March 31, 1972
A STUDY OF
THE FATE OF SO2IN FLUE GAS
Contract No. CPA 70-121
dBatteiie
Columbus Laboratories
A report of research conducted for the
ENVIRONMENTAL PROTECTION AGENCY
AMERICAN PETROLEUM INSTITUTE
BITUMINOUS COAL RESEARCH, INC.
EDISON ELECTRIC INSTITUTE
-------
FINAL REPORT
on
A STUDY OF THE FATE OF S02 IN FLUE GAS
Contract No. CPA 70-121
to
ENVIRONMENTAL PROTECTION AGENCY
AMERICAN PETROLEUM INSTITUTE
BITUMINOUS COAL RESEARCH, INC.
EDISON ELECTRIC INSTITUTE
March 31, 1972
by
R. W. Coutant, E. L. Merryman, R. E. Barrett,
R. D. Giammar, and A. Levy
BATTELLE
Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
-------
TABLE OF CONTENTS
Page
MANAGEMENT SUMMARY.
. . . . . . . . .
. . . . . . . . .
. . . . .
INTRODUCTION. .
. . . . .. .
. . . . . . . . . . . . .
. . . . . .
.--
SUMMARY. . . . . . . . . . . . . . . . . . . .
. . . . . .
. . . . .
2
EXPERIMENTAL PROCEDURE. . . . . . . . . . .
. . . . . . .
. . . .
3
EXPERIMENTAL RESULTS. . .
. . . . . . . .
. . . . . . . . . . . . .
4
General Trends. . . . . . . . . . . . . . . . . . . . . . . . . .
Specific Fuel Effects. . . . . . . . . . . . . . . . . . . . . . . .
S03' . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sulfur in Ash. . . . . . . . . . . . . . . . . . . . . . . .
NOx Emissions. . . . . . . . . . . . . . . . . . . . . . .
General Observations. . . . . . . . . . . . . . . . . . . . .
4
7
7
8
8
8
OTHER INVESTIGATIONS OF S02 DECAY IN PLUMES. . . . . .
CONCLUSIONS. . . . . . . .
. . . . . .
9
. . . . . . . . .
. . . . . . . . . .
. . 10
ACKNOWLEDGMENTS. . . .
. . . . .
. . . . . . . . .
. . . . . .
. . 11
REFERENCES. . . .
. . . . . . .
. . . .
. . . . . . . . . . . .
. . 11
APPENDICES
APPENDIX A - EXPERIMENTAL EQUIPMENT AND METHODS. . . . . . . . A-1
APPENDIX B - FURNACE-STACK DATA. . . . . . . . . . . . . . . . . . B-1
APPENDIX C - PLUME-CHAMBER DATA. . . . . . . . . . . . . . . . . . C-1
APPENDIX D - PARTICULATE ANALYSES. . . .
. . . . . . . . . . .
. . 0-1
BATTELLE - COLUMBUS
-------
A STUDY OF THE FATE OF SO2 IN FLUE GAS
MANAGEMENT SUMMARY
Previous studies attempting to determine the fate of SO2 in power-plant flue gases have
indicated a possible rapid loss of S02 either within the stack or in the early plume. Sampling
plumes with fixed wing aircraft to examine the fate of S02 at distances of a mile or less from
the stack is difficult. It was the purpose of this program to provide additional data to support
and/or to clarify these observations through the use of a laboratory-scale system designed to
simulate the time-temperature profile of a central-station power plant and the early plume. This
was accomplished using the Battelle Multifuel Furnace Facility. This facility included a
multipurpose furnace fired either with pulverized coal at approximately 30 Ib/hr or with residual
oil at 3 gal/hr; a simulated boiler/economizer section; an electrostatic precipitator for use with
coal firing; a stack section, in which temperature distribution was controlled independently by
electrical heating; and a dilution and expansion chamber to simulate the early stages of plume
development.
The five specific objectives of the program were:
1. Identification of sections of the system wherein major depletion in S02 could
be observed
2. Determination of the effect of fuel type on SC>2 depletion
3. Determination of the significance of the contribution of fly ash to the overall
S02 depletion
4. Investigation of the rate of oxidation of SO2 in the early stages of plume
development, e.g., equivalent to effective ranges of less than one-half mile from
the stack exit
5. Assessment of the effects of relative humidity, temperature, and process
variables on the rate of SC>2 loss in the early plume.
To meet these objectives an experimental work plan was developed, in conjunction with
the EPA/API/BCR/EEI Steering Committee, which included measurement of the sulfur content
of both the flue gas and the particulate matter at selected points within the system. Results of
this work indicate little difference in the overall behavior of SC>2 produced by coal or oil firing.
In general, there was about a 10 percent loss in SC>2 concentration in the flue gas within the
boiler/economizer section of the unit. With coals, this sulfur was found to be associated
primarily with the fly ash collected in the electrostatic precipitator, and the fraction of the fuel
sulfur in the fly ash was roughly proportional to the ash content of the coal. Data with oils were
insufficient to identify the source of the loss of SC>2 with these fuels.
No loss in S02 in the flue gas was observed in the stack section of the unit. Data for the
early plume showed considerable scatter, but, when a loss of S02 was noted, the observations
could be described in terms of a first-order rate process with a rate constant in the range of 2 x
10'3 to 13 x 10"3 min'1. This is equivalent to the S02 half-life of about 1-6 hr, which is in
BATTELLE — COLUMBUS
-------
agreement with the findings of earlier full-scale plume-sampling studies. It appears that humidity
effects, of themselves, are insufficient to explain the observed variations in rate of loss of 502 in
plumes. It thus may be necessary to examine the role of droplets in more detail than has been
done in this or other investigations in order to establish actual rates of loss of 502 in plumes.
Implications of the results of this program are that: (1) On the average, about 90 percent
of the sulfur in pulverized coal or fuel oil can be expected to leave the stack as 502; (2) The
percentage of fuel sulfur leaving the stack as 502 is affected only slightly by the nature of the
fuel; and (3) The effect of relative humidity on the half-life of 502 in the plume needs to be
further clarified.
ii
BATTELLE - COLUMBUS
-------
FINAL REPORT
on
A STUDY OF THE FATE OF S02 IN FLUE GAS
Contract No. CPA 70-121
to
ENVIRONMENTAL PROTECnON AGENCY
AMERICAN PETROLEUM INSTITUTE
BITUMINOUS COAL RESEARCH, INC.
EDISON ELECTRIC INSTITUTE
from
BATTELLE
Columbus Laboratories
March 31, 1972
INTRODUCTION
Sulfur dioxide emissions are a major contribution to air pollution in the United States.
Effective and economic control of such emissions must be based on sufficient knowledge of the
behavior and manner of dispersal of S02 within the boiler, the stack, and the plume.
Ideally, of course, the most positive S02 control is accomplished by burning low-sulfur
fuels. Current availability and technology makes this generally uneconomical. To provide
adequate and economical regulation and control therefore, it would be desirable to know the
maximum level of sulfur that can realistically remain in a fuel for which sufficiently low-cost
removal of S02 by other control techniques can be achieved. To provide the basis for such
decisions, information is needed on the fate of S02 from the time the fuel is burned to its exit
and dispersal in the atmosphere.
It is generally accepted that, in combustion of pulverized coal and fuel oil, most of the
sulfur in the fuel leaves the stack as S02. About 1 to 2 percent of the sulfur is converted to
S03(1)*, and another 5 percent or less is claimed to be absorbed by the fly ash during transit
through the boiler up to the base of the stack(2).
In an earlier program conducted by GCA, the evidence indicated rapid decay of S02
either within the stack or in the early plume.(3) Recent work at a Florida power station
indicated less rapid consumption of the S02 except when the relative humidity of the surround-
ing atmosphere was greater than 78-80 percend4) In both of these studies, sampling of plumes
was conducted using fixed-wing aircraft. This is an extremely difficult experiment to conduct
with meaningful accuracy, especially at distances of one mile or less from the stack.
*References are listed at the end of the report.
BATTELLE - COLUMBUS
-------
2
The purpose of the current program was to provide additional data to support and/or
clarify these observations through the use of a laboratory-scale system designed to simulate the
time-temperature profile of a power-generation station. Specific objectives of the program
included:
1. Identification of sections of the system wherein major depletion in S02
could be observed
2. Determination of the effect of fuel type on S02 depletion
3. Determination of the significance of the contribution of fly ash to the
overall S02 depletion
4. Investigation of the rate of oxidation of S02 in the early stages of plume
development, e.g., equivalent to effective ranges of less than one-half mile
from the stack exit
5. Assessment of the effects of relative humidity, temperature, and process
variables on the rate of S02 loss in the early plume.
SUMMARY
A study of the fate of S02 in flue gas has been conducted for both residual oil and
pulverized coal firing with a laboratory-scale system designed to . simulate the combustion,
boiler/economizer, stack, and early plume portions of a power-generation station. Three residual
oils and two coals typical of those in current use were fired. These fuels included a high
vanadium (0.026 percent) residual oil from a Venezuelan crude, a desulfurized residual oil from
the same Venezuelan crude, a midcontinent residual oil, a raw Pittsburgh-seam coal, and a
washed coal from the same mine. The oils were fired at 3 gal/hr and the coals at 30 Ib/hr.
In general, the behavior of S02 in the laboratory-scale system was relatively independent
of the type of fuel being fired. A loss of S02 from the flue gas amounting to about 10 percent
was noted across the boiler-economizer section of the system. S02 losses in the stack section
were very slight at the most, being less than 3 percent for either coal or oil firing. In the early
plume, the data may be represented in terms of a first-order rate process with an average rate
constant of 8 x 10-3 min-l and a probable range of 2 x 10-3 to 13 x 10-3 min-l (half-life of 1-6
hr) for both coal and oil firing. A weak correlation was found between the rate constants and
the relative humidity of the dilution air but only about 40 percent of the variance in the data is
attributed to variations in relative humidity.
Particulate analyses indicated that about 3 per.ce~t. of th~ fuel sulfur was associated with
the fly ash in the stack section for both coal a~d 0111 fmng. W;~h coals, the amount of sulfur
associated with the precipitator catch was apprmamate y propor lOnal to the ash content of the
coal - as high as 15 percent with 18 percent ash coal.
With the coal runs, the S03 content of the flue gas in. the ~ta~~ section was less than 1
ppm, on the average, compared with about 10 ppm observed wIth 011 fmng. The low S03 in the
BATTELLE - COLUMBUS
-------
3
coal-fired flue gas was attributed to the stack section being operated at temperatures (250-275 F)
below the dew point of sulfuric acid. For oil firing, the stack was operated at slightly higher
temperatures (300-325 F) that allowed the sulfuric acid to remain a vapor in the flue gas.
Incidental measurements were also made of the NOx content of the flue gas. The NO
levels for oil firing correlated roughly with the nitrogen content of the fuels. With coal firing, th~
fuel nitrogen did not vary significantly among the coals employed, hence no comparison can be
made.
EXPERIMENTAL PROCEDURE
Apparatus used in the experimental work consisted of the Battelle Multifuel Furnace
,
along with an associated simulated stack and plume simulation chamber that were designed and
constructed for this program. The flexibility of this system allowed firing with either residual oil
or pulverized coal and permitted production and conditioning of flue gas and fly ash under
conditions closely simulating those of a typical central-station power plant. The facility and
associated equipment are described in Appendix A.
Normal operating procedure for the furnace was to fire natural gas during "off periods",
when data were not being taken. This permitted ready establishment of steady state temperature
upon firing of either the residual oils or coals. When a run was to be made, the furnace was
switched from gas firing to coal or oil firing and the entire system was allowed to equilibrate
over a period of several hours. During this time, appropriate adjustments were made to obtain
the desired operational conditions, and S02 and 02 concentrations in the flue gas were taken to
certify the attainment of a steady state. Oxygen readings were made at the furnace exit, and
S02 readings were taken via a gas-manifold sampling system at the three gas-sampling points
indicated in Figure A-I.
The oxygen content of the flue gas was measured continuously throughout each run,
both as a check on the stability of the combustion system and to aid in interpretation of the
S02 readings. Temperatures throughout the system were also monitored continuously. Through
the use of a manifold sampling system, readings for S02 could be obtained quickly at each of
the three gas sampling points. Goks~yr-Ross condensers were incorporated into the S02 sampling
lines so that S03 samples could be taken simultaneously with the S02 samples.
In operation of the plume chamber, the appropriate mixture of flue gas and humidified
air was established, and the S02 concentration and temperature of the chamber were monitored
until a steady state was achieved. Samples for S02 were then taken along the centerline of the
chamber. Whenever the dilution ratio was changed in the chamber, the system was restabilized
before data were taken.
Particulate samples were taken at appropriate points in the system simultaneously with
the S02 sampling. For this, the standard EPA probe-filter-impinger assembly was used. After
completion of a particulate run, the rig was immediately disassembled, and the probe and
impinger catches were washed into glass bottles for storage prior to analysis. These then were
analyzed colorimetrically for sulfate content using barium chloranilate as the reagent. The filter
BATTELLE - COLUMBUS
-------
4
plus the filter catch were analyzed for sulfur using X-ray fluorescence. In this procedure, a
weighed fraction of the filter plus particulate was homogenized by grinding to form the analysis
sample. A blank was prepared from a sample of the filter material obtained from the same stock.
A standard reference sample for the analysis was prepared similarly, using the same stock filter
material and prestandardized sodium sulfate.
Details of the sampling and analytical procedures are given in Appendix A.
EXPERIMENTAL RESULTS
Details of the firing conditions, system temperatures, and analytical data are given in
Appendixes B, C, and D.
GENERAL TRENDS
In this study of the fate of S02 with several types of both residual oils and coals, a
number of qualitatively similar trends have been observed. These similarities are readily apparent
from the data cited in Table 1. The observed decreases in S02 throughout the experimental
system are further illustrated for the oils and coals in Figures 1 and 2, respectively.
TABLE 1. PERCENTAGE S02 DECAy(a) WITHIN
COMBUSTION SYSTEM
Fuel
Su perheater IEconom izer
Stack
V-954fb)
V-950(d)
SX-7812(e)
Raw Coal(l)
Washed Coal(g)
91 -jc)
1214
1215
-1 12
o
914
913
-3 1 3
-0.4 1 3
0.7 12
Averages
Oils
Coals
All fuels
1114
914
1014
-0.414
-0.113
-0.2 1 3
(a) Relative to measured values at furnace exit.
(b) Venezuelan residual oil.
(c) Standard deviation.
(d) Desulfurized V-954.
(e) Mid-continent residual oil.
(I) Raw Pittsburgh-seam coal.
(g) Washed Pittsburgh-seam coal.
BATTELLE - COLUMBUS
-------
100 ----
C\I 90
~
Q)
CI
o
.....
c
Q)
~ 80
If
70
Furnace
Exit
100 ----
C\I
o 90
(f)
Q)
CI
o
.....
c
Q)
~ 80
~
70
Furnace
Exit
Boi ler / Economi zer
5
Particulate
"'3%
+
Stack
Figure 1. General S02 Loss Profile for Oil
,
Precipitator
8-150/0
Boiler /Economizer/
Precipitator
Particulate
'" 3 0/0
~
Stack
Figure 2. General S02 Loss Profile for Coal
k=8xI0-3
min-I
Early Plume
k= 8x 10-3
min-I
Early Plume
-------
6
For both fuels, a loss of approximately 10 percent of the S02 from the flue gas was
noted across the boiler/economizer section of the system. Recent data obtained by TV A at the
Shawnee plant in Paducah(5) indicate similar losses of S02 in a boiler under some operating
conditions. The TV A data show losses of S02 across the superheater/economizer amounting to
5-10 percent for some of the test conditions.
In the stack section of the laboratory system, losses were very slight, being no more than
o to 3 percent for either the oils or the coals. Sulfur associated with the particulate material at
the entrance to the stack also amounted to about 3 percent of the total sulfur on the average for
both the oils and the coals.
In the plume section, loss of S02 was not always observed for firing with either fuel.
However, loss of S02 was noted in the plume for 15 experiments with residual oils and 27 runs
with coal. Approximately 65 percent of these runs showed first-order rate constants in the range
of 1 x 10-3 to 2 x 10-2 min-l (see Table C-3). Figure 3 shows the distribution of rate constants
in this group. A least-squares analysis of these data indicates a best value of 8 x 10-3 min-l with
a probable range of 2 x 10-3 to 13 x 10-3 min-l.
10
2
r-'
-
J<..
X
X
-
- )( x
-
-
x
x
- x
X J<..
X X
X
X X
X
X
X
x X
x
x
x X
x
2
4
6
8
10
kx 103
12
14
16
18
20
9
8
7
c:
o
+=
c 6
>
~
c3 5
'0
~ 4
i
:3
C' 3
~
lJ...
00
Figure 3. Distribution of Rate Constants
BATTELLE - COLUMBUS
-------
7
An attempt was made to correlate the observed rate constants with the major variables of
the system; the relative humidity of the dilution air, the plume temperature, and degree of
dilution (concentration). Results of these correlations are shown in Table 2.
TABLE 2. CORRELATION OF RATE CONSTANTS WITH
SYSTEM VARIABLES
Variable
Correlation Coefficient
Degree of Determination(a)
Relative humidity
Temperature
Dilution
0.63
-0.21
0.13
0.39
0.04
0.02
(a) Fraction of data variance accounted for by this correlation.
It is readily apparent that the relative humidity of the dilution air was the most
important factor in determining the rate of reaction of S02 for these plume experiments.
However, it should be noted from the data in Table C-3 that this conclusion is heavily weighted
by results taken without any dilution air. The fact that a first-order rate expression seemed to fit
the data best is in agreement with the low correlation coefficient obtained for dilution, i.e., the
half-life is not affected by dilution. The negative correlation coefficient obtained for temperature
is reasonable in as much as it is expected that the solubility of S02 in the plume mist, and
hence its availability for reaction within the droplets, decreases with increasing temperature.
These results imply that the general behavior of S02 in a power-plant combustion-plume
system is relatively independent of whether pulverized coal or oil is being burned. However,
some differences need to be cited to qualify this conclusion.
SPECIFIC FUEL EFFECTS
Although the general trends apply to both coal and oil, some specific differences in
distribution of sulfur within the combustion system occur due to the different firing practices
for the two fuels. With oil firing, the ash content is low and an electrostatic precipitator is
generally not used to scavenge fly ash from the flue gas. Also, stack temperatures with oil firing
are generally slightly higher than those with coal firing.
S03
In the coal experiments, the stack simulator was generally run at temperatures of 250 to
275 F, Le., at temperatures below the dew point of sulfuric acid with normal flue-gas composi-
tions. As a result, little or no S03 was observed in the stack. On the other hand, runs with oil
firing were made with stack temperatures of 300-350 F, and S03 amounting to about I to 2
percent of the total sulfur was observed in the stack.
BATTELLE - COLUMBUS
-------
8
Sulfur in Ash
In the coal-fIred runs, appreciable amounts of sulfur were found in the precipitator catch;
the collected ash contained approximately 12 to 17 percent sulfur expressed as S04. Further-
more, as indicated in Table D-3, the amount of sulfur found in the precipitator catch varied with
the two coals fIred. With the raw Pittsburgh-seam coal, the percentage of fuel sulfur associated
with the ash in the precipitator was about twice as much as with the washed Pittsburgh-seam
coal. Since the raw coal contained approximately twice as much ash, it appears that the
percentage of fuel sulfur associated with the precipitator catch was proportional to the ash
content of the coal.
NOx Emissions
The study of NOx emissions was not a prime objective of this work. An interesting
observation, however, merits attention. Listed in Table 3 are the nitrogen contents of the three
residual oils used. Also listed in this table are typical ranges of values of NOx measured at similar
excess air levels (02 = 2.4-2.7 percent). It is interesting to note that the trends indicated by the
fuel nitrogen values correlate with observed NOx levels. It therefore appears that the nitrogen
content of the fuels plays a significant role in determining the level of NOx in the flue gas under
the firing conditions employed. With the coals, the range of nitrogen content was too limited to
estimate the influence of fuel nitrogen on NOx formation.
TABLE 3. EFFECT OF NITROGEN IN FUEL OIL
Nitrogen Content, Measured
Fuel weight percent NOx, ppm
V-954 0.44 550-750
SX-7812 0.38 570-750
V.950 0.23 300-450
General Observations
Several aspects of the data for both the oil and coal runs merit attention.
The particulate data for the coal runs present a reasonable picture of the sulfur distribu-
tion in the particulate, and the amount of sulfur removed from the flue gas in the electrostatic
precipitator for this laboratory system. However, the paucity of particulate data for the oil runs
mitigates against any firm conclusions concerning the amount of sulfur associated with the
particulate in those runs. The data obtained are reasonable, but any conclusions based on these
data must be considered only in a qualitative sense.
The fact that a loss of S02 was not observed consistently in the plume chamber is
perplexing. Although a reasonably large number (42? of inc~dences of S02 loss in the plume
chamber were observed, many of these occurred wIth relatIvely long residence times. Design
BATTELLE - COLUMBUS
-------
9
parameters of the plume chamber and initial verification of the plug-flow operation of the
chamber do not, in general, cover these longer residence times, so the actual dynamics of flow,
upon which treatment of the data is based, cannot be stated with certainty. Plug flow was
assumed for all calculations of rate constants in the plume chamber.
OTHER INVESTIGATIONS OF S02 DECAY IN PLUMES
The decay of S02 in real and simulated plume systems has been studied by a number of
other investigators. Johnstone and Coughanowr(6), Johnstone and Moll(7), and Matteson et al(8)
showed that the oxidation of S02 in aerosols is much faster than the photochemical oxidation
of S02 in dry air and that this oxidation could be greatly accelerated in the presence of iron and
manganese salts normally found as fly ash constituents. The work of Matteson indicates that the
observed rates of oxidation of S02 in aerosols are consistent with rates of oxidation of S02 in
solution, implying that the oxidation occurs within aqueous droplets formed in a plume.
Foster(9) has extended this notion with the development of a model based on oxidation of the
S02 within droplets which form and grow as a result of the rapid cooling of flue gas during the
early stages of plume development.
GartrellO 0), Dennis(3), and, most recently, Stephens and McCaldin( 4) have employed
aerial sampling of power station plumes as a means for direct measurement of the rates of
oxidation of S02 under totally realistic conditions. Although each of these studies was
confounded to some extent by the meteorological variability inherent in any real plume system
and the difficulties of aerial sampling, the results agree, at least qualitatively, with those of the
earlier laboratory studies. The conclusions of these full-scale studies can be summarized as
follows:
1. The overall rate of oxidation of S02 can be described in terms of a
first-order process with an apparent rate constant of the order of 10-3 to
10-2 min-l,
2. The relative humidity and/or the existence of a mist or fog in the
atmosphere are important in determining the apparent oxidation rate.
According to Stephens, the rate of oxidation of S02 is appreciable only
when the relative humidity of the ambient air is greater than about 40
percent.
Because of the appreciable scatter in the data for these full-scale studies, they cannot readily be
subjected to analysis with respect to any of the models developed from laboratory studies. The
assumption of a simple first-order rate process cannot be fully justified on the basis of existing
data. The importance of relative humidity of the ambient air is still not adequately resolved; in
fact, the use of this variable is probably somewhat misleading. The relative humidity within a
plume is probably close to 100 percent in the early stages of plume development. According to
Foster's model, the droplet concentration and size distribution are more important parameters to
be considered. Although these parameters are influenced by the relative humidity of the
surrounding atmosphere, they cannot be determined directly from a knowledge of the relative
humidity.
BATTELLE - COLUMBUS
-------
10
As indicated in the previous section, a decline in S02 concentration was not noted
consistently in the current plume-chamber experiments. However, for those experiments where a
decline was observed, a best value of about 8 x 10-3 min-l was obtained from a least-squares
treatment of the data. This value is intermediate between the values of 4.7 x 10-3 and 9.9 x
10-3 min-l reported by Stephens for relative humidity ranges of 40-55 and 78-80 percent,
respectively. It is toward the upper end of the range of rate constants which is calculated from
Gartrell's results and is about the same as the value of 7.6 x 10-3 min-l cited by Stephens for
the work of Dennis, but each of these values is certainly within the limits of experimental error
of the others. Indeed, the scatter in data for all of these investigators, our own included, is such
that statement of a specific value of k is of questionable validity. This only emphasizes the need
for a more detailed and precise investigation of the kinetics and modeling of real systems.
Unfortunately, the current work has not provided any firm conclusions concerning the
effect of relative humidity on the rate of oxidation of S02. Although a weak correlation
between rate constants and relative humidity was found, the data do not establish this variable as
the main influence on the rate of loss of S02 in the plume.
CONCLUSIONS
Indications of this work as they relate to the five objectives are:
1. The major source of decay of S02 within the combustion-boiler-stack
system was in the boiler-economizer section, wherein sorption of about
10 percent of the S02 by fly ash occurs. Essentially no loss of S02 was
observed in the stack. \
2. Within the range of fuels studied, the type of fuel used had little effect
on the behavior of S02, either within the combustion-boiler-stack system
or in the plume chamber.
3. With coals, the fraction of the fuel sulfur retained by the fly ash collected
in the electrostatic precipitator was approximately proportional to the ash
content of the coal.
4. First-order rate constants for the decay of S02 in the plume agreed with
those found by other investigators. These rate constants indicate a half-
life for S02 on the order of 1-6 hours.
5. The effect of relative humidity on the rate of decay of S02 in the plume
was not adequately resolved in this program. Special effort in further
defining this effect is clearly required. Such an effort should also include
the role of droplet concentration and size distribution in the plume.
BATTELLE - COLUMBUS
-------
11
ACKNOWLEDGMENTS
The authors express their appreciation to the members of the Steering Committee; L. E.
Niemeyer, Environmental Protection Agency; A. R. Rescorla, American Petroleum Institute; F.
W. Church, Esso Research & Engineering Co.; J. W. Tieman, Bituminous Coal Research, Inc.; J.
Endres, EEl; W. L. Wingert, The Detroit Edison Co.; J. R. Garvey, Bituminous Coal Research,
Inc.; and J. Wagman, Environmental Protection Agency, who assisted both in the design of the
experimental program and in preparation of this report. Special thanks are due to Mr. L.
Montgomery and Dr. F. Gartrell of the Tennessee Valley Authority for their helpful participation
in Steering Committee meetings.
(10)
(11 )
REFERENCES
(1)
Wickert, K., "Chemical Reactions in the Combustion Chamber of a Slag-Tap Boiler",
Brennstaff-Warme-Kraft,9, 104 (1957).
(2)
Smith, W. S., and Gruber, C. W., "Atmospheric Emissions from Coal Combustion - An
Inventory Guide", PHS Pub. No. 999-AP-24, April, 1966.
(3)
Dennis, R., et aI, "Measurement of Sulfur Dioxide Losses from Stack Plumes", APCA
Paper No. 69-156 presented at the 62nd Annual Meeting of the Air Pollution Control
Association, June 26, 1969, New York; "Study of Reactions of Sulfur in Stack Plumes",
Second Annual Report by GCA Corporation for National Air Pollution Control
Association, December, 1969.
(4)
Stephens, N. T., and McCaldin, R. 0., "Attenuation of Power Station Plumes as Deter-
mined by Instrumented Aircraft", Environ. Sci. Techno!., 5, 615 (1971).
(5)
Private communication from Mr. L. Montgomery of Tennessee Valley Authority.
(6)
Johnstone, H. F., and Coughanowr, D. R., "Absorption of Sulfur Dioxide from Air",
I & EC, 50, 1169 (1958).
(7)
Johnstone, H. F., and Moll, A. J., "Formation of Sulfuric Acid in Fogs", 1& EC, 52, 861
(1960).
(8)
Matteson, M. J., et aI, "Kinetics of Oxidation of Sulfur Dioxide by Aerosols of
Manganese Sulfate", 1& EC Fundamentals, 8, 677 (1969).
(9)
Foster, P. M., "The Oxidation of Sulfur Dioxide in Power Station Plumes", Atmos.
Environ., 3, 157 (1969).
Gartrell, F. E., et aI, "Full-Scale Study of Dispersion of Stack Gases", TV A Summary
Report (August, 1964).
Gokspyr, H., and Ross, K., "The Determination of Sulfur Trioxide in Flue Gases", J.
Inst. Fuel, 35, 177-179 (1962).
BATTELLE - COLUMBUS
-------
(12)
(13)
(14)
12
Bertolacini, R. J., and Barney, J. E., II, "Colorimetric Determination of Sulfate with
Barium Chloranilate", Anal. Chern., 29, 281-83 (1957).
Eschka, A., Ost.Z. Berg. u. Huttenw., 22, 11-13 (1874); Dinglers Poly tech., J., 212,403-4
(1874).
"Standards of Performance for New Stationary Sources", Federal Register, 36, No. 159,
15713-14, Aug. 17,1971.
BATTELLE - COLUMBUS
-------
APPENDIX A
EXPERIMENTAL EQUIPMENT AND METHODS
BATTELLE - COLUMBUS
-------
A-I
APPENDIX A
EXPERIMENTAL EQUIPMENT AND METHODS
MULTIFUEL FURNACE FACILITY
Design Features
The multifuel furnace used for this program was designed to generate flue gas and fly ash
under conditions closely simulating those of a power-generation station. This implies combustion
at a high enough temperature with a proper cooling schedule to produce flue gas and fly ash
having physicochemical properties similar to those of a typical central-station boiler and its
associated stack and plume. In addition, the laboratory-scale system used in this program had to
be flexible enough to permit firing with either pulverized coal or residual oil.
The Multifuel Furnace Facility was operated with an electrostatic precipitator for coal
firing but without the electrostatic precipitator in firing oils. The time-temperature profiles in the
other sections of the facility were appropriately adjusted for the inclusion or exclusion of the
precipitator.
Figure A-I is a schematic of the gas-combustion and flue-gas-conditioning system with
major sections and sampling points indicated. Design and operation of the plume chamber are
discussed later. The other major sections of the system are discussed below.
The Multifuel Furnace. Figure A-2 is a photograph of the Battelle multifuel furnace used
on this program. This small-scale furnace consists of a cylindrical combustion chamber approxi-
mately 17 inches in diameter by 90 inches in length. The furnace is lined with three layers of
firebrick and insulation to accommodate surface temperatures up to 2900 F. At the outlet, the
diameter of the furnace is reduced to 5 inches to enclose the flame, provide for normal
recirculation, limit radiation losses, and provide sufficient gas velocity to keep fly ash suspended
in the gas stream. Viewports along the axial dimension of the furnace provide for visual access
during periods of adjustment of firing conditions.
In normal operation of the furnace, natural gas was fired to maintain system tempera-
tures at approximately the desired levels on a more or less continuous basis while runs were not
being made. Upon switching to either coal or oil firing, the entire system was allowed to
equilibrate for several hours before any data were taken.
An adjustable-flow, positive-displacement pump that was pre calibrated was used to
regulate the supply of residual oil to the furnace at about 3 gal/hr, and the oil was preheated to
insure the desired viscosity at the burner nozzle. With coal firing, a dispersion of the fuel in air
was fed to the burner (at a rate of about 30 lb/hr) via a screw feeder mounted within a
pressurized coal hopper.
BATTELLE - COLUMBUS
-------
Burner
Air
Fuel
A-2
Plume Chamber
1
Simulated stack
section
,---
I
I
I
I
I
G-3
P-3
P-2
Furnace
--~
Electrostatic
Precipitator
G-2
G= Gas-Sampling Port
P= Particulate Sampling Port
Exhaust
G-5
P-I
Simulated boiler
sect ion
i---l
II
I I
I I
I I
I I
I I
I I
I I
~ I
I
I
I
~
.........
"
Exhaust
Figure A-I. Schematic of Laboratory System
-------
m
~
-4
-4
m
,..
,..
m
n
o
,..
c
~
m
c
IJI
~
w
Figure A-2. Battelle Multifuel Furnace
-------
A-4
Simulated Boiler/Economizer Section. The simulated boiler/economizer section of the rig
was constructed of stainless steel pipe lined with a castable refractory material. Gas velocities
within this section were modulated using a variable exhaust duct at the head of the section. This
operation also helped in maintaining desired temperatures, and additional control over tempera-
ture profiles was gained through the use of removable insulation on the outside of the section.
Gas velocities in horizontal portions of this section were typically 60 ft/sec, and velocities in
vertical portions were about 5 ft/sec. Temperatures dropped from about 2600 F at the inlet to
about 400 F or less at the outlet.
Electrostatic Precipitator. An electrostatic precipitator was used for removal of fly ash
between the boiler and stack sections of the system for runs made with coal firing. Typically,
the inlet and outlet temperatures of the precipitator were 375 F and 300 F, respectively.
Stack. The 37-foot-long simulated stack section of the rig was constructed of 5-inch-OD
stainless steel pipe. Temperatures in the stack section were controlled through the use of heating
tape and insulation applied throughout the length of the section. For runs with residual oils, the
stack temperature was maintained at about 300 F. With coal firing of the unit, the stack
temperature was maintained at 250-275 F. These values are typical of central-station operation
with these fuels. Sampling points were provided at 3-foot intervals along the stack section, but as
little or no S02 loss was observed in the stack, only the ports nearest the entrance and exit of
the stack were used.
Operational Characteristics
The operational characteristics of prime interest to this program concerned the time-
temperature profiles obtained in the system. Typical time-temperature profiles for oil and coal
firing are shown in Figures A-3 and A-4. Residence times with coal firing were similar to those
with oil firing except for the extra 5-second residence time in the precipitator. Temperatures in
the system were also similar for both types of fuel except for the slightly lower stack
temperatures used with coals.
PLUME CHAMBER
Design Features
Figure A-5 is a schematic of the plume-dilution chamber. This apparatus consists of a
small chamber for mixing of the flue gas with humidified air and a semiconical section to serve
as an expansion and reaction chamber. The chamber was constructed of aluminum, with the
walls Teflon coated to minimize chemical interaction between them and the simulated plume.
The 6-degree angle of the conical portion of the chamber was specifically designed to minimize
dynamic interaction effects between the walls and the flowing gas stream. The chamber was
heated electrically to maintain constant temperature, and sampling of the flue gas was
accomplished with a movable probe along the centerline of the chamber.
BATTELLE - COLUMBUS
-------
A-5
2600
Oil Firing
2400
?OOO
~ 1600
~
.2
e
'"
a.
E
~ 1200
600
400
Bumer- I
Furnace i
o
Boder / Economizer
/ Air - reofer
Stack
-4see --.1...
-8 see
I..
Figure A-3. Time-Temperature Profile Typical of Oil Firing
2400
~ooo
u..
~ 1600
:>
E
'"
a.
E
o!!!
1200
Coal Firing
600
400
Burner - Ii
Fu rnace
J
,
I PreCIpItator
I
Stack
BOller/ Economizer
/ Air - heater
1
r--- -4 see
-5 see ---I"
-I..
I
-8 see
Figure A-4. Time-Temperature Profile Typical of Coal Firing
~I
-I
-------
NDIR
A-6-
Q)
.c
o
L..
E
c
(J)
Hu~idified ~
air
Teflon-coated
plume chamber
Scale: 3/4 in. :: I ft
Mixer
L Flue gas from furnace
Figure A-S. Schematic of Plume Chamber Layout
-------
A-7
Operational Characteristics
Probe Assembly. The sampling pro be used in the plume chamber consisted of a 10-ft
length of 1/4-inch-OD Teflon tubing, the tip of which was tapered to approximately 1/16-inch
OD. The probe was mounted on a movable pulley system, fully contained within the chamber
and exhaust duct. Thus, the entire probe was kept at temperature, and a constant probe length
was maintained. Gas was pumped through the probe into a condenser-trap-arrangement where
samples were collected for sulfuric acid analyses. The remaining gas was then directed into an
NDIR instrument or an electrochemical transducer (Faristor) for continuous monitoring of 802
or NOx concentrations, respectively.
The ID of the Teflon tube used as a probe was approximately 3/16 inch, and gas was
drawn through the probe at a rate of approximately 1500 cm3/min. This is equivalent to a linear
flow of 4.6 ft/sec, thus giving about 2 seconds residence of the gas in the probe.
Mixer. Compressed air was used as a source for dilution. The supply stream was divided
into two branches, with appropriate orifice metering on each segment. Provision was made for
injection of steam into one branch of the air supply to saturate that part of the air with water
vapor. This saturated portion of the air was then led through a cooled cyclone-type separator to
remove excess water and return the air temperature to near ambient. This humidified air was
mixed with relatively dry air from the second branch of the air supply system and passed
through a baffle chamber to remove any entrained water droplets prior to entrance into the
mixing chamber at the bottom of the plume chamber. Through adjustment of the air flows
through the two branches of the system, any desired relative humidity up to approximately 100
percent could be achieved. The humidity was monitored continuously at a point just prior to
entry into the dilution chamber.
Flow Profiles. The plume-dilution chamber was designed to provide for plug flow of
gases. This aspect of the performance was checked out using both hot-wire anemometers and
boron trifluoride for visual display. The hot-wire anemometer proved to be unsatisfactory for use
in the plume chamber experiments because of the low linear flow rates to be used. However,
injection of boron trifluoride provided a smoke which enabled visualization of the flow patterns.
Results of this work indicated no appreciable eddy or jet formation. It therefore appears that
flow through the chamber under conditions employed in full-scale runs can best be described as
plug flow.
Temperature Profiles. The plume chamber was designed to operate as an isothermal
chamber, with automatic control of the chamber temperature to match that of the flue gas-air
mixture in the mixing chamber. The control system was sufficiently flexible, however, to permit
operation of the chamber at higher temperatures for some of the runs.
Temperature profiles of the chamber were obtained both with and without gas flowing
through the chamber. Results of these measurements indicate that temperatures within the
chamber were constant to within :t10 F.
BATTELLE - COLUMBUS
-------
A-8
ANAL VSIS METHODS
Flue Gas
502- Sulfur dioxide concentrations in the flue gas were monitored continuously using a
Beckman Model 315 A non dispersive infrared (NDIR) instrument. Water vapor was removed prior
to entering the instrument because it interferes with the S02 analysis. Other constituents in the
gas phase do not seriously interfere with the S02 readings. Under dry conditions, the S02
standards could be reproduced to within II percent. To further substantiate the S02 levels
recorded by the NDIR method, spot checks were made from time to time using the Goks~yr-
Ross method to analyze for soil}). In this method, the S02 is oxidized by hydrogen peroxide
to sulfuric acid and the acid is titrated with standard sodium hydroxide solutions.
503' The sulfur trioxide level in the flue gas was determined, after condensation as
sulfuric acid, by titration or by a colorimetric method involving barium chloranilate(l2). For low
values of S03 «5 ppm) or for short sampling times, the colorimetric method was generally used
because considerably smaller quantities of S03 are required for this method. Otherwise, a
sufficient sample of acid was collected using the Goks~yr-Ross technique and the acid was
titrated with standard sodium hydroxide solution.
NOx' Nitrogen oxides were monitored continuously using an Enviro-Metrics Faristor
detector that detects both NOx and S02. To obtain the correct NOx values in the flue gas, the
S02 contribution to the total readout values either was subtracted electronically using an
additional Faristor specifically for S02 or the total readout values were corrected for S02
contribution by standardizing the NOx-S02 Faristor with both NO and S02 and subtracting the
appropriate amount of S02. The latter method was used almost exclusively in this program.
Instrument specifications indicate a reproducibility of about I2 percent. However, problems
encountered with baseline drift in the instrument probably can account for an additional 10
percent error or more in the NOx data.
Fuels
Fuels used on this program were three residual oils and three coals. These materials were
supplied to Battelle-Columbus by the Sponsors and some were accompanied by analyses. All of
the materials were reanalyzed at Battelle-Columbus, and additional checks were obtained from
independent analyses by other laboratories. For the residual oils, additional sulfur analyses were
obtained from Esso R&E. The three coals were reanalyzed by Bituminous Coal Research, Inc.
Residual Oils. Samples of the three residual oils were analyzed for C, H, N, and S using
standard procedures. C, H, and N values were obtained using a microcombustion procedure, and
the nitrogen contents of the oils were verified using a micro-Kjeldahl method. The sulfur
contents of the oils were determined by the peroxide-bomb and X-ray methods; the latter is
probably more accurate. A listing of the results of these analyses is given in Table A-I.
BATTELLE - COLUMBUS
-------
A-9
TABLE A-1. RESIDUAL OIL ANALYSES
Percentage of Elemental Constituents
Oil C H N(a) N(b) flc) S(d) S(e)
V-954([) 85.1 10.9 0.4 0.44 2.28 2.37 2.43
V-950(g) 86.1 12.2 0.2 0.23 0.82 0.9 0.96
SX-7812(h) 85.3 10.7 0.4 0.38 2.39 2.33 2.64
(a) Microcombustion method.
(b) Kjeldahl method.
(c) Peroxide-bomb method.
(d) Supplier's analysis.
(e) X-ray method by Esso R&E.
([) Venezuelan oil.
(g) Desulfurized V-954.
(h) Mid-continent oil.
Coals. Samples of the three coals were analyzed for C, H, N, S, ash, and H20. C, H, and
N values were obtained by a micro combustion procedure using a Perkin Elmer Model 240
Elemental Analyzer; ash content was determined by ashing the coal at 1382 F; H20 was
determined by weight loss at 220 F; and sulfur was determined by the Eschka(l3) method. Data
obtained by Battelle-Columbus and BCR are listed in Table A-2.
Particulates
Particulate samples were collected using the standard EPA sampling rig(l4). This rig ..1
consists of a heated probe and filter assembly followed by a set of Greenburg-Smith impingers
immersed in an ice bath. Flue gas is pumped through the sampler at a rate determined to
maintain isokinetic sampling, and the flow rate is measured dry by a dry-gas meter. Particulate
samples were taken with this apparatus at a point between the boiler/economizer and stack
sections of the system when firing with oil (Point pol on Figure A-I), and both before and after
the precipitator when firing with coal (Points pol and P-3 on Figure A-I). In addition, samples
were withdrawn by hand from the precipitator catch when firing with coal (Point P-2 on Figure
A-I).
Analyses of the particulate samples consisted of separate analyses of probe, filter, and
impinger catches. These analyses were carried out using two different procedures. For most of
the filter catches, X-ray fluorescence (XRF) by a Norelco X-ray Fluorescence Vacuum
Spectrograph was used to determine sulfur content. Probe and impinger samples were analyzed
by dissolution of the remaining particulate using an ion-exchange resin followed by barium
chloranilate (BCA) colorimetric determination. The BCA data were further checked using a
gravimetric precipitation procedure. Results of the XRF, BCA, and gravimetric determinations
are listed in Appendix D.
BATTELLE - COLUMBUS
-------
m
]:I
-i
-i
m
r
r
m
TABLE A-2. COAL ANALYSES
Percentage Percentage Percentage Elemental Constituents S(a)
Coal Moisture Ash (a) c(a) c(b) H(a) H(b) N(a) N(b) Inorganic Organic s(b) Die)
Unwashed(d) 1.3 15.4 68.8 68.9 5.01 4.7 1.2 1.2 2.82 1.08 3.94 4.37 ~
-
Washed (e) 0
1.44 7.3 76.6 17.0 5.46 5.1 1.4 1.3 1.84 1.14 3.04 4.78
n
o
r
I:
s:
m
I:
UI
(a) Dry basis, determined by Bituminous Coal Research, Inc.
(b) Dry basis, determined by Battelle-Columbus.
(e) By difference.
(d) Raw Pittsburgh-seam coal.
(e) Washed Pittsburgh-seam coal.
-------
APPENDIX B
FURNACE-STACK DATA
BATTELLE - COLUMBUS
-------
B-1
TABLE B-1. FURNACE-STACK RUNS WITH RESIDUAL OILS
Firing and Sampling Conditions
Flue Gas Residence Ory Basis
Furnace Oxygen, Sampling Time from Sampling Concentrations, ppm
Run Fuel Temp, F percent Point Burner, sec Temp, F S02 S03 NOx
1-A V-954 2840 2.7 2 0.8 > 2240 880 105 865
1-8 V-954 2840 2.7 3 6.5 ~300 1030 9 560
1-C V-954 2840 2.7 5 11.9 315 1050 23 530
2-A V-954 2810 3.7 2 1.0 1800 1110 13 480
2-8 V-954 2810 3.7 3 6.7 405 855 6 360
2-C V-954 2810 3.7 5 12.1 355 900 5 425
3-A V-954 2770 4.8 2 1.0 1800 1040 17 430
3-8 V-954 2770 4.8 3 6.7 380 910 7 420
3-C V-954 2770 4.8 5 12.1 340 910 10 430
4-A V-954 2840 2.6 2 1.0 1920 1190 15 690
4-8 V-954 2840 2.6 3 6.7 400 1080 17 650
4-C V.954 2840 2.6 5 12.1 355 1100 23 630
4-0 V-954 2880 2.4 2 1.0 1880 1120 12 760
4-E V-954 2880 2.4 3 6.7 357 1010 11 790
4-F V-954 2880 2.4 5 12.1 322 1100 12 765
4-G V-954 2880 2.4 2 1.0 1880 1080 960
4-H V-954 2880 2.4 3 6.7 350 1135 810
4-1 V-954 2880 2.4 5 12.1 315 1110 780
5-A V-954 2830 2.4 2 0.9 2000 1180 24 570
5-8 V-954 2830 2.4 3 6.7 350 1115 7 660
5-C V-954 2830 2.4 5 12.2 350 1080 8 660
6-A V-954 2850 2.4 2 0.9 1980 1180 33 525
6-8 V-954 2850 2.4 3 6.5 305 1100 12 550
6-C V-954 2850 2.4 5 11.8 325 1100 13 570
7-A V-950 2850 2.4 2 0.9 2000 450 10 290
7-8 V-950 2850 2.4 3 6.7 298 380 3 335
7-C V-950 2850 2.4 5 12.6 314 380 4 345
7-0 V-950 2850 2.4 2 0.9 2000 430 9 470
7-E V-950 2850 2.4 3 6.7 300 445 4 400
7-F V-950 2850 2.4 5 12.6 317 390 4 445
8-A SX-7812 2850 2.4 2 1.1 1750 1425 26 600
8-8 SX-7812 2850 2.4 3 6.8 290 1240 7 610
8-C SX-7812 2850 2.4 5 12.4 312 1280 6 580
8-D SX-7812 2850 2.4 2 1.1 1750 1360 18 690
8-E SX-7812 2850 2.4 3 6.8 290 1085 6 710
8-F SX-7812 2850 2.4 5 12.4 312 1160 7 745
9-A SX-7812 2850 2.5 2 1.1 1680 1370 21 570
9-8 SX-7812 2850 2.5 3 6.9 325 1190 8 630
9-C SX-7812 2850 2.5 5 12.4 348 1190 9 690
10-A V-954 2830 2.6 2 1.1 1910 1150 412
10-8 V-954 2830 2.6 3 6.7 320 1124 404
10-C V-954 2830 2.6 5 12.3 325 1137 408
ll-A V-954 2830 2.7 2 1.0 1930 1133 423
11-8 V-954 2830 2.7 3 6.8 320 1102 456
13-A(a} V-954 2736 2.7 5 12.7 305 973 456
13-8 V-954 2825 2.7 5 12.7 305 973 563
13-C V-954 2835 2.7 5 12.7 320 623
13-D V-954 2850 2.7 5 12.7 320 1044 581
14-A SX-7812 2800 2.7 2 1.0 1860 1345 607
14-8 SX-7812 2800 2.7 5 12.9 320 1217 650
fa) Samples 13A through 0 used to check reproducibility 01 results; samples 13A and B taken in morning,
13C and 0 in afternoon-
BATTELLE - COLUMBUS
-------
B-2
TABLE B-2. FURNACE-STACK RUNS WITH COALS
Firing and Sampling Conditions
Flue Gas Residence Dry Basis
Furnace Oxygen, Sampling Time from Sampling Concentrations, ppm
Run Fuel Temp, F percent Point Burner, see Temp, F S02 S03 NOx
1-A Unwashed 2730 3.2 5 15.2 3350 440
2-A Unwashed 2900 3.5 2 1.02 1860 3525 290
2-8 Unwashed 2900 3.5 3 8.4 305 3450 437
2-C Unwashed 2900 3.5 5 13.5 278 3450 537
2-D Unwashed 2860 3.5 2 1.05 1860 3310 405
2-E Unwashed 2860 3.5 3 -(a) 294 3100 495
2-F Unwashed 2860 3.5 5 270 3200 554
2-G Unwashed 2860 3.5 2 1.05 1750 3475 561
2-H Unwashed 2860 3.5 3 280 3070 595
2-1 Unwashed 2860 3.5 5 265 3010 593
2-J(b) Unwashed 2860 3.5 5 240 3200 494
2-K Unwashed 2850 3.4 2 1.05 1800 4100 369
2-L Unwashed 2850 3.4 3 7.2 285 3850 506
2-M Unwashed 2850 3.4 5 11.4 260 4050 587
3-A Unwashed 2740 2.9 2 1.01 1900 2850 459
3-8 Unwashed 2740 2.9 3 10.1 287 2500 618
3-C Unwashed 2740 2.9 5 16.5 260 2470 736
4-A Unwashed 2800 3.5 2 1.03 1900 3275 433
4-8 Unwashed 2800 3.5 3 262 2610 649
4-C Unwashed 2800 3.5 5 245 2470 696
5-A Unwashed 2840 3.0 2 1.04 1995 3220 475
5-8 Un washed 2840 3.0 3 8.1 305 2950 625
5.C Unwashed 2840 3.0 5 12.7 285 2800 676
5-0 Unwashed 2880 3.4 2 1.05 2065 3050 972
5-P Unwashed 2880 3.4 3 257 2680 904
5.Q Unwashed 2880 3.4 5 243 2600 910
5-R Unwashed 2800 3.4 2 1.03 1930 3200 406
5-5 Unwashed 2800 3.4 3 9.3 270 3040 498
5-T Unwashed 2800 3.4 5 14.9 250 3140 481
6-A Unwashed 2770 3.4 2 1.02 1830 3570 7.4 362
6-8 Unwashed 2770 3.4 3 7.6 308 3650 16.5 516
6-C Unwashed 2770 3.4 5 11.9 282 3770 13.0 566
6-M Unwashed 2720 4.0 2 1.01 1860 2360 626
6-N Unwashed 2720 4.0 3 295 2740 685
6-0 Unwashed 2720 4.0 5 270 2800 730
6-P Unwashed 2720 7.1 2 1.01 1860 3200 15.8 718
6.Q Unwashed 2720 7.1 3 303 2875 24.6 687
6-R Unwashed 2720 7.1 5 272 2975 16.1 708
6-D' Unwashed 2730 7.2 2 1.01 3500 523
6-E' Unwashed 2730 7.2 3 7.4 3000 601
6-F Unwashed 2730 7.2 5 11.6 3050 625
BATTELLE - COLUMBUS
-------
B-3
TABLE B-2. (Continued)
Firing and Sampling Conditions
Flue Gas Residence Dry Basis
Furnace Oxygen, Sampling Time from Sampling Concentrations, ppm
Run Fuel Temp, F percent Point Burner, sec Temp, F S02 S03 NOx
7-A Unwashed 2800 3.8 2 1.03 1710 5500 10 208
7-8 Unwashed 2800 3.8 3 10.1 265 5450 0.78 357
7-G Unwashed 2800 3.8 5 16.3 255 5210 0.35 414
7-D(b) Unwashed 2850 3.8 5 3650 632
7-N Unwashed 2850 3.8 2 1800 3000 679
8-A Washed 2880 3.2 2 1.04 1900 2360 689
8-8 Washed 2880 3.2 3 18.7 290 2070 730
8-G Washed 2880 3.2 5 30.5 265 2070 750
8-D(b) Washed 2880 3.2 2 1900 2300 798
8-N Washed 2840 3.4 2 1.04 1920 1900 673
8-0 Washed 2840 3.4 3 15.0 275 1750 666
8-P Washed 2840 3.4 5 24.5 250 1750 686
9-A Washed 2800 3.7 2 1.02 1880 1960 439
9-8 Washed 2800 3.7 3 9.5 305 1825 519
9-G Washed 2800 3.7 5 15.0 345 1775 548
9-K Washed 2850 3.6 2 1.04 1880 2000 575
9-L Washed 2850 3.6 3 275 1875 569
9-M Washed 2850 3.6 5 270 1850 584
9-N Washed 2850 3.4 2 1.04 1885 2060 438
9-0 Washed 2850 3.4 3 13.1 270 1875 469
9-P Washed 2850 3.4 5 21.4 250 1700 578
9-A'(b) Washed 2890 3.6 3 260 1850 211
10-A Washed 2790 3.7 2 1.02 1805 1950 663
10-8 Washed 2790 3.7 3 11.2 275 1800 904
1Q-G Washed 2790 3.7 5 18.0 270 1750 938
10-D Washed 2800 3.8 2 1.03 1822 2060 457
1Q-E Washed 2800 3.8 3 9.2 283 2010 399
10-F Washed 2800 3.8 5 14.8 285 2060 457
11-A Washed 2780 3.4 2 1.02 1840 2550
11-8 Washed 2780 3.4 3 8.6 275 2300
11-G Washed 2780 3.4 5 13.6 265 2125
11-1 Washed 2800 3.4 2 1.03 1820 2490
11-J Washed 2800 3.4 3 7.9 235 2550
11-K Washed 2800 3.4 5 12.7 233 2300
11-P Washed 2800 3.4 2 1.03 2190
11-Q Washed 2800 3.4 3 8.7 2420
11-R Washed 2800 3.4 5 14.1 2700
11-S(b) Washed 2800 3.4 2 2500
12-A Unwashed 2780 3.6 2 1.02 1900 3340
12-8 Unwashed 2780 3.6 3 7.8 260 3200
12-G Unwashed 2780 3.6 5 12.6 270 3200
12-F Unwashed 2910 3.6 2 1.04 1900 3550
12-G Unwashed 2910 3.6 3 7.1 305 3650
12-H Unwashed 2910 3.6 5 11.2 280 3600
(a) Residence times not reported in a given series within residence times reported at beginning and end of
a series for each sampling pomt.
(b) Repeat of a prevIous sample (in same series) taken under similar sampling conditions.
BATTELLE - COLUMBUS
-------
APPENDIX C
PLUME-CHAMBER DATA
BATTELLE - COLUMBUS
-------
C-I
TABLE Co,. PLUME-CHAMBER RESULTS WITH RESIDUAL OILS
RelativeŁ' b)
Run Temp, Residencef a) Dilution Humidity, S02 Concentration, ppm
No. Fuel F Time, sec Ratio percent Bottom Center Top
1-D V-954 -325 57 0 NA 1010 1050
2-D V-954 320 58 0 NA 900 980
2-E V-954 215 3:1 325 320
4-H V-954 325 58 0 NA 1090 1070
5-D V-954 350 55 0 NA 1162 1162
5-E V-954 255 10 5: 1 <40 233 229 229
6-D V-954 272 55 0 NA 1030 994 1003
6-E V -954 205 10 5:1 <40 238 220 211
6-F V-954 145 4 15: 1 <40 75 70 75
6-G V-954 173 10 5:1 <40 224
6-H V-954 184 10 5: 1 >90 224 211 216
6-1 V-954 131 4 15: 1 >90 79 79 77
6-J V-954 109 4 15: 1 >90 85 85 85
6-K V-954 109 4 15: 1 <40 90
6-L V-954 135 10 5: 1 <40 207 211 213
6.M V-954 186 55 0 NA 1074 1056
7-D V-950 242 55 0 NA 374 374 374
7-E V-950 240 178 0 NA 387
7-F V-950 175 12 15: 1 >90 29 28 26
7-G V-950 180 25 7: 1 >90 82 82 82
7-H(c) V-950 180 25 7: 1 >90 82
7-1 V-950 180 178 0 NA 380
8-G SX-7812 253 55 0 NA 1280 1219
8-H(c) SX-7812 264 55 0 NA 1188 1157
8-1 SX-7812 201 10 5: 1 <40 249 262
8.J SX-7812 150 4 15: 1 <40 95 95
8-K SX-7812 144 4 15: 1 >90 92 95
8-L SX-7812 152 10 5: 1 >90 253 253
9.D SX-7812 268 55 0 NA 1214 1214
9-E SX-7812 217 10 5: 1 <40 161 161
9-F SX-7812 175 4 15: 1 <40 99 99
9-G SX-7812 195 10 5: 1 <40 223
9-H SX-7812 165 10 5: 1 >90 223 216 209
9-1 SX-7812 154 10 5: 1 >100(d) 209
9-J SX-7812 154 >15 <5:1 >100(d) 152 161
10-D V-954 150 1920 0 NA 403 336
10-F V-954 145 320 5: 1 <40 104 104
10-H V-954 150 120 15: 1 <40 31 35 34
Footnotes appear at end of table.
BATTELLE - COLUMBUS
i i ~L,
-------
C-2
TABLE Co,. (CONTINUED)
Relativefb)
Run Temp, Residencef a) Dilution Humidity, 502 Concentration, ppm
No. Fuel F Time, sec Ratio percent Bottom Center Top
10-J V -954 155 320 5:1 >90 93 111
10-L V-954 155 320 5: 1 <40 97
11-C V-954 195 1920 0 NA 403 327
11-E V-954 185 320 5: 1 >70 111 142 124
11-F(c) V -954 180 320 5: 1 >70 115 133
11-G V-954 165 120 15: 1 >70 49 49 49
11-1 V-954 160 320 5: 1 >70 119 142
12-D SX-7812 160 1920 0 NA 938 885 872
12-K(c) SX-7812 1920 0 NA 827 752 743
12-M SX-7812 150 320 5: 1 <40 93 128 128
12-P SX-7812 320 5: 1 <40 73
12-Q SX-7812 150 320 5:1 >70 75 95 84
12-T SX-7812 190 320 5: 1 »100(d) 71 59
13-E V-954 130 1920 0 NA 735 699 690
13-G V-954 175 1920 0 NA 752 681 673
13-1 V-954 170 320 5: 1 <40 124 137 135
13-K V-954 160 120 15: 1 <40 52 52 52
13-L V-954 158 120 15: 1 >70 52 52
13-N V-954 152 320 5:1 >70 131 131
13-P V-954 320 5: 1 »1Oofd) 137
13-Q V-954 320 5: 1 <40 127
14-C SX-7812 196 1920 0 NA 938 788
14-D(c) SX-7812 196 1920 0 NA 947
14-E SX-7812 203 1920 0 NA 1018 805
(a) Residence time for full-chamber length.
(b) Relative humidity of dilution air; NA means no dilution air.
(c) Repeat of previous samples under similar operating conditions.
(d) Excess steam injected with dilution air.
BATTELLE - COLUMBUS
-------
C-3
TABLE C-2. PLUME CHAMBER RESULTS WITH COALS
Relativefb )
Run Temp, Residencef a) Dilution Humidity, S02 Concentration, ppm
No. Fuel F Time, sec Ratio percent Bottom Center Top
1.8 Unwashed 640 0 NA 1050
1-e Unwashed 640 0 NA 1400
1.0 Unwashed 640 0 NA 1650
2.N Unwashed 213 1920 0 NA 2050 1925 1925
2.0(e) Unwashed 238 1920 0 NA 2150
2-P Unwashed 384 5: 1 <40 300
2.Q Unwashed 210 1920 0 NA 2110 1610 1610
2-R(e) Unwashed 238 1920 0 NA 2100
3-D Unwashed 130 1920 0 NA 2350 2270 2250
3.E(e) Unwashed 220 1920 0 NA 2250
3-F Unwashed 384 5: 1 <40 290
5-0 Unwashed 258 1920 0 NA 2740 2550 1700
5-E Unwashed 256 1920 0 NA 2420 1875 1750
5-F(e) Unwashed 280 1920 0 NA 2490
5-G Unwashed 243 384 5:1 <40 450 510 460
5-H(e) Unwashed 260 384 5:1 <40 410
5.1 Unwashed 230 128 15: 1 <40 145 135 125
5-ia) Unwashed 225 128 15: 1 <40 140
5.K Unwashed 218 384 5: 1 >70 370 380 385
5-L(e) Unwashed 230 384 5: 1 >70 365
5.M Unwashed 384 5:1 <40 300
5.N Unwashed 240 1920 0 NA 2360
5-U Unwashed 232 1920 0 NA 2275 1650 1625
5-V(e) Unwashed 245 1920 0 NA 2280
5-W Unwashed 232 384 5: 1 <40 305 380 365
5-X(e) Unwashed 248 384 5: 1 <40 360
5-Y Unwashed 221 128 15: 1 <40 105 95 92
5-Z(e) Unwashed 208 128 15: 1 <40 90
5-A Unwashed 214 384 5: 1 >70 300 300 315
5-8(e) Unwashed 384 5: 1 >70 295
5-C Unwashed 384 5: 1 <40 265
5.D Unwashed 1920 0 NA 2330
6-D Unwashed 225 1920 0 NA 3275 2650 2610
6-E(e) Unwashed 257 1920 0 NA 3200
6-F Unwashed 221 384 5: 1 <40 550 560 550
6.Gf e) Unwashed 240 384 5: 1 <40 565
6.H Unwashed 208 128 5:1 <40 185 200 205
6-1 Unwashed 226 384 5:1 <40 415
6-J Unwashed 210 384 5:1 >70 380 440 435
6-K(e) Unwashed 224 384 5: 1 >70 385
6-L Unwashed 224 384 5: 1 <40 390
Footnotes appear at end of table.
BATTELLE - COLUMBUS
-------
C-4
TABLE C-2. (Continued)
Relativefb)
Run Temp, Residence' a) Dilution Humidity, 502 Concentration, ppm
No. Fuel F Time, see Ratio percent Bottom Center Top
6-R Unwashed 220 1920 0 NA 2260 1700 1675
6-T(e) Unwashed 240 1920 0 NA 2275
6-U Unwashed 220 384 5: 1 <40 400 450 425
6-V(e) Unwashed 235 384 5: 1 <40 375
6-W Unwashed 210 128 15: 1 <40 155 150 145
6-X(e) Unwashed 128 15: 1 <40 145
6-Y Unwashed 220 384 5:1 <40 370
6-Z Unwashed 204 384 5: 1 >70 340 385 370
frA'(e) Unwashed 217 384 5: 1 >70 340
frS' Unwashed 217 384 5: 1 <40 340
frC' Unwashed 1920 0 NA 2060
7-E Unwashed 223 1920 0 NA 2740 2530 2510
7-F(e) Unwashed 250 1920 0 NA 2610
7-G Unwashed 226 384 5: 1 <40 450 420 365
7.1 Unwashed 220 128 15: 1 <40 105 100 95
7-Jfe) Unwashed 208 128 15: 1 <40 95
7-K Unwashed 384 5: 1 <40 270
7-L Unwashed 210 384 5: 1 >70 270 285 270
8-E Washed 220 1920 0 NA 1125 1125 1100
8-F(e) Washed 247 1920 0 NA 1350
8-G Washed 218 384 5: 1 <40 300 335 355
84 e) Washed 234 384 5:1 <40 365
8-J Washed 208 128 15: 1 <40 165 180 205
8-K( e) Washed 200 128 15: 1 <40 215
8-L Washed 205 384 5:1 >70 320 355 380
8-M( e) Washed 1920 0 NA 1290
9-D Washed 145 1920 0 NA 1225 1050 1025
9-E(e) Washed 234 1920 0 NA 1150
9-F Washed 170 384 5: 1 <40 150 180 160
9-G Washed 170 128 15: 1 <40 55 50 45
9-H Washed 160 384 5: 1 >70 110 120 115
9-I(e) Washed 210 384 5: 1 >70 85
9-J Washed 210 384 5: 1 <40 85
9-Q Washed 250 1920 0 NA 1280 1020 810
9-R(e) Washed 240 1920 0 NA 1210 1000 830
9-T Washed 233 384 5:1 <40 150 162 177
9-U( e) Washed 241 384 5: 1 <40 145
9-V Washed 215 128 15: 1 <40 45 40 37
9-W( e) Washed 214 128 15: 1 <40 35
9-X Washed 215 384 5: 1 >70 110 115 110
9-y(e) Washed 218 384 5: 1 >70 105
9-Z Washed 218 384 5:1 <40 100
10-G Washed 185 1920 0 NA 1550 1185 1150
10-H(e) Washed 183 1920 0 NA 1490
10-1 Washed 187 384 5: 1 <40 200 210 200
10-J Washed 180 384 5:1 >70 165 170 160
10-K(e) Washed 225 384 5: 1 >70 150 170 160
Footnotes appear at end of table.
BATTELLE - COLUMBUS
-------
C-5
TABLE C-2. (Continued)
Relativefb)
Run Temp, Residence' a) Dilution Humidity, 802 Concentration, ppm
No. Fuel F Time, sec Ratio percent Bottom Center Top
11-0 Washed 264 873 0 NA 1375 1375 1200
11-E(c) Washed 264 873 0 NA 1375
11-F Washed 241 175 5: 1 <40 200 200 200
11-G Washed 232 175 5: 1 >70 120 140 140
11-L Washed 256 800 0 NA 1890 1910 1700
11.M Washed 227 160 5: 1 <40 360 350 360
11-N Washed 208 160 5: 1 >70 400 360 350
12-0 Unwashed 256 800 0 NA 2550 2490 2040
12-E Unwashed 237 160 5: 1 <40 425 440
12-1 Unwashed 230 800 0 NA 2740 2550 2550
12-J Unwashed 214 160 5: 1 <40 440 430 420
12-K(c) Unwashed 800 0 NA 2370
12-L Unwashed 230 160 5: 1 >70 440 400 400
12.M(c) Unwashed 160 5: 1 >70 460
12-0(c) Unwashed 800 0 NA 2360
(a) Residence time for full-chamber length.
(b) Relative humidity of dilution air; NA means no dilution air.
(c) Repeat runs.
BATTELLE - COLUMBUS
-------
C-6
TABLE C-3. SUMMARY OF S02 LOSSES OBSERVED IN THE PLUME CHAMBER
RelativJ a)
Residence Humidity, 5°2, ppm
Fuel Run Time, see percent Input Output k, min-1
Coal 2-n 1920 NA 2050 1925 2.0 x 10-3
2-q 1920 NA 2110 1610 8.4 x 10-3
3-d 1920 NA 2350 2250 1.4 x 10-3
5-d 1920 NA 2740 1700 1.5 x 10-2
5-e 1920 NA 2420 1750 1.0 x 10-2.
5-i 128 <40 145 125 7.0 x 10-2
5-u 1920 NA 2275 1625 1.1 x 10-2
5-y 128 <40 105 92 6.2 x 10-2
6-d 1920 NA 3275 2610 7.1 x 10-3
6-R 1920 NA 2260 1675 9.4 x 10-3
6-w 128 <40 155 145 3.1 x 10-2
7-e 1920 NA 2740 2510 2.7 x 10-3
( 3.3 x 10-2
7-9 384 <40 450 365
7-i 128 <40 105 95 4.7 x 10-2
8-e 1920 NA 1250 1100 4.0 x 10-3
9-d 1920 NA 1225 1025 5.6 x 10-3
9-9 128 <40 55 45 9.4 x 10-2
9-q 1920 NA 1280 810 1.4 x 10-2
9-r 1920 NA 1210 830 1.2 x 10-2
9-v 128 <40 45 37 9.2 x 10-2
10-9 1920 NA 1550 1150 9.3 x 10-3
11-d 800 NA 1375 1200 1.0 x 10-2
11-n 800 >70 400 350 1.0 x 10-2
12-d 800 NA 2550 2040 1.7 x 10-2
12-i 800 NA 2740 2550 5.4 x 10-3
12-j 800 <40 440 420 3.5 x 10-3
12-Q 800 >70 440 400 7.1 x 10-3
Oil 4-H 58 NA 1090 1070 1.9 x 10-2
5-E 10 <40 233 229 1.0 x 10-1
6-E 10 <40 238 211 7.2 x 10-1
6-i 4 >90 79 77 3.8 x 10-1
6-M 55 NA 1074 1056 1.8 x 10-2
7-F 12 >90 29 26 5.4 x 10-1
8-G 55 NA 1280 1219 5.3 x 10-2
8-H 55 NA 1188 1157 2.9 x 10-2
9-H 10 >90 223 209 3.9 x 10.1
10-D 1920 NA 403 336 5.7 x 10-3
11-C 1920 NA 403 327 6.5 x 10-3
12-D 1920 NA 938 872 2.2 x 10.3
12-K 1920 NA 827 743 3.3 x 10-3
13-E 1920 NA 7j5 690 2.0 x 10-3
13-G 1920 NA 752 673 3.5 x 10-3
(a) Relative humidity of dilution air; NA = no dilution air.
BATTELLE - COLUMBUS
-------
"
APPENDIX D
PARTICULATE ANALYSES
BATTELLE - COLUMBUS
-------
D-l
TABLED-1. PARTICULATE SAMPLES....,
BEFORE PRECIPITATOR
Coal
Total,
S04= mg( a)
Gas
Volume,
cu ft at 68 F
Equivalent
PPM S02
Unwashed
Unwashed
Washed
Washed
Washed
Washed
Washed
Washed
Washed
Washed
Washed
Washed
261
224
190
271
165
72
110
170
114
165
274
180
16.35
18.28
13.92
21.3
11.88
11.90
23.4
13.7
16.4
11.8
11.5
13.3
145
111
124
115
126
55
42
112
88
126
102
118
(a) XRF analysis.
TABLE D-2. PARTICULATE SAMPLES-
AFTER PRECIPITATOR
Coal
Total,
S04= mg(a)
Gas
Volume,
cuftat68F
Equivalent
PPM S02
Washed
Washed
Unwashed
48.1
156.2
183
13.525
19.07
15.928
32
74
104
(a) SCA analysis.
BATTELLE - COLUMBUS
-------
D-2
TABLE D-3. PARTICULATE SAMPLES-
PRECIPITATOR CATCH
Equivalent
Percentage Percentage
Coal 804= of Coal Sulfur
Unwashed 15.9( a) 20.9
18.2(b)
Unwashed 13.3( a) 11.5
Washed 9.7(a) 7.9
Washed 1 0.9( a) 8.8
10.9(b)
(a) SCA analysis.
(b) Gravimetric analysis after carbonate fusion.
TABLE D-4. PARTICULATE SAMPLES
Oil
Gas Sample
S04= Volume, Equivalent S02
Wt, mg cuftat68F in Gas, ppm
26.2 10.1 23
25.3 14.7 15
V -954
SX-7812
BATTELLE - COLUMBUS
------- |