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Characteristics of Fly Ashes From Full-Scale Coal-Fired Power Plants and Their Relationship To Mercury Adsorption
Characteristics of Fly Ashes From Full-Scale Coal-Fired Power Plants and Their Relationship To Mercury Adsorption
Characteristics of Fly Ashes From Full-Scale Coal-Fired Power Plants and Their Relationship To Mercury Adsorption
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.
coal. c Low-sulfur eastern bituminous coal. d Overfire air. e Low NOx burner.
mance of activated carbon for mercury adsorption11 and, in some tion of mercury by fly ash. Efforts were made to determine both
cases, even reduce physical adsorption of mercury.12 Mercury the inter-relations between these properties and their separate
adsorption capacity of inorganic fractions appears to be very effects on the mercury capture by UBC. A better understanding
low compared to the UBC present in fly ash.13 However, of relations between various properties of UBC and their roles
magnetite in fly ash may play a role in enhancing the oxidation in mercury capture could potentially reduce the cost associated
of elemental mercury.2,6,14 with mercury emission control from coal-fired power plants by
Mercury adsorption on unburned carbon in fly ash is a reducing the amount of mercury to be removed from the flue
complex phenomenon that depends upon temperature, secondary gas and enhancing the performance of wet flue gas desulfur-
flue gas components (including SOx, HCl, and NOx),14 UBC ization processes for mercury capture.
particle size,15 surface area,15 porosity, and surface chemistry.
The amount and properties of native UBC in turn depend upon Experimental Section
fuel selection (coal type) and combustion conditions. Previous
studies mainly have sought to correlate the total mercury capture Nine fly ash samples were collected from the particulate
to a single property of UBC. In reality, however, it could be collection devices [electrostatic precipitator (ESP) or baghouse] of
attributed to the effects of multiple properties of the UBC. The seven full-scale utility pulverized coal and cyclone boilers firing
detailed mechanisms of the interactions of unburned carbon in eastern bituminous, Powder River Basin (PRB) sub-bituminous, or
blended coals. The sources of the fly ash samples are presented in
fly ash with mercury in flue gas are not yet well-understood
Table 1. Four ashes (FA1-FA4) were generated from burning
mainly because of the heterogeneous properties of the fly ash, eastern bituminous coals in pulverized coal boilers and are classified
the complex time-temperature history of the coal particles as EB-PC ashes. The remaining five ashes were generated from
during the combustion process, and the presence of various gas burning either PRB coals (FA6-a, FA6-b, and FA7), a blend of
species in the flue gas. Available data in the literature provide 70% PRB plus 30% EB (FA5), or a blend of PRB with tires (FA8)
some insight into how some macroscopic properties of fly ash in cyclone boilers. These samples were classified as PRB-CYC
carbon impact mercury capture and oxidation in flue gas. ashes. The FA1 and FA2 ashes were collected at the same power
However, little fundamental work has been performed to plant but from different boilers. The FA6-a and FA6-b ashes were
determine the effect of coal and boiler types on the performance collected at the same power plant but on different test dates. Ashes
of UBC in mercury capture and oxidation. FA7 and FA8 were collected from burning their corresponding fuels
(PRB and PRB plus tire, respectively) in the same boiler. The latter
In this study, fly ash samples collected from full-scale coal-
ash was generated while operating a low NOx burner.
fired power plants were tested to gain some insight on the
About 50 pounds of each of the as-received fly ash samples was
impacts of boiler and coal types as well as particle size, surface subjected to a riffle-splitting process to obtain 400-1000 g of a
area, carbon structure, and morphology of UBC on the adsorp- representative sample for the subsequent sieving and characteriza-
tion studies. Fly ash samples were then mechanically sieved to
(10) Maroto-Valer, M. M.; Zhang, Y.; Granite, E. J.; Tang, Z.; Pennline, obtain +100 mesh (>150 µm), 100-200 mesh (75-150 µm), 200-
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, 270 mesh (75-53 µm), 270-325 mesh (53-45 µm), and -325
105-108. mesh (<45 µm) standard U.S. mesh size fractions. For some ashes,
(11) Ghorishi, S. B.; Keeney, R. M.; Serre, S. D.; Gullett, B. K.; Jozewicz, the 53-45 and 75-53 µm fractions were combined because only
W. S. Development of a Cl-Impregnated Activated Carbon for Entrained- small amounts of these size fractions were present in the samples.
Flow Capture of Elemental Mercury. EnViron. Sci. Technol. 2002, 36, A carbon separation unit based on the incipient fluidization
4454-4459.
(12) Kwon, S.; Borguet, E.; Vidic, R. D. Impact of Surface Heterogeneity principle16 was employed to enrich UBC contents in several size
on Mercury Uptake by Carbonaceous Sorbents under UHV and Atmospheric fractions of ashes. The unit was modified to include an automatic
Pressure. EnViron. Sci. Technol. 2002, 36, 4162-4169. gas pulsation to improve the efficacy of UBC separation. A
(13) Hasset, D. J.; Eylands, K. E. Mercury Capture on Coal Combustion schematic diagram of the separation process is shown in Figure 1.
Fly Ash. Fuel 1999, 78, 243-248. A 2 cm diameter glass tube, fitted with a 20-50 µm sintered disk
(14) Norton, G. A.; Yang, H.; Brown, R. C.; Laudal, D. L.; Dunham, G. at the bottom, was filled with an ash sample to a height of 4-5 cm
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.; (16) Hurt, R.; Davis, K.; Yang, N.; Hardesty, D. The Origin and
Chang R. Properties of Unburned Carbons from Three Coal-Fired Power Properties of Unburned Carbon from Pulverized-Coal Combustion. Techni-
Plants and Their Relations to Mercury Capture. In Proceedings of the Air cal Report for Electric Power Research Institute, Palo Alto, CA, November
Quality V Conference, Arlington, VA, September 18-21, 2005. 1995.
2114 Energy & Fuels, Vol. 21, No. 4, 2007 Lu et al.
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).
Figure 12. Surface areas of different size fractions of ashes. Figure 13. Relationship between the Hg and UBC content in ash.
CYC ashes, the surface areas of the UBCs are not strongly The dependence of Hg/UBC on the particle size can be
dependent upon the particle size. Surface areas of several UBC- correlated using the following equation:
free ashes were also measured. They revealed that the surface
areas of the raw ash sample are mainly associated with the UBC
W ) Adpn (1)
content, with very small contributions from the inorganic where W is the mercury content of UBC (in g/g of UBC), A is
constituents in the ashes, confirming the results from a previous a constant coefficient for a given ash (in m-n), n is an exponent,
study.22 and dp is the particle size (in m). The correlation results are
The lower surface area of the EB-PC ashes indicates that listed in Table 2. The value of n, which represents the
the UBC particles in these ashes were sintered more severely dependence of the mercury content of the UBC on the particle
than the UBC particles in the PRB-CYC ashes. It is also size of UBC, is ∼ -2 for the PRB-CYC ashes and ranges from
possible that a more porous structure was developed in the UBCs 0 to ∼ -1 for the EB-PC ashes.
generated from the PRB coals because the lower rank coals are Equation 1 relates the dependence of W on dp regardless of
generally easier to activate with oxidizing gases (to develop an adsorption mechanism. If the adsorption mechanism is
porosity) than the higher rank EB coals.23 As was shown earlier, controlled by an external mass transfer, the rate of adsorption
the Hg contents of the PRB-CYC ashes were about 8 times can be expressed as
higher than the EB-PC ashes (Figure 10).
N ) kga(Cg - C*) )
[ ]
It has been previously reported that the mercury content of
2D M
fly ash increases with an increasing UBC content.4,5 This
relationship was not observed for the fly ashes investigated in
( )
dp π 3
dp Fp
(πdp2) (Cg - C*) ∝ dp-2 (2)
this study (Figure 13). Each data point in Figure 13 marks the 6
mercury and UBC contents of a given size fraction of an ash.
where N is the adsorption rate (in g s-1 m-3), a is the external
Because different size fractions of a fly ash (and UBC) were
surface of the particles (in m2/m3), D is the diffusion coefficient
all exposed to the same flue gas conditions, such as Hg
(in m2/s), M is the particle concentration (in g/m3), Cg and C*
concentration, temperature, and comparable contact time, the
are the Hg concentrations in bulk and at the surface (in g/m3),
mercury content of a given size fraction of the same ash can
and kg is the mass-transfer coefficient (in m/s). Equation 2
only be connected to the same property of the UBC in that size
indicates that when the external mass transfer is dominant, the
fraction alone. The lack of a correlation between the mercury
rate of adsorption is proportional to dp by a power of -2.
and UBC contents shown in Figure 13 indicates that the UBC
If surface adsorption is the dominant step, the rate of
content alone might not be the controlling factor in the Hg
adsorption can be expressed according to the Langmuir equation
capture.
The impact of the particle size on the Hg capture could be N ) ka(Wmax - W)Cg - kdW ∝ dp0 (3)
important because the UBC particles are distributed in the
different size fractions (Figure 3). The mercury content of the where ka is the adsorption rate constant (in s-1), kd is the
UBC (Hg/UBC) in the different size fractions of the ashes desorption rate constant (in g s-1 m-3), Wmax is the adsorption
generally increased with a decreasing particle size (Figure 14). capacity of UBC (in g/g), and W is the amount of Hg in the
The correlation between the particle size and the Hg/UBC was UBC (in g/g). Equation 3 indicates that the rate of adsorption
more significant for the PRB-CYC ashes (Figure 14a) than is independent of the particle size and increases with an
the EB-PC ashes (Figure 14b). increasing adsorption capacity (Wmax) of the UBC. Assuming
that the adsorption capacity (Wmax) can be correlated to the
(22) Schure, M. R.; Soitys, P. A.; Natusch, D. F. S.; Mauneys, T. Surface surface area of the UBC (SA/UBC, in m2/g), the rate of
Area and Porosity of Coal Fly Ash. EnViron. Sci. Technol. 1985, 19, 82- adsorption also increases with increasing SA/UBC.
86. The above analysis suggests that for the PRB-CYC ashes
(23) Suuberg, E. M.; Aarna, K. I.; Callejo, M.; Hsu, A. Study of
Activation of Coal Char. Final Technical Progress Report, DE-FG26- (FA5-FA8), which had higher surface areas than the EB-PC
99FT40582, 2003. 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
(24) Rostam-Abadi, M.; Hsi, H. C.; Chen, S.; Rood, M. J.; Chang, R.; (25) Puri, B. R. Surface Complexes on Carbon. In Chemistry and Physics
Carey, T. R.; Richardson, C. F.; Rosenhoover, B. Development of Carbon- of Carbon; Walker, P. L. Ed.; Marcel Dekker: New York, 1970; Vol. 6,
Based Adsorbent for Removal of Mercury Emissions from Coal Combustion pp 191-282.
Flue Gas. In Adsorption and Its Application in Industry and EnVironmental (26) Laine, N. R.; Vastola, F. J.; Walker, P. L. The Importance of Active
Protection; Dabrowski, A., Ed.; Elsevier Science Pub. Co., Inc.: Amsterdam, Surface Area in the Carbon-Oxygen Reaction. J. Phys. Chem. 1963, 67,
The Netherlands, 1998; pp 459-483. 2030-2034.
2120 Energy & Fuels, Vol. 21, No. 4, 2007 Lu et al.