xvEPA
•
Air Emissions from
Combustion of Solvent
Refined Coal
Interagency
Energy/Environment
R&D Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gorfes were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
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The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
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mental issues.
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This report has been reviewed by the participating Federal Agencies, and approved
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-79-004
January 1979
Air Emissions from Combustion
of Solvent Refined Coal
by
Kenneth G. Budden and Subhash S. Patel
Hittman Associates, Inc.
9190 Red Branch Road
Columbia, Maryland 21045
Contract No. 68-02-2162
Program Element No. EHE623A
EPA Project Officer: William J. Rhodes
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
ABSTRACT
This report details the air emissions associated with
the Solvent Refined Coal (SRC) combustion test, conducted at
Georgia Power Company's Plant Mitchell, during the months of
March, May, and June, 1977. A larger study and evaluation
of SRC combustion test is being done by the Department of
Energy and its contractors. The purpose of the test was to
determine whether SRC is an acceptable substitute for coal,
and to demonstrate the assumed advantages of SRC. The test
was conducted in three phases, with coal being fired during
the first and second phases, and SRC during the third. Flue
gas samples were collected for modified U.S. Environmental
Protection Agency (EPA) Level I analysis, and analytical
results are reported. Air emissions from the combustion of
coal and SRC are compared for various organic and inorganic
constituents, and SOo and NOX. Finally, the impact of the
air emissions from the combustion of SRC is assessed by
comparison with EPA's Multimedia Environmental Goals and
existing New Source Performance Standards.
Air quality emissions test data indicated that SRC S02
and NOX emissions were 0.46 and 0.19 kg/GJ (1.06 and 0.43
Ib/lO^ Btu) respectively. This is about 12 and 39 percent
under the existing New Source Performance Standards (NSPS)
of 0.52 kg/GJ (1.2 lbs/100 Btu) for SOX and 0.30 kg/GJ (0.7
lbs/106 Btu). If the S02 standard is reduced to 0.26 kg/GJ
(0.6 lbs/10° Btu), SRC derived from high sulfur coal may not
meet this standard. The low NOX emissions may be a result
of abnormally high excess air that was used during the
combustion test and additional testing at normal conditions
is required.
Particulate emissions can be controlled well below the
EPA standard of 0.04 kg/GJ (0.1 Ibs/lO^ Btu) by installing a
modern precipitator having a particulate collection effi-
ciency of approximately 95 percent.
ii
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CONTENTS
Abstract ii
Figures and Tables iv
List of Abbreviations and Symbols vi
Acknowledgement vii
1. Introduction 1
2. Conclusions and Recommendations 4
3. Combustion Test 5
Sample collection 6
Sampling locations 7
Sampling schedule 8
4. Analyses 10
Grab samples 10
SASS train samples 10
5. Comparison of Air Emissions 27
Organics 27
Inorganics 28
S02 and NOX 29
6. Assessment of Air Emissions 32
Organics 32
Inorganics 32
S02 and N0x 34
Bibliography 37
iii
-------
FIGURES AND TABLES
Figure
Number Page
1 SASS Train Flowsheet 6
2 Diagram of Sampling Locations 8
3 Analytical Procedures Followed in SASS Train
Run Analysis 15
4 MEG Chart, November 1977 Version 33
Table
Number Page
1 Phase II - Coal Combustion Test Sampling
Schedule 9
2 Phase III - SRC Coal Combustion Test Sampling
Schedule 9
3 On-Site Analysis of Grab Samples, Phase II -
Coal Combustion 11
4 On-Site Analysis of Grab Samples, Phase III -
SRC Combustion 12
5 Combustion Test, Phase II - Coal Samples .... 13
6 Combustion Test, Phase III - SRC Samples .... 13
7 Process Information 14
8 GC Analysis for Cj through C-,, Hydrocarbons . . 16
9 IR Examination of Nonvolatile Hydrocarbons,
June 16, 1977 18
10 IR Examination of Nonvolatile Hydrocarbons,
June 19, 1977 18
IV
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Table
Number Page
11 Total Hg, As, and Sb in Particulates and
XAD-2 Resin Samples 19
12 SSMS Elemental Analysis of SASS Train Samples. . 20
13 SSMS Analysis of SRC Sample 22
14 Elements Selected for Part II Inorganic
Analysis 23
15 Process Information 24
16 GC Analysis for Cy through C-,« Hydrocarbons . . 25
17 AA Analysis for Inorganics 26
18 Organic Air Emissions for Coal and SRC 28
19 Inorganic Air Emissions for Coal and SRC .... 29
20 S09 and NC- Emissions for Coal and SRC 30
fc 2x
21 Comparison of SRC Air Emissions with MEG's ... 35
-------
LIST OF ABBREVIATIONS AND SYMBOLS
MW
ABBREVIATIONS
AA -- atomic absorption spectrophotometry
Btu -- british thermal unit
CFM -- cubic feet per minute
DSCF -- dry standard cubic feet
EOD -- elimination of discharge
EPC -- estimated permissible concentrations
ESP -- electrostatic precipitator
GC -- gas chroma tography
GC/MS -- gas chromatography/mass spectrometry
IR -- infrared spectra «
kg/GJ -- kilogram per giga (10 ) joules
LRMS -- low resolution mass spectrometry
MATE -- minimum acute toxicity effluents
MC -- mass constituent
MEG -- multimedia environmental goals
MJ/kg -- mega joules per kilogram
-- megawatt
-- cubic meter
mg -- milligram
ml -- milliliter
mg/m3 -- milligram per cubic meter
nm -- nanometer
PAH -- polynuclear aromatic hydrocarbon
ppb — parts per billion
ppm -- parts per million
SASS -- source assessment sampling system
SRC — solvent refined coal
SSMS -- spark source mass spectrometry
SYMBOLS
As -- arsenic
C - - carbon
CH2C12 — methylene chloride '
CO -- carbon monoxide
C0£ -- carbon dioxide
Hg -- mercury
NOX -- nitrogen oxides
Sb -- antimony
S02 -- sulfur dioxide
M — micron
Mg/g -- microgram per gram
Mg/m3 — microgram per cubic meter
vi
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ACKNOWLEDGMENT
We gratefully acknowledge the contributions made to
this report by the following individuals: Richard McRanie
and Robert Gehri of Southern Company Services; Walter Dixon
of Southern Research Institute; Richard Corey of Department
of Energy; and Mike Hartman, Arnie Grant and Carol Zee of
TRW.
vxx
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SECTION 1
INTRODUCTION
The U.S. has more energy available in the form of coal
than in the combined resources of petroleum, natural gas,
oil shale, and tar sands. In light of nationwide energy
shortages, the increased use of our abundant coal reserves
is vital to the nation's total supply of clean energy.
Consequently, converting coal to liquid and gaseous fuels is
fundamental to ensuring the availability of fuel as these
alternate sources become less certain.
The primary users of coal are the electric utilities,
which mechanically clean, pulverize and burn coal in solid
form. Coal combustion, however, is a major source of air
pollution, i.e., sulfur oxides, nitrogen oxides, and partic-
ulate matter. The combustion of coal by electric utilities
is also a potential source of water and land pollution.
To minimize air pollution from the combustion of coal
by electric utilities, the Solvent Refined Coal Process is
being developed. This process cleans coal prior to its
firing in boilers by the removal of sulfur and mineral
matter, for the purpose of eliminating the need for stack
gas cleaning. The product, Solvent Refined Coal (SRC), is
lower in sulfur and ash, and has a higher heating value than
the original coal.
In 1972 an all-industry group, presently consisting of
•Electric Power Research Institute and Southern Company Ser-
vices, .initiated a pilot plant project to study the tech-
nological feasibility of the SRC process. Operating infor-
mation from this pilot plant was used to design and build a
45 metric ton per day pilot plant in Fort Lewis, Washington.
This project funded by the U.S. Department of Energy (DOE)
is developed by Pittsburgh & Midway Coal Mining Company, a
subsidiary of Gulf Oil Corporation. The pilot plant has
been in operation since October 1974 and has produced 2,720
metric tons of SRC for the functional product testing in a
boiler.
With the company's involvement in developing the SRC
process, Southern Company Services was awarded a separate
-------
contract by DOE to evaluate the shipping, handling, and
burning characteristics of SRC. To determine whether SRC
can be an acceptable substitute for coal and to demonstrate
the assumed advantages of SRC a combustion test was performed
in March, May and June of 1977 at Georgia Power Company's
Plant Mitchell. The test was conducted in three phases and
marked the first time SRC had been burned, on a large scale,
in a conventional utility boiler.
In Phase I, low sulfur Kentucky coal was burned in an
existing, unmodified 22.5 MW pulverized coal boiler. In
Phase II, following replacement of the original burners with
dual register burners and accompanying modifications, the
boiler was again fired with low sulfur Kentucky coal. In
Phase III, following adjustment of the burners and pulver-
izers, SRC was burned. The SRC had been produced at the
Fort Lewis pilot plant from western Kentucky coals having a
sulfur content of approximately 4 percent and an ash content
of 10 to 12 percent. Sulfur and ash in the SRC were nomi-
nally 0.7 and 0.6 percent respectively. In each of the
three phases, the boiler was operated at full (~21 MW),
medium (~14 MW) , and low (~7 MW) load conditions. Phases II
and III are discussed in detail in this report.
During Phases II and III, flue gas sampling was con-
ducted using a Source Assessment Sampling System (SASS)
train to collect samples for modified EPA Level 1 laboratory
analysis. Grab samples were also obtained for on-site
analysis of GI through C^ hydrocarbons, S02, N£, CO, C02 and
02. Sampling and analysis are discussed in detail in later
sections of this report.
Participants in the combustion test included:
• Southern Company Services - co-sponsor and owner
• DOE (formerly ERDA) - co-sponsor and supplier of
SRC
• Southern Research Institute (SRI) - SASS train
sampling and resistivity tests
• TRW - grab sampling and on-site analysis for CO,
C02» SO^, N£, Q£ and C^ through Cg hydrocarbons
• York Research - EPA-5 and ASME trains, gaseous
emissions, and precipitator efficiency
• Babcock & Wilcox - boiler efficiency
• Rust Engineering (a subsidiary of Wheelabrator-
Frye) - resistivity tests
-------
• Wheelabrator-Frye - precipitator modeling for
control of SRC combustion particulates
• Hittman Associates, Inc. - development and coor-
dination of SASS train and grab sampling plan,
sample analysis, and interpretation
The results of the tests concerning resistivity, and
precipitator and boiler efficiencies, are not discussed in
this report. The EPA sponsored precipitator evaluation as a
supplement to the DOE plan is presented in "Evaluation of
Electrostatic Precipitator During SRC Combustion Tests,"
EPA-600/7-78-129, June 1978.
The results of the emissions measurement work performed
by York Research Corporation under contract to Southern Com-
pany Services, Inc., will be incorporated in a report being
prepared by Southern Company Services, Inc.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
The results of the combustion test at Plant Mitchell
indicated that SRC can be combusted in place of coal to fuel
today's utility boilers. No major operational problems
were encountered during the firing of SRC.
Significant reductions in S0£, NOX, and inorganic
emissions were observed. During combustion of SRC, S0£
emissions were reduced to compliance with the existing New
Source Performance Standards (NSPS) of 0.52 kg/GJ (1.2
lbs/106 Btu) input. If, however, this standard is reduced
to 0.26 kg/GJ (0.6 lb/106) Btu, as is currently being con-
templated by the U.S. Environmental Protection Agency (EPA),
compliance is doubtful.
NOX emissions were well below the NSPS of 0.3 kg/GJ
(0.7 lbs/10° Btu). NOX concentrations increase with in-
crease in excess air but use of abnormally high excess air
has an effect of lowering NOX emissions. During the combus-
tion test abnormally high excess air was used, and it is
therefore recommended that additional testing should be
conducted at normal conditions.
The electrostatic precipitator used throughout the test
was an old (1946) Research Cottrell unit which was inef-
ficient for SRC flyash collection (16.89 to 45.68 percent).
When a more modern precipitator was briefly tested, collec-
tion efficiency increased to approximately 95 percent. It
is therefore recommended that additional testing be con-
ducted, using a more efficient precipitator, to provide a
more accurate account of actual atmospheric particulate
emissions associated with the combustion of SRC.
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SECTION 3
COMBUSTION TEST
One of the primary purposes of the combustion test was
to demonstrate the assumed advantages of SRC as a boiler
fuel. This was attempted by retrofitting a small utility
boiler and burning approximately 2,722 metric tons of SRC
under carefully measured conditions. The work was regarded
as a significant milestone in the objective of qualifying
coal-derived fuels for future energy needs.
The unit selected for the test, Boiler No. 1, is
located at Georgia Power Company's Plant Mitchell, near
Albany, Georgia, and has a nameplate rating of 22.5 MW. The
Babcock & Wilcox (B&W) natural circulation pulverized coal-
fired boiler is rated at 104,320 kilograms of steam per hour
at 58 atmospheres and 480 C. The unit is equipped with B&W
E-35 pulverizers and a Research Cottrell perforated plate
electrostatic precipitator. Turbines and generators were
manufactured by General Electric.
The test was conducted in a three-phase program.
During Phase I, low sulfur (~1 percent) Kentucky coal was
burned in the unmodified boiler. The purpose of this phase
was to provide a data base to isolate the effects of the
changed boiler configuration used during Phase II. All
pulverizers, burners, and controls were operated normally.
SASS train samples were not collected during this phase.
Once again burning low sulfur (~1 percent) Kentucky
coal, Phase II was initiated May 24, 1977 and concluded June
6, 1977. The original burners were replaced prior to this
phase with dual register burners and accompanying modifica-
tions. This phase was to establish a base-line of operation
for later comparison with Phase III results. The pulver-
izers and controls were operated normally. SASS train and
grab samples were collected throughout this phase.
Phase III began June 10, 1977 and continued through
June 25, 1977. Solvent Refined Coal I, which had been
produced at the Fort Lewis pilot plant in Washington, was
fired. The SRC had been produced from western Kentucky
coals having a sulfur content of approximately 4 percent and
an ash content of 10 to. 12 percent. Minor modifications
-------
were made to the pulverizers and dual register burners. The
purpose of this phase was to demonstrate the assumed advan-
tages of SRC as a boiler fuel. SASS train and grab samples
were also collected during this phase.
SAMPLE COLLECTION
SASS Train
During Phases II and III, flue gas sampling was con-
ducted using SASS train and grab samples for modified EPA
Level I laboratory analysis. Grab samples were obtained for
on-site analysis of C-, through C,. hydrocarbons, S09, N9, CO,
C02 and 02> L b z z
A diagram of the SASS train is shown in Figure 1. This
sampling device includes cyclones and a filter to collect
particulates, a sorbent trap to collect organic constitu-
ents, impingers, and associated temperature controls, pumps,
and meters. The sample is obtained from the flue gas duct
by means of a probe inserted through the duct work and
positioned to intersect the gas flow at a point having flow
characteristics representative of the bulk flow.
STACK T.C.
CONVECTION
/ OVEN
FILTER
GAS COOLER
-* ft
XAD-2
CARTRIDGE
DRY GAS METER ORIFICE METER
CENTRALIZED TEMPERATURE
AND PRESSURE READOUT
CONTROL MODULE
IMP/COOLER
TRACE ELEMENT
COLLECTOR
CONDENSATE
COLLECTOR
H>W
X_X10 CFM VACUUM PUMP
Figure 1. SASS Train Flowsheet
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Particulates were removed from the sample flue gas
first, when the gas passed through a series of cyclones
maintained at 205°C. Particulates were collected in three
size ranges, >10y, 3 to 10U, and 1 to 3u. A standard fiber-
glass filter following the cyclones collected a fourth size
range,
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INLET SAMPLING
PORT
A
PRECIPITATOR NO. 1
CONTINUOUS
X SAMPLER
PRECIPITATOR NO. 2
OUTLET
B SAMPLING
PORT
OUTLET SAMPLING
PORT
DAMPER
PRECIPITATOR NO. 3
PRECIPITATOR NO. 4
Figure 2. Diagram of Sampling Locations
Since precipitator No. 1 is a vintage Research Cottrell
unit, it was requested that additional tests be performed on
precipitator No. 3, a newer unit, for modeling purposes.
To facilitate these tests, boiler No. 2 and precipitators
No. 1 and No. 2 were shut down, and SASS train and grab
samples were collected at outlet port C.
SAMPLING SCHEDULE
The schedules for test Phases II and III were developed
by Southern Company Services after consultation with the
participants. The boiler load condition and test precipi-
tator were designated for each day of the test. Tables 1
and 2 indicate these schedules as well as the location for
SASS train and grab samples.
Because only one SASS train was available, it was
impossible to simultaneously collect samples at both the
inlet and outlet ports of the precipitator. During each
phase the SASS train location was varied to permit sampling
at both ports A and B. SASS train and grab samples were
collected from the same locations.
8
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TABLE 1. PHASE II - COAL COMBUSTION TEST SAMPLING SCHEDULE
Date
Load Condition
SASS Train
Sampling Location
.May 24
May 25
May 26
May 27
May 28
May 29
May 30
May 31
June 1
June 5
June 6
Full
Medium
Low
Full
Full
Medium
Medium
Low
Low
Full
Full
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Inlet ESP #1
Inlet ESP #1
Outlet ESP #1
Outlet ESP #1
Inlet ESP #1
Outlet ESP #3
Outlet ESP #3
TABLE 2. PHASE III - SRC COAL COMBUSTION TEST SAMPLING
SCHEDULE
Date
Load Condition
SASS Train
Sampling Location
June 13
June 14
June 15
June 16
June 17
June 18
June 19
June 20
June 21
June 22
June 23
June 24
Full
Medium
Low
Full
Full
Low
Low
Medium
Medium
Full
Full
"wide open"
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Outlet ESP #1
Inlet ,ESP #1
Inlet ESP #1
Outlet ESP #1
Inlet ESP #1
Outlet ESP #1
Outlet ESP #3
Outlet ESP #3
Outlet ESP #1
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SECTION 4
ANALYSES
GRAB SAMPLES
Flue gas grab samples were analyzed for GI through
hydrocarbons, S02, N£, CO, C02, and 02, usually within 30
minutes after sample collection. The GI through Cg hydro-
carbons were determined by means of a flame ionization
detector in a Perkin-Elmer gas chromatograph. During the
first three days of Phase II, the detection limit was 5 ppm
due to improper grounding of the instrument. During the
remainder of Phases II and III, the detection limit was 0.5
ppm.
The 02, N2* CO, C02, and S02 levels were measured with
a thermal conductivity detector in an A.I.D. portable gas
chromatograph. The accuracy of this instrument was + 2
percent of the reading taken.
York Research also continuously monitored NOX and S02
levels in the flue gases. Thermo Electron analyzers (Model
10 for NOX and Model 40 for S02) with a reported accuracy of
+ 10 ppm, were used for this purpose. The emissions mea-
surement results will be included in a report being prepared
by Southern Services, Incorporated.
Flue gas grab sample analytical results are reported in
Tables 3 and 4. For comparison, typical SOX and NOX concen-
trations obtained from continuous analyzers are also given.
Analytical results for coal and SRC grab samples were pro-
vided by Southern Services, Inc., and are shown in Tables 5
and 6. The coal and SRC analyses were performed by Commer-
cial Testing and Engineering Co. of Golden, Colorado.
SASS TRAIN SAMPLES
The analysis of the SASS train samples was conducted in
two parts.
10
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TABLE 3. ON-SITE ANALYSIS OF GRAB SAMPLES, PHASE II - COAL COMBUSTION
May 24 to June 6, 1977
On-Site Gas
Date
5/26
5/31
6/02
5/25
5/29
5/30
5/24
5/27
5/28
6/05
6/06
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
Chromatography Analysis
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
C0<3>
ND
ND
ND
ND
ND
ND
--
ND
ND
ND
ND
13.31Z
14.24Z
14.91Z
15.73Z
13.70Z
12.602
13.78Z
11.25*
12.14*
11.16*
co.,'1'
7.40Z
7.50Z
6.56Z
5.51Z
7.59Z
7.35Z
6.65Z
9.86Z
9.31Z
9.69Z
„ (1)
N2
79.29Z
78.26Z
78.53Z
78.76Z
78.71Z
80.05Z
79.66Z
78.89Z
78.55Z
79.15Z
254
329
174
413
209
413
311
381
214
210
Continuous
Sampler
S0y<2>
260
360
200
500
220
400
745
330
330
200
180
110
110
100
170
160
150
225
215
220
170
110
Time
1500
1140
0300
1400
1400
1240
1200
1530
1420
1330
1030
Load
Condition
Low
Low
Low
Med
Med
Med
Full
Full
Full
Full
Full
Sample
Location
0-1
0-1
1-1
0-1
1-1
0-1
0-1
0-1
1-1
0-3
0-3
ND - None Detected
SO and NO values are in ppm
X X
1-1 - Inlet to precipitator 01
0-1 - Outlet to precipitator 01
0-3 - Outlet to precipitator #3
(1) - + 2Z of total concentration
(2) - + 10 ppm
(3) - 40 ppm detectable limit
(4) - 5 ppm detectable limit 5/25, 5/26, and 5/27, 0.5 ppm detectable limit 5/28 through 6/06
-------
TABLE 4. ON-SITE ANALYSIS OF GRAB SAMPLES, PHASE III - SRC COMBUSTION
June 13 to June 24, 1977
On-Site Gas Chromatography Analysis
Date
6/15
6/18
6/19
6/14
6/20
6/21
6/13
6/16
6/17
6/22
6/23
6/24
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND-
ND
ND
ND
ND
ND
ND
ND .
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
ND
ND
ND
ND
ND
ND
C0<3>
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
14.79Z
13.25Z
14.00Z
13.65Z
11.39Z
10.62Z
11. HZ
11.20Z
10.75Z
10.76Z
5.88Z
6.73Z
6.26Z
7.53Z
9.86Z
9.12Z
9.15Z
9.25Z
t
8.90Z
9.29Z
N2 X
79.33Z
80.02Z
79.74Z
78.82Z
78.75Z
80.26Z
79.74Z
79.55Z
80.35Z
79.95Z
198
216
218
248
371
410
404
400
393
449
Continuous
Sampler
225
220
235
260
325
335
345
345
325
380
125
120
125
160
190
190
190
200
220
260
Time
1030
1200
1230
1200
1300
1145
1100
1030
1000
1100
Load
Condition
Low
Low
Low
Med
Med
Med
Full
Full
Full
Full
Full
23.5
Sample
Location
0-1
1-1
0-1
0-1
0-1
1-1
0-1
0-1
1-1
0-3
0-3
0-1
ND - None Detected
SO and NO values are in ppm
1-1 - Inlet to precipitator II
0-1 - Outlet to precipitator II
0-3 - Outlet to precipitator 13
(1) - + 2Z of total concentration
(2) - + 10 ppm
(3) - 40 ppm detectable limit
(4) - 0.5 ppm detectable limit
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TABLE 5. COMBUSTION TEST, PHASE II - COAL SAMPLES
Proximate Analysis
Date
5/26
5/31
6/2
5/25
5/29
5/30
5/24
5/27
5/28
6/5
6/6
% Sulfur
0.64
1.05
NA
1.09
0.62
1.15
1.34
0.73
0.72
0.66
0.64
% Nitrogen
1.38
1.81
NA
1.29
1.82
1.82
1.19
1.51
1.45
1.60
1.81
Heating*
Value, MJ/kg
7.144
7.043
NA
7.007
7.139
7.139
7.042
7.081
7.079
NA
7.143
NA - Not Available
*Moisture and Ash Free Basis
TABLE 6. COMBUSTION TEST, PHASE III - SRC SAMPLES
Date
% Sulfur
Proximate Analysis
% Nitrogen
Heating*
Value, MJ/kg
6/15
6/18
6/19
6/14
6/13
6/16
6/17
6/22
6/23
6/24
0.70
0.74
0.66
0.72
0.73
0.73
0.72
0.70
0.64
0.66
1.54
1.80
1.82
1.62
2.02
1.77
1.47
1.37
1.37
1.71
7.530
NA
7.496
7.525
7.459
7.464
7.546
7.485
7.431
7.418
NA - Not Available
*Moisture and Ash Free Basis
13
-------
Part I
In Fart I, two complete SASS train runs were analyzed
by TRW. Samples selected for analysis were SRC runs of June
16 and, June 19, 1977. Relevant process information per-
taining to these runs is given in Table 7. Organic and
inorganic analyses were conducted separately. Figure 3
shows the analytical procedures followed.
TABLE 7- PROCESS INFORMATION
Date: June 16, 1977
Load:
Fuel Flow:
Heating Value:
Stack Gas Temperature:
Sample Volume:
Precipitator:
Sample Port:
Precipitator Efficiency:
Gas Flow, ESP #1 Outlet:
21 MW
8,063 kg SRC/hr (17,775 Ib/hr)
7.464 MJ/kg SRC (15,602 Btu/lb)
166°C (331°F)
28,46 m3 (1,005 DSCF)
#1
B (Outlet #1)
16.89%
3,620 m3/minute (127,858 ACFM)
Date: June 19, 1977
Load:
Fuel Flow:
Heating Value:
Stack Gas Temperature:
Sample Volume:
Precipitator:
Sample Port:
Precipitator Efficiency:
Gas Flow,. ESP #1 Outlet:
7.5 MW
3,379 kg SRC/hr (7,450 Ib/hr)
7.496 MJ/kg SRC (15,668 Btu/lb)
147°C (296°F)
30.16 m3 (1,065 DSCF)
#1
B (Outlet #1)
45.68%
2,005 m3/minute (70,793 ACFM)
14
-------
o •— z o
—I O Z —•
a a. 1-1 t3 (_
z c/i wi I— 3 i/j
(/) Z O- S Z S «-^
a = •*! fc •- -1 °
< O <9 tn uj rs. i o
SAMPLE
GRAB SAMPLE
10 CYCLONE
3 CYCLONE
FILTER
COMBINE
COMBINE
PROBE HASH, etc.
XAD-Z CARTRIDGE
FIRST IHPINGER -
SPLIT
°-°
L
AQUEOUS CONDENSATE
ORGANIC RINSE
COMBINED
SECOND AND THIRD
IHPINGERS
SRC OR COAL
-O—O
Figure 3. Analytical Procedures Followed
in SASS Train Run Analysis
Organic Analysis —
Samples requiring solvent extraction for organic analy-
ses were the XAD-2 resins and the cyclone and filter par-
ticulate samples. For XAD-2 resins, virtually all of the
sample material was taken for extraction. A small portion
of each XAD-2 resins was removed for inorganic analysis.
Two composite particulate samples for each run were pre-
pared, one by combining small portions of lOy sample and 3u
sample, and the second by combining lu sample and filter
sample. Methylene chloride was the solvent used in all
extractions. Other required sample preparations included
filtering the solids out of the probe rinses and concentra-
ting all samples to 10 ml volumes .
C? through Cifi gas chromatography — The gas chroma-
tography was performed using the parameters and procedures
specified by EPA for Level 1 analysis. On the instrument
used, these parameters provided a lower detectable limit of
approximately 0.2 ug/m3- Analytical results are expressed
in terms of the quantity of n-alkanes boiling in the fol-
lowing temperature ranges:
15
-------
C7
C8
C9
CIO
Cll
90-110°C
110-140°C
140- 160 °C
160-180°C
180-200°C
C12
CIS
C14
CIS
C16
200-220°C
220-240°C
240-260°C
260-280°C
280-300°C
To calibrate the instrument for these Cy through
boiling point ranges, chromatograms of n-alkane mixtures
were obtained and a plot of normal boiling points versus
retention times was constructed. The retention times cor-
responding to the appropriate boiling ranges were summed
within each retention time interval in order to convert to
quantities of components designated as n-alkanes. The
results of these analyses are given in Table 8.
TABLE 8. GC ANALYSIS FOR C? THROUGH C16 HYDROCARBONS
June 16, 1977
June 19, 1977
C7
nig** mg/m
0* 0
0 0
C8
3
mg mg/m
3.73 0.12
2.52 0.09
C9
3
mg mg/m
0 0 z
1.51 0.05
C10
3
mg mg/m
0.53 0.20
0.80 0.03
Cll
3
mg mg/m
1.82 0.06
2.68 0.09
June 16, 1977
June 19, 1977
C12
3
mg mg/m
0.85 0.03
1.29 0.05
C13
3
mg mg/m
0 0
0 0
cu
3
mg mg/m
0.11 0.004
1.08 0.04
C15
3
mg mg/m
0 0
0 0
C16
3
mg mg/m
0 0
0 0
* Zero values represent a detection limit of 0.007 mg.
**Total amount of compound detected in the samples.
For the particulate samples, all data for Cg through
appeared to be significant, whereas for the probe rinse
and XAD-2 module condensate extract plus module rinse samples
probably none of the sample values were significant because
of the high blank values.
Grayimetry and infrared spectrometry—To determine the
nonvolatile contents of the samples,1 ml aliquots were
taken from each of the 10 ml concentrates and evaporated to
dryness. The primary tool for understanding the signifi-
cance of Level 1 gravimetry data is the infrared spectra
16
-------
(IR), because the spectra can show qualitative differences
between samples and blanks. The nonvolatile residues from
the gravimetric procedure were scanned by an IR spectro-
meter, with the exception of the particulate extract sam-
ples, which all produced insufficient residues to be able to
perform the IR analysis. The classes of compounds iden-
tified are listed in Tables 9 and 10. Due to the high blank
values, none of the values appear significant.
Polynuclear aromatic hydrocarbons (PAH's) by combined
gas chromatography/mass spectrometry (GC/MS;--For the
GC/MS analysis,1 ml aliquots of the 10 ml concentrated
sample volumes were evaporated under a stream of inert gas
and then brought up to a total volume of 2 ml, with 1 ml
internal standard and 1 ml of benzene. The resulting solu-
tions were analyzed with a Finnigan Model 4023 automated
GC/MS instrument. The compounds in each sample were sep-
arated on a 1.8 meter x 2 millimeter ID glass column packed
with three percent Dexsil 300 on 100-120 Chromosorb WHP.
This column is operated from 100° to 295°C, programmed at
4°/min. The detection limit for this work was 0.1 g in
the aliquots analyzed. The only polycyclic compound iden-
tified is most likely naphthalene (CioH8) or azulene (also
CioHo)• Because the naphthalene was also present in the
blank, and because the blank also contained some of the
styrenes, benzoates, and other compounds typically found as
residual materials even in pre-cleaned XAD-2 resins; it was
concluded that the samples did not contain organic materials
significantly different from, or above, the blank materials.
Inorganic Analysis--
Two types of sample preparation were required for the
inorganic analyses. The first was the Parr bomb combustion
of the XAD-2 resin and SRC samples. For each of these
samples, a 1-gram aliquot was combusted for Spark Source
Mass Spectrometry (SSMS) and a 2-gram aliquot was combusted
for the antimony, arsenic, and mercury analyses. All
combustion solutions were made to a 100 ml volume. The Parr
bomb combustion procedure utilized a quartz bomb liner and
platinum electrodes and firing wire in order to minimize
contamination of the samples from the stainless steel bomb.
The second type of preparation was the aqua regia
digestion of particulate samples. Two composite particulate
samples for each run were prepared, one by combining small
portions of 10U sample and 3P sample, and the second by
combining lu sample and filter sample. The samples were
refluxed with constant-boiling aqua regia for six hours,
filtered, and made up to 100 ml for antimony, arsenic, and
mercury analyses. Because of their negligible organic
content, the particulate samples did not require any
17
-------
TABLE 9. IR EXAMINATION OF NONVOLATILE HYDROCARBONS
June 16, 1977
Sample
Classes of Compounds Identified
Probe Rinse
XAD-2 Module Condensate
Extract plus Module Rinse
XAD-2 Resin
Methylene Chloride Blank
Methanol Blank
Methylene Chloride-Methanol
Blank (50%-50%)
XAD-2 Resin Blank
Esters of benzoic acid and other carboxylic
acids, glycol, and phenolic resin (640 ppm)
Phthalic acid ester, other carxobylic acid
esters, and phenolic resin (1,600 ppm)
Aliphatic carboxylates, glycol; minor-
benzene derivatives (1,100 ppm)
Esters of benzoic acid and other carboxylic
acids, and phenolic resin (3,700 ppm)
Phthalic acid ester, salt of carboxylic
acid, and phenolic resin (500 ppm)
Esters of benzoic acid and other carboxylic
acids, glycol, and phenolic resin (1,200
ppm)
Trace of benzene derivatives (680 ppm)
TABLE 10. IR EXAMINATION OF NONVOLATILE HYDROCARBONS
June 19, 1977
Sample
Classes of Compounds Identified
Probe Rinse
XAD-2 Module Condensate
Extract plus Module Rinse
XAD-2 Resin
Methylene Chloride Blank
Methanol Blank
Methylene Chloride - Methanol
Blank (50%-50%)
XAD-2 Resin Blank
Esters of benzoic acid and other carboxylic
acids, glycol, and phenolic resin (660 ppm)
Major - aliphatic carboxylates; minor -
phthalates, benzoates, and phenolic resin
(1,700 ppm)
Esters of aliphatic carboxylic acid and ben-
zoic acid, glycol, and traces of benzene
derivatives (700 ppm)
Esters of benzoic acid and other carboxylic
acids, and phenolic resin (3,700 ppm)
Phthalic acid ester, salt of carboxylic acid,
and phenolic resin (500 ppm)
Esters of benzoic acid and other, carboxylic
acids, glycol, and phenolic resin (1,200 ppm)
Trace of benzene derivatives (680 ppm)
_.
-------
preparation for the SSMS analysis. The condensates and
impingers also required no preparation.
Antimony, arsenic, and mercury elemental analyses—The
specific elemental analyses were performed using the ex-
panded and modified Level 1 procedures compiled by Research
Triangle Institute at EPA's direction. Briefly, these
methods are as follows:
• Mercury - reduction to elemental mercury with
stannous chloride, sparging through a detection
cell and measurement of the mercury at 253.7 nm.
• Arsenic - reduction to the hydride with stannous
chloride and metallic zinc, sparging into an
argon-hydrogen flame in an atomic absorption
spectrophotometry (AA) instrument and measurement
of the arsenic at 193.7 nm.
• Antimony - reaction with a series of reagants to
form stibine, sparging into a hydrogen diffusion
flame in an AA instrument, and measurement of the
antimony at 217.6 nm.
The results obtained by analyzing the particulate and XAD-2
resin samples are reported in Table 11.
TABLE 11. TOTAL HG, AS, AND SB IN PARTICULATES
AND XAD-2 RESIN
June 16, 1977
June 19, 1977
SRC Sample
Hg
As
191.53 yg*
(6.73 yg/m3)
351.61 yg
(11.66 yg/m3)
45 ppb
2,240 yg
(78.72 yg/m3)
650 yg
(21.55 yg/m3)
14 ppm
Sb
yg
^ ys 0
(1.89 yg/m3)
53 yg
(1.76 yg/m3)
ND**
* - Total amount of element detected in the samples.
**ND - None detected, antimony detection limit is 0.005 ppm.
Spark source mass spectrometry--The SSMS analysis was
performed by Commercial Testing and Engineering Co. of
Golden, Colorado. The results for the SASS train and SRC
samples are presented in Tables 12 and 13. During the SSMS
analysis, several of the elements were found to be mass
constituents, and had too high a concentration to be
19
-------
TABLE 12. SSMS ELEMENTAL ANALYSIS OF SASS TRAIN SAMPLES
Constituent
Uranium
Thorium
Lead
Thallium
Platinum
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Cadmium
Silver
Molybdenum
Niobium
June 16,
ng*
958
674
141
13
5
5
73
30
73
16
121
15
96
121
212
48
129
65
322
468
138
584
485
22,200**
52
16
11
66
230
38
6
772
1,790
1977
Hg/m
34
24
5
0.5
0.2
0.2
3
1
3
0.6
4
0.5
3
4
7
2
5
2
11
16
5
21
17
780
2
0.6
0.4
2
8
1
0.2
27
63
June 19,
ug*
581
250
78
15
7
4
36
31
31
9
47
5
15
31
47
10
31
14
64
68
36
233
176
1,333
6
31
7
47
97
32
123**
505
904
1977
ug/m3
19
8
3
0.5
0.2
0.1
1
1
1
0.3
2
0.2
0.5
1.
2
0.3
1
0.5
2
2
1
8
6
44
0.2
1
0.2
2
3
1
4
17
~30
(continued)
20
-------
TABLE 12. (continued)
June 16, 1977
June 19, 1977
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Sodium
Fluorine
Boron
Beryllium
Lithium
Aluminum
Magnesium
Ug*
8,400**
3,355
4,254**
115
80
296
1,611
218
803
1,111
1,252
2,654
525
2,002,018**
8,859
2,004,011**
1,008,338**
1,302,045**
852
4,008,022**
1,000,084**
447
620,000**
1,030,252**
600,506**
9,420**
541
7,300
394
141
6 , 008**
. 600,506**
u.g/m
295
118
149
4
3
10
57
8
28
39
44
93
18
70,345
311
70,415
35,430
45,750
30
140,830
35,140
16
21,785
36,200
21,100
331
19
257
14
5
211
21,100
ug*
3,416
1,258
2,054
43
890
15
1,303
352
881
2,636
1,230**
1,137
243
1,201,866**
4,830**
11,200**
7,260**
400,826**
601
1,502,873**
24,060**
2,130**
22,020**
20,100**
330,252**
11,010**
719
8,727
300
159
4,403**
330,252**
|ig/m
113
42
68
1
30
2
43
12
29
87
41
38
8
39,850
160
371
241
13,290
20
49,830
798
71
730
666
10,950
365
24
289
10
5
146
10,950
* Total amount of element detected in the samples of particulates.
**Mass Constituent (MC) - too high in concentration to be quantified.
reported represent the lower estimated limit.
21
Values
-------
TABLE 13. SSMS ANALYSIS OF SRC SAMPLE
Element
Uranium
Lead
Platinum
Cerium
Lanthanum
Barium
Cesium
Silver
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Concentration
yg/g**
1
5
0.9
0.2
0.3
4
0.5*
0.2
6
0.3
2
0.9
2
0.5
0.6
0.5
0.1
0.4
8
4
Element
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Boron
Beryllium
Lithium
Concentration
Ug/g**
5
0.2
30
3
3
2
30
0.1
200
20
3
30
9
300
10
40
30
40
10
0.2
0.2
* Elements designated as "_<" were identified, but because of their low
concentrations, could not be quantified as accurately.
^^Concentration of element in yg per gram of SRC sample.
22
-------
quantified. For these elements, the lower estimated limits
are reported.
Interpretation of Results--
Additional analyses, based on the results of Part I,
were to be performed under Part II to provide a comparison
of coal and SRC flue gases. The analytical results from the
organic analysis indicated that only volatile Cy through Ci2
hydrocarbons were present in appreciable quantities.
Nonvolatile hydrocarbons and polynuclear aromatic hydrocar-
bons were not found in significant quantities above the
blank values. It was therefore decided to analyze two
additional SASS train runs, one SRC and one coal, for Cy
through Ci2 hydrocarbons to provide a comparison of the
organic content of the respective flue gases.
Based upon the SSMS results, 17 elements were selected
to be analyzed by Atomic Absorption Spectrophotometry for
the two additional SASS train runs. Elements selected
included several of the MC elements, and other elements of
interest present in significant quantities. Table 14 lists
the 17 elements selected for analysis.
TABLE 14. ELEMENTS SELECTED FOR PART II INORGANIC ANALYSIS
Mass Elements of
Constituents (MC) Interest
Aluminum Antimony
Barium Arsenic
Chromium Boron
Copper Lead
Iron Mercury
Magnesium Nickel
Manganese Thorium
Vanadium , Uranium
Zinc
Part II
In. Part II, two additional SASS train runs were analy-
zed by the Hittman laboratory. Samples selected for analy-
sis included a coal run of May 25, 1977, an SRC run of June
14, 1977, and respective coal and SRC grab samples. Rele-
vant process information is given in Table 15.
23
-------
TABLE 15. PROCESS INFORMATION
Date: May 25, 1977
Load:
Fuel Flow:
Heating Value:
Stack Gas Temperature:
Sample Volume:
Precipitator:
Sample Port:
Precipitator Efficiency:
Gas Flow, ESP #1 Outlet:
14 MW
6,940 kg coal/hr
(15,300 Ib/hr)
7.007 MJ/kg (14,648 Btu/lb)
147°C (296°F)
29.65 m3 (1,047 DSCF)
11
B (Outlet #1)
94.81%
3,002 m3/minute (105,997 ACFM)
Date: June 14, 1977
Load:
Fuel Flow:
Heating Value:
Stack Gas Temperature:
Sample Volume:
Precipitator:
Sample Port:
Precipitator Efficiency:
Gas Flow, ESP //I Outlet:
14 MW
5,460 kg SRC/hr
(12,038 Ib/hr)
7.525 MJ/kg (15,729 Btu/lb)
144°C (291°F)
28.60 m3 (1,010 DSCF)
#1
B (Outlet II)
21.96%
3,076 m3/minute (108,632 ACFM)
Organic Analysis—
Samples were prepared as in Part I, Organic Analysis,
and run on the Packard Model 419 Becker gas chromatograph.
Analytical results are again expressed in terms of the
quantity of n-alkanes boiling in the following temperature
ranges:
C9
90-110°C
110-140°C
140-160°C
Cll
Cl2
160-180°C
180-200°C
200-220°C
The results of these analyses are given in Table 16.
24
-------
TABLE 16. GC ANALYSIS FOR
C? THROUGH C12 HYDROCARBONS
Coal-May 25, 1977
SRC-June 14, 1977
C7
/ 3
nig* mg/m
17.34 0.58
ND
C8
3
mg mg/m
j>
3.09 0.11
C9
3
mg mg/m
10.21 0.34
8.60 0.30
Coal-May 25, 1977
SRC-June 14, 1977
ND - None Detected
T - Trace (<1 ppm)
C10
mg mg/m
2.45 0.08
5.36 0.19
Cll
mg mg/m
15.30 0.52
23.97 0.84
C12
/ 3
mg mg/m
16.83 0.57
; 14.10 0.49
* - Amount of compound detected.
Inorganic Analysis--
Samples were prepared as in Part I, Inorganic Analysis,
and run on the Perkin Elmer Model 603 Atomic Absorption
Spectrophotometer. The results of these analyses are
reported in Table 17.
25
-------
TABLE 17. AA ANALYSIS FOR INORGANICS
Constituent
Aluminum
Antimony
Arsenic
Barium
Boron
Chromium
Copper
Lead
Iron
Magnesium
Manganese
Mercury
Nickel
Thorium
Uranium
Vanadium
Zinc
Coal SASS
train
May 25,
yg*
run
1977
3
yg/m
24,016
135
69
1,430
7
1,694
246
185
37,624
4,096
884
17
2,441
236
6
364
382
809.98
4.55
2.32
48.23
0.24
57.13
8.30
6.24
1,268.94
138.15
29.81
0.57
82.33
7.96
0.20
12.28
12.88
SRC
train
June 14
yg*
SASS
run
, 1977
3
yg/m
6,150
102
41
335
56
475
18
40
22,869
1,656
1,789
59
385
31
101
1,269
258
215.03
3.57
1.42
11.71
1.95
16.61
0.63
1.40
799.62
57.90
62.55
2.06
13.46
1.08
3.53
5.91
9.02
Coal grab
May
Sample
yg/g**
samples
25, 1977
I Sample II
yg/g**
5,223.0
1.7
2.9
58.0
ND
13.0
16.0
9.0
3,352.0
340.0
21.0
0.3
12.0
4.7
1.3
24.1
12.5
4,506.0
—
—
—
—
4.5
14.0
7.5
2,503.0
370.0
21.0
—
10.5
4.2
1.4
20.0
50.0
SRC
grab
samples
June 14, 1977
Sample I
yg/g**
Sample II
yg/g**
60.0
0.1
1.8
2.0
0.2
4.0
1.2
0.5
187.0
8.0
14.5
0.8
2.0
5.0
0.8
11.4
6.5
95.0
—
—
—
0.5
6.0
1.5
ND
250.0
12.0
18.0
—
2.3
3.7
1.3
10.9
7.5
to
ON
ND - None Detected
* - Total amount of element detected in sample
** - Concentration of element per gram of sample
-------
SECTION 5
COMPARISON OF AIR EMISSIONS
Prior to attempting to compare the emissions resulting
from the combustion of SRC and coal at Plant Mitchell,
several factors must be considered. First, the results
obtained from the SRC analyses conducted under Part I should
not be used for comparison purposes. The load conditions
during the period of sampling (7.5 MW and 21 MW) do not
compare with the load conditions of the coal run analyzed
under Part II (14 MW). Also, the difficulty in quantifying
the MC elements poses serious questions about the accuracy
of the SSMS results. Results obtained from Part I analyses
were used only to provide an indication of the presence or
absence of constituents in SRC flue gas streams. Only
analytical results from Part II should be used for the
comparison of SRC and coal air emissions.
The second factor which must be considered is the
difference in the efficiency of precipitator #1 between
when SRC and coal are fired. For the coal run of May 25,
1977 and the SRC run of June 14, 1977, precipitator effi-
ciencies were 94.81 and 21.96 percent respectively. Pre-
cipitator #1 is an old (1946) Research Cottrell unit.
During the latter part of Phase III, precipitator #3 was
used, and the collection efficiency for SRC increased to
approximately 95 percent. Therefore, it should be noted
that the particulate air emissions given in this report
resulting from the combustion of SRC may be assumed to
represent maximum values. The precipitator efficiency had
no impact on gaseous emissions (organics, SOX, NOv, etc.).
For further information concerning precipitator efficiency
during the combustion test, readers are referred to a report
by Southern Research Institute, Evaluation of Electrostatic
Precipitator at Plant Mitchell, January 19757 under EPA Con-
tract No. 68-02-2610.
ORGANICS
Table 18 shows the comparison of the Cy through C^2
hydrocarbons present in the combustion flue gases for SRC
and coal. Detectable quantities of all Cy through C]_2
hydrocarbons were present in both coal and SRC flue gases.
27
-------
However, during combustion of SRC, Cy, Cg and C^2 hydro-
carbon emissions decreased, while Cg, CIQ and C]^ emissions
increased. The comparison of coal and SRC emissions offers
no clear indication of the effects on Cj through C]9 emis-
sions by the substitution of SRC for low sulfur coal.
TABLE 18. ORGANIC AIR EMISSIONS FOR COAL AND SRC
Coal SRC
May 25. 1977 June 14. 1977
Hydrocarbon
c_
7
C.
8
C_
9
C10
Cll
C12
0.58
T
0.34
0.08
0.52
0.57
ND
0.11
0.30
0.19
0.84
0.49
ND - None Detected
T - Trace
INORGANICS
The resulting air emissions from the combustion of coal
on May 25, 1977 and SRC on June 14, 1977 at Plant Mitchell,
are shown in Table 19. The coal used to produce the SRC was
not from the same source as the coal fired on May 25, 1977.
The quantity of minerals present in the respective coal have
a direct impact on the resulting air emissions. During coal
combustion highly volatile trace elements may appear in com-
bustion gases. During solvent refining along with sulfur and
ash reduction some highly volatile trace elements may also be
removed from coal. Due to this reason when SRC is burned
lower concentrations of trace elements generally appear in
the combustion gases. As shown in Table 19 concentrations
of most of the trace elements in combustion gases from SRC
derived from high sulfur coal are lower than those resulting
from direct combustion of low sulfur coal.
28
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TABLE 19. INORGANIC AIR EMISSIONS FOR COAL AND SRC
Constituent
Aluminum
Antimony
Arsenic
Barium
Boron
Chromium
Copper
Lead
Iron
Magnesium
Manganese
Mercury
Nickel
Thorium
Uranium
Vanadium
Zinc
Coal
May 25. 1977
/ig/m3*
809.98
4.55
2.32
48.23
0.24
57.13
8.30
6.24
1,268.94
138.15
29.81
0.57
82.33
7.96
0.20
12.28
12.88
SRC
June 14. 1977
pg/m3*
215.03
3.57
1.42
11.71
1.95
16.61
0.63
1.40
799.62
57.60
62.55
2.06
13.46
1.08
3.53
5.91
9.02
*The concentrations are based on amount of a constituent detected in the
total particulates collected.
S09 AND N0v
*• 2t
The values of S02 and NOX in the SRC and coal combus-
tion gases obtained from continuous analyzers are shown in
Table 20. The emission of S0£ is reduced approximately 37
percent, and NOX by 12 percent, when SRC is fired. These
29
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TABLE 20. SO,
AND NOV EMISSIONS FOR COAL AND SRC
X
Load Condition
Low ( 7.5 MW)
Low
Low
Average
Medium ( 14 MW)
Medium
Medium
Average
Full ( 21 MW)
Full
Full
Average
Total Average
Date
5/26/77
5/31/77
6/01/77
5/25/77
5/29/77
5/30/77
5/24/77
5/27/77
5/28/77
0.645
1.023
0.598
0.757
0.800
0.791
0.791
0.796
1.002
0.443
0.456
0.727
Coal
so2*
(1.50)
(2.38)
(1.39)
(1.76)
(1.86)
(1.84)
(1.84)
(1.85)
(2.33)
(1.03)
(1.06)
(1.47)
1.69
0.198
0.224
0.215
0.211
0.194
0.215
0.215
0.201
0.215
0.201
0.220
0.215
0.211
NO *
X
(0.46)
(0.52)
(0.50)
(0.49)
(0.45)
(0.50)
(0.50)
(0.48)
(0.50)
(0.48)
(0.51)
(0.50)
0.49
Date
6/15/77
6/18/77
6/19/77
6/14/77
6/20/77
6/21/77
6/13/77
6/16/77
6/17/77
0.520
0.452
0.486
0.486
0.439
0.477
0.447
0.456
0.426
0.412
0.434
0.426
SRC
(1.21) 0.201
(1.05) 0.176
(1.13) 0.176
(1.13) 0.185
(1.02) 0.194
(1.11) 0.211
(1.04) 0.194
(1.06) 0.198
(0.99) 0.176
(0.97) 0.168
(1.01) 0.172
(0.99) 0.172
(1.06) 0.185
it
(0.48)
(0.41)
(0.41)
(0.43)
(0.45)
(0.49)
(0.45)
(0.46)
(0.41)
(0.39)
(0.40)
(0.40)
(0.43)
Z Reduction
S02 N0x
19.33
55.88
18.71
35.80
45.16
39.67
43.48
42.70
57.51
5.83
4.72
32.65
37.28
-4.35
21.15
18.00
12.24
0.00
2.00
10.00
4.17
18.00
18.75
21.57
20.00
12.24
OJ
o
*Values are in kg/GJ and (lb/10 Etu)
-------
values represent substantial reductions in total S02 and
NOX emissions. However, during the combustion test abnor-
mally high excess air was used, which would have an effect
of lowering NOX. The combustion test should therefore be
run under normal conditions to obtain the NO emissions
data. x
31
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SECTION 6
ASSESSMENT OF AIR EMISSIONS
ORGANICS
The release of organic constituents to the air via the
combustion of SRC is not an area of major environmental con-
cern. The objective of the combustion process is to convert
all carbon present in the feedstock to carbon dioxide.
Therefore, significant quantities of organic constituents
will only be discharged during incomplete combustion. This
is not the case with today's sophisticated boiler opera-
tions. The emissions of Cy through C^2 hydrocarbons during
the combustion of SRC do not appear to differ significantly
from the direct combustion of coal. Therefore, these emis-
sions are not at present an area of major environmental
concern. Also, no carcinogenic PAH's were found in the SRC
flue gases.
INORGANICS
The method used to assess the impact of the inorganic
air emissions resulting from the combustion of SRC will be
the Multimedia Environmental Goals (MEG's). MEG's, cur-
rently being developed by EPA, are levels of significant
contaminants or degradents (in ambient air, water, or land,
or in emissions or effluents conveyed to the ambient media)
that are judged to be (1) appropriate for preventing certain
negative effects in the surrounding populations or ecosys-
tems, and (2) representative of the control limits achiev-
able through technology. MEG's are divided into two dis-
tinct sections, Ambient Level Goals and Emission Level
Goals, and have been published for more than 200 compounds.
The November 1977 version of the MEG's chart is shown in
Figure 4.
Emission Level Goals presented in the top half of the
MEG's chart pertain to gaseous emissions to the air, aqueous
effluents to water, and solid waste to be disposed to land.
Only the gaseous emissions to the air are addressed by this
report.
32
-------
MULTIMEDIA
ENVIRONMENTAL
GOALS
EMISSION LEVEL GOALS
Mr.mfat3
(PPMVott
IppmWt)
Und.dB/l
(ppmWt)
anBMTtdMoloir
Mfft.irr.iAT
(MOO**)
II. B«»d on
ToMty IMOTN
HMl«ttffM«l
•To ta imHliplM by dflution tetor
AMBIENT LEVEL GOALS
Air.OT/m3
(ppmVoll
Ippm'wtt
(ppmWO
1* Cmwit or PrapoMo Anbimt
H^-tXl
•JIJTi^o,
^•miiHiow ConoHivnton
ttalAHtaai
•!££.
III. ZwoTNMhofelPoautinti
Ettfcnmd Paii^ifcli Commmmimi
M.M..M.
Figure 4. MEG Chart, November 1977 Version
33
-------
Emission Level Goals based on best technology have not
as yet been developed. Emission Level Goals based on
ambient factors have been developed for more than 200
compounds and include consideration of:
(1) Minimum Acute Toxicity Effluents (MATE's) - con-
centrations of pollutants in undiluted emission
streams that will not adversely affect those
persons or ecological systems exposed for short
periods of time.
(2) Ambient Level Goals, i.e., Estimated Permissible
Concentrations (EPC's) - concentrations of pol-
lutants in emission streams which, after dis-
persion, will not cause the level of contamination
in the ambient media to exceed a safe continuous
exposure concentration.
(3) Elimination of Discharge (EOD) - concentrations of
pollutants in emission streams which, after
dilution, will not cause the level of contamina-
tion to exceed levels measured as "natural back-
ground."
Columns are provided on the MEG chart under Emission Level
Goals for each of these. For additional information con-
cerning MEG's, readers are referred to Multimedia Environ-
mental Goals for Environmental Assessment. Volumes 1 and 2,
(EPA-600/ 7-7 7rTl6a and b) .
Table 21 provides a comparison of SRC air emissions
with the MEG values for the inorganic elements analyzed in
Part II. Chromium is the only element which fails to meet
the MATE value. Zinc and boron are the only elements which
meet the ambient level goal values. However, as shown in
the table, the MEG value for zinc is not much lower than
ambient level and if sampling and analytical uncertainties
were added, zinc would not meet the goal. None of the
elements meets the elimination of discharge values.
S09 AND NO
te 2£
One method of assessing the environmental impact of S02
and NOX emissions from the combustion of SRC is by com-
parison with existing New Source Performance Standards
(NSPS). The existing NSPS for S0£ and NOX are 0.52 and 0.30
kg/GJ (1.2 and 0.7 lb/106 Btu) input, respectively. The
average emission rates for SOo and NOX during the combustion
of SRC at Plant Mitchell were 0.46 and 0.19 kg/GJ (1.06 and
0.43 lb/106 Btu) respectively, well within the existing
standards. However, EPA is currently considering reducing
34
-------
TABLE 21. COMPARISON OF SRC AIR EMISSIONS WITH MEG's
Constituent
Aluminum
Antimony
Arsenic
Barium
Boron
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Thorium
Uranium
Vanadium
Zinc
Minimum Acute
Toxicity Effluent
Based on
Health
Effects*
5,200
500
2
500
3,100
1
200
150
6,000
5,000
50
15
9
500
4,000
Based on
Ecological
Effects*
— — —
10
1
Ambient Level Goal
Based on
Health
Effects*
12.6
1.2
0.005
1
74
0.002
0.5
0.36
14
12
0.01
0.035
0.5
1.2
9.5
Based on
Ecological
Effects*
___
1
0.1
Elimination
of Discharge
Natural
Background*
0.007
0.00005
0
0.012-0.001
0.01-0.41
0.002-0.47
1.4-800
0.005-0.047
0.0006-0.021
0.005-0.024
0.013-0.2
SRC
June 14, 1977*
215.03
3.57
1.42
11.71
1.95
16.61
0.63
799.62
1.40
57.90
62.55
2.06
13.46
1.08
3.53
5.91
9.02
GJ
Ul
* Values are in yg/m
Values have not yet been developed
-------
the S02 NSPS to 0.26 kg/GJ (0.6 lb/106 Btu). It is ques-
tionable whether SRC can meet this standard.
As discussed earlier abnormally high excess air was
used during the combustion test. Table 4 shows high concen-
trations (10.6 to 14.8%) of free oxygen in the flue gas.
This high oxygen content is equivalent to about 240 to 100%
excess air. The combination of molecular No and Oo by ther-
mal fixation is an equilibrium reaction with 'the final con-
centration of NO primarily dependent on the reaction tem-
perature. The higher the temperature the higher the equili-
brium concentration of NO in presence of excess air. How-
ever, at very high excess air the temperature decreases and
so does the concentration of NO.
36
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BIBLIOGRAPHY
Cleland, J.G. and G.L. Kingsbury. 1977. Multimedia Envi-
ronmental Goals for Environmental Assessment, Volumes I
and II. EPA-600/7-77-136a and b. U.S. Environmental •
Protection Agency, Washington, D.C. 148 pp.
Hamersma, J.W., S. L. Reynolds, and R.F. Maddalone. 1976.
IERL-RTP Procedures Manual: Level 1 Environmental
Assessment. EPA-600/2-76-160a. U.S. Environmental
Protection Agency, Washington, D.C. 131 pp.
Koralek, C.S. and V.B. May. Flue Gas Sampling during the
Combustion of Solvent Refined Coal in a Utility Boiler.
Paper presented at Third Symposium on Environmental
Aspects of Fuel Conversion Technology, III. EPA-600/7-
78-063. Hollywood, Florida, September 13, 1977.
Nichols, G.B., S.M. Banks, J.R. McDonald, W.J. Barrett,
W.R. Dickson, and J.E. Paul. 1978. Evaluation of
Electrostatic Precipitator at Plant Mitchell. Contract
No. 68-02-2610. EPA-609/7-78-129. U.S. Environmental
Protection Agency, Washington, D.C. 48 pp.
Rubin, E.S. and F.C. McMichael. Impact of Regulations on
Coal Conversion Plants. Environmental Science and Tech-
nology, Vol. 9, No. 2, February 1975. 112-117 pp.
37
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-79-004
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Air Emissions from Combustion of Solvent
Refined Coal
5. REPORT DATE
January 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Kenneth G. Budden and Subhash S. Patel
8. PERFORMING ORGANIZATION REPORT NO.
H1T-C165/860-78-733D2
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Hittman Associates, Inc.
9190 Red Branch Road
Columbia, Maryland 21045
10. PROGRAM ELEMENT NO.
EHE623A
11. CONTRACT/GRANT NO.
68-02-2162
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD CO
Task Final; ^/77 - 9/78
VERED
14. SPONSORING AGENCY CODE
EPA/600/13
IS. SUPPLEMENTARY NOTES
2851.
IERL-RTP project officer is William J. Rhodes, MD-61, 919/541-
. ABSTRACT
of & Solvent Refined Coal (SRC) combustion test at
Georgia Power Company's Plant Mitchell, March, May, and June 1977. Flue gas
samples were collected for modified EPA Level 1 analysis; analytical results are
reported. Air emissions from the combustion of coal and SRC are compared for
various organic and inorganic constituents , and SO2 and NOx. The impact of the
air emissions from the combustion of SRC is assessed by comparison with EPA's
Multimedia Environmental Goals and existing New Source Performance Standards.
Air quality emissions test data indicated that SRC SO2 and NOx emissions were 1. 06
and 0.43 Ib/million Btu, respectively; or about 12 and 39% under the existing NSPS
of 1.2 Ib/million Btu for SOx and 0. 7 Ib/million Btu for NOx. If the SO2 standard is
reduced, SRC derived from high sulfur coal may not meet the new standard. The low
NOx emissions may be a result of the abnormally high excess air that was used du-
ring the test: additional testing at normal conditions is required. Particulate emis-
sions can probably be controlled well below the EPA standard of 0. 1 Ib/million Btu
by installing a modern ESP, with a particulate collection efficiency of about 95%.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Coal
Liquefaction
Combustion
Flue Gases
Analyzing
Nitrogen Oxides
Sulfur Oxides
Dust
Air Pollution Control
Stationary Sources
Solvent Refined Coal
Particulate
13B
21D
07D
21B
14B
07B
11G
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport/
Unclassified
21. NO. OF PAGES
45
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
38
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