S. Miguel 64.61 21.49 2.75 4.85 0.10 3.34 1.80 0.9 1 0.03 0.12 0.01 0.00 Beulah 30.81 32.51 16.40 7.35 3.27 6.49 1.45 0.65 0.38 0.60 0.02 0.01

U. Freeport SiO, Al@, Fe@, CaO MgO Na,O K,O TiO, P*O, BaO Clb SO,b 51.36 27.51 13.05 2.59 0.23 0.53 3.16

Illinois 49.39 21.09 18.96 2.94 0.90 1.44 2.17 0.68 0.19 1.58 0.64 0.02

1.08
0.40 0.08 0.02 0.00

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

during

slag preparation

Fuel 1995 Volume 74 Number 4

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Physical characterization Density classljkation

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

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 , which subjected the ash to an to - 2000 rev min- 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

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

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 Density classification (wt%) of fly ashes 1 <1.6 1.0 1.2 1.3 0.5 0.2 35.6 2 1.6-2.0 7.6 7.2 6.1 0.2 2.1 52.9 3 2.0-2.4 26.1 42.8 27.0 3.5 10.2 7.0

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

Class Density (g cmm3) Kentucky No. 9 Illinios No. 6 Upper Freeport Eagle Butte Beulah San Miguel

4 2.4-2.8 59.6 42.0 57.0 21.4 16.3 3.5

5 2.8-3.2 1.4 2.8 2.4 68.5 8.9 1.0

6 > 3.2 3.1 4.0 5.6 5.9 2.3 0.0

Density of whole ash (gcme3) 2.15 2.12 2.29 2.16 2.31 1.73

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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 . The differential information is available outside (a, b)l volume distribution is the fractional volume contributed by particles with diameters within d(ln D), and is given by dF:,b D) ( d(ln D) =
Inb _2:lna,r.P( -l(zr]

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

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Physical characterization

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

0.8
0.6 8 I?

0.4

0.2

810 D WI

20

40

60

80 100

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

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

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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

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 J l-Pt2.2 P22.2

Table 5

Characterization

of cenosphere

content

(wt%) of fly ashes

Proportion (wt%) of ash with density (g cme3) < 2.2 (A) Kentucky No. 9 Illinois No. 6 Upper Freeport Eagle Butte Beulah San Miguel Cenosphere content 19.3 14.6 23.9 3.6 7.7 96.9 2.O<p<2.2 10.7 6.2 15.9 2.9 5.4 8.4 (B) B/A (%) 55.4 42.5 66.5 80.6 70.1 8.7

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

For example, measurements

0.012 F 1 0.010

I I I III

A g 0.006

s 0.008
0.004

0.006

0.004

E! m
%

0.002 0.002 0 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

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100

Table 6 Size parameters for best-fit log-normal functions for cenospheric and non-cenospheric (solid) ash fractions; D,, a and b in pm Density (g cm- ) D Illinois No. 6 Kentucky No. 9 Upper Freeport Eagle Butte Beulah 32.5 19.3 24.7 40.0 43.3 cg 1.63 1.88 2.01 1.96 1.61 <2.2 (a, b) 4.9,88.0 3.563.0 3.5,63.0 9.8J80.0 4.9, 88.0 D, 13.7 8.4 7.7 14.4 13.4 >2.2 og 3.40 2.10 2.41 3.21 2.17 (a, b) 1.7,33.0 1.7,33.0 1.7,33.0 1.7,33.0 3.563.0

9 r 3
B

Keatucky#9 UpperFreeport

SO_
-

0 Illinois#6
0

g 8 u

60 I

0 EagleButte + Beulah

011 lo1 I 0 10
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 illite2 j 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.

20

30

40

I-I 50

Mineral Content (Mass %) 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.

528

Fuel 1995

Volume

74 Number

Physical characterization

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

ACKNOWLEDGEMENTS 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.

12 13

14 15

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