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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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45 0.3 1.40 0. P*O.88 33.02 0.6 23.2 25.25 0.24 1.08 0.8 1. 6.6 3. 6 ashes had the highest iron oxide content (16-19 wt%).06 0.85 0. Chemical analyses of the coals and the ashes are given in Tables I and 2 respectively.11 0. This coal from the Powder River Basin is known to contain much organically associated calcium.0.58 0.6 20.49 1.6 30.5 4. W.04 0.4 20.64 0.b 51. because the mass ratios of baghouse to cyclone ashes were not available.3 1. Kentucky No.Physical characterization of ashes: S.19 1. The Eagle Butte subbituminous coal ash had an unusually high calcia content (CaO:SiO.19 28.53 17. were not available. 9 Proximate Volatile Ash Moisture Ultimate analysis Carbon Hydrogen Oxygen Nitrogen Sulfur Forms of sulfur Pyritic Organic ” R.75 4.8 11.27 6. Freeport SiO. The coals were Illinois No. The ashes showed no detectable solubility in water.61 21. personal analysis matter Beulah 29.03 0. ND.3 2.3 4.7 3.O.2 41.90 1. BaO Clb SO. the ashes could not be reconstituted. PA (all three bituminous).50 1.47 1.15 2.2 41.02 0.60 0.3 23.10 3. However.2 3. the cyclone ash was found to be quite similar to the baghouse ash for each coa19.4 12. Upper Freeport.00 ’ From ref.12 0. Beulah. Self size distribution measurements of each of the density classes with the Coulter Multisizer. TX (both lignites) and Eagle Butte.3 0. A.00 E. Their properties. An estimate is made of the total cenosphere content of the ash by density classification.95 12.9 31. Bryers. Miguel 64.1 2.8 1.1 58.8 0. For the Foster-Wheeler ashes. and the SiO.53 3.8 4.49 2. Except for a slightly different size distribution.96 2. 9.:A1./Al.17 0. The remaining two composite ashes came from full-scale power plants in Colorado (Eagle Butte) and San Miguel (Texas lignite).81 32.4 1.01 0.3 2.38 0. The first four samples came from the baghouse of Foster-Wheeler’ s pilot-scale combustor.36 27. Fe@.27 2. 1987 36.51 16. WY (subbituminous). The silica contents of the three bituminous coal ashes were .59 0.3 40. however. EXPERIMENTAL Fly ash samples The ashes originated from coals typical of those burned in US power plants.8 0.0 2.00 7. The SiOJAl. Ghosal and S.00 1.05 2.2 2. The San Miguel lignite ash was rich in silica (65 wt%).59 5.9 18.27 2. have been studied extensively13. ratio for the Beulah lignite slag was close to unity.94 0.01 U. The average ash compositions were obtained by electron microprobe measurements on slags produced by melting 40-50g of each ash.8 1. Table 1 Analyses (wt% as-received) of parent coals of fly ashes” Illinois No.9 13.6 1.34 1.23 0.O K. the fractions collected in the cyclone were also supplied. Butte 28.9 1 0.0 1.2 2.4 _ _ 29.12 0.35 3.4 12.0 32.68 0.3 3.0 communication.3 9.3 2.00 Beulah 30. and the size distributions of the two components are reported for each ash.0 4. The parameters for the best-fit log-normal functions to the size data are tabulated for all density classes.02 1. including mineral transformation during combustion.6 0.9 9.8 1.01 S.O TiO.6 12. 9 b Most of the S and Cl volatilized during slag preparation Fuel 1995 Volume 74 Number 4 523 .3 7.16 Illinois 49.0 0. It is seen that Beulah and Illinois No. Al@.8 0.44 6. CaO MgO Na.80 0.2 62.1 0.51 13.17 0. ratio was -2:l. The combustor conditions.O. and hence the measurements described here were made only on the baghouse ashes.50 wt%.0 Table 2 Compositions (wt%) of slags by electron microprobe analysis” Kentucky 47.76 0.65 0.00 0.39 21.08 0. 6 Upper Freeport Eagle Butte San Miguel Kentucky No.2 3. and San Miguel.2 61.40 7.44 2.09 18.=33:29:17).

5 10.8-3.1 42. For effective deagglomeration. the lowest density (in the pure state) is that of silica (2. The ash particles were thus subjected to a rapidly alternating magnetic field that gradually decreased to zero. A detailed method for sizing ashes is described elsewhere”.‘ acceleration of w 10009.4-2.0 6 > 3. more than two-thirds of which falls in the class 2. the liquid of density 2. Examination by scanning electron microscopy showed that the first two classes (density < 2. For a few classes the mass fraction of ash was small and the sample sizes were restricted to 70 OO&lOO000 particles.6 1. Self The density classification followed the scheme of Furuya et al. Separation was carried out in this manner for the other density classes.9 g cm. 2.4.1 4. embedded in acrylic.3 0.2 7.0 5. As seen in Table 2. 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.) Samples of Beulah and Eagle Butte ashes from each density class. dibromomethane and di-iodomethane (density 1. The reproducibility of the separation process was within 3%. A.28 gcme3 for crystalline and fused forms respectively).5 8. The other exception is the Eagle Butte ash.8 g in 40 ml of liquid) were initially deagglomerated by ultrasonic agitation and gravitationally separated for 10min. which subjected the ash to an to .4 16.73 524 Fuel 1995 Volume 74 Number 4 . In general.2 g cmm3 were created by mixing carbon tetrachloride.2000 rev min.0 and 2. 2.2 1. 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 <1.2-2. who assumed that only those ash particles lighter than water were cenospheric.8 g cm-3 on the floats and sinks respectively.8-3. Hence it is important to measure the dispersion of the size distribution (i.4 26. and average densities in the range 2. In particular. Consequently.4g cmm3 was used for initial separation.0 21.9 3 2. As a result the magnetic domains within the particles were randomly orientated. such as fly ash. Centrifugal separation was carried out with liquid of density 2.0-2.31 1.3 3. the minimum density of a solid (non-cenospheric) ash particle is in the range 2. 2.5 5 2. for calculations. among the oxides typically present in fly ash. Of the two prominent exceptions.6. 100. and whose density varies from particle to particle.29 2.0 57.0 Density classification The results of the density classification are shown in Table 3. Furthermore. Small ash particles were sometimes observed inside the voids of the cenospheres (such particles are discussed later).6 2 1.0 1.3.594.0-2. that are spherical and insulating.2 35.2 gcme3. 50.12 2.3 0.1 52.3.2 g cmm3 can be expected to contain significant voids.9 1. Ghosal and S. 2.5 0.2 6.3 on the six ashes to determine their cenosphere contents. 9 Illinios No. a suitable mathematical function is needed to describe the size distribution.4 2. allowing measurement of particle diameters in the range 1. Orifices of diameter 30. The Coulter Multisizer is particularly suited for accurate sizing of agglomerated powders.2-180 pm.16 2.9 2.2 g cmm3. Because the density of most of the ash was expected to fall between 2 and 3 g cme3.3.28 g cm. were ground and polished to expose sections of the ash particles.Physical characterization Density classljkation of ashes: S. These measures minimized the carryover of smaller particles into the larger-sized and lighter cenospheric fraction.2 1.1 0.1-2.6 7.0 3. All but two ashes have mass fractions of 2 80% in the density range 2.8 g cme3.4 g cm.2 g cmm3 may also contain bubbles. Separation liquids of density 1.8 2. the reason for its relatively high density is its high calcia content. A standard centrifugal separation procedure l 5 was used.0 g cm. it is to be noted that particles with density >2.0. The centrifuge speed was gradually increased .8 59.4 68. For each density class. However.3. 70. 100 000-200 000 particles were sampled by the Multisizer in 334 min.8 and 3.2 g cm .6 42.2 3. with diameters spanning more than three orders of magnitude.15 2.8 27.0 7.2 2. Centrifugal separation was next performed with the liquids of density 2. Relatively dilute ash suspensions (-0. with some modifications to improve accuracy.14. size data available in the literature give only the median diameters.6-2. 6 Upper Freeport Eagle Butte Beulah San Miguel 4 2. the total char content of each ash was < 1 wt% as determined with a high-temperature Class Density (g cmm3) Kentucky No. (The density of lime is 3. Determination of cenosphere content The presence of cenospheres in fly ash was noted by Raask5. Hence the cenospheric fraction was defined here as that having a density ~2. However. Size analysis coil. the standard deviation).0 Density of whole ash (gcme3) 2.325 g cme3 respectively) in appropriate proportionsg. ash particles with average density 52. the smallest possible Multisizer orifice that was not clogged by the larger ash particles in that class was used for sizing. For most classes.6 5. but the ‘ effective’density of CaO in aluminosilicate glassi is N 3. consisted almost entirely of cenospheres.e. 140 and 280pm were used. The low density indicates that the ash is overwhelmingly cenospheric.4 gcmP3.2 and 2. RESULTS AND DISCUSSION Fly ash has an unusually broad size distribution. Small amounts of char were present in class 1.497 and 3.

(TV. and is given by dF:“. the denominator +l and the distribution shown in Equation (1) approaches the standard form of the untruncated distribution. A value of a. A few particles composed of >90 wt% iron oxide were noted. and ogDv. A modified form of the function. Self elemental analyser. non-glassy particles consist primarily of magnetite (Fe. D. The size parameters are listed in Table 4. A. is a measure of the breadth of the distribution. b)l’ volume distribution is the fractional volume contributed by particles with diameters within d(ln D). and ggg. is magnetic.) produced from combustion of excluded pyrite grains I7 .18. Half the volume is due to particles with diameters smaller than the median diameter. 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. Bubble formation was minimized by gradually adding water to ash in the bottle with an eye-dropper. 5 and 6.+l. The geometric standard deviation.76 gcmm3 (the high-calcia Eagle Butte ash).>2 indicates a very broad distribution. The log-normal function (Equation (1)) was fitted to the size data of all density classes for the six ashes.Physical characterization of ashes: S. Ghosal and S. In class 3. Other quantities of interest such as the number and area median diameters can be obtained from D.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. as found in several studies7*8. Few cenospheres are seen in classes 4. The differential information is available outside (a. all the particles of diameter > 15 pm are cenospheric.) or haematite (Fe.. The results are shown in the last column of Table 3.b’ D) ( d(ln D) = Inb _2:lna. since no size . All the ash in class 6. The average density ranges from 1.O. These large. Multiple measurements yielded a precision of 1.fo. For comparison with the density-classified ash. but graphs of size distributions are given here only for the Upper Freeport Fuel 1995 Volume 74 Number 4 525 ./L exp[ -kr$y]d(lnx) In IT. Size-density relation The two-parameter log-normal function is often used to represent broad particle size distributions”. and a large fraction in class 5. whereas a closely monodisperse powder has o.r. The ash particles in classes 5 and 6 are darker than the corresponding unseparated ashes. truncated outside the measurement limits a and b. Energy-dispersive X-ray spectroscopy (SEM-EDS) of 20-30 particles of the two classes showed that they contained high proportions of iron.73 g crnm3 (the highly cenospheric San Miguel ash) to 2.O. The suspension was ultrasonically agitated to allow the bubbles to rise to the surface and escape. is used here. However. the average density of the whole (unseparated) ash was measured using a specific gravity bottle and distilled water. About 68% of the particles have diameters between D.P( -l(zr] 1 ” s lna . D a6Ddb (1) In the limit a-+0 and b-+oo.5%.

+l) and a lower density. A possible explanation for the relatively large sizes of denser. The exception is the San Miguel ash. the particle that is ‘ blown’ more will produce a cenosphere with a larger diameter. These oxides are present in ash particles with a broad range of diameters. For clarity. It was found that the Fe. For all the ashes except San Miguel.2 c eBc 2. it is seen that for all ashes. A. However. this simple model (after Raask5) can be useful in characterizing the general nature of the cenospheric fraction. the maximum mass fraction in class 2. The lightest class (containing thin-walled cenospheres with R. has a V-shaped distribution when plotted as a function of density (class). If two molten ash particles of comparable diameter are subjected unequally to the blowing action. Hence this class has the highest value of (r8. a simplified model for a cenosphere is considered: one consisting of a single concentric bubble within the particle. containing 95 wt% cenospheres. In the following discussion.e. has the smallest D. This skewness probably arises because the median diameters in classes 1 and 2 are larger than those in classes 5 and 6.8 0. and the former type form more ash. but it is interesting to find that the size distributions of the density classified fractions too are very well represented by log-normal functions.e. closest to unity) also has the largest median diameter. which is assumed constant for all particles. and containing no cenospheres. D. the situation is far more complex.4 0. The median diameter decreases progressively to classes 2 and 3. with the corresponding best-fit log-normal functions. The unseparated ash encompasses all diameter classes and has the highest eB (bottom row of Table 4). The 100 80 2 a’ ISo 40 0 0 1 2 3 4 5 6 I Density Class Figure 2 Distribution of volume median diameter. it is observed that the average density of each ash falls in the class containing the second-highest mass fraction. the ratio of the inner to the outer diameter. The data for cumulative distribution by volume. as a function of density class 526 Fuel 1995 Volume 74 Number 4 . with its high calcia content. Self 0. and characterized by the quantity R. Nevertheless.(D). Ghosal and S. are plotted in Figure 1 for all six size classes. the class with the largest mass fraction (class 5 for Eagle Butte. The values of gB for most classes lie in the range 1.0. the carbon) of the latter type of coal particles is converted to gaseous form during combustion. and alumina for the others). The two exceptions are Eagle Butte and San Miguel. Particles that are high in pyrite content do not decrease in size as much as coal particles of average mineral content. the mass fractions in classes 3 and 4 are almost equal).. D. and the average density in class 1. F. only every twelfth datum point is plotted. has the smallest size and largest mass fraction in class 5. The lines show the best-fit log-normal functions ash. with multiple (isolated or interconnected) voids that may be non-concentric. 6 ash. The ash particles in this class contain few bubbles and are the most representative of the unseparated ash. a thinner wall (i. The San Miguel ash. of course. or when gas is generated within the ash particle during melting. iron-rich particles may lie in their formation processes.6 8 I? 0. 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. R. The size distributions of unseparated fly ashes are known to be closely log-normal ‘ * . In reality. Classes 1 and 2 have smaller values of og than do the other classes.O. class 4 for the rest) also has the smallest median diameter and is closest in median diameter to the unseparated ash. which is the density class just below that containing the highest mass fraction. either when a molten ash droplet on a char particle surface blocks a pore emitting gas under pressure. with the exception of the Beulah ash. represents the largest mass fraction for four of the ashes (although for the Illinois No. F. A possible mechanism of cenosphere formation is a process similar to glass blowing. of densityclassified ashes. having the smallest D. for all six density classes of Upper Freeport ash. Class 4. A larger mass fraction (i. where the median diameter increases as the class number decreases from 3 to 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. This observation is borne out by the first three classes.Physical characterization of ashes: S. From Figure 2. indicating that cenospheres have narrower size distributions than do non-cenospheric particles.2 g cm..3. The Eagle Butte ash. contains particles that are rich in iron and other relatively heavy oxides (especially calcia for the Eagle Butte ash. which is almost entirely cenospheric. in class 3. Class 5 (2. with variable shell thickness.(D).8-3.2 0 1 2 4 6 810 D WI 20 40 60 80 100 Figure 1 Cumulative volume distribution.

004 E! m % 0.2 15. 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. and a sample size of a few thousand particles is not statistically large enough to detect sufficient numbers of such particles’ . noncenospheric ash particles are carried over into the lighter fraction during centrifugal separation. A.2.9 3. Again the prominent exception is the San Miguel ash.2 g cme3) are cenospheric. However.2= 2.4 (B) B/A (%) 55.Physical characterization of ashes: S.6 7.e. resulting in overestimation of the cenosphere content and underestimation of D.1 8. whereas the Eagle Butte ash have very few cenospheres. with significantly higher median diameters. density show that p < 2. First. because iron plays an important role in radiative transfer through its absorption in the wavelength range l-4 ~m21. Cenosphere content The results of the determination of cenosphere contents are shown in Table 5.2 g cmm3).002 0.23 estimated the cenosphere content of fly ash sampled from a coal-fired boiler at 32.2.36 g cme3.4 42.5 80.7 for the Upper Freeport ash. However.6 wt %.2 g cm-j. so they are fewer in number.. The size distributions of both density fractions (above and below 2. average densities) less than expected for solid materials of their composition. and non-cenospheric (>2.e.01 g cme3 and p. 6 Upper Freeport Eagle Butte Beulah San Miguel “Cenosphere content 19.9 5.7 96. it is found that the ash fraction with ~~2. Figure 3 shows the volume distributions for the two fractions of the Upper Freeport ash.2 =2. 9 Illinois No.002 0 0 Figure 3 Differential size distributions of cenospheric solid lines represent the best-fit lognormal functions ( < 2. There are two sources of uncertainty in the method used for determining cenosphere content. assume that the shell is made of material of the non-cenospheric fraction (p .=0.2 g cme3.2 g cmm3) fractions of Upper Freeport ash. i. with 5 10% porosity. some of the smaller.9 2.008 0.2). The three bituminous coal ashes have cenosphere contents of 14-24 wt%. Casuccio et a1.2 P22. measurements 0.2 Table 5 Characterization of cenosphere content (wt%) of fly ashes Proportion (wt%) of ash with density (g cme3) < 2. for the other ashes it is seen from Table 5 that a large fraction of the cenospheres (-4&80%) contains such small voids.6 70.010 I I I III” A g 0. For comparison.16 wt% of the ash (two-thirds of the cenospheres) have a density between 2.0 and 2.7 6.6 23. these two effects may cancel each other out to some extent. The San Miguel ash is almost entirely cenospheric.006 0. If the average density of the cenospheric fraction is pt2. SEM examination of sections of ash particles showed that only a small fraction of the heavier ash particles (p>2. Second. The Fuel 1995 Volume 74 Number 4 527 .3 14. Distributions for other ashes can be found elsewhere’ .9 2.006 s 0.O<p<2.012 F ’ ’ ’ ’ ’’1 0.22.2 10. this method does not encompass cenospheres with particle density >2.2 g cmm3) were measured with the Coulter Multisizer for all the ashes except the San Miguel ash.4 8.0 g cmm3 forms only 8 wt% of the whole. Ghosal and S. most of the cenospheres in which are thin-walled. it can be shown that the diameter ratio is given by Q3 J l-Pt2. The resulting R.5 66. The location of the iron is especially important for optical characterization. which was almost entirely cenospheric. In the simple concentric-sphere model of a cenosphere. Similarly. Thus .53 shows that the average wall thickness of a cenosphere is about half its diameter.2 (A) Kentucky No. Self reason for this discrepancy is that high-iron ash particles and magnetite particles belong to density classes 5 and 6.004 0. From the density classification data (Tables 3 and 5). The distributions appear to be For example.2.

Ghosal and S.O. 8.7.2 og 3.33. The median diameter of the cenospheric fraction is significantly larger (two.88 2.2 g cm . since the most dense ash fractions are rich in oxides that are dense in their pure states (CaO. The cenospheric fraction of the ash.) classes are considerably larger than that of the whole (unseparated) ash.to threefold) than that of the non-cenospheric fraction.O. together with complementary data’ . Fe.01 1. This observation contradicts an earlier hypothesis’ that the cenospheric fraction of an ash is positively correlated with its iron oxide content.4 >2. This relation suggests a significant role of the mineral matter. 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.0 1. To the authors’ knowledge.0 3.. varies from < 5 wt% for Eagle Butte to >95 wt% for San Miguel. 6 Kentucky No. Some investigator&l4 have referred to such particles as plerospheres (Greek pleres. but none contained smaller particles. and the parameters for the best-fit functions for all the ashes (except San Miguel) are presented in Table 6. Fe.5.33. 88. 13. The fact that the cenospheric components contain lower-than-average Fe. For example.2 (a. However.2 g cm .7 40. b) 4. The observations of Carpenter et a1.3 24. is apparent from their lighter colour compared with the solid fraction for all the ashes.O.. and will contribute to better understanding of fly ash formation.0 43.0 D.0 4. The cenosphere content of an ash is directly related to the total ash content of the coal. A few large cenospheres with broken walls were observed under the microscope to contain smaller ash particles. full). this technique helps in detecting the distribution of infrared-active oxides such as Fe. gas generation during pyrolysis).563. The connection between cenosphere formation and the mineralogy and association of the minerals within the coal matrix needs further investigation. v ” 20 ” ” ” ’ ” ’ 30 ” 40 ” I-I 50 Mineral Content (Mass %) Figure 4 Dependence of cenosphere content of fly ash on total mineral content of coal.33.). However. which consists almost entirely of cenospheres.c2.8 g cme3.7.0 1. hence the need to quantify the cenospheric fraction. More than 95 wt% of the San Miguel ash. and the transformation of the minerals during combustion (e. and Al. Self 100 Table 6 Size parameters for best-fit log-normal functions for cenospheric and non-cenospheric (solid) ash fractions.O. They crushed several large.0 9.33.0 9 r 3 B - 0 Keatucky#9 UpperFreeport SO_ - 0 Illinois#6 0 g 8 u 60 I 0 EagleButte + Beulah 011 lo1” ’ I 0 10 log-normal.96 1.O. for some of the ashes. low-density ash particles in situ under an optical microscope. 9 Upper Freeport Eagle Butte Beulah 32.25 appear to support this hypothesis. defined as that of density < 2 g cmm3. Further useful data (outside the scope of this work) may be obtained from chemical analysis of the density classes. such studies are currently available for only two ashes7. Some idea of the chemical composition may however be obtained from physical properties. b) 1.7. shows that as much as half of the Fe.0 3.O. content. Density classification of an ash is a useful technique in optical characterization because the optical properties (more specifically. is of density < 2. All the particles contained voids.63.0 1.. It is seen that D. D.3. has the highest cenosphere content. Hence the influence of iron in radiative transfer is less than if it is distributed more uniformly in the ash.17 (a.8J80. and illite2’ j in the Upper Freeport coal).O.40 2.4 7. However.3 cg 1. the complex refractive index) of a fly ash particle depend on its composition.5 19. A simpler and more plausible explanation is that the small particles filled the cenospheres after their thin walls had been ruptured during collection. 528 Fuel 1995 Volume 74 Number 4 . from the standpoint of radiative properties. This study. the effective cenosphere content is somewhat lower than the measured value because for particles of low porosity ( < 10 vol. However. The scattering and absorption characteristics of a fly ash particle also depend on its geometry. it is difficult to conceive of processes that could result in their direct formation. are expected to be important factors in cenosphere formation. a and b in pm Density (g cm-‘ ) D” Illinois No.4 g cmm3.9.61 <2.7 8. the lightest fractions (cenospheres) will be poor in these oxides and hence relatively rich in SiO. its average density is 2.s (though without data on coal mineralogy).Physical characterization of ashes: S. 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. The median diameters of the low-density (cenospheric) classes and the highdensity (rich in CaO.%) the radiation penetrating the particle will be absorbed before it detects the presence of the bubble(s). with the lowest Fe.21 2.s2.O.10 2.4 13. as well as the mineral type (such as zeolites in the Texas lignite coal. Al.8-3.g. a considerable fraction of the cenospheres contains only small bubbles (i. Truncated log-normal functions describe the size distributions of the ashes very well.63 1.3). in the formation of cenospheres.e.9.7 14.0 3. from Figure 4 it is clear that the cenosphere content is positively correlated with the total ash content of the coal.88. and since density and composition are correlated. and more than two-thirds of the high-calcium Eagle Butte ash is of density 2.41 3. Surface tension and viscosity of the melt. storage or sample preparation.563. The present data show that the San Miguel ash.7. for the cenospheric fraction of an ash is two to three times larger than that for the non-cenospheric fraction. A.

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