2112 Energy & Fuels 2007, 21, 2112-2120

Characteristics of Fly Ashes from Full-Scale Coal-Fired Power

Plants and Their Relationship to Mercury Adsorption
Yongqi Lu,† Massoud Rostam-Abadi,*,†,‡ Ramsay Chang,*,§ Carl Richardson,| and
Jennifer Paradis|
Illinois State Geological SurVey, 615 East Peabody DriVe, Champaign, Illinois 61820, Department of CiVil
and EnVironmental Engineering, UniVersity of Illinois at Urbana-Champaign, Urbana, Illinois 61801,
EPRI, 3412 HillView AVenue, Palo Alto, California 94303, and URS Corporation,
9400 Amberglen BouleVard, Austin, Texas 78729

ReceiVed March 22, 2007. ReVised Manuscript ReceiVed May 17, 2007

Nine fly ash samples were collected from the particulate collection devices (baghouse or electrostatic
precipitator) of four full-scale pulverized coal (PC) utility boilers burning eastern bituminous coals (EB-PC
ashes) and three cyclone utility boilers burning either Powder River Basin (PRB) coals or PRB blends (PRB-
CYC ashes). As-received fly ash samples were mechanically sieved to obtain six size fractions. Unburned
carbon (UBC) content, mercury content, and Brunauer-Emmett-Teller (BET)-N2 surface areas of as-received
fly ashes and their size fractions were measured. In addition, UBC particles were examined by scanning electron
microscopy, high-resolution transmission microscopy, and thermogravimetry to obtain information on their
surface morphology, structure, and oxidation reactivity. It was found that the UBC particles contained amorphous
carbon, ribbon-shaped graphitic carbon, and highly ordered graphite structures. The mercury contents of the
UBCs (Hg/UBC, in ppm) in raw ash samples were comparable to those of the UBC-enriched samples, indicating
that mercury was mainly adsorbed on the UBC in fly ash. The UBC content decreased with a decreasing
particle size range for all nine ashes. There was no correlation between the mercury and UBC contents of
different size fractions of as-received ashes. The mercury content of the UBCs in each size fraction, however,
generally increased with a decreasing particle size for the nine ashes. The mercury contents and surface areas
of the UBCs in the PRB-CYC ashes were about 8 and 3 times higher than UBCs in the EB-PC ashes,
respectively. It appeared that both the particle size and surface area of UBC could contribute to mercury
capture. The particle size of the UBC in PRB-CYC ash and thus the external mass transfer was found to be
the major factor impacting the mercury adsorption. Both the particle size and surface reactivity of the UBC in
EB-PC ash, which generally had a lower carbon oxidation reactivity than the PRB-PC ashes, appeared to be
important for the mercury adsorption.

Introduction of UBC in fly ash. Several studies have attempted to correlate

Recent interpretations of data from several full-, pilot-, and
bench-scale studies reveal that unburned carbon (UBC) in fly
ash can both adsorb and oxidize mercury in coal combustion
flue gases.1-6 These studies indicate that mercury capture and
oxidation generally increase with an increasing concentration
* To whom correspondence should be addressed. E-mail: massoud@
isgs.uiuc.edu (M.R.-A.) or rchang@epri.com (R.C.).
† Illinois State Geological Survey.
‡ University of Illinois at Urbana Champaign.
§ Electric Power Research Institute (EPRI).
| URS Corporation.
(1) Rosenhoover, W. A.; Carty, R. Correlate Fly Ash Capture of Hg
with Ash Carbon Content and Flue Gas Temperature. Technical Report for
Illinois Clean Coal Institute, Carterville, IL, October 31, 1999.
(2) Hassett, D. J.; Eylands, K. E. Mercury Capture on Coal Combustion
Fly Ash. Fuel 1999, 78, 243-248.
(3) Sakulpitakphon, T.; Hower, J. C.; Trimble, A. S.; Schram, W. H.;
Thomas, G. A. Mercury Capture by Fly Ash: Study of the Combustion of
a High-Mercury Coal at a Utility Boiler. Energy Fuels 2000, 14, 727-
733.
(4) Gullett, B. K.; Ghorishi, B.; Jozewicz, W.; Ho, K. The Advantage
of Illinois Coal for FGD Removal of Mercury. Technical Report for Illinois
Clean Coal Institute, Carterville, IL, October 31, 2001.
(5) Pavlish, J. H.; Sondreal, E. A.; Mann, M. D.; Olson, E. S.; Galbreath,
K. C.; Laudal, D. L.; Benson, S. A. Status Review of Mercury Control
Options for Coal-Fired Power Plants. Fuel Process. Technol. 2003, 82, 89-
165.
mercury adsorption capacity and oxidation reactivity of UBC
with forms of carbon,7-8 Brunauer-Emmett-Teller (BET)-
N2 surface area,6 and the mass ratio of UBC to Hg in flue gas
(UBC/Hg).8 Petrographic analyses of UBCs derived from
burning bituminous and anthracitic coals reveal a general trend
toward higher mercury retention in anisotropic carbon, followed
by isotropic carbon and inertinite.7,9 Mercury adsorption may
further be associated with the presence of various surface
functional groups (O, S, and Cl) of the UBC. A recent study
indicates that oxygen functional groups of UBC might promote
mercury adsorption.10 In contrast, other studies have suggested
that oxygen functional groups have no impact on the perfor-
(6) Dunham, G. E.; DeWall, R. A.; Senior, C. L. Fixed-Bed Studies of
the Interactions Between Mercury and Coal Combustion Fly Ash. Fuel
Process. Technol. 2003, 82, 197-213.
(7) Hower, J. C.; Maroto-Valer, M. M.; Taulbee, D. N.; Sakulpitakphon,
T. Mercury Capture by Distinct Fly Ash Carbon Forms. Energy Fuels 2000,
14, 224-226.
(8) Senior, C. L.; Johnson, S. A. Impact of Carbon-in-Ash on Mercury
Removal Across Particulate Control Devices in Coal-Fired Power Plants.
Energy Fuels 2005, 19, 859-863.
(9) Suarez-Ruiz, I.; Hower, J. C.; Thomas, G. A. Hg and Se Capture
and Fly Ash Carbons from Combustion of Complex Pulverized Feed Blends
Mainly of Anthracitic Coal Rank in Spanish Power Plants. Energy Fuels
2007, 21, 59-70.

10.1021/ef070145s CCC: $37.00 © 2007 American Chemical Society

Published on Web 06/22/2007
Fly Ashes Relationship to Mercury Adsorption
Table 1. Power Plant Sources of Collected Fly Ash Samples
fly ash boiler type coal type
FA1b PC F-fired (Riley)/ EB baghouse
PC T-fired (CE)
FA2 PC F-fired (Riley) EB ESP
FA3 PC F-fired (Riley) EB baghouse
FA4 PC LSEBc ESP
FA5 cyclone 70% PRB plus 30% Bit ESP
FA6-a B&W7 cyclone PRB ESP
(partial OFAd)
FA6-b B&W7 cyclone PRB ESP
(partial OFA)
FA7 cyclone (OFA) PRB ESP
FA8 cyclone (LNBe/OFA) PRB plus tire ESP
a Equivalent Hg concentration in the flue gas calculated from the Hg content in coal. b A blend of ash collected from two PC boilers burning the same
coal. c Low-sulfur eastern bituminous coal. d Overfire air. e Low NOx burner.
mance of activated carbon for mercury adsorption11 and, in some
cases, even reduce physical adsorption of mercury.12 Mercury
adsorption capacity of inorganic fractions appears to be very
low compared to the UBC present in fly ash.13 However,
magnetite in fly ash may play a role in enhancing the oxidation
of elemental mercury.2,6,14
Mercury adsorption on unburned carbon in fly ash is a
complex phenomenon that depends upon temperature, secondary
flue gas components (including SOx, HCl, and NOx),14 UBC
particle size,15 surface area,15 porosity, and surface chemistry.
The amount and properties of native UBC in turn depend upon
fuel selection (coal type) and combustion conditions. Previous
studies mainly have sought to correlate the total mercury capture
to a single property of UBC. In reality, however, it could be
attributed to the effects of multiple properties of the UBC. The
detailed mechanisms of the interactions of unburned carbon in
fly ash with mercury in flue gas are not yet well-understood
mainly because of the heterogeneous properties of the fly ash,
the complex time-temperature history of the coal particles
during the combustion process, and the presence of various gas
species in the flue gas. Available data in the literature provide
some insight into how some macroscopic properties of fly ash
carbon impact mercury capture and oxidation in flue gas.
However, little fundamental work has been performed to
determine the effect of coal and boiler types on the performance
of UBC in mercury capture and oxidation.
In this study, fly ash samples collected from full-scale coal-
fired power plants were tested to gain some insight on the
impacts of boiler and coal types as well as particle size, surface
area, carbon structure, and morphology of UBC on the adsorp-
(10) Maroto-Valer, M. M.; Zhang, Y.; Granite, E. J.; Tang, Z.; Pennline,
H. W. Effect of Porous Structure and Surface Functionality on the Mercury
Capacity of a Fly Ash Carbon and Its Activated Sample. Fuel 2005, 84,
105-108.
(11) Ghorishi, S. B.; Keeney, R. M.; Serre, S. D.; Gullett, B. K.; Jozewicz,
W. S. Development of a Cl-Impregnated Activated Carbon for Entrained-
Flow Capture of Elemental Mercury. EnViron. Sci. Technol. 2002, 36,
4454-4459.
(12) Kwon, S.; Borguet, E.; Vidic, R. D. Impact of Surface Heterogeneity
on Mercury Uptake by Carbonaceous Sorbents under UHV and Atmospheric
Pressure. EnViron. Sci. Technol. 2002, 36, 4162-4169.
(13) Hasset, D. J.; Eylands, K. E. Mercury Capture on Coal Combustion
Fly Ash. Fuel 1999, 78, 243-248.
(14) Norton, G. A.; Yang, H.; Brown, R. C.; Laudal, D. L.; Dunham, G.
E.; Erjavec, J. Heterogeneous Oxidation of Mercury in Simulated Post
Combustion Conditions. Fuel 2003, 82, 107-116.
(15) Rostam-Abadi, M.; Lu, Y.; Funk, C.; Richardson, C.; Paradis, J.;
Chang R. Properties of Unburned Carbons from Three Coal-Fired Power
Plants and Their Relations to Mercury Capture. In Proceedings of the Air
Quality V Conference, Arlington, VA, September 18-21, 2005.
Energy & Fuels, Vol. 21, No. 4, 2007 2113
particulate
collector
temperature Hg in coal Hg in flue gas
(°F) (ppm) (µg N-1 m-3) at 3% O2a
290-315 n/a n/a
280-300 n/a n/a
270-300 n/a n/a
n/a 0.88 10.12
n/a n/a n/a
284 n/a n/a
284 0.051 6.63
292 0.057 7.12
292 0.057 7.12
tion of mercury by fly ash. Efforts were made to determine both
the inter-relations between these properties and their separate
effects on the mercury capture by UBC. A better understanding
of relations between various properties of UBC and their roles
in mercury capture could potentially reduce the cost associated
with mercury emission control from coal-fired power plants by
reducing the amount of mercury to be removed from the flue
gas and enhancing the performance of wet flue gas desulfur-
ization processes for mercury capture.
Experimental Section
Nine fly ash samples were collected from the particulate
collection devices [electrostatic precipitator (ESP) or baghouse] of
seven full-scale utility pulverized coal and cyclone boilers firing
eastern bituminous, Powder River Basin (PRB) sub-bituminous, or
blended coals. The sources of the fly ash samples are presented in
Table 1. Four ashes (FA1-FA4) were generated from burning
eastern bituminous coals in pulverized coal boilers and are classified
as EB-PC ashes. The remaining five ashes were generated from
burning either PRB coals (FA6-a, FA6-b, and FA7), a blend of
70% PRB plus 30% EB (FA5), or a blend of PRB with tires (FA8)
in cyclone boilers. These samples were classified as PRB-CYC
ashes. The FA1 and FA2 ashes were collected at the same power
plant but from different boilers. The FA6-a and FA6-b ashes were
collected at the same power plant but on different test dates. Ashes
FA7 and FA8 were collected from burning their corresponding fuels
(PRB and PRB plus tire, respectively) in the same boiler. The latter
ash was generated while operating a low NOx burner.
About 50 pounds of each of the as-received fly ash samples was
subjected to a riffle-splitting process to obtain 400-1000 g of a
representative sample for the subsequent sieving and characteriza-
tion studies. Fly ash samples were then mechanically sieved to
obtain +100 mesh (>150 µm), 100-200 mesh (75-150 µm), 200-
270 mesh (75-53 µm), 270-325 mesh (53-45 µm), and -325
mesh (<45 µm) standard U.S. mesh size fractions. For some ashes,
the 53-45 and 75-53 µm fractions were combined because only
small amounts of these size fractions were present in the samples.
A carbon separation unit based on the incipient fluidization
principle16 was employed to enrich UBC contents in several size
fractions of ashes. The unit was modified to include an automatic
gas pulsation to improve the efficacy of UBC separation. A
schematic diagram of the separation process is shown in Figure 1.
A 2 cm diameter glass tube, fitted with a 20-50 µm sintered disk
at the bottom, was filled with an ash sample to a height of 4-5 cm
(16) Hurt, R.; Davis, K.; Yang, N.; Hardesty, D. The Origin and
Properties of Unburned Carbon from Pulverized-Coal Combustion. Techni-
cal Report for Electric Power Research Institute, Palo Alto, CA, November
1995.
2114 Energy & Fuels, Vol. 21, No. 4, 2007 Lu et al.

Figure 1. Schematic of the incipient fluidization unit for fly ash

enrichment.

in the glass tube. A flow of helium gas was pulsed into the tube
through the sintered disk to force the ash particles upward and then
allow them to settle. The gas flow rate, depending upon the particle
size of the ash, was adjusted to allow for a local particle motion
without leading to a full fluidization and mixing in the ash bed.
The gas pulsing was controlled by a relay timer (National Controls
Figure 2. Size distribution of as-received fly ash samples.
Corp.). The on- and off-relays of the timer were set at ∼5 s intervals,
allowing the gas pulse to travel through the bed and the sample to
fully settle after each pulse. The less dense, darker carbonaceous
particles rose to the top of the ash bed, and the heavier inorganic
particles settled at the bottom of the bed. At the conclusion of a
run, a small vacuum pump was used to collect the enriched UBC
fraction from the top of the bed. A typical run took about 2 h.
Physical and chemical properties of the as-received fly ash
samples, their size fractions, and their carbon concentrates were
characterized using various analysis techniques. The UBC, ash, and
moisture contents were measured with a LECO MAC-400 proxi-
mate analyzer. The UBC content was measured by heating a fly
ash sample to 740 °C in N2 and then burning the sample in air for
about 30 min. In this study, the amount of UBC in ash is reported
as the weight loss measured during the oxidation stage. The UBC
measured by this method can be considered to closely represent
the total unburned organic carbon in fly ash. The mercury content
was measured with a LECO AMA254 mercury analyzer, and the
BET surface area was measured using a single-point N2 adsorption
apparatus (Quantachrome, Model Monosorb). The morphology of
selected UBC samples was examined using a cold-field-emission
high-resolution scanning electron microscope (SEM, Hitachi S-4700).
The carbon structure in selected UBC samples was examined with
a high-resolution transmission electron microscope (HRTEM)
system (JEOL JEM-2010).

Results and Discussion

Size Distribution of Ashes. Mass distributions of different
size fractions of the as-received ashes are shown in Figure 2.
For samples FA6-a, FA6-b, FA7, and FA8, the 45-53 and 53-
75 µm fractions were combined because the 45-53 µm fraction
contained less than 5% of the total mass of the raw ash samples.
As was described earlier, the FA1 and FA2 ashes were collected
at the same power plant but from different boilers and FA6-a
and FA6-b ashes were collected at the same power plant but
on different test dates. This could explain the similarity between
the size distributions of these two pairs of ashes. For most ash
samples, the smaller particle size fractions had higher mass
fractions. For example, the <45 µm size fraction accounted for Figure 3. UBC contents in different size factions of ashes.
about 21-65% of the total mass of the as-received ash samples,
while the >150 µm size fraction accounted for about 5-30%. fractions of the ashes ranged from 3 to 90%. The UBC content
The FA8 ash was coarser than the other ashes because it was decreased with a decreasing particle size range for all ashes.
collected from the first field of an ESP. This observation is consistent with previously reported studies.16-18
UBC Contents of Ashes. The UBC contents of the as-
(17) Hurt, R. H.; Gibbins, J. R. Residual Carbon from Pulverized Coal
received ashes varied from about 5 to 36% of the total mass Fired Boilers: 1. Size Distribution and Combustion Reactivity. Fuel 1995,
(Figure 3). However, the UBC contents of the different size 74, 471-480.
Fly Ashes Relationship to Mercury Adsorption
Figure 4. UBC distribution of different size fractions of ashes.
The distributions of UBCs in the different size fractions of the
EB-PC and PRB-CYC ashes differed significantly (Figure 4).
The PRB-CYC ashes exhibited the highest UBC content in
their >150 µm fractions (>75% of the total UBC for all ashes).
In comparison, large amounts of UBC in the EB-PC ashes were
also distributed in the 75-150, 45-75, and <45 µm fractions
(>60% of the total UBC). The observed differences in the
distribution of UBC in the PRB-CYC and EB-PC ashes could
be attributed in part to the fact that the average particle size of
coal burned in a cyclone boiler (100% < 6350 µm) is much
larger than in a PC boiler (70% < 75 µm). In addition, sub-
bituminous coals generally have higher combustion reactivity
than bituminous coals,17 and thus for a comparable particle size
fraction, sub-bituminous coals burn more efficiently than
bituminous coals.
UBC Morphology and Structure. The SEM images of a
UBC particle and an inorganic particle from the FA4 ash are
shown in Figure 5. The UBC particle (Figure 5a) has a porous
structure. Some spherical inorganic particles are attached to the
external surface, and some are penetrated inside the cavities
and large pores of the UBC particle (Figure 5b).
Three carbon structures, amorphous, ribbon-shaped graphitic,
and highly ordered graphite, were observed in the UBC from
the HRTEM analysis (Figure 6). The amorphous carbon form
(Figure 6a) shows a flat surface and does not have a long-range
crystalline order. However, a short-range order with varying
carbon atomic distances and bond angles in the presence of
dangling bonds and voids is present. The microstructure of the
UBC in fly ash has been described as having isotropic and
anisotropic carbon forms from petrographic analyses.9,19,20
Isotropic carbon has a more disordered microstructure than
anisotropic carbon. Carbon materials with less ordered structures
have higher surface areas than those with more ordered
(18) Kulatos, I.; Hurt, R. H.; Subberg, E. M. Size Distribution of
Unburned Carbon in Fly Ash and Its Implications. Fuel 2004, 83, 223-
230.
(19) Baltrus, J. P.; Wells, A. W.; Fauth, D. J.; Diehl, J. R.; White, C.
Characterization of Carbon Concentrates from Coal-Combustion Fly Ash.
Energy Fuels 2001, 15, 455-463.
(20) Hower, J. C.; Trimble, A. S.; Eble, C. F.; Palmer, C. A.; Kolker,
A. Characterization of Fly Ash from Low-Sulfur and High-Sulfur Coal
Sources: Partitioning of Carbon and Trace Elements with Particle Size.
Energy Sources 1999, 21, 511-525.
Energy & Fuels, Vol. 21, No. 4, 2007 2115
Figure 5. SEM images of the UBC particles in FA4 ash.
structures. In addition, disordered carbon materials, such as coal-
based activated carbons, have a larger number of active sites
for adsorption than carbon materials with more ordered struc-
tures, such as graphitic materials. The surface area of the UBC
is mainly attributed to the amorphous form of the carbon and
thus is believed to be the carbon structure with the most activity
for mercury adsorption.
Ribbon-shaped graphitic carbon (Figure 6b) is highly curved
with tangled bonds and voids. Stresses because of the nonuni-
form distribution of temperature inside a coal particle during
combustion may cause the curvature of the graphite. The regular
highly ordered graphite carbon (Figure 6c) is a layered material
where sheets of hexagonally arranged carbon atoms are stacked
and held together. Commercial graphite is prepared by process-
ing a carbonaceous precursor, such as petroleum coke, at
temperatures as high as 3000 °C. The high-temperature treatment
develops a highly ordered, low-porosity structure in the carbon
skeleton. Similarly, the graphite carbon in the UBC could be
formed when the temperature inside the coal particle during
the combustion rose high enough to transform a portion of the
carbon skeleton into the graphitic structure.
Several ash samples and their corresponding carbon-free ash
(prepared by burning the ash samples in air at 750 °C), one
commercial activated carbon, and one graphitic carbon were
examined by X-ray diffraction (XRD) to identify and quantify
the relative amounts of the different carbon forms in the UBCs.
Interpretation of the XRD data did not provide any conclusive
information regarding these parameters. This work is, however,
continuing.
The SEM instrument used in this study was equipped with
an energy-dispersive X-ray fluorescence detector (EDX), which
can produce compositional maps of the UBC particles. Typical
images obtained for the UBC particles in FA3 are shown in
2116 Energy & Fuels, Vol. 21, No. 4, 2007
Figure 6. HRTEM images of the UBC in the 75-150 µm fraction of
FA4 ash: (a) amorphous, (b) ribbon-shaped graphitic, and (c) graphitic.
Figure 7. Only the carbon, sulfur, silicon, and aluminum maps
are shown. The images show that carbon and sulfur are dispersed
across the UBC surface, whereas aluminum and silicon are
concentrated in the large inorganic particles embedded in the
carbon.
UBC-Enriched Ashes. The enrichment of UBC with the gas-
pulsing incipient fluidized-bed process increased the UBC
contents of ash samples between 4 and 322%, depending upon
the size fraction tested (Figure 8). As was shown earlier, some
inorganic particles were embedded in the skeletal structure of
the UBC particles (Figure 5b). Separating these impurities from
the UBC particles will be difficult even when employing a very
efficient separation process. The largest increase in UBC
contents was observed for the 75-150 µm size fractions. The
reason for the lower enrichment in the >150 µm size fraction
is because the UBC content initially present in this size fraction
was relatively high (85%). During enrichment of the <53 µm
Figure 7. Compositional maps of a UBC particle in FA3.
Lu et al.
Figure 8. UBC contents in raw ashes and carbon-enriched
ashes.
Figure 9. Hg contents in fly ashes and carbon-enriched samples.
fractions, ash particles formed aggregates as large as several
millimeters, which kept the bed from achieving a stable
fluidization, resulting in negligible separation efficiency.
A comparison between the Hg/UBC content (in ppm) of the
UBC-enriched samples and their raw counterparts (Figure 9)
revealed that Hg was mainly associated with the UBC particles,
confirming a similar conclusion from a previous study.13
However, at Hg/UBC values larger than about 4 ppm, the UBC-
enriched samples had a slightly lower Hg/UBC than the raw
ash samples, indicating that a small fraction of Hg might be
associated with the inorganic constituents of the fly ash. These
observations and the fact that preparing UBC-enriched samples
by the incipient fluidization method is a time-consuming process
Fly Ashes Relationship to Mercury Adsorption
Figure 10. Hg contents in different size fractions of raw ashes.
are the main reasons that we measured the Hg contents of the
raw size fractions of ashes and then used these values to
calculate the Hg contents of the UBCs.
Contents and Distribution of Mercury in Ashes. The
mercury contents in different size fractions of the ash samples
are presented in Figure 10. The Hg content in the as-received
EB-PC ashes (0.1-0.3 ppm) (Figure 10a) was lower than that
in the PRB-CYC ashes (0.9-2.4 ppm) (Figure 10b). However,
no general relationship between the mercury content (in ppm)
and particle size of ash is apparent. The contributions of each
size fraction to the total mercury content of the ashes (in %)
are shown in Figure 11. The values were calculated by dividing
the mass of Hg in each size fraction by the total mass of Hg in
the whole ash (in g/g). In general, more of the mercury was
distributed in the smaller particle sizes for most of the fly ash
samples. The <45 µm fractions contained between 35 and 77%
of the total mercury in an ash. The exceptions are the FA3 and
FA4 ashes, which had considerable shares of Hg in their >150
and 75-150 µm fractions. These two EB-PC ashes were
coarser (Figure 2), and the UBC distributions in their <45 µm
fraction were also lower (Figure 4) than the other EB-PC
ashes. The FA1 and FA3 ashes were collected from baghouses
(Table 1). The distribution of mercury in different size fractions
of theses ashes was more uniform (possibly because of the
longer contact time with flue gas) than the ashes collected from
ESPs.
Energy & Fuels, Vol. 21, No. 4, 2007 2117
Figure 11. Hg distribution in different size fractions of raw ashes.
Impact of the UBC Surface Area, Particle Size, and
Reactivity on the Hg Capture. The ability of a UBC particle
to capture mercury in the flue gas partly depends upon its
physical and chemical properties. Obviously, coal type, boiler
type, combustion conditions, and flue gas composition and
temperature are some of the parameters that impact the
properties of the UBC. The time-temperature history of a UBC
particle during combustion in a boiler also affects the degree
of sintering and crystallization of the UBC structure. For
example, in a PC boiler, pulverized coal particles (70 wt % is
<75 µm)21 are subjected to very fast heating. In contrast, in a
cyclone boiler, coarser coal particles (100 wt % is <6350 µm)21
require a longer time to heat, burn, and form ash.
As was described earlier, the UBC particles contained three
forms of carbon structures (Figure 6). A higher degree of
sintering increases the concentration of the graphitic carbon
structure and lowers the surface area and number of active sites
of the UBC for adsorption. Therefore, the surface area of the
UBC particles in fly ash may provide some insight on the
tendency of the UBC to capture mercury. A plot of the surface
area of different size fractions of ash samples against the UBC
content is presented (Figure 12). Surface areas of different size
fractions of the ashes increased linearly with an increase in the
UBC content of the EB-PC and PRB-CYC ashes. The values
of the slopes (SA/UBC) in Figure 12, which represent the
surface areas of the UBC in the ashes (m2/g of UBC), are about
50 m2/g for the EB-PC and about 150 m2/g for the PRB-
CYC ashes. According to one study,18 surface areas of UBCs
in bituminous coal fly ashes from four PC boilers were between
20 and 80 m2/g UBC and surface areas of UBCs in sub-
bituminous coal fly ashes from three PC boilers were between
230 and 400 m2/g UBC. The average surface area of the UBC
in the EB-PC ashes is comparable to the previously reported
values. However, the surface area of the UBC in the PRB-
CYC ashes is lower than the reported values. This can be
explained by the differences in the initial particle size of coal
and combustion conditions employed in cyclone and PC boilers.
Figure 12 also shows that, for both the EB-PC and PRB-
(21) United States Environmental Protection Agency (U.S. EPA).
Compilation of Air Pollutant Emission FactorssVolume 1: Stationary Point
and Area Sources, 5th ed.; January 1995; http://www.epa.gov/ttn/chief/ap42/
ch01/index.html.
2118 Energy & Fuels, Vol. 21, No. 4, 2007
Figure 12. Surface areas of different size fractions of ashes.
CYC ashes, the surface areas of the UBCs are not strongly
dependent upon the particle size. Surface areas of several UBC-
free ashes were also measured. They revealed that the surface
areas of the raw ash sample are mainly associated with the UBC
content, with very small contributions from the inorganic
constituents in the ashes, confirming the results from a previous
study.22
The lower surface area of the EB-PC ashes indicates that
the UBC particles in these ashes were sintered more severely
than the UBC particles in the PRB-CYC ashes. It is also
possible that a more porous structure was developed in the UBCs
generated from the PRB coals because the lower rank coals are
generally easier to activate with oxidizing gases (to develop
porosity) than the higher rank EB coals.23 As was shown earlier,
the Hg contents of the PRB-CYC ashes were about 8 times
higher than the EB-PC ashes (Figure 10).
It has been previously reported that the mercury content of
fly ash increases with an increasing UBC content.4,5 This
relationship was not observed for the fly ashes investigated in
this study (Figure 13). Each data point in Figure 13 marks the
mercury and UBC contents of a given size fraction of an ash.
Because different size fractions of a fly ash (and UBC) were
all exposed to the same flue gas conditions, such as Hg
concentration, temperature, and comparable contact time, the
mercury content of a given size fraction of the same ash can
only be connected to the same property of the UBC in that size
fraction alone. The lack of a correlation between the mercury
and UBC contents shown in Figure 13 indicates that the UBC
content alone might not be the controlling factor in the Hg
capture.
The impact of the particle size on the Hg capture could be
important because the UBC particles are distributed in the
different size fractions (Figure 3). The mercury content of the
UBC (Hg/UBC) in the different size fractions of the ashes
generally increased with a decreasing particle size (Figure 14).
The correlation between the particle size and the Hg/UBC was
more significant for the PRB-CYC ashes (Figure 14a) than
the EB-PC ashes (Figure 14b).
(22) Schure, M. R.; Soitys, P. A.; Natusch, D. F. S.; Mauneys, T. Surface
Area and Porosity of Coal Fly Ash. EnViron. Sci. Technol. 1985, 19, 82-
86.
(23) Suuberg, E. M.; Aarna, K. I.; Callejo, M.; Hsu, A. Study of
Activation of Coal Char. Final Technical Progress Report, DE-FG26-
99FT40582, 2003.
Lu et al.
Figure 13. Relationship between the Hg and UBC content in ash.
The dependence of Hg/UBC on the particle size can be
correlated using the following equation:
W ) Adpn (1)
where W is the mercury content of UBC (in g/g of UBC), A is
a constant coefficient for a given ash (in m-n), n is an exponent,
and dp is the particle size (in m). The correlation results are
listed in Table 2. The value of n, which represents the
dependence of the mercury content of the UBC on the particle
size of UBC, is ∼ -2 for the PRB-CYC ashes and ranges from
0 to ∼ -1 for the EB-PC ashes.
Equation 1 relates the dependence of W on dp regardless of
an adsorption mechanism. If the adsorption mechanism is
controlled by an external mass transfer, the rate of adsorption
can be expressed as
N ) kga(Cg - C*) )
[ ]
2D M
( )
dp π 3
dp Fp
(πdp2) (Cg - C*) ∝ dp-2 (2)
6
where N is the adsorption rate (in g s-1 m-3), a is the external
surface of the particles (in m2/m3), D is the diffusion coefficient
(in m2/s), M is the particle concentration (in g/m3), Cg and C*
are the Hg concentrations in bulk and at the surface (in g/m3),
and kg is the mass-transfer coefficient (in m/s). Equation 2
indicates that when the external mass transfer is dominant, the
rate of adsorption is proportional to dp by a power of -2.
If surface adsorption is the dominant step, the rate of
adsorption can be expressed according to the Langmuir equation
N ) ka(Wmax - W)Cg - kdW ∝ dp0 (3)
where ka is the adsorption rate constant (in s-1), kd is the
desorption rate constant (in g s-1 m-3), Wmax is the adsorption
capacity of UBC (in g/g), and W is the amount of Hg in the
UBC (in g/g). Equation 3 indicates that the rate of adsorption
is independent of the particle size and increases with an
increasing adsorption capacity (Wmax) of the UBC. Assuming
that the adsorption capacity (Wmax) can be correlated to the
surface area of the UBC (SA/UBC, in m2/g), the rate of
adsorption also increases with increasing SA/UBC.
The above analysis suggests that for the PRB-CYC ashes
(FA5-FA8), which had higher surface areas than the EB-PC
ashes (Figure 12), the rate of mercury capture by the UBC
Fly Ashes Relationship to Mercury Adsorption Energy & Fuels, Vol. 21, No. 4, 2007 2119

Figure 15. Oxidation profiles of selected ash samples (75-150 µm).

the overall rate of mercury adsorption (values of n in Table 2

are from ∼0 to ∼ -1).
It was shown that the Hg contents (Figure 10) of the higher
surface-area PRB-CYC ashes (Figure 12) were about 8 times
greater than the EB-PC ashes. These observations indicate that
the UBCs in PRB-CYC ashes had higher reactivity for mercury
adsorption than the UBCs in the EB-PC ashes. It appears that
there might be a relationship between the surface area and
reactivity of UBC to adsorb mercury. In this study, the oxidation
reactivities of selected UBC samples were measured. If mercury
is adsorbed on some of the same active sites of the UBC that
participate in the oxidation reaction, then the oxidation reactivity
might be used as an approximate indication for the reactivity
of UBC for adsorption of mercury. The first step in oxidation
of a carbonaceous material is the chemisorption of oxygen on
active sites of carbon to form C-O groups.25,26 The oxidation
reactivity increases with an increase in the concentration of
active sites. The oxidation reactivities of the UBCs were
determined by performing burning profile tests using a ther-
mogravimetric analyzer. Samples (75-150 µm) were heated in
air at a rate of 20 °C/min from ambient temperature to 800 °C.
A major weight loss observed at temperatures above 400 °C
Figure 14. Mercury contents of UBCs in different size fractions of was attributed to the oxidation of the UBC in the fly ash. The
ashes. temperatures at the onset of the oxidation were used for ranking
Table 2. Correlation of Hg/UBC and Particle Size the relative oxidation reactivity of the UBCs. They ranged from
360 to 500 °C for the four PRB-CYC ashes tested (FA5, FA6-
n R2 n R2 n R2
a, FA6-b, and FA7) and about 530 °C for the one EB-PC ash
FA1 -0.44 0.87 FA4 -0.07 0.04 FA6-b -1.87 0.82 (FA4) tested (Figure 15.) The higher oxidation temperature
FA2 -0.98 0.98 FA5 -2.16 0.87 FA7 -1.87 0.92
FA3 -0.49 0.63 FA6-a -1.81 0.84 FA8 -1.37 0.9 observed for the EB-PC ash indicates that UBC in this ash
has less oxidation reactivity than UBC in the PRB-CYC ashes.
particles (which relates to mercury content) was potentially The specific surface area, which relates to the internal pore
controlled by their external mass-transfer resistances (values of structure and the number of active sites, affects the oxidation
n in Table 2 are ∼ -2). A similar conclusion was reported when rate of the UBC. As was discussed earlier, the surface areas of
powdered activated carbon was injected into a coal combustion UBCs in the EB-PC and PRB-CYC ashes were about 50 and
flue gas upstream of an ESP to capture mercury.24 In contrast, 150 m2/g carbon, respectively (Figure 12). Therefore, the PRB-
the more sintered, lower surface-area UBC particles in the EB- CYC ashes are expected to have higher oxidation reactivity than
PC ashes (FA1-FA4) were less reactive, resulting in a slow the EB-PC ashes. This is consistent with the results from the
rate of mercury adsorption. Under this scenario, both the external burning profile tests. It also supports the conclusions from the
mass transfer and the reactivity of the UBC particles impacted earlier analysis that the differences in the reactivities of the

(24) Rostam-Abadi, M.; Hsi, H. C.; Chen, S.; Rood, M. J.; Chang, R.;
Carey, T. R.; Richardson, C. F.; Rosenhoover, B. Development of Carbon-
Based Adsorbent for Removal of Mercury Emissions from Coal Combustion
Flue Gas. In Adsorption and Its Application in Industry and EnVironmental
Protection; Dabrowski, A., Ed.; Elsevier Science Pub. Co., Inc.: Amsterdam,
The Netherlands, 1998; pp 459-483.
(25) Puri, B. R. Surface Complexes on Carbon. In Chemistry and Physics
of Carbon; Walker, P. L. Ed.; Marcel Dekker: New York, 1970; Vol. 6,
pp 191-282.
(26) Laine, N. R.; Vastola, F. J.; Walker, P. L. The Importance of Active
Surface Area in the Carbon-Oxygen Reaction. J. Phys. Chem. 1963, 67,
2030-2034.
2120 Energy & Fuels, Vol. 21, No. 4, 2007
Figure 16. Impact of the original particle size on the ignition
temperature (all samples grinded to <45 µm).
UBCs resulted in different mechanisms of mercury adsorption
(mass transfer and adsorption kinetics) for the EB-PC and
PRB-CYC ashes.
Additional tests were performed with ash FA4 to evaluate
the impact of the particle size of UBC on the oxidation
reactivity. Three size fractions, <45, 75-150, and >150 µm,
of ash FA4 with surface areas of 29, 34, and 37 m2/g UBC,
respectively, were tested. The 75-150 and >150 µm fractions
were ground to <45 µm to eliminate the impact of the particle
size on oxidation reactivity. The mass of the sample employed
for measuring the burning profiles was less than 5 mg to
minimize interparticle diffusion inside the sample bed. The
results showed that oxidation reactivity increased with an
increase in the original particle size and the surface area of the
UBC (Figure 16). As was described earlier, both the adsorption
kinetics and the mass-transfer limitations impacted the ability
of the EB-PC ashes, including the FA4 ash, to capture mercury.
The fact that the mercury contents of the various size fractions
of FA4 ash were comparable (Figure 14b) indicate that mass-
transfer limitations had more impact on the larger UBC particles.
It remains to be determined whether the larger UBC particles
have higher reactivity for mercury adsorption.
Conclusions
This study compared the properties of UBCs in nine ashes
collected from full-scale boilers. These ashes were designated
as either EB-PC or PRB-CYC because they were generated
Lu et al.
from two different rank coals in two different types of boiler.
Three carbon structures were observed in the UBC: amorphous,
ribbon-shaped graphitic, and ordered graphitic. More UBC were
found in the larger ash size fractions. The mercury contents in
the UBCs (Hg/UBC, in ppm) were comparable in as-received
ash samples and the UBC-enriched ash, indicating that the
mercury was mainly adsorbed on the UBC in fly ash. Contrary
to the results from some previous studies, no direct correlation
between the mercury and UBC contents of different size
fractions of the as-received fly ashes was found.
The amount of mercury adsorbed in the PRB-CYC ashes
was about 1 order of magnitude higher than the EB-PC ashes.
The UBC in the PRB-CYC ashes also had about 3 times higher
surface areas and higher oxidation reactivity than the UBC in
the EB-PC ashes. For the PRB-CYC ashes, the particle size
(and thus the external mass transfer) was found to be the main
factor affecting mercury capture. In comparison, both the particle
size (mass transfer) and reactivity (adsorption kinetics) affected
the adsorption of mercury on the EB-PC ashes because of the
lower reactivity of the UBC based on the surface area,
morphology, and carbon oxidation measurements.
This study showed that a better understanding of the
properties of UBC carbon in fly ash can provide valuable
information regarding its potential for capturing mercury in coal-
fired boilers. Thus far, the data show that cyclone boilers firing
PRB coals can produce highly reactive UBC compared to
bituminous coal-fired PC boilers. This can be attributed to less
exposure of the coal particles to high-temperature sintering and
perhaps the higher reactivity of the coal particles. To further
delineate if the exposure time and temperature or the coal type
are important in the UBC produced, samples of ash from PRB-
fired PC boilers and bituminous-fired cyclones will help. In
addition, laboratory time-temperature exposures of various
pulverized coal types in hot gases can be used to produce UBC
in various stages of formation. This can help provide further
information on more effective ways of producing UBC in the
boiler or in a separate reactor, where the optimal UBC can be
produced separately under more controlled conditions and
injected into the flue gas stream.
Acknowledgment. Funding support from EPRI’s Technology
Innovation program (Grant EP-P14791/C7268) is greatly appreci-
ated. The SEM, HRTEM, and XRD experiments were carried out
in the Center for Microanalysis of Materials, University of Illinois
at Urbana-Champaign, which is partially supported by the U.S.
Department of Energy under Grant DEFG02-91-ER45439. Publica-
tion of this paper was approved by the Chief of the Illinois State
Geological Survey.
EF070145S