Investigation of polycyclic aromatic hydrocarbons in fly ash from fluidized bed combustion systems

Article abstract of DOI:10.1021/es990944s

A laboratory scale fluidized bed reactor and a bench scale 0.1 MW(th) fluidized bed combustor were used to study the effect of operating conditions on the formation of Polycyclic Aromatic Hydrocarbons (PAHs) in fly ash from fluidized bed combustion systems. A high volatile bituminous coal was chosen to investigate PAH emissions during the entire pyrolysis to oxygen-rich combustion process. During the experiments, the fluidized bed reactor was operated at temperatures between 700°C and 900°C, while the excess air ratio was varied from 0 to 1.3. An extraction and GC/MS analysis of PAHs was used in this study. Approximately 40 different PAHs were identified during the tests, of which only a few are specified by the U.S. EPA. The experimental results indicate the majority of the PAHs in the solid phase (bed and fly ash) are derived from the breakdown reactions during the processes of combustion and/or pyrolysis in a Fluidized Bed Combustion (FBC) system, although FBC systems have an efficient solid-gas mixing process and relatively long residence time. The total amount of PAHs in the fly ash was much higher than that in the raw coal and in the gas phase. Three-and four- ring aromatic compounds were the major PAHs from pyrolysis conditions, while naphthalene (two-rings) is the dominant compound in bed ash collected from oxygen-rich combustion conditions. Only naphthalene was detected in the bed ash in the FBC system. High-speed secondary air (air staging) injected into the freeboard of the FBC system is an effective method for minimizing PAH emissions, along with the other benefits including minimizing NO(x) and SO(x) emissions. A laboratory scale fluidized bed reactor and a bench scale 0.1 MW_th fluidized bed combustor were used to study the effect of operating conditions on the formation of Polycyclic Aromatic Hydrocarbons (PAHs) in fly ash from fluidized bed combustion systems. A high volatile bituminous coal was chosen to investigate PAH emissions during the entire pyrolysis to oxygen-rich combustion process. During the experiments, the fluidized bed reactor was operated at temperatures between 700°C and 900°C, while the excess air ratio was varied from 0 to 1.3. An extraction and GC/MS analysis of PAHs was used in this study. Approximately 40 different PAHs were identified during the tests, of which only a few are specified by the U.S. EPA. The experimental results indicate the majority of the PAHs in the solid phase (bed and fly ash) are derived from the breakdown reactions during the processes of combustion and/or pyrolysis in a Fluidized Bed Combustion (FBC) system, although FBC systems have an efficient solid-gas mixing process and relatively long residence time. The total amount of PAHs in the fly ash was much higher than that in the raw coal and in the gas phase. Three-and four-ring aromatic compounds were the major PAHs from pyrolysis conditions, while naphthalene (two-rings) is the dominant compound in bed ash collected from oxygen-rich combustion conditions. Only naphthalene was detected in the bed ash in the FBC system. High-speed secondary air (air staging) injected into the freeboard of the FBC system is an effective method for minimizing PAH emissions, along with the other benefits including minimizing NO_x and SO_x emissions.

Full text of DOI:10.1021/es990944s

Environ. Sci. Technol. 2000, 34, 2273-2279
In the atmosphere, PAHs are mainly associated with
Investigation of Polycyclic Aromatic
Hydrocarbons in Fly Ash from
aerosols (dispersions or suspensions of solid particulate),
liquid drops, or a mixture of both (5). The main source of
concern with this class of compounds is that some members
are known mutagens or carcinogens. PAHs have a strong
electrophilic character and interact with biological nucleo-
phyles in metabolic processes. The result of such interactions
may obstruct their regular functions and promote carcino-
genesis due to transformation of PAHs into diolepoxides of
aromatic rings inside the organism (6). To date, the U.S. EPA
has prioritized 16 PAH compounds as hazardous air pol-
lutants; these compounds are acenaphthene, acenaphthyl-
ene, anthracene, benzo[a]anthracene, benzo[a]pyrene, benzo-
[b]fluoranthene, benzo[ghi]perylene, benzo[k]fluoranthene,
chrysene, dibenzo[a,h]anthracene, fluoranthene, fluorene,
indeno[1,2,3-cd]pyrene, naphthalene, phenanthrene, and
pyrene (7).
Fluidized Bed Combustion Systems
K U N L E I L I U , W E I X I E ,
Z H E N G - B A O Z H A O , W E I - P I N G P A N , * A N D
J O H N T . R I L E Y
Combustion Laboratory, Department of Chemistry,
Western Kentucky University, Bowling Green, Kentucky 42101
A laboratory scale fluidized bed reactor and a bench
scale 0.1 MWth fluidized bed combustor were used to study
the effect of operating conditions on the formation of
Polycyclic Aromatic Hydrocarbons (PAHs) in fly ash from
fluidized bed combustion systems. A high volatile bituminous
coal was chosen to investigate PAH emissions during
the entire pyrolysis to oxygen-rich combustion process.
During the experiments, the fluidized bed reactor was operated
at temperatures between 700 °C and 900 °C, while the
excess air ratio was varied from 0 to 1.3. An extraction and
GC/MS analysis of PAHs was used in this study.
Approximately 40 different PAHs were identified during
the tests, of which only a few are specified by the U.S. EPA.
The experimental results indicate the majority of the
PAHs in the solid phase (bed and fly ash) are derived
from the breakdown reactions during the processes of
combustion and/or pyrolysis in a Fluidized Bed Combustion
(FBC) system, although FBC systems have an efficient solid-
gas mixing process and relatively long residence time.
The total amount of PAHs in the fly ash was much higher
than that in the raw coal and in the gas phase. Three-
and four-ring aromatic compounds were the major PAHs
from pyrolysis conditions, while naphthalene (two-rings) is
the dominant compound in bed ash collected from oxygen-
rich combustion conditions. Only naphthalene was detected
in the bed ash in the FBC system. High-speed secondary
air (air staging) injected into the freeboard of the FBC system
is an effective method for minimizing PAH emissions,
Most PAH formation and emission is associated with soot
emissions during the incomplete combustion of fossil fuels
(such as start-up and shut down process of combustion
facilities including troubleshooting) and as a consequence
of the pyrolytic process that precedes combustion (8, 9). Also,
as a consequence of the thermion process and by cyclization
and aromatization reactions, other aromatic clusters can be
developed (10, 11). It has been experimentally shown that
it is possible to synthesize benzo[a]pyrene from ethane under
pyrolysis conditions (3). When coal is heated, its structure
undergoes chemical and physical changes, and organic
fractions are released. These fractions undergo cyclization
reactions leading to polycyclic compounds that can exist in
gaseous and in solid phases, depending on the surrounding
temperature and their molecular volume (12-14). They can
exist in the gas phase (<4-ring PAHs), in the solid phase
(>6-ring PAHs), or in both phases (four- and five-ring PAHs)
in the air depending on their molecular mass (15).
Fluidized bed combustion technology has been widely
used throughout the world in an effort to reduce sulfur oxide
emissions at low cost compared to conventional pulverized
combustion (PC) and vortex combustion boilers. The major
advantages of fluidized bed combustion (FBC) of fossil fuels
are (1) low SO2 emission due to absorption by limestone
directly in the combustor; (2) low NOx emission due to low
combustion temperatures; (3) fuel flexilibilty, while even
burning low rank coal; and (4) combustion stability with low
CO emission levels through high turbulence between solids
and gases in the combustor.
along with the other benefits including minimizing NO
x
and SO emissions.
x
The distribution and relative abundance of PAHs arising
from fluidized bed combustion (FBC) is a function of
operating temperature and process conditions (16-18). The
emission of small unburned fragment of coal or char due to
incompleted combustion can be minimized by optimizing
combustion parameters. Published information (19-21)
about operating FBC systems to reduce PAH emissions is
still limited. Also, most attention has been paid to PAH
emissions in the gas phase emitted in the flue gas. However,
PAHs adsorbed on solids (fly ash and bed ash) also can cause
pollution when they evaporate into atmosphere. To better
understand how to control and reduce the emission of PAHs
during coal combustion and pyrolysis, the identification of
PAHs, their concentrations, and modes of emission must be
known. For environmental reasons it is necessary to know
the amount and distribution of PAHs so that appropriate
treatment procedures may be followed. The study reported
in this paper focuses on the effect of operating conditions
on PAH production in fly ash.
Introduction
Coals are derived from plant material such as cellulose, lignin,
resins, spores, leaves, stems, and roots under intense heat
and pressure. The organic matter of coal is generally regarded
as being composed of two complementary structures (1-4).
The dominant component is a macromolecular, insoluble,
three-dimensional network composed of condensed aromatic
and hydroaromatic units connected by ether or thioether
linkages and short alkyl bridges. The second structure is a
molecular phase of compounds which are typically soluble
in organic solvents. This molecular phase contains varying
distributions of aliphatic hydrocarbons, polycyclic aromatic
and hydroaromatic hydrocarbons, hydroxylated polycyclic
aromatic compounds, and heterocyclic compounds.
* Corresponding author phone: (270)745-5322; fax: (270)745-5361;
e-mail: Wei-Ping.Pan@wku.edu.
9
10.1021/es990944s CCC: $19.00
Published on Web 04/15/2000
2000 Am erican Chem ical Society
VOL. 34, NO. 11, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 2 2 7 3

FIGURE 1. The schematic diagram of WKU-FBC facility used in this study.
MWth bench FBC system has a 0.3-m i.d. and 4.0-m effective
Experimental Section
height, using limestone as the bed material in the system. In
this study, an under-bed continuous fuel/ limestone (particle
size <4 mesh) feeding system was installed 0.1 m point above
the air distributor in the FBC system. Six moveable heat
exchangers in the bed area were also added. Typical operation
of the FBC system involves setting the correct coal/ limestone
feeds and air flows and then using the moveable tubes to
adjust the bed temperature to the desired setting. Another
66 gas heat exchange tubes are in a fixed position located
approximately a half meter from the top of the combustor
to protect the wet cyclone. The operating parameters (air/
water flow, coal/ lime feed, bunker weight, temperatures, and
pressure) are controlled and logged to file with a computer
controller. A Shimadzu GC-8A gas chromatograph was used
to continuously monitor the concentration of oxygen, carbon
monoxide, and carbon dioxide in the flue gas during the
tests. The results were used to adjust the coal and limestone
feeding rates and combustion air flow rate.
This study was conducted with a laboratory scale stainless
steel fluidized bed reactor (i.d. of 45 mm and height of 95
mm) and a 0.1 MWth (heating capacity, 0.3 m i.d.) bench
scale FBC combustor, as shown in Figure 1.
Lab-Scale FBC Reactor. The lab scale bubbling FBC
reactor was mainly used for pyrolysis without oxygen (N2 as
carrier gas) or excess air ratio less than 1 (air and N2 as carrier
gas) to simulate the start up and shut down processes of
boilers. The lab scale reactor was installed in an electric
furnace, preheated to the desired temperature. The premixed
(nitrogen and/ or air) gas, total 3 L/ min, was injected into the
reactor through the distributor which was in the bottom of
the reactor. Coal with a particle size <40 mesh (150 g) was
fed into the combustor at a steady rate from the top of the
reactor through a mechanical auger at a rate of approximately
0.5 g/ min. The carbon utilization efficiency is typically less
than 70%. During the test, no limestone was fed into reactor
with coal. All the effluent gas was drawn to a vent with a
vacuum pump after it went through a sampling line. The
sampling line, which was a modified EPA Method 5-type,
includes a high temperature (400 °C) cyclone to collect the
particulate matter. The reaction products were swept into
the sampling line containing a 37 mm nylon and Teflon filter,
a 20 cm condenser, and a tube filled with 1.0 g of Tenax. The
tars emitted from the furnace during pyrolysis were collected
by the filter and condenser. Precleaned Teflon tubing,
glassware, and holders of sampling materials were used in
the trapping line. Before each sampling, the Tenax and filters
was kept at 150 °C for 1 h to remove any contamination of
organics. The effect of temperature and excess air ratio on
the formation of PAHs was studied during the pyrolysis study.
The 0.1 MWth Bench Scale FBC Facility. Major combus-
tion studies (excess air ratio >1.0) were conducted with the
bench scale bubbling FBC system similar to the normal
operation of a boiler. The Western Kentucky University 0.1
Fly ash was collected using a high efficiency cyclone at
a high temperature (∼400 °C) at the outlet pipe 8 h after
changing test conditions and the combustor had stabilited.
The bed ash was removed from the distributor. The solid
samples collected were extracted using a Tecator Soxtec 1045
extraction system. In each run, 15 g of the -60 mesh (250
µm) ash was placed in the extraction thimble with dichlo-
romethane. The extractor was heated to 120 °C to extract
materials from the ash over a period of 1 h. Then, the thimble
and ash were removed from the apparatus, and the extract
was heated with the refluxing dichloromethane (80 mL) for
another 5 h. The extracted solution was condensed and
transferred to a 10 mL volumetric flask. A Shimadzu QP 5000
system with a NIST/ EPA/ NIH 62 000 compound database
was used for GC/ MS analysis. Aliquots of 2 µL of sample
were injected in the splitless mode onto RTX-5 fused silica
capillary column (60 m × 0.32 mm and a stationary phase
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2 2 7 4 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 11, 2000

thickness of 1.0 µm). Helium was used as the carrier gas. The
surrounding temperature for injector, interface, and detector
was 230 °C. The mass spectrometer was operated in the
selected ion monitoring (SIM) mode for each PAH (EPA
Method 8270). The detection limit is 0.1 ppb when the selected
ion monitoring (SIM) mode is chosen. The temperature of
the gas chromatography oven was programmed from 70 °C
to 150 °C at a rate of 8.0 °C/ min and then to 250 °C at a rate
5.0 °C/ min, held for 5.0 min, and finally raised to 300 °C at
a rate of 7.0 °C/ min. The temperature was also held for 5.0
min at 300 °C. The PAH compounds were identified using
the NIST library search program, and the 16 U.S. EPA specified
PAHs were confirmed and quantified using the retention
times and calibration curves from the standard PAH com-
pounds. During the analysis process, five fly ash samples
were doped with a known amount of deuterated PAH
compounds (naphthalene-d8, anthracence-d10, and benz-
[a]anthracene-d12) before extraction to determine the re-
covery rate for the analysis process. A 96.2% recovery rate
was achieved for the study. A high volatile bituminous coal,
10.5% ash, 34.6% volatile matter, 50.4% fixed carbon, and
5.2% hydrogen, was used in this study.
TABLE 1. U.S. EPA Specified PAHs Identified in the Ashes
[µg/(g ash)]
OC
PF1
PF2
CF1
CF2
CF3
PAHs in Fly Ash
Two-Rings
naphthalene
2.78 65.82 20.28 23.81 19.91 6.50
Three-Rings
acenaphthene
acenaphthylene
fluorene
1.36 4.18
2.30
b
b
b
b
b
b
75.21
76.42 15.01 3.53
48.02 27.14 54.89 13.80 2.39
phenanthrene
anthracene
subtotal
1.46 60.04 42.11 70.02 30.08 6.01
27.03 15.39 31.39 15.02 2.51
2.82 214.48 86.94 232.72 73.91 14.44
b
Four-Rings
fluoranthene
pyrene
b
b
49.08 42.08 48.02 41.70 5.80
32.61 28.22 29.31 30.23 4.22
benzo[a]anthracene b
21.82 27.21
b
37.28 5.59
chrysene
subtotal
b
19.28 11.30 13.39 20.71 2.01
122.79 108.81 90.72 129.92 17.62
Five-Rings
benzo[e]pyrene
totals
b
36.20
b
b
b
b
5.60 439.29 216.02 347.25 223.74 38.56
Results and Discussion
PAHs in Bed Ash
At the beginning of this study, the same sample was extracted,
concentrated, and analyzed under the same conditions three
times to determine the analysis system errors. The results
indicate that the error range in this study is (5%. Three- and
four-ring aromatic compounds were the major products from
pyrolysis conditions, while naphthalene (two-rings) is the
dominant PAH in fly ash collected from oxygen-rich com-
bustion conditions. Only naphthalene was detected in the
bed ash of the FBC system.
Lab-Scale FBC Reactor. The effects of pyrolysis temper-
ature and excess air ratio were determined in a series of
experiments. Approximately 40 different PAH compounds
were identified with the GC/ MS through the 60 000 com-
pound NIST library search. However, only a few U.S. EPA-
specified PAHs were confirmed, using the retention times
from a PAH standard mixture, as listed in Table 1. Three-
and four-ring aromatic compounds were the major PAHs in
the fly ashes from the different experimental conditions. The
total amount of PAHs obtained at 800 °C is almost twice that
obtained at 900 °C using pyrolysis conditions. The higher
temperature may provide more energy to break more bonds
in the PAHs. This is also supported by the fact that no five-
ring compounds was determined when the temperature was
increased to 900 °C. There was almost 80 times more PAHs
produced at 800 °C than the PAHs extracted with solvents
from the raw coal, as shown in Table 1. This suggests that
the majority of PAHs are formed in breakdown reactions,
with condensation and cyclization mechanisms playing less
important roles.
In general, during coal combustion (even with an excess
air ratio less than 1, partial thermal decomposition) the total
amount of PAHs produced decreased with an increase in the
level of excess air. The amount of PAHs produced dropped
sharply after the excess air level was raised above 1. No
significant difference is observed in the behavior of each
aromatic ring compound; in each case the quantity of the
PAHs that is observed in the reaction products decreases as
excess air ratio increases. The results also suggest that
incomplete combustion is the main reason for the emission
of PAHs. The content of PAHs in the fly ashes (the minimum,
at excess air ratio of 1.14) is seven times more than the PAHs
extracted from the raw coal. This also indicates that the
formation of PAHs is mainly through converting coal
macromolecular aromatic structures into different size
fragments and then decomposing and cracking the fragments
into lower molecular weight PAHs under the FBC combustion
naphthalene
b
b
10.31 9.43
12.71
a
OC - original coal; PF1 - 800 °C, pyrolysis; PF2 - 900 °C, pyrolysis;
CF1 - 800 °C, com bustion, excess air ratio ) 0.50; CF2 - 800 °C,
com bustion, excess air ratio ) 1.00; CF3 - 800 °C, com bustion, excess
b
air ratio ) 1.14. Under the detection lim it (0.1 ppb when the SIM m ode
is chosen).
conditions. In the oxygen-rich conditions, the PAHs will
further undergo oxidation reactions and produce more
carbon dioxide and water in the flue gas. However, if there
is a lean oxygen condition in the fluidized bed combustor,
more PAHs will be emitted with fly ashes.
Very small amounts of naphthalene was the only PAH
identified in the bed ash, as shown in Table 1. This small
amount may be due to the last second PAH products formed
and surviving combustion before the furnace was turned off.
The results from the study of the gas phase PAHs in flue
gas shows a different trend than with the PAHs in fly ash. The
effects of pyrolysis temperature on PAHs in the gas-phase
collected by the filter, condenser, and Tenax are listed in
Table 2. Naphthalene was identified as the most prominent
peak in the chromatograms when pyrolysis temperature was
less 700 °C. The reason may be that naphthalene has the
lowest boiling point among the PAHs and the highest stability,
thus avoiding decomposition. With an increase in pyrolysis
temperature, the amount of the smaller PAH molecules of
PAH like naphthalene and fluorene decreased, while the
emission of larger molecules increased with an increase in
temperature. The minimum PAH emissions were produced
around 600 °C. This may mean that both pathways of
degradation of the coal matrix and the intermolecular
cyclization from small species may occur above 400 °C for
PAH formation in the flue gas under fuel-rich conditions. At
the low temperature, the major pathway for PAH formation
is degradation to emit smaller products during the devola-
tilization process. However, the effect of intermolecular
cyclization becomes more and more important with an
increase in the temperature, where large PAHs are produced
from the combination of smaller PAHs. It is also possible
that large PAHs are produced during the deep degradation
of char.
The 0.1 MWth FBC System . The FBC system with vortexing
secondary air in the freeboard was used to conduct an
experiment to determine the PAHs produced during com-
bustion. From previous experiments run to study NOx, SOx,
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VOL. 34, NO. 11, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 2 2 7 5

TABLE 2. Amount (µg/g Coal) of PAHs in the Coal and Collected by the Filter, Condenser, and Tenax in the Pyrolsis Process at
Different Temperaturesa
400 °C
500 °C
600 °C
700 °C
800 °C
PAH
coal 97025
A
B
A
B
A
B
A
B
A
B
Two-Rings
naphthalene
1.34
1.10
0.22
1.26
0.31
0.63
0.40
0.39
0.45
0.16
0.85
Three-Rings
fluorene
anthracene
phenanthrene
0.13
0.05
0.07
0.29
0.51
0.77
0.03
0.07
0.80
0.61
0.33
0.32
0.37
0.28
0.95
0.66
0.45
0.30
0.77
0.79
0.65
0.47
0.30
1.10
0.16
Four-Rings
0.12
chrysene
pyrene
subtotal
total
0.28
0.12
3.07
0.04
0.03
0.37
3.47
0.61
0.32
4.09
0.20
0.22
2.07
0.09
0.15
1.41
3.48
0.35
0.43
2.40
0.06
0.22
1.84
4.24
0.35
0.53
2.11
0.13
0.27
2.69
4.80
0.01
1.60
0.04
1.24
5.30
a
In the table, A represents the am ount of PAHs collected by the filter and condenser, while B represents the am ount collected with a Tenax
trap.
FIGURE 2. The effect of combustion temperature on the number of fused rings in PAHs in the fly ash.
and HCl emissions, there was evidence that factors including
temperature, excess air ratio, residence time (fluidizing
velocity or bed height), and the secondary/ primary air ratio
greatly effected the amount of these compounds emitted
during combustion.
0.4% for the combustion runs in the WKU-FBC facility.
Naphthalene was detected in every fly ash sample, while its
content varied from 20 ng/ (g ash) to 480 ng/ (g ash),
depending on the temperature, excess air ratio, and other
factors. Upon comparison with the results [in the order of
µg/ (g ash)] obtained from the lab-scale FBC reactor (without
limestone fed), the PAH content in the fly ash from the bench-
scale study is much less. The PAH content in the bench-scale
is only in the order of ng/ (g ash). The major reason for this
behavior may be due to good solid and gas mixture and
addition of limestone in the bench-scale FBC facility.
The combustion temperature has been found to be one
of the most important factors affecting fossil fuel combustion
in FBC systems, in which the burning speed of fuel is
kinetically controlled due to high intensity turbulence
between the solid and gas phases in the fluidizing condition.
Higher combustion temperatures typically result in high
degrees of burn-out in shorter times. In this study, high
combustion efficiency (99.4%) was reached at high combus-
tion temperature (882 °C), while 98.4% was obtained at 787
°C. The relationship between the PAH content in fly ash and
combustion temperature is shown in Figure 2. An increase
in combustion temperature causes a decrease in the PAH
content in the fly ash. The PAH content decreased from 720
ng/ (g ash) to 30 ng/ (g ash) when the temperature was raised
During this study the temperature, excess air ratio, bed
height, and secondary/ primary air ratios and their effects on
PAH formation and emission were examined. Each of these
parameters was investigated independently in this study,
since they can be controlled in different ways. The combus-
tion efficiency for all tests was in the range of 98.5-99.5%
with carbon content ranging in the fly ash from 15% to 5%.
From all test runs, incomplete combustion of coal is the
main factor resulting in the emission of PAHs with the fly
ash. The total amount of PAHs was much higher in the fly
ash than in the bed ash. PAHs in quantifiable amounts were
only found in the fly ash samples. The largest detectable
PAHs were those with four fused rings, including fluoranthene
and pyrene. No detectable amounts of PAHs were determined
in the bed ash samples. The most probable explanation is
that bed ash has a very long residence time (average 30-60
min) with high temperatures and undergoes thorough mixing
and contact with the oxidant gas. All combustible compounds
were burned before the bed ash was removed from the
combustor. The average carbon content in bed ash is only
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2 2 7 6 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 11, 2000

FIGURE 3. The effect of excess air ratio on the number of fused rings in PAHs in the fly ash.
from 787 °C to 882 °C (static bed height ) 0.65 m; excess air
ratio ) 1.25).
exchange tubes are immersed, the temperature is uniform,
and only a 10-20 °C difference exists in the entire space.
Typically, 80-85% of the combustible coal is burned in this
zone. In some ways, it also can represent the residence time
of fuel particles inside the combustor. Usually, long residence
times for particles can be reached at high bed heights when
the fluidizing velocity is kept constant. The results of a study
of bed height on the PAH content in fly ash at a bed
temperature of 810 °C and excess air ratio of 1.25 is plotted
in Figure 4. Compared to the results from the effects of
combustion temperature and excess air ratio on the PAH
content in the fly ash, the bed height showed the same general
trend on PAH emissions. A very significant drop of PAH
content in fly ash occurs with a bed height increase from 0.5
to 0.7 m (static condition), but no further decrease in PAH
emissions occurred for bed heights more than 0.7 m. The
final value for PAHs at 0.81 m bed height is 190 ng/ (g ash),
which is six times the final amount of combustion temper-
ature effect. The PAHs with three fused rings was still detected
at high percentages (∼50%) of the total PAHs at the 0.81 m
static bed height. Thus, the results indicate the effects of
combustion, excess air ratio, and bed height on PAH
reduction in this study are in the following order: combustion
temperature > excess air ratio > bed height.
Considering the number of rings in the PAHs in the fly
ash, the major reductions in PAH emissions occur for the
two and three fused ring PAHs which are more completely
combusted when the temperature is increased from 787 °C
to 810 °C. The amount of four fused ring PAHs remained
fairly constant in this temperature range. After the temper-
ature is raised to 843 °C, no PAHs with more than three fused
rings were found in this study. However, PAHs with two and
three fused rings were still detected even at the highest
temperature studied (882 °C). Considering another point,
major compounds in three-rings PAHs at 843 °C are
phenanthrene, acenaphthylene and anthracene. So, increases
in the three-ring content in the fly ash may come from the
decomposition of four-ring PAHs, such as pyrene or chrysene.
The excess air ratio is another important factor that
influences the combustion of fossil fuels. In a series of tests,
the combustion air flow rate (76 Nm3/ h), bed temperature
(810 °C), and bed height (0.67 m) were kept constant, and
the excess air ratio was only adjusted by the coal feeding
rate. Figure 3 shows the relationship between the PAH content
in the fly ash and the excess air ratio. There is a direct
relationship between PAH emissions and the excess air ratio,
in that, as the amount of excess air is increased for the
combustor, the PAH content in the fly ash decreases
(combustion efficiency raised from 99.1% to 99.4%). With an
increase in excess air, the amount of oxygen readily available
to react also increases. When this occurs, the PAH fragments
from the coal have the opportunity to react with the oxygen
to form CO2 and H2O.
The number of rings in the PAHs in fly ash versus the
excess air ratio illustrates that at the first step, large PAHs
with three and four fused rings burned out with an increase
in excess air ratio; at the second step, the excess air ratio is
greater than 1.25, the major reduction in the total PAHs in
fly ash occurs with naphthalene.
Fluidizing velocity is related to the erosion rate of metal
in an FBC system. A small increase in fluidizing velocity will
cause a severe erosion effect of particles on heat exchange
tubes. Therefore, in the general operation of an FBC boiler,
any load change of the boiler is achieved through adjusting
the bed height (dense zone), with fluidizing velocity kept
almost constant. In an FBC system, bed height represents a
high solid density and a high turbulence zone in which heat
The effect of particle size of fly ash on PAH content was
also investigated in this study. The results are illustrated in
Figure 5. The PAH content in the fine particle fly ash (Dp <
0.10 mm) is five times higher than that in the coarse particle
fly ash with (0.10 < Dp < 0.30 mm). The major reasons for
this occurrence may be the combustor residence time for
the fly ash and the surface area. The carbon content in the
fine particle fly ash (17.2%) is higher than in the coarse
particles (6.5%) in the WKU-FBC system. The coarse particle
fly ash may fall near the wall of furnace, due to gravitational
forces, to increase its residence time in the combustor,
whereas the fine particle fly ash is lost from the combustor
rapidly and has a short residence time. The fine particle fly
ash has more surface area per unit mass than the coarse
particles, thus more condensed PAHs can be absorbed as
compared to absorption by the coarse particles. The results
also suggest that the sampling system and methods should
address the fine particle fly ash collection (such as the ash
in the baghouse or the last stages of the electrostatic
precipitator) in PAH studies with industrial boilers.
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FIGURE 4. The effect of bed height on the PAH content in the fly ash.
FIGURE 5. The effect of particle size on the PAH content in the fly ash.
It is known that air staging combustion can effectively
control NOx emission in the effluent gas during combustion
processes. Up to 50% reduction of the NO concentration in
the flue gas can be achieved at a secondary/ primary air ratio
of 30-50%. In some ways, air staging combustion technology
can also improve SOx capturing efficiency. An understanding
of the role of air staging combustion on PAH emissions from
FBC systems is not presently known. The effect of the
secondary/ primary air ratio on the PAH contents in fly ash
is presented in Figure 6. The secondary air has a significant
effect on the PAH emissions in fly ash. At a low location in
the combustor (1.8 m from the distributor) and below the
level of the secondary air nozzles, the fly ash (with 25.2%
carbon content) collected with the secondary air on had a
PAH content about fives times that in the fly ash sample
(with 14.3% carbon content) collected without secondary
air. However, at a high location (4.3 m above distributor,
near the combustor exhaust), the PAH content in the fly ash
sample with secondary air (4.8% carbon content) was only
one-fourth that in the fly ash sample without secondary air
(7.5% carbon content). Only naphthalene was detected in
the 4.3 m samples with secondary air. In this series test, the
total air flow (primary and secondary air) and coal feeding
rate were kept constant. When a given secondary air flow
was used, the primary air was reduced by the same volume.
Thus, the actual excess air ratio in the fluidizing zone (below
the level of secondary air nozzles) when air is being injected
into the freeboard as secondary air is lower than that when
secondary air is not being used. Low excess air ratios always
cause high PAH emissions in the fly ash. Another factor to
be considered for the high location (4.3 m) position is that
the secondary air nozzles inject the air tangentially at an
angle of 30 degrees into the freeboard to form a strong vortex
flow. Under this tangential flow, particles escaping from the
fluidized bed are separated from the flow. The large particles
fall back into the bed along the wall, while the small particles
form a suspended layer to prolong their residence time in
the combustor. Thus, a more complete burn-out can be
obtained with the tangential flow. Very low PAH contents
were determined in the fly ash samples with the secondary
air influence. As a consequence, high vortex secondary air
(air staging) injected into the freeboard of the FBC system
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2 2 7 8 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 11, 2000

FIGURE 6. The effect of secondary air on the PAH content in the fly ash.
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is an effective method to minimize PAH emissions, along
with the other benefits including reduction of NOx and SOx
emissions. Fewer PAHs will be produced in fluidized bed
combustion systems if the bed temperature and the excess
air ratio are at optimal conditions.
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Received for review August 12, 1999. Revised manuscript
received February 14, 2000. Accepted March 7, 2000.
ES990944S
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