&EPA
United States
Environmental Protection
Agency
EPA-600/7-86-012a
Aoril 1986
Research and
Development
ENVIRONMENTAL ASSESSMENT
OF A COAL/WATER SLURRY FIRED
INDUSTRIAL BOILER
Volume I. Technical Results
Prepared for
Office of Air Quality Planning and Standards
Prepared by
Air and Energy Engineering Research
Laboratory
Research Triangle Park NC 27711
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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-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
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
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-86-012a
April 1986
ENVIRONMENTAL ASSESSMENT OF A COAL/WATER SLURRY
FIRED INDUSTRIAL BOILER
Volume I
Technical Results
By
D. Van Buren and L. R. Waterland
Acurex Corporation
Energy & Environmental Division
555 Clyde Avenue
P.O. Box 7555
Mountain View, California 94039
EPA Contract No. 68-02-3188
EPA Project Officer: J. A. McSorley
Air and Energy Engineering Research Laboratory
Research Triangle Park, North Carolina 27711
For
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ACKNOWLEDGEMENTS
The authors wish to extend their gratitude to R. Perkins and
S. Hodorowski of the E. I. du Pont de Nemours & Company and R. Manfred of
the Electric Power Research Institute. Their interest and cooperation in
this test program and their efforts in arranging the opportunity to test the
unit are gratefully acknowledged. Special recognition is also extended to
the Acurex field test team of B. C. Daros, S. Smith, M. Murray, P. Kaufmann,
and K. Brewster.
ii
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CONTENTS
Acknowledgements ii
Figures iv
Tables v
1 Introduction 1-1
2 Source Description and Operation and Test Protocol . . . 2-1
2.1 Boiler Description and Operation 2-1
2.2 Test Protocol « 2-4
3 Test Results 3-1
3.1 Criteria Pollutant and Other Gas Phase Species
Emission Results 3-1
3.2 Trace Element Emission Results 3-5
3.3 Organic Emission Results 3-6
3.3.1 TCO, GRAY, GC/MS, and IR Analyses of Sample
Total Extracts 3-9
3.3.2 Volatile Organic Compound Emissions 3-12
4 Environmental Assessment 4-1
4.1 Discharge Assessment 4-1
4.2 Bioassay Results 4-2
4.3 Summary 4-4
5 Test Quality Assurance Activities 5-1
5.1 GI to Cg Hydrocarbon Analysis Precision 5-1
5.2 Total Chromotographable Organic (TCO) Analysis
Precision 5-4
Appendix A A-l
Appendix B 8-1
111
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FIGURES
Number
A-l
A-2
A-3
A-4
A-5
A-6
A-7
A-8
Continuous Monitoring System
Schematic of Particulate and SOX Sampling Train
(EPA Method 5 and 8)
SASS Train Schematic
Flue Gas Analysis Protocol for SASS Samples
Flue Gas Analysis Protocol
Organic Analysis Methodology
N20 Sampling System
Schematic of Volatile Organic Sampling Train (VOST) . . .
Page
A-2
A-5
A-7
A-8
A-9
A-ll
A-l?
A-14
IV
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TABLES
Number
Page
1-1 Completed Tests During the Current Program 1-4
2-1 Boiler Operating Conditions 2-2
2-2 CWS Fuel Composition 2-3
3-1 Criteria Pollutant and Other Gas Species Emissions. . . . 3-2
t
3-2 Particle Size Distribution 3-4
3-3 Particulate Carbon and Hydrogen Content 3-4
3-4 Sulfur Mass Balance 3-5
3-5 Flue Gas Trace Element Emissions 3-7
3-6 Trace Element Mass Balance Results 3-8
3-7 Compounds Sought in the GC/MS Analysis and Their
Detection Limits (ng/ul Injected) 3-10
3-8 Summary of Total Organic Emissions 3-11
3-9 Summary of IR Spectra of SASS Sample Total Extracts . . . 3-13
3-10 Semivolatile Organic Priority Pollutant Emissions
(ug/dscm) 3-13
3-11 Stack Gas Volatile Organic Compound Concentrations . . . 3-14
4-1 Flue Gas Pollutants Emitted at Levels Exceeding
10 Percent of Their Occupational Exposure Guideline . . . 4-3
4-2 Bioassay Results 4-4
5-1 Area Counts and Relative Standard Deviations for C^ to
CQ Analyses 5-2
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SECTION 1
INTRODUCTION
This report describes and presents results of environmental assessment
tests performed for the Air and Energy Engineering Research Laboratory/
Research Triangle Park (AEERL/RTP) of the Environmental Protection Agency
(EPA) under the Combustion Modification Environmental Assessment (CMEA)
i
program, EPA Contract No. 68-02-3188. The CMEA started in 1976 with a 3-year
study (NOX EA), EPA Contract No. 68-02-2160, having the following four
objectives:
9 Indentify potential multimedia environmental effects of stationary
combustion sources and combustion modification technology
« Develop and document control application guidelines to minimize
these effects
o Identify stationary source and combustion modification R&D
priorities
« Disseminate program results to intended users
During the first year of the NOX EA, data for the environmental
assessment were compiled and methodologies developed. Furthermore,
priorities for the schedule and level of effort for the various
source/fuel/control combinations were identified. This effort revealed major
data gaps, particularly for noncriteria pollutants (organic emissions and
1-1
-------
trace elements) for virtually all combinations of stationary combustion
sources and combustion modification techniques. Consequently, a series of
seven environmental field test programs were undertaken to fill these data
gaps. The results of these tests are documented in seven individual reports
(Ref. 1-1 through 1-7) and in the NOX EA final report summarizing the entire
3-year effort (Ref. 1-8).
The current CMEA program has as its major objective the continuation of
multimedia environmental field tests initiated in the original NOX EA
program. These tests, using standardized Level 1 sampling and analytical
procedures (Ref. 1-9) are aimed at filling the remaining data gaps and
addressing the following priority needs:
• Advanced NOX controls
• Alternate fuels
• Secondary sources
• EPA program data needs
— Residential oil combustion
— Wood firing in residential, commercial, and industrial sources
— High interest emissions determination (e.g., listed and
candidate hazardous air pollutant species)
• Nonsteady-state operations
Coal/water slurries (CWS) have received attention in recent years as an
alternative to oil fuels. CWS has the advantage of allowing certain
oil-fired boilers to eliminate their oil requirements without completely
redesigning the boiler. Thus, CWS has a potential for conversion of some
existing industrial oil-burning facilities to coal firing and thereby
1-2
-------
offsetting higher oil prices and frequently uncertain supply situations.
In response to the need for environmental data on burning CWS, as well
as other coal-liquid mixtures such as coal/oil/water (COW) and coal/oil
mixtures (COM), tests of two COW-fired firetube industrial boilers (Ref. 1-10
and 1-11), a COM-fired watertube boiler (Ref. 1-12), and two CWS-fired
watertube industrial boilers (this report and Ref. 1-13) have been performed.
This report presents the results of the emissions assessment of a CWS-fired
industrial boiler. The boiler tested was retrofit to burn CWS under an
Electric Power Research Institute (EPRI) sponsored project to demonstrate the
feasibility of modifying an oil-fired boiler to use CWS. The tests described
t
in this report evaluated flue gas emissions from the retrofit unit under
typical routine operating conditions while firing CWS.
Table 1-1 lists all tests performed to date in the CMEA effort and
outlines the source, fuel, combustion modifications, and level of sampling
and analysis in each case. Results of these test programs are discussed in
separate reports.
1-3
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TABLE 1-1. COMPLETED TESTS DURING THE CURRENT PROGRAM3
Source
Spark-Ignited, natural-
gas-fueled reciprocating
internal combustion
engine
Compression ignition.
diesel-fueled.
reciprocating internal
combustion engine
Low-N0x. residential.
condensing-heating
system furnished by
(Carlsons Blueburner
Systems Ltd. of Canada
Description
Large bore. 6-cylinder.
opposed piston. 186-kU
(250 Bhp)/cy1. 900-rpm
Model 38TOS8-1/8
Large bore, 6-cy Under
opposed piston. 261-kW
(350 Bhp)/cyl. 900-rpm
Model 38TOD8-1/8
Residential hot water
heater equipped with
H.A.N. low-NO.. burner.
0.55 ral/s (0.5 gal/hr)
firing capacity, con-
densing flue gas
Test points
unit operation
— Baseline (pre-NSPS)
— Increased air-fuel
ratio aimed at
meeting proposed NO,
NSPS of 700 ppm
corrected to 15
percent 02 and
standard atmospheric
conditions
— Baseline (pre-NSPS)
— Fuel Injection retard
aimed at meeting pro-
posed NOX NSPS of
600 ppm corrected to
15 percent 02 and
standard atmospheric
conditions
Low-NO, burner design
by H.A.N.
Sampling protocol
Engine exhaust:
— SASS
-- Method 5
— Gas sample (Ci-Ce HC)
-- Continuous NO. NO,. CO.
C02, 02. CH4. TUHC
Fuel
Lube oil
Engine exhaust:
— SASS
— Method 8
-- Method 5
~ Gas sample (Cj-Cg HC)
— Continuous NO. NO-. CO,
C02, 02. CH4, TUHC
Fuel
Lube oil
Furnace exhaust:
— SASS
~ Method 5
— Method 8
— Gas sample (Ci-C6 HC)
— Continuous NO. NOX. CO.
Test collaborator
Fairbanks Morse
Division of Colt
Industries
Fairbanks Morse
Division of Colt
Industries
New test
Fuel
Waste water
Rocketdyne/EPA
low-NOx residential
forced warm air furnace
Residential warm air
furnace with modified
high-pressure burner and
firebox, 0.83 ral/s
(0.75 gal/hr) firing
capacity
Low-N0x burner design
and integrated furnace
system
Furnace exhaust:
— SASS
— Method 5
-- Controlled condensation
— Method 8
~ Gas sample (Cj-Cg HC)
— Continuous NO. NOX. CO.
C02. 02. CH4. TUHC
Fuel
New test
(continued)
-------
TABLE 1-1. (continued)
Source
Description
Test points
unit operation
Sampling protocol
Test collaborator
Pulverized coal-fired
utility boiler.
Conesvllle station
tn
400-MH tangentlally
fired; new NSPS
design aimed at
meeting 301 ng/J
NOX emission limit
ESP Inlet and outlet,
one test
ESP Inlet and outlet
— SASS
-- Method 5
— Controlled condensation
— Gas sample (Ci-Cc HC|
— Continuous NO, NOX, CO,
COj, Oj
Coal
Bottom ash
ESP ash
Exxon Research and
Engineering (ERIE)
conducting cor-
rosion tests
Nova Scotia Technical
College Industrial
boiler
Adelphi University
Industrial boiler
Pittsburgh Energy
Technology Center (PETC)
1.14 kg/s steam
(9.000 Ib/hr) ft re tube
fired with a mixture
of coal /oil /water (COM)
1.89 kg/s steam
(15,000 Ib/hr)
hot water
f1 re tube fired with a
mixture of coal/oil/
water (COM)
3.03 kg/s steam
(24,000 Ib/hr) water tube
— Baseline (COM)
-- Controlled SO?
emissions with
limestone Injection
— Baseline (COM)
— Controlled SO?
emissions with soda
ash (Ni2C03)
Injection
— Baseline test only
with COM
Boiler outlet
- SASS
— He t hod 5
- Method 8
— Controlled Condensation
— Gas sample (CpCe HC)
— Continuous Oo, COj,
CO, NOX
Fuel
Boiler outlet
— SASS
- Method S
-- Method 8
»- Controlled Condensation
— Gas Sample (Cj-Cg HC)
— Continuous 02, C02, NO.,
S02. CO
Fuel
Boiler outlet
— SASS
Envlrocon per-
formed particular
and sulfur
emission tests
Adelphi University
PETC and General
Electric (GE)
Industrial boiler
fired with a mixture of
coal/oil (COM)
-- Method 5
— Controlled Condensation
~ H2° grab sample
— Continuous 02, CO;, NO,,
CO. TUHC
Fuel
TconffnuedT
-------
TABLE 1-1. (continued)
Source
TOSCO Refinery vertical
crude oil heater
Mohawk-Getty Oil
industrial boiler
Description
2.54 Ml/day
(16.000 bbl/day) natural
draft process heater
burning oil/refinery gas
8.21 kg/s steam
(65,000 Ib/hr)
Test points
unit operation
— Baseline
— Staged combustion
using air injection
lances
— Baseline
-• Ammonia InlecHnn
Sampling protocol
Heater outlet
— SASS
-- Method 5
— Controlled condensation
-- Gas sample (Ci-C6 HC)
-- H2" fab sample
— Continuous 02. HOX. CO.
COo , HC
Fuel oil
Refinery gas
Economizer outlet
-. ctcc
i i
Test collaborator
KVB coordinating
the staged com-
bustion operation
and continuous
emission monitoring
Mohawk-Getty Oil
Industrial boiler
Industrial boiler
water tube burning a
mixture of refinery gas
and residual oil
using the noncatalytic
Thermal DeNOx
Process
— Method 5, 17
-- Controlled condensation
— Gas Sample (Cj-C6 HC)
~ Ammonia emissions
NO.
-- NgO grab sample
— Continuous Op
CO. C02
Fuels (refinery gas and
residual oil)
2.52 kg/s steam
(20,000 Ib/hr) watertube
burning wood waste
Baseline (dry wood)
Green wood
Boiler outlet
— SASS
~ Method 5
~ Controlled condensation
~ Gas sample (CrC6 HC)
~ Continuous 02. HO,. CO
Fuel *
Flyash
North Carolina
Department of
Natural Resources,
EPA ItRL-RTP
3.16 kg/s steam
(29.000 Ib/hr)
firetube with refractory
firebox burning wood waste
— Baseline (dry wood)
Outlet of cyclone particular
collector
— SASS
— Method 5
— Controlled condensation
— Gas sample (CrC6 HC)
— Continuous Oj. NOX. CO
North Carolina
Department of
Natural Resources.
EPA I£RL-RTI>
Fuel
Bottom ash
(continued)
-------
Source
Enhanced oil recovery
steam generator
Pittsburgh Energy
Technology Center
(PETC) Industrial
boiler
Spark-Ignited, natural
gas-fired reciprocating
Internal combustion
engine — nonselectlve
HOX reduction catalyst
Industrial boiler
TABLE
Description
15-MH (50 million Btu/hr)
steam generator burning
crude oil equipped with
an HHI low-NOx burner
3.03 kg/s steam
(24.000 Ib/hr) water tube
fired with a coal/water
slurry (CHS)
610-lcH (818-hp) Haukesha
rich-burn engine equipped
with DuPont NSCR system
180 kg/hr steam
(400 Ib/hr) stoker, fired •
with a mixture of coal
and waste plastic
beverage containers
1-1. (continued)
i
Test points
unit operation
— Performance mapping
— Low-N0x operation
— Baseline test only
with CHH
-- Low NOX (with
catalyst)
~ 15-day emissions
monitoring
-- Baseline (coal)
— Coal and plastic waste
Sampling protocol Test collaborator
Steamer outlet: Getty Oil Company.
— SASS CE-Natco
— Method 5
— Method 8
~ Gas sample (Cj-Cg HC)
— Continuous Op, NO-. CO
C02 " *
— N20 grab sample
Fuel
Boiler outlet: PETC and General
— SASS Electric
— Method 5
— Method 8
— Gas sample (Cj-Ct HC)
— Continuous Oo, HO. CO
C02. TUHC
— NpO grab sample
Fuel
Bottom ash
Collector hopper ash
Catalyst inlet and outlet Southern California
"" SASS Gas Company
— HH3
-3 HCN
— N20 grab sample
— Continuous 02. C02. NO,
TUHC *
Lube oil
Boiler outlet Vermont Agency of
— SASS Environmental
" V°ST Conservation
-- Method 5
~ Method 8
— HC1
— Continuous Oo, NO,. CO,
CO,. TUHC *
— N20 grab sample
Fuel
Bottom ash
Cyclone ash
TcontfnuedT
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TABLE 1-1. (continued)
i
CO
Source
Industrial boiler
Enhanced oil
recovery steam
generator
Spark-Ignited natural-
gas-flred reciprocating
Internal combustion
engine — selective NOX
reduction catalyst
Description
7.6 kg/s steam
(60.000 Ita/hr) water tube
retrofit for coal/water
slurry (CMS) firing
1S-MH (50 million Btu/hr)
steam generator burning
crude oil, equipped with
the EPA/EER low-NOx
burner
1,490-kH (2.000-hp)
Ingersoll-Rand lean-burn
engine equipped with
Englehard SCR system
Test points
unit operation
— Baseline test with CMS
— 30-day emissions
monitoring
-- Low NOX (with burner)
— 30-day emissions
monitoring
— Low NO. (with
catalyst)
— 15-day emissions
monitoring
Sampling protocol Test collaborator
Boiler outlet EPRI, DuPont
- SASS
— VOST
— Method 5
— Method 8
~ Gas sample (Cj-C6 HC)
— N^O grab sample
— Continuous NO,. CO, COo,
Oz. TOHC, S02
Fuel
Steamer outlet Chevron U.S.A..
— SASS EERC
— VOST
— Method 5
-- Method 8
— Controlled condensation
— Anderson Impactor
— Gas sample (Ci-Cg HC)
— N20 grab sample
— Continuous NO,, CO. C02,
02. S02
Fuel
Catalyst inlet and outlet Southern
— SASS California Gas
— VOST Company
-Nth
— HCH
— NjO grab sample
— Continuous 02, CO?. CO.
NO. NOX. NOX+NH3
Lube oil
"Acronyms used In the table: EERC. The Energy and Environmental Research Corporation; EPA IERL-RTP, The Environmental Protection
Agency's Industrial Environmental Research Laboratory-Research Triangle Park; EPRI, The Electric Power Research Institute;
HC. hydrocarbons; HSCR, nonselectlve catalytic reduction; NSPS, new source performance standard; SASS. source assessment sampling
system; SCR, selective catalytic reduction; TUHC. total unburned hydrocarbon; VOST, volatile organic sampling train
-------
REFERENCES FOR SECTION 1
1-1. Larkin, R., and E. B. Higginbotham, "Combustion Modification Controls
for Stationary Gas Turbines: Volume II. Utility Unit Field Test,"
EPA-600/7-81-122b, NTIS PB 82-226473, July 1981.
1-2. Higginbotham, E. B., "Combustion Modification Controls for Residential
and Commercial Heating Systems: Volume II. Oil-fired Residential
Furnace Field Test," EPA-600/7-81-123b, NTIS PB 82-231176, July
1981.
1-3. Higginbotham, E. B., and P. M. Goldberg, "Combustion Modification NOX
Controls for Utility Boilers: Volume !. Tangential Coal-fired Unit
Field Test," EPA-600/7-81-124a, NTIS PB 82-227265, July 1981.
1-4. Sawyer, J. W., and E. B. Higginbotham, "Combustion Modification NOX
Controls for Utility Boilers: Volume II. Pulverized-Coal Wall-fired
Unit Field Test," EPA-600/7-81-124b, NTIS PB 82-227273, July 1981.
1-5. Sawyer, J. W., and E. B. Higginbotham, "Combustion Modification NOX
Controls for Utility Boilers: Volume III. Residual-Oil Wall-Fired
Unit Field Test," EPA-600/7-81-124c, NTIS PB 82-227281, July 1981.
1-6. Goldberg, P. M., and E. B. Higginbotham, "Industrial Boiler Combustion
Modification NOX Controls: Volume II. Stoker Coal-Fired Boiler Field
Test -- Site A,fr EPA-600/7-81-126b, NTIS PB 82-231085, July 1981.
1-7. Lips, H. I., and E. B. Higginbotham, "Industrial Boiler Combustion
Modification NOX Control: Volume III. Stoker Coal-Fired Boiler Field
Test ~ Site B,ft EPA-600/7-81-126c, NTIS PB 82-231093, July 1981.
1-8. Waterland, L. R., et al., "Environmental Assessment of Stationary
Source NOX Control Technologies — Final Report," EPA-600/7-82-034,
NTIS PB 82-249350, May 1982.
1-9. Lentzen, D. E., et al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)," EPA-600/7-78-201,
NTIS PB 293795, October 1978.
1-10. Castaldini, C., "Environmental Assessment of an Industrial Boiler
Burning Coal/Oil/Water Mixture," Acurex Draft Report TR-81-86/EE,
August 1984.
1-11. DeRosier, R., "Environmental Assessment of a Firetube Boiler Firing
Coal/Oil/Water Mixtures," EPA 600/7-84-095a/b, September 1984.
1-9
-------
1-12. DeRosier, R., "Environmental Assessment of a Water-tube Boiler Firing a
Coal/Oil Mixture," Acurex Draft Report TR-81-87/EE, March 1984.
1-13. DeRosier, R. and L. R. Waterland, "Environmental Assessment of a
Watertube Boiler Firing a Coal/Water Slurry," EPA 600/7-86-004a/b,
January 1985.
1-10
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SECTION 2
SOURCE DESCRIPTION AMD OPERATION AND TEST PROTOCOL
As part of EPRI's CWS demonstration program, an oil-fired industrial
boiler was retrofit to fire CWS, and a 35-day demonstration burn involving
two CWS formulations was performed (EPRI project RP-1895-7). The tests
reported herein were performed during the demonstration burn period.
2.1 BOILER DESCRIPTION AND OPERATION
The tests were performed on a Babcock and Nil cox integral furnace, bent
tube boiler rated at 7.6 kg steam/s (60,000 Ib/hr) at 1.2 MPa (175 psig)
located at the Memphis, Tennessee, plant of the E. I. du Pont de Nemours &
Company. The unit was orginally designed to fire distillate fuel oil,
process gas, and natural gas. It had been previously modified to accommodate
residual fuel oil, and most recently modified to burn a coal/water slurry
(CWS).
During the comprehensive emissions testing on August 25, 1983, three
burners (burners 2, 3, and 4) of the available five were fired with CWS. In
addition to the CWS, a small amount of natural gas was fired into the direct
air preheater and through burner 4. The CWS fired was an Atlantic Research
Corporation formulation (ARC-coal).
Table 2-1 summarizes the boiler operating data during the test. As
shown in the table, a portion of the heat input was from the natural gas.
Based on a CWS heating value of 34.37 MJ/kg (14,810 Btu/lb), a specific
2-1
-------
TABLE 2-1. BOILER OPERATING CONDITIONS
Parameter Range Average
Steam flow, kg/s (103 Ib/hr) 6.89 to 7.13 (54.6 to 56.5) 7.01 (55.5)
Steam pressure, MPa (psig) 1.19 to 1.21 (173 to 176) 1.21 (175)
CWS flow, 1/s (gpmla 0.60 to 0.61 (9.5 to 9.7) 0.61 (9.6)
Natural gas flow to burner No. 4, scm/min (Ifl3 scfh) 1.39 to 1.79 (2.94 to 3.79) 1.48 (3.14)
Natural gas flow to air heater, scra/min (103 scfh) 1.58 to 1.76 (3.35 to 3.73) 1.68 (3.55)
Inlet air temperature, *C (*F) 29 to 39 (85 to 102) 36 (96)
Windbox air temperature, °C (°F) '• 274 to 283 (525 to 542) 279 (535)
windbox air pressure, kPa (in. HC) 279 (11.2) 279 (11.2)
CWS heater temperature, °C CF) 37 to 38 (98 to 101) 38 (100)
CWS strainer discharge pressure, MPa (psig) 1.35 to 1.38 (196 to 200) 1.37 (198)
Feedwater temperature, °C (°F) 129 (265) 129 (265)
Stack gas temperature, °C (°F) 293 to 304 (559 to 580) 299 (571)
Atomizing air pressure, MPa (psig)
Burner No. 2 1.41 to 1.42 (204 to 205) 1.42 (206)
Burner No. 3 1.42 to 1.43 (206 to 208) 1.43 (208)
Burner No. 4 1.41 to 1.42 (204 to 206) 1.42 (206)
CWS burner pressure, MPa (psig)
Burner No. 2 1.13 to 1.16 (164 to 168) 1.14 (166)
Burner No. 3 1.12 to 1.14 (162 to 166) 1.14 (165)
Burner No. 4 1.16 to 1.23 (168 to 179) 1.21 (176)
Furnace pressure, Pa (in. WC) -77 to -37 (-0.31 to -0.15) -60 (-0.24)
Excess air (percent)b 45
Boiler efficiency (percent)0 72
aAverage of two flowmeters Installed; one magnetic and one mass
^Calculated from flue gas composition
Calculated using "ASME test form for abbreviated efficiency test"
2-2
-------
TABLE 2-2. CMS FUEL COMPOSITION*
Component
Moistureb
Solidsb
Carbon
Hydrogen
Oxygenb»c
Ni trogen
Sulfur
Ash
Higher heating value, MJ/kg
(Btu/lb)
Percent by weight
(dry basis unless noted)
29.7
70.3
83.3
5.1
5.0
1.4
0.61
4.6
34.374
(14,810)
aRef. 2-1
bAs fired
cBy difference
gravity of 1.20 (10.0 Ib/gal), a moisture content of 29.7 percent, and a
natural gas fuel value of 36.9 MJ/scm (991 Btu/scf), the average heat input
was about 90 percent from the CMS and 10 percent from the natural gas.
Table 2-2 summarizes the CMS composition as reported by DuPont (Ref. 2-1).
The boiler efficiency, calculated using the ASME heat loss method, of
72 percent, as shown in Table 2-1, is slightly lower than the average
efficiency of 73.7 percent determined by DuPont personnel during subsequent
days of the test burn.
2-3
-------
2.2 TEST PROTOCOL
The sampling matrix for the comprehensive tests consisted of:
o Fuel grab sample
» Flue gas:
— Continuous monitors for 02, C02, CO, NOX, and total unburned
hydrocarbon (TUHC)
— Volatile organic sampling train (VOST) sampling
— Source assessment sampling system (SASS) sampling
— Combined EPA Method 5/8 sampling for particulate and sulfur
oxides
— Gas grab sampling for onsite determination of C^ to Cg
hydrocarbons by gas chromatography/flame ionization detector
(GC/FID)
— Gas grab sampling for N20 determination
All flue gas sampling was performed in a vertical section of breeching
located downstream of the boiler's induced draft fan, but upstream of the
breeching transition section to the stack. Details of the specific sampling
protocols used are given in Appendix A.
The analysis protocol for collected samples included:
9 Analyzing fuel and SASS train samples for 73 trace elements using
spark source mass spectrometry (SSMS) supplemented by atomic
absorption spectrometry (AAS) and other methods
» Analyzing VOST traps for the volatile organic priority pollutants in
accordance with the VOST protocol (Ref. 2-2)
2-4
-------
• Analyzing SASS train organic extract samples for total organic
content in two boiling point ranges: 100° to 300°C by total
chromatographable organics (TCO) analysis, and >300°C by gravimetry
(GRAY)
• Performing infrared spectrometry (IR) analysis of the GRAV residue
of all organic extract samples
• Analyzing the SASS train sorbent module extract in accordance with
EPA Method 625 for the semivolatile organic priority pollutants, a
set which includes many polynuclear aromatic hydrocarbon (PAH)
compounds
• Performing mutagenicity and cytotoxicity bioassay testing of SASS
train samples
This sampling and analysis matrix conforms to a modified and extended EPA
Level 1 protocol (Ref. 2-3).
REFERENCES FOR SECTION 2
2-1. Perkins, R. P., "Coal/Water Slurry Test in an Industrial Boiler," Final
Report to the Electric Power Research Institute, EPRI Project
RP-1895-7, November 1984.
2-2. Hansen, E. M., "Protocol for the Collection and Analysis of Volatile
POHC's using VOST," EPA-600/8-84-007, NTIS PB84-170042, March 1984.
2-3. Lentzen, D. E., etal., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)", EPA 600/7-78-201, NTIS
PB293795, October 1978.
2-5
-------
SECTION 3
TEST RESULTS
The objective of this test program was to measure flue gas emissions
from the coal/water slurry-fired boiler tested at the Memphis plant of the
E. I. du Pont de Nemours & Company. The tests were performed in conjunction
with an EPRI-sponsored CWS demonstration burn program which sought to
r
establish the operational feasibility of using CWS in an industrial boiler
originally designed to fire liquid fuels. Succeeding discussion of the test
results has been arranged by pollutant grouping. Criteria pollutant and
other gas phase species emissions are discussed in Section 3.1, inorganic
trace element emissions in Section 3.2, and organic emissions in Section 3.3.
Section 4 presents an environmental assessment of the emissions and the
results of biological testing of the samples collected.
3.1 CRITERIA POLLUTANT AND OTHER GAS PHASE SPECIES EMISSION RESULTS
Table 3-1 summarizes gaseous compound and particulate emissions measured
during the test. As shown in the table, NOX and CO emissions averaged about
400 to 220 ppm as measured, respectively, or 510 and 285 ppm corrected to
i
3 percent Q^» respectively. TUHC emissions were low, in the 1 ppm range.
N20 emissions, at 54 ppm as measured or 70 ppm corrected to 3 percent Og were
about 14 percent of the correspnding NOX (NO + N02) emission level (NgO does
not elicit a response in the chemiluminescent technique employed by the
3-1
-------
TABLE 3-1. CRITERIA POLLUTANT AND OTHER GAS SPECIES EMISSIONS
Component
Range
(by volume
as noted)
Average
(by volume
as noted)
Boiler outlet 02 (percent dry, by DuPont
analyzer)
Downstream of boiler I.D. fan, as measured
by Acurex continuous gas analyzers:
0? (percent dry)
C&2 (percent dry)
CO (ppm dry)
NOX (ppm dry)
TUHC (ppm dry)
Moisture (percent)
SO 2 (ppm dry)
SO 3 (ppm dry)
N20 (ppm dry)
6.6 to 7.0
6.6 to 7.4
8.9 to 9.8
205 to 370
385 to 435
1 to 2
..a
— a
—a
18 to 98&
6.8
7.0
9.5
222
397
1
7.7
350
2.0
54
Corrected gaseous emissions
ppmc
ng/Jd lb/106 Btud
NOX (as N02)
CO
TUHC (as CH4)
S02
S03
N20
510
285
1
450
2.6
70
443
151
0.4
540
3.9
57
1.03
0.35
0.001
1.26
0.009
0.13
Solid particulate mass emissions
g/dscm ug/J lb/106 Btu
Method 5
SASS
4.31
3.14
2.51
1.83
5.84
4.26
Extractive sample by EPA Method 5/8 over test duration; range not
applicable
bRange for three grab samples
Corrected to 3 percent 02, dry
dHeat input basis
3-2
-------
continuous NOX analyzer). This is at the low end of the range (about
20 percent) seen in tests of other external combustion sources (Ref. 3-1).
Solid particulate emissions as measured using EPA reference Method 5
were relatively high, at 4.31 g/dscm. However, the boiler had no particulate
control device, so a relatively high emission rate would be expected.
Particulate emissions as measured using the SASS train are in reasonable
agreement (within 30 percent) of the reference method measurement.
The emitted particle size distribution as determined by the SASS train
is given in Table 3-2. As noted, the distribution is heavily weighted to
coarse particulate. Over half the particulate mass was greater than 10 urn
particles; over 90 percent was greater than '3 urn particles.
The combustible content of two composite particulate fractions in terms
of their carbon and hydrogen contents was measured. Results are given in
Table 3-3. As shown, the carbon content of the coarse (>3 urn) particulate
was quite high, over 42 percent; that of the fine (<3um) particulate was
about 13 percent. Weighting these by the size distribution data noted in
Table 3-2 gives a composite particulate carbon content of about 40 percent,
with hydrogen content of about 0.1 percent. This combustibles content
corresponds to a heating value of about 13.7 MJ/kg (5,920 Btu/lb).
Table 3-1 also shows that S02 and $03 emissions from the boiler, as
determined by Method 8, were 350 ppm and 2.0 ppm as measured, respectively,
or 450 ppm and 2.6 ppm corrected to 3 percent Og, respectively. The ratio of
503 to total SOX (S02 + $03), at about 0.6 percent, is lower than the range
typical for coal-fired sources (generally 2 to 5 percent). Sulfur analyses
of the two SASS particulate size fractions indicated that the course (>3um)
3-3
-------
TABLE 3-2. PARTICLE SIZE DISTRIBUTION
Weight percent
of particulate
Size range in size range
m 51.4
3 to 10 um 40.4
1 to 3 Mm 7.8
<1 um 0.4
TABLE 3-3. PARTICULATE CARBON AND HYDROGEN CONTENT
Carbon content Hydrogen content
Size range (weight percent) (weight percent)
>3 um (10 um + 3 um 42.67 0 13
cyclone catch)
<3 Mm (1 um + filter 13.13 0.09
catch)
Composite 40.19 0.13
3-4
-------
particulate contained 0.064 percent sulfur and the fine particulate contained
0.3 percent sulfur -
A sulfur mass balance based on the above is summarized in Table 3-4. As
noted, boiler output sulfur (dominated by S02 emissions) accounted for
173 percent of input sulfur. The authors suspect that the sulfur analysis of
the fuel was in error- With a fuel sulfur content of approximately
1 percent, the sulfur mass balance would close. This may have been the case.
Additional separate fuel ultimate analyses also reported by OuPont had sulfur
content at 0.92 percent, dry basis (Ref. 3-2). Of course, some variation in
composition is possible with solid fuel samples.
f
3.2 TRACE ELEMENT EMISSION RESULTS
The boiler flue gas SASS train samples were analyzed for 73 trace
elements using spark source mass spectrography (SSMS) supplemented by atomic
absorption (AAS) for mercury, antimony, arsenic, and selected major
components of samples present at levels greater than the quantitation limit
TABLE 3-4. SULFUR MASS BALANCE
Fuel sulfur content (percent, dry basis) 0.61
Sulfur input (g/s) 3.11
emission concentration (mg/dscm) 930
emission rate (g/s as S) 5.30
S02 emission concentration (mg/dscm) 6.8
emission rate (g/s as S) 0.03
Composite particulate sulfur content (percent) 0.083
emission rate (g/s as S) 0.04
Total sulfur output (g/s) 5.37
Mass balance, out/in (percent) 173
3-5
-------
of SSMS. Specific ion electrode, col crimetrie, turbidimetrie, or X-ray
fluorescence spectrometry techniques were used for other major components in
samples as appropriate. Once the trace element concentrations were
determined, trace element flowrates for the flue gas vapor and condensed
phases could be calculated. Appendix B presents trace element concentrations
in the SASS train components and summed to give the total flue gas stream
concentration as well as flowrates on a mass per time and mass per heat input
basis.
Table 3-5 summarizes the total flue gas trace element concentrations for
those elements present above their limit of detection. Table 3-6 presents
the trace element mass balance results for the test for those elements
quantitated in both the fuel and the flue gas (SASS train components). Mass
balance closure for the elements noted was quite good. Of 43 elements noted
in the table, only eight had outlet flowrate more than about a factor of
three different from inlet flowrate. Most element balances closed within a
factor of 50 percent.
3.3 ORGANIC EMISSION RESULTS
Organic analyses were performed on selected SASS samples according to
an extended EPA Level 1 protocol (Ref. 3-3), as outlined in appendix A.
Total volatile organics having boiling points nominally in the GI to CQ range
of -160° to 90°C (-256° to 194*F) were determined by onsite gas
chromatographic analyses of grab samples. The SASS train particulate (in 1wo
size fractions, >3um and <3um), organic module sorbent (XAD-2), and organic
module condensate (OMC) samples were extracted with methylene chloride in a
Soxhlet apparatus. The extracts (the XAD-2 and OMC extracts were combined)
were then subjected to total chromatographable organic (TCO) and gravimetric
(GRAY) analyses to determine the total concentration of organics within the
3-6
-------
TABLE 3-5. FLUE GAS TRACE ELEMENT EMISSIONS*
Flue gas concentration
Element (ug/dscm)
Flue gas concentration
Element (ug/dscm)
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Cerium
Cesium
Chromium
Cobalt
Copper
Dysprosium
Erbium
Europium
Gadolinium
Gallium
Germanium
Gold
Hafnium
Hoi mi urn
Iodine
Iron
Lanthanum
Lead
Lithium
Lutetium
271,000
25.6
55.6
1,270
430
4.2
79.6
109
<3.9
12,900
105
7.5
2,260
120
329
23.9
10.5
3.9
14.7
163
24
<0.2
3.6
14
22
79,900
137
166
258
0.824
Magnesium
Manganese
Mercury
Molybdenum
Neodymi urn
Nickel
Niobium
Phosphorus
Potassium
Praseodymium
Rubidium
Samarium
Scandium
Selenium
Si 1 i con
Silver
Sodi urn
Strontium
Tantalum
Tellurium
Terbi urn
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttri urn
Zinc
Zirconium
7,670
90
0.37
44.1
42.4
1160
58.3
1,850
28,000
29.1
63.9
25.5
77.8
31.0
385,000
4.1
47,500
883
6.0
<0.4
3.6
3.7
62
1.7
11.8
16,700
5.1
39.2
443
5.7
140
425
164
alridium, osmium, palladium, platinum, rhenium, rhodium, and ruthenium
were also analyzed for but not present above method detection limits
3-7
-------
TABLE 3-6. TRACE ELEMENT MASS BALANCE RESULTS
Aluminum
Antimony
Arsenic
Ban* urn
Beryllium
Boron
Bromi ne
Calcium
Cerium
Chromium
Cobalt
Copper
Europium
Gallium
Germanium
lodi ne
Iron
Lanthanum
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Niobium
Phosphorus
Potassium
Praseodymium
Rubidium
Scandium
Selenium
Silicon
Sodium
Strontium
CWS fuel
(ug/s)
3,590,000
1,020
512
118,000
4,600
4,100
4,100
138,000
2,050
15,900
1,540
4,100
154
1,540
307
2,560
871,000
3,070
1,540
25,600
102,000
3,070
10.2
1,020
1,540
512
236,000
41,000
461
1,020
1,540
4,100
6,560,000
35,900
8,710
Boiler outlet
(iig/s)
3,090,000
292
634
14,500
4,900
907
1,240
148,000
1,190
25,700
1,370
3,750
44
1,860
275
251
911,000
1,560
1,890
2,940
87,500
1,030
4.24
503
13,200
664
21,100
319,000
331
729
0.887
353
4,390,000
541,000
10,100
Mass balance
(out/in)
0.86
0.285
1.24
1.23
1.06
0.221
0.302
1.07
0.582
1.62
0.89
0.916
0.286
1.21
0.89
0.0978
1.05
0.508
1.23
0.115
0.853
0.334
0.414
0.491
8.59
1.30
0.0896
7.78
0.718
0.711
0.577
0.0861
0.670
15.1
1.16
(continued)
3-8
-------
TABLE 3-6. (continued)
Thorium
Tin
Titanium
Uranium
Vanadi urn
Yttrium
Zinc
Zirconium
CWS fuel
Cug/s)
2,050
256
205,000
1,020
4,100
2,050
3,070
3,070
Boiler outlet
(wg/s)
700
134
191,000
447
5,050
1,600
4,840
1,870
Mass balance
(out/in)
0.34
0.523
0.93
0.436
1.23
0.778
1.57
0.61
100° to 300°C (212° to 572°F), and greater than 300°C (572CF) boiling point
*
ranges, respectively. Infrared (IR) spectra of the GRAV residues of the
extracts were also obtained. In addition the SASS train extract samples were
analyzed for the 58 senrivolatile organic priority pollutants (a category
which contains several polynuclear aromatic hydrocarbon (PAH) species) by gas
chromatography/mass spectrometry (GC/MS) in accordance with EPA Method 625
(Ref. 3-4). Table 3-7 lists the compounds sought in this analysis and their
method detection limits. The volatile organic sampling train (VOST) sorbent
traps taken during the tests were analyzed per VOST protocol (Ref. 3-5) for
the volatile organic priority pollutants by GC/MS in accordance with EPA
Method 624.
Results of all these analyses are discussed in the following
subsections.
3.3.1 TCP, GRAV, GC/MS, and IR Analyses of Sample Total Extracts
Table 3-8 summarizes the total organic emission results. As indicated
in the table, vapor-phase hydrocarbon (Ci to Cg) emissions averaged
3-9
-------
TABLE 3-7. COMPOUNDS SOUGHT IN THE GC/MS ANALYSIS AND THEIR DETECTION
LIMITS (ng/pl INJECTED)
Acid compounds
2,4,6-trichlorophenol
p-chloro-m-cresol
2-chlorophenol
2,4-dichlorophenol
2,4-dimethy!phenol
5 2-nitrophenol
5 4-nitrophenol
5 2,4-dinitrophenol
5 4,6-dinitro-o-cresol
5 pentachlorophenol
phenol
5
20
20
20
5
1
Base neutral compounds
1,2,4-tri chlorobenzene
1,2-di chlorobenzene
1,2-di pheny1hydrazi ne
(as azobenzene)
1,3-di chlorobenzene
1,4-di chlorobenzene
2,4-di ni trotoluene
2,6-di ni trotoluene
2-chloronaphthalene
3,3'-dichlorobenzidine
3-methyl cholanthrene
4-bromophenyl phenyl ether
4-chlorophenyl phenyl ether
7,12-dimethyl benzo(a)anthracene
N-ni trosodi-n-propyl ami ne
N-nitrosodimethylamine
N-nitrosodiphenylamine
acenaphthene
acenaphthylene
anthracene
benzo(ghi)perylene
benzidine
benzo(b)fluoranthene
benzo(k)fluoranthene
benzo(a)anthracene
benzo(a)pyrene
1 benzo(c)phenanthrene 40
1 bis(2-chloroethoxyjmethane 1
1 bis(2-chloroethyl)ether 1
bis(2-chloroisopropylJether 1
1 bis(2-ethylhexyl)phthalate 1
1 butyl benzyl phthalate 1
1 chrysene 1
1 di-n-butyl phthalate 1
1 di-n-octyl phthalate 1
5 dibenzo(a,h)anthracene 5
40 dibenzo(c,g)carbazole 40
1 diethy! phthalate 1
1 dimethyl phthalate 1
40 fluoranthene 1
5 fluorene 1
NA hexachlorobenzene 1
1 hexachlorobutadiene 1
1 hexachlorocyclopentadiene 1
1 hexachloroethane 1
1 indeno(l,2,3-cd)pyrene 5
5 isophorone 1
20 naphthalene 1
1 nitrobenzene 1
1 perylene 40
1 phenanthrene 1
1 pyrene 1
3-10
-------
TABLE 3-8. SUMMARY OF TOTAL ORGANIC EMISSIONS
Organic Emissions
r
C2
C3
C4
Total Cj-Cg
Total semivolatile organics analyzed by TCO:
Sorbent module extract
Total C7-C16
Total nonvolatile organics analyzed by GRAV:
Filter + 1 ym parti cul ate
3 pm + 10 pm participate
XAD-2 + organic module condensate
Total C16+
Total organics
(mg/dscm)
Total volatile organics analyzed in the field by gas
chromatography:
0.0
3.9
7.9
2.7
0.0
0.6
15.1
0.05
0.05
<0.3
<1.0
0.3
0.3 to 1.6
15.5 to 16.8
3-11
-------
15.1 mg/dscm. These were somewhat evenly divided among the €2, 03, and 04
boiling point ranges. The C^ to CQ fraction accounted for over 90 percent of
the total organic emissions. Flue gas levels of semivolatile and nonvolatile
organics (TCO + GRAV) were quite low.
Table 3-9 presents a summary of the IR spectra of the GRAV residue of
each extract sample analyzed. As noted, the <3 \an particulate
(1 ym + filter) extract spectrum were too weak to interpret. The spectrum of
the >3 pm particulate (10 + 3 jim particulate) extract suggests only the
presence of aliphatic hydrocarbons. The sorbent module extract (XAD-2 + OMC)
spectrum suggests these plus some oxygenated compounds such as aldehydes
and/or ketones.
Table 3-10 summarizes the results of the GC/MS analysis of the SASS
train extracts. Only naphthalene was detected and only in the sorbent module
extract. The noted naphthalene emission rate at less than 5 pg/dscm is quite
low, in keeping with the overall low total organic content of the SASS
samples.
Since no extract sample contained more than 15 mg of total organic,
further Level 1 analyses, specifically liquid column (CC) chromatography
separation, were not performed.
3.3.2 Volatile Organic Compound Emissions
Table 3-11 summarizes analysis results for the VOST train samples
collected during the tests. As noted in the table, several chlorinated GI
and C2 aliphatics, chlorobenzene, benzene, and ethylbenzene were detected at
levels up to about 25 yg/dscm. The levels of the aromatic hydrocarbons
(benzene and ethylbenzene) noted are typical of what has been seen in recent.
3-12
-------
TABLE 3-9. SUMMARY OF IR SPECTRA OF SASS SAMPLE TOTAL EXTRACTS
SASS component Wave number (cm"1) Intensity3 Assignment
Possible
compound
categories
present
1 urn + filter
parti culate
extract
No peaks
10 yjn + 3 ym
parti culate
extract
Sorbent module
extract
2930
2840
2960
2920
2840
1740
1450
1280
S
M
M
S
M
VI
W
CH alkyl
CH alkyl
* CH alkyl
CH alkyl
CH alkyl
C=0 stretch
C-H bend
C-0 stretch
Aliphatic
hydrocarbons
Aliphatic
hydrocarbons,
oxygenated
hydrocarbons
such as
aldehydes and
ke tones
aS ~ strong
M — moderate
W — weak
TABLE 3-10. SEMIVOLATILE ORGANIC PRIORITY POLLUTANT EMISSIONS
(yg/dscm)
Sample
Compound
Naphthalene
All other semi volatile
XAD-2
extract
1.7
<0.3
Filter + 1 ypn
parti culate
extract
<0.7
<0.7
10 + 3 urn
parti culate
extract
<2.7
<2.7
Total
1.7 to 5.
<2.7
1
organic priority
pollutants
3-13
-------
TABLE 3-11. STACK GAS VOLATILE ORGANIC COMPOUND CONCENTRATIONS
Stack gas concentration^,
Compound3
Chl orome thane
Vinyl chloride
Chloroe thane
1,2-di chl oroe thane
Benzene
Chlorobenzene
Ethyl benzene
Tenax
trap
0.4
<0.3
<0.3
0.4
20.9
<0.3
<0.3
Trap set 1
Tenax/
charcoal
trap
27.6
5.2
8.2
<0.3
<0.3
<0.3
2.4
Total
28
5.2
8.2
0.4
21
<0.3
2.4
c (ug/dscm)
Trap set 3
Tenax
trap
<0.3
<0.3
<0.3
<0.3
25.4
1.5
<0.3
Tenax/
charcoal
trap
12.8
8.3
12.9
<0.3
<0.3
<0.3
1.1
Total
13
8.3
12.9
<0.3
25
1.5
1.1
Average
total
21
6.8
11
0.4
23
0.9
1.8
aBromomethane, chloroethane, methylene chloride, 1,1-dichloroethylene,
1,1-dichloroethane, t-l,2-dichloroethylene, chloroform,
1,1,1-trichloroethane, carbon tetrachloride, dichlorobromomethane,
1,2-dichloropropane, t-1,3-dichloropropene, trichloroethylene,
2-chloroethyl vinyl ether, bromoform, tetrachloroethylene,
1,1,2,2-tetrachloroethane, toluene, ally! chloride, ethylene oxide,
propylene oxide, and 2-nitropropane were also analyzed for and not
detected above a detection limit of 0.3 ug/dscm
bpield blank corrected
cTriplicate sets of traps samples; trap set 2 not analyzed
3-14
-------
YOST test of combustion sources (Refs. 3-6, 3-7, and 3-8). The source of the
chlorinated hydrocarbons is not clearly understood, although these compounds
certainly arise whenever chlorine containing fuels are burned. Although the
fuel composition cited in Table 2-2 did not note a chlorine level, other
additional analysis reported by DuPont (Ref. 3-2) indicate the chlorine
content of the fuel as 0.11 percent (dry basis). This level is more than
sufficient to account for the levels of the chlorinated compounds noted in
Table 3-11.
3-15
-------
REFERENCES FOR SECTION 3
3-1. Waterland, L. R., et al., "Environmental Assessment of Industrial
Boilers Firing Coal-Liquid Mixtures and Wood," in Proceedings of the
1982 Joint Symposium on Stationary Combustion NOX Control Volume II,
EPA-600/9-85-022b, July 1985.
3-2. Perkins, R. P., "Coal/Water Slurry Test in an Industrial Boiler," Final
Report to the Electric Power Research Institute, EPRI Project
RP-1895-7, November 1984.
3-3. Lentzen, D. E., eta!., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)", EPA 600/7-78-201, NTIS
PB293795, October 1978.
3-4. 44 CFR 69532, December 3, 1979.
3-5. Hansen, E. M., "Protocol for the Collection and Analysis of Volatile
POHC's Using YOST," EPA-600/8-84-007, NTIS PB84-170042, March 1984.
3-6. Castaldini, C., S. Unnasch, and H. B. Mason, "Engineering Assessment of
Hazardous Waste Cofiring in Industrial Boilers," Acurex Draft
Report TR-84-159/EED, May 1984.
3-7. Castaldini, C., et al., "Environmental Assessment of an Enhanced Oil
Recovery Steam Generator Equipped with the EPA Low NOX Burner," Acurex
Draft Report TR-35-174/EED, January 1985.
3-8. DeRosier, R., et al., "Environmental Assessment of a Commercial Boiler
Fired with a Coal/Waste Plastic Mixture," Acurex Draft Report
TR-85-175/EE, February 1985.
3-16
-------
SECTION 4
ENVIRONMENTAL ASSESSMENT
This section discusses the potential environmental impact of the boiler
tested and discusses the results of the bioassay testing of flue gas samples
collected. As a means of ranking pollutants discharged for possible further
consideration, flue gas stream pollutant concentrations are compared to
occupational exposure guidelines. Biosassay analyses were conducted as a
more direct measure of the potential health effects of the emission stream.
Both of these analyses are aimed at identifying potential problem areas and
providing the basis for ranking pollutant species and discharge streams for
further consideration.
4.1 DISCHARGE ASSESSMENT
To obtain a measure of the potential significance of the discharge
stream analyzed in this test program, discharge concentrations were compared
to an available set of health-effects-related indices. For the flue gas
discharge the indices used for comparison were occupational exposure
guidelines. Two sources of such guidelines were used: the time-weighted-
average threshold limit values (TLV's) defined by the American Conference of
Governmental Industrial Hygienists (ACGIH) (Ref. 4-1) and 8-hour
time-weighted-average exposure limits established by the Occupational Safety
and Health Administration (OSHA) (Ref. 4-2).
4-1
-------
The comparisons of the discharge stream concentrations to these indices
should only be used for ranking pollutant discharge levels for further
testing and analyses.
Table 4-1 lists those pollutants emitted in the flue gas at levels
greater than 10 percent of their occupational exposure guideline. As noted
in the table, particulate emissions were at levels over 400 times the
nuisance particulate TLV. Of course the unit had no particulate control
device during the demonstration burn tested, so particulate emissions were
high. The other criteria pollutants, NOX and S02, were emitted at levels
between 130 and 190 times their respective TLV's. CO and 803 emissions were
at levels between five and seven times their TLV's.
Table 4-1 also notes that two elements were emitted at levels over
100 times their TLV's and another eight were emitted at levels over 10 times
their TLV's. However, again, these elements are associated with the flue gas
particulate, emissions of which were not controlled. In fact, five of the
first eight elements noted (silicon, aluminum, iron, sodium, and potassium)
are major components of the coal ash (Ref. 4-3).
4.2 8IOASSAY RESULTS
Health effects bioassay tests were performed on the SASS organic sorbent
(XAD-2) extract and the flue gas particulate. The bioassay tests performed
(Ref. 4-3) were the Ames assay, based on the property of Salmonella
typhinurium mutants to revert due to exposure to various classes of mutagens,
and a cytotoxicity assay (CHO) with mammaliam cells in culture to measure
cellular metabolic impairment and death resulting from exposure to soluble
toxicants.
4-2
-------
TABLE 4-1. FLUE GAS POLLUTANTS EMITTED AT LEVELS EXCEEDING 10 PERCENT
OF THEIR OCCUPATIONAL EXPOSURE GUIDELINE
Pollutant
Major constituents
Particulate
S02
S03
NOX (as N02)
CO
Trace Elements
Beryllium
Aluminum
Iron
Chromium
Silicon
Sodium
Phosphorous
Potassium
Nickel
Lithium
Vanadium
Calcium
Arsenic
Lead
Copper
Barium
Titanium
Cobalt
Magnesium
Zinc
Silver
Selenium
Bromi ne
Yttrium
Flue gas
concentration
(mg/dscm)
4,310
930
6.7
760
260
0.43
270
80
2.3
385
48
1.9
28
1.2
0.26
0.44
13
0.056
0.17
0.33
1.3
0.17
0.12
7.7
0.43
0.0041
0.031
0.11
0.14
Occupational
exposure
guideline3
(mg/m3)
IQb
5.0
1.0
6.0
55
0.002
2.0
1.0
0.050
IQb
2.QC
0.10
2.0C
0.10
0.025
0.050
2.0
O.OlOd
O.OSQd
O.lQd
0.50
10b
0.10
10
1.0
0.010
0.20
0.70
1.0
jTime-weighted-averge TLV (Ref. 4-1) unless noted
DFor nuisance particle
^Ceiling limit
d8-hr time-weighted-average OSHA exposure limit
(Ref. 4-2)
4-3
-------
Table 4-2 summarizes the results of these tests. The results suggest
that the XAD-2 extract was of moderate mutagenicity and toxicity and both
SASS particulate size fraction were of nondetectable mutagenicity and low
toxicity. The positive responses for the sorbent module extract in the
assays performed are typical of the SASS tests of combustion source flue gas,
Current studies sponsored by EPA's Air and Energy Engineering Research
Laboratory/Research Triangle Park are investigating whether such responses
are due to artifact compounds formed when combustion gas containing NOX is
passed over XAD-2 resin.
4.3 SUMMARY
A comprehensive emissions testing program was performed on a CWS-fired
industrial boiler. The slurry fired was an Altlantic Research Corporation
formulation (ARC-Coal) containing about 70 percent beneficiated coal and
30 percent water.
TABLE 4-2. BIOASSAY RESULTS
Bioassay
Sample Amesa CHOb
XAD-2 extract: M M
<3 urn particulate ND L
(1 ym + filter)
>3 ym particulate ND L
(3 ym + 10 urn)
^Mutagenicity test
bToxicity test
M: Moderate, L: Low,
ND: Nondetectable
4-4
-------
NOX> S02, 503, CO, and TUHC emissions over the one day test period
averaged 510, 450, 2.6, 285, and 1 ppm (corrected to 3 percent 02)
respectively. The SOX (SOg and $03) emissions measured are consistent with
expectations from a source burning about 1 percent sulfur fuel. The test
site's reported fuel ultimate analysis indicated that the CWS sulfur content
was 0.61 percent (dry basis), though additional analyses presented in
Reference 3-2 suggest that is would have been about 1 percent.
NgO emissions were measured at 70 ppm (corrected to 3 percent 02). The
ratio of this level to the NOX (NO and N02) emission level was about
15 percent. Other recent tests suggest that this ratio is generally in the
20 to 25 percent range from external combustion sources.
Particulate emissions, at 4.3 g/dscm, were quite high, the direct result
of the absence of a particulate control device on the test unit for the
demonstration burn. Emitted particle size distribution was heavily weighted
to coarse particulate; over half the particulate mass had size greater than
10 pm, over 90 percent was greater than 3 urn. Combustibles losses in the
flue gas particulate were quite high; composite particulate had carbon
content of about 40 percent.
The elements aluminum, calcium, iron, magnesium, potassium, silicon,
sodium, and titanium were emitted from the boiler at the highest rates
(emissions greater than 0.1 g/s). This is, again, the result of the absence
of a particulate control device on the unit. Most of these elements were
major components of the ash fraction of the CWS fuel. Mass balance closure
within a factor of two to three existed for most of the elements determined.
Total organic emissions from the boiler were 15 to 17 mg/dscm, with
90 percent of these in the volatile C2, Cs, and 64 boiling point range.
4-5
-------
Correspondingly, flue gas levels of total semlvolatile and nonvolatile
organics were relatively low, less than 1.6 mg/dscm.
Of the semi volatile organic priority pollutants, only naphthalene was
emitted in the flue gas at detectable levels. Emissions, at less than
5 yg/dscm, were low, which is consistent with the relatively low flue gas
total organic emissions.
Of the volatile organic priority pollutants, emissions of several Cj and
G£ chlorinated aliphatic hydrocarbons, chlorobenzene, benzene, and
ethylbenzene were detected in the flue gas at levels in the 1 to 20 yg/dscm
range. The aromatic hydrocarbons (benzene and ethylbenzene) are commonly
present at these levels in combustion source flue gas. The chlorinated
compounds noted arise when chlorine-containing fuels are burned. The
chlorine content of the CMS was reported in the 0.1 percent (dry basis)
range.
Results of bioassay testing of SASS train samples showed that the
sorbent module extract was of moderate mutagenicity and toxicity. Such
positive responses for the sorbent module extract in the assays performed are
common for SASS tests of combustion sources. Both particulate size fractions
(>3 ym and <3 urn) were of nondetectable mutagenicity and low toxicity.
4-6
-------
REFERENCES FOR SECTION 4
4-1. "Threshold Limit Values for Chemical Substances and Physical Agents in
the Work Environment with Intended Changes for 1983-84," American
Conference of Governmental Industrial Hygienists, Cincinnati, Ohio,
1983.
4-2. OSHA Safety and Health Standards, 29 CFR 1910, Subpart Z.
4-3. Brusick, D. J., and R. R. Young, "IERL-RTP Procedures Manual: Level 1
Environmental Assessment, Biological Tests," EPA-600/8-81-024, NTIS PB
81-228966, October 1981.
4-7
-------
SECTION 5
TEST QUALITY ASSURANCE ACTIVITIES
Quality assurance (QA) activities implemented for this test included:
o Performing replicate standards and sample injections in the onsite
determination of GI to C$ hydrocarbons
e Performing a duplicate injections of ttte SASS sorbent module extract
for TCO analyses
5.1 Ci TO Cfi HYDROCARBON ANALYSIS PRECISION
Replicate gas chromotograph injections were perfomred for the Cj to Cg
hydrocarbon analysis. The calibration standard used was a mixture of normal
GI to Cg hydrocarbons at about 15 ppm each.
Area counts and the corresponding percent relative standard deviation of
replicate injections are summarized in Table 5-1. As noted in the table, of
19 measurements (a measurement being one boiling point range, e.g., Cj, for
one sample), 13 had precision within the project QA objective of 15 percent
(Ref. 5-1). This yields imply a percent completeness of 68 percent, which
fails the project objective of 90 percent.
Of the six measurements failing the precision goal of 15 percent, two
were for a GI measurement. These failures have no effect on project
conclusions since no GI was reported detectable in the stack gas sampled
(sample measurements were not significantly different from blank values).
5-1
-------
TABLE 5-1. AREA COUNTS AND RELATIVE STANDARD DEVIATIONS
FOR CL TO C6 ANALYSES
Relative
standard
Injection Injection Injection Injection Injection deviation
1 2 3 4 5 (%)
Calibration standards
ci
C2
CA
Cc
C6
37,696
10,250
11,741
15,356
19,637
24,715
39,376
10,600
11,982
15,354
20,154
22,598
35,199 24,262 24,923
12,602 11,251 10,927
14,730 14,232 13,713
19,045 17,735 17,228
24,736 22,270 21,973
26,915 23,932 23,733
22.3
8.1
10.1
9.4
9.3
6.6
Sample at 10:55
Cl
C2
C3
"6
22,411
5,472
2,035
982
20,250
—
2,019
924
20,009
— — — --
1,957
__ _.. — —
6.3
™ —
2.1
4.3
Sample at 14:35
Cl
C2
16,122
3,561
1,610
16,219
3,880
2,751
16,669
3,738
7,296
1.8
4.3
77.4
iconuinuea;
5-2
-------
TABLE 5-1. (continued)
Relative
standard
Injection Injection Injection Injection Injection deviation
1 2 3 4 5 (%)
Sample at 15:55
c
C2
03
C4
15,409
3,603
2,503
—
16,034
3,685
1,766
—
2.8
1.6
24.4
—
3,121
c2
c3
c4
c5
c6
Sample at 17:20
c
C2
C4
C5
8,125
773
9,171
1,445
—
7,738
1,511
3,544
—
—
8,043
941
1,463
—
—
2.6
36.0
84.4
—
—
Bomb blank
13,422 19,395 — — -- 25.7
5-3
-------
Three of the remaining four failures of the QA precision objectives were
for the 03 boiling range measurement. The final failure was for the Cg
boiling range measurement. Project conclusions were that the bulk of the
organic emissions (over 50 percent) were of volatile organics (C^ to 05
hydrocarbons) and that over half of these were of 63 boiling range
commponents. The poor precision of this measurement suggests that the actual
63 emission level may have been as much as a factor of 2 different from the
reported value. Such a difference would not alter the conclusion that most
of the organic emitted form the boiler was in the volatile boiling point
range, although conclusions regarding the distribution of emissions within
this range might change.
5.2 TOTAL CHROMOTOGRAPHABLE ORGANIC (TCO) ANALYSIS PRECISION
Replicate injections were made of the concentrated sorbent module
extract from the SASS train. The first injection yielded an analysis result
of 1.6 mg/train of TCO, while the second injection yielded 1.5 mg/train.
This corresponds to a RSD of 4.6 percent, which is within the QA objective
for this measurement of 10 percent (Ref. 5-1).
REFERENCES FOR SECTION 5
5-1. "Quality Assurance Plan for the Combustion Modification Environmental
Assessment," prepared under EPA Contract No. 68-02-3188, September 10,
1982.
5-4
-------
APPENDIX A
SAMPLING AND ANALYSIS METHODS
Emissions test equipment was provided by Acurex Corporation. Onsite
equipment included a continuous monitoring system for emissions measurements
of 02, C02, CO, NOX, and total unburned hydrocarbon (TUHC); a combined EPA
Method 5/8 train for particulate, S02, and $03 emissions; the SASS train for
particulate mass and size distribution, trace element, and semivolatile and
nonvolatile organic emissions; a YOST train for volatile organic emissions;
gas grab sampling equipment for determing Cj to Cg hydrocarbons by onsite gas
chromatography/flame ionization detector (GC/FID); and gas grab sampling
equipment for determining N20 emissions by laboratory GC/electron capture
detector (ECD). The following sections summarize the sampling and analysis
equipment and methods used in the field and laboratory.
A.I CONTINUOUS MONITORING SYSTEM
Rack-mounted monitors and recorders located in a mobile emission
laboratory were used for continuous measurement of 02, C02, NOX, CO, and
TUHC. Figure A-l illustrates the continuous flue gas extractive sampling
system and monitors arrangement. Flue gas was drawn through an in-stack
filter and a heated stainless steel probe to a gas conditioning and
refrigeration system designed to remove water. An unheated line was then
used to bring the conditioned gas to the monitors. Calibration gases were
used to monitor and correct the drift in the instruments. The calibration
A-l
-------
1. In vit_M filter
99.99^ percent
ro
2. Exhaust duct
3. 316 stainless steel probe
4. Four pass conditioner-dryer, 316 stainless steel internals
5. 3/8- inch unheated Teflon
6. Teflon-lined sample punip
7. 3/8- Inch heated teflon
B. Rotameter
9. 1/4-inch Teflon tubing
10. Calibration g*s manifold
11. Calibration gas selector waive
12. Calibration gas cylinders
13. Backpressure regulator
Duel
Figure A-l. Continuous monitoring system.
-------
gases follow the same path as the flue gas being monitored In that both are
conditioned at the stack prior to analysis. Table A-l lists the
instrumentation constituting the continuous monitoring and flue gas
extractive sampling system used in this test program.
A.2 PARTICULATE AND SULFUR OXIDE EMISSIONS
Particulate mass emissions were measured in accordance with
EPA Reference Method 5, and SOg and $03 emissions were measured in accordance
with EPA Reference Method 8. A combined Method 5/8 train employing the
Acurex High Volume Stack Sampler (HVSS), illustrated schematically in
Figure A-2, was used in this program. A glass-,!ined stainless-steel probe
was used to isokinetically extract the gas sample from the stack.
Particulate was removed by a heated 142 mm (5.6 in.) diameter glass fiber
filter. Both the filter and the sampling probes were maintained at 120"C
(250°F) as specified by Method 5.
The impinger train consisted of four glass impingers with a fritted
glass filter placed between the first and second impingers as specified by
Method 8. The first impinger contained 100 ml of 80 percent isopropanol
(20 percent water); the second and third impingers contained 100 ml of
3 percent H2®2 in water; and the fourth impinger contained 200g of silica
gel.
Solid particulate emissions were determined by gravimetric analysis of
the probe wash and the heated glass fiber filter.
S02 and S03 emissions were measured by titration of the impinger
solutions per EPA Method 8. Sulfuric acid mist and any vapor phase $03 is
trapped in the isopropanol impinger with the backup filter trapping any
carryover mist. S02 is absorbed in the ^2 impingers. After completion of
A-3
-------
TABLE A-l. CONTINUOUS MONITORING EQUIPMENT IN THE MOBILE LABORATORY
Instrument
NO
NOX
CO
TUHC
C02
02
Sample gas
conditioner
Strip chart
recorder
Principle of
operation Manufacturer
Chemi luminescence Thermo Electron
Nondispersive ANARAD
infrared (NDIR)
Flame ionization Beckman
detector
Nondispersive ANARAD
infrared (NDIR)
Fuel cell Teledyne
Refrigerant Hankinson
dryer-condenser
Dual pen Linear
analog
Instrument
model Range
10 AR 0-100 ppm
0-500 ppm
0-1,000 ppm
0-5,000 ppm
500R 0-1,000 ppm
400 0-10 ppm
0-100 ppm
0-1000 ppm
AR500 0-20 percent
0-5 percent
0-25 percent
E-4G-SS 10 scfm
400 0-10 mV
0-100 mV
0-1V
0-10V
A-4
-------
-Sample nozzle
Probe
142 mm (diameter)
F filter
Teflon
» £/
r v
\ '" i
V "S" type
pilot tube
t~ '—
— -\
1
n
r
J Filter
u
(1
11
Oven
T.C.
• |
•
—connecting
/ line
/
Proportional
temperature
controllers
Ice/water
bath ~~\^
100 ml — .
80 J I PA ^x
1
Impinger
~1
^J*
1.
1 100 ml
1 3% H202
L
Fritted
glass
filter
iP Hagnchelic
gauge
AH orifice
plate
Gas meter thermocouples
<
«
Check
valve
Impinger
hermocouple
Silica gel
desslcant
flodified
Smlth-Greenberg
Impinger
adjustment |
y~bypass valve |
Digital temperature
Indicator
Control module
Orifice fiH
Hagnehelic
Dry test meter
Vacuum line
Vacuum gauge
4—Coarse adjustment valve
Airtight vacuum pump
Figure A-2. Schematic of particulate and
(EPA Method 5 and 8).
sampling train
-------
a test, the filter was rinsed with isopropanol and the rinse solution added
to the isopropanol impinger solution. Absorbed $03 in the isopropanol and
S02 in the ^02 were determined separately by barium-thorin titration.
A.3 TRACE ELEMENT AND ORGANIC EMISSIONS
Emissions of inorganic trace elements and organic compounds were sampled
with the source assessment sampling system (SASS).. Designed for Level 1
environmental assessment (Reference A-l), the SASS collects large quantities
of gas and solid samples required for subsequent analyses of inorganic and
organic emissions as well as particle size measurement.
The SASS, illustrated in Figure A-3, is generally similar to the system
utilized for total particulate mass emission tests (HVSS) with the exception
of:
o Particulate cyclones heated in the oven with the filter to 230'C
(450°F)
o The addition of a gas cooler and organic sampling module
o The addition of necessary vacuum pumps
Schematics outlining the sampling and analytical procedures using the
SASS equipment are presented in Figures A-4 and A-5. The following
paragraphs briefly describe analytical procedures used in measuring stack
outlet trace elements and organic emissions.
Inorganic analyses of solid and liquid samples from the SASS train were
performed with spark source mass spectroscopy (SSMS) for most of the trace
elements. Atomic absorption spectrometry (AAS) was used for analyses of
volatile mercury (Hg), antimony (Sb), and arsenic (As) and for backup
analyses for those elements identified as major components by SSMS. Other
major component backup methods used were specific ion electrode for fluorine,
A-6
-------
Heated oven
T i I lor
>
Stainless
steel
sample
nozzle
Stack T.C.
1/2" Tefloi]
line
Isolation
ball valve
VI
o
Organic module
Gas temperature T.C.
1/2" Teflon line
Stack
velocity
AP magnetic lie
gauges
Stainless steel
probe assembly
Oven T.C
Sorbent cartridge
Heater controller
VTTefbnliL
m Condensate '
collector vessejl
Imp/cooler trace
element collector —-^
Coarse adjustment
Vacuum gauge
Fine adjustment
valve
Orifice All
macjnehelic
gauge
Vacuum pumps
10 ft^/mln each)
Heavy wall
vacuum line
| Control nodulV ' _^_r>rjf_s«-J^1
Impinger
T.C.
Ice bath
COO grams
sll lea gel
deslcant
.500 ml
0.2 H AgNOj
0.2 M (NH4J2 S20fl
500 ml
301
Figure A-3. SASS train schematic.
-------
SAMPLE
1flu CYCLflNE
Itr PYTt flNF _
v rvrtQwr -
PflflBP WAtU PTT — —
SORBENT CARTRIDGE —
AQUEOUS CONOENSATE
FIRST IMPINGER
SECOND AND THIRD
iMoiMftcae rnuQiuen
M
2 z
2 5 °
3" «*a S
u u 3 <
2 ? N/
» 2* s H
i- So ° "
fj S Ul Q.
J §5 s. ^
x u c c o
ui o o a M
^Si 9^ SW.IT
^f ^S.
^S^ ^^ SPLIT
^r ^^^
^•i ^X *
*
N •
s
SPLIT \
5 GRAMS
.» AQUEOUS PORTION
\^ ORGANIC EXTRACT
Z
a
h-
M
a
a M
CA a ^
j 3 «• <
5 < < S
> i CM >• -?
< o * e s s a
O t- J a. <4 Z <
• A
•. -%
•.-,.,•- •
COMBINE
^09 \^ ^
TOTALS
525
S 1
* " ••ouirad. iimala ihould 0« wt n«J« tor biolagieal analytit *t thi* point.
Thn mo t xqucad 10 aa'in*
-------
to
Figure A-5. Flue gas analysis protocol.
-------
colon" me trie for phosphorus, and either turbidimetric or x-ray fluorescence
spectrometry for sulfur.
Quantitative information on total organic emissions was obtained by gas
chromatography for total chromatographable organics (TCO) and by gravimetry
(GRAV) of particulate, sorbent module (XAD-2), and condensate trap organic
extracts. Infrared spectroscopy (IR) of extract sample GRAV residues was
used for identification or organic functional groups. Gas
chromatography/mass spectrometry (GC/MS) was used to quantitate the
semivolatile organic priority pollutant species in extract samples. This
class contains several of the polynuclear aromatic hydrocarbon (PAH)
compounds of interest from combustion sources. Figure A-6 illustrates the
organic analysis methodology followed.
Specifics of the Level 1 methodology followed (with extension) are
detailed in Ref. A-l.
A.4 Cj. TO C6 HYDROCARBON SAMPLING AND ANALYSIS
Samples of flue gas were collected for C^ to 05 hydrocarbon analysis
using a grab sampling procedure. The samples were collected using the
apparatus illustrated in Figure A-7. The equipment consisted of a heated,
0.64-cm (1/4-in.) OD pyrex-lined, stainless-steel probe fitted with a 0.7-ym
sintered stainless steel filter at the probe inlet. The outlet of the probe
was directly attached to a diaphragm vacuum pump which was in turn attached
to a 500 ml heated stainless steel sampling cylinder. The sampling cylinder
was insulated with heat tape powered by a varying voltage controller. The
heated jacket kept the sample gas above the dew point to minimize sample loss
due to water condensation.
A-10
-------
Organic Extract
or
Neat Organic Liouid
o
,, " iuu Analysis jj
Concentrate
Extract
t t .
GC/MS Analysis,
POK, and other In'rared Analysis
oroanic species
•<
t t
Repeat TCO
Gravi'metric Analysis
if necessary
Aliquot containing
15-100 mg
\
Solvent
Exchanae
i
i
Liquid
Chroma tograohic
Separation
? t t '
t f f
Seven Fractions
t
Infrared Analysis
f- t
Mass Spectra
Analysis
TCO
Gravimetric
Analysis
Figure A-6. Organic analysis methodology.
A-ll
-------
•0.7 pra sintered stainless-steel filter
1/4-ln. stainless-steel
probe
H
Teflon diaphragm pump
Pressure gauge
Inlet valve
500-cm stainless-steel
sample cylinder
Ceramic Insulation -'
and heat tape
Resistive heat tape
Outlet
valve
Thermocouple
Figure A-7, N20 sampling system.
-------
Prior to sampling, the gas cylinder was purged with stack gas for 3 min
and then sealed. The trapped flue gas was then analyzed onsite with a Varian
Model 940 gas chromatograph (GC) equipped with a flame ionization detector.
A 3.05m (10-ft) long, 0.32-cm (1/8-in.) diameter stainless-steel column
packed with Porapak R was used to separate the hydrocarbons into their
respective components (C]_ to 65). The GC was calibrated with repeated
injections of a standard gas containing Cj to 65 hydrocarbons (each having a
concentration of about 15 ppm). The chromatographie responses for the
standards and the samples were recorded on a Hewlett-Packard Model 3390A
reporting integrator.
A.5 N20 EMISSIONS
Stack gas grab samples were extracted into stainless steel cylinders,
similar to those used for C^ to Cg hydrocarbon sampling, for laboratory
analysis for NgO.
For analysis, each sample cylinder was externally heated to 120°C
(250°F), then a 1-ml sample was withdrawn with a gas-tight syringe for
injection into a gas chromatograph. The analytical equipment consisted of a
gas chromatograph equipped with a 63Ni electron capture detector and a 5.5m
(18-ft) stainless-steel column packed for 3.7m (12-ft) with Poropak R
80/100 mesh and 1.8m (6-ft) with Poropak Super Q. The injector temperature
was kept at 120*C, the detector at 350°C, and the column temperature at 39°C.
Elution time for N20 was approximately 7.5 min.
A.6 VOLATILE ORGANIC EMISSIONS
A volatile organic sampling train (VOST), shown schematically in
Figure A-8, was used to measure the low molecular weight volatile organic
compounds (boiling points _<110°C) in the flue gas according to the EPA
A-13
-------
'T' bore stopcock
Glass wool
participate
filter
Charcoal
backflush trap
Stack
(or test
system)
Thermocouple
insert port
Exhaust
Dry gas
meter
Condensate
trap impinger
Empty Silica
impinger gel
Figure A-8. Schematic of volatile organic sampling train (VOST),
A-14
-------
protocol (Ref. A-2). The train consists of two organic sorbent traps
connected in series. The first trap contained ~1.6g of the porous polymer
Tenax-GC; 35/60 mesh. The second trap contained ~1.0g each of Tenax-GC and
petroleum-based charcoal. Prior to their use in the field, each trap was
conditioned to remove organic compounds. Conditioning consisted of baking
each trap at 190*C with a N2 purge for an 8-hour period. The traps were then
desorbed at 190°C directly into a GC/FID. If a trap showed no contaminant
peaks greater than 20 ng as benzene or toluene, it was sealed at each end
with compression fittings, and considered ready for sampling.
Before the field testing, the entire system was leak-checked at -15 to
20-in. of vacuum. A leakage rate of 0.05 liter/min was considered
acceptable. Ambient air was drawn through a charcoal-filled tube to prevent
organic contamination while bringing the system back to ambient pressure.
Three pairs of sample traps, a field blank pair, and a trip blank pair
were obtained for the test program. For each sample pair, a total sample
volume of 20 liters was taken over a 40-min period (0.5 1/min). Upon
completion of the test, the sample traps were removed from the train, and
sealed. All traps were analyzed by GC/MS according to the EPA VOST protocol
{Ref. A-2). Each trap in a pair was thermally desorbed and analyzed for the
EPA Method 624 (volatile) priority pollutants. Only two pairs of sample
traps and the field blank pair were analyzed.
A-15
-------
REFERENCES FOR APPENDIX A
A-l. Lentzen, D. E., et al., "IERL-RTP Procedures Manual: Level 1
Environmental Assessment (Second Edition)," EPA-600/7-78-201,
NTIS PB293795, October 1978.
A-2. Hansen, E. M., "Protocol for the Collection and Analysis of Volatile
POHC's Using VOST," EPA-600/8-84-007, NTIS PB84-170042 March 1984.
A-16
-------
APPENDIX B
TRACE ELEMENT CONCENTRATIONS
The following tables present sample trace element analysis results and
trace element discharge stream concentrations. The tables labeled "input
data" give element analysis results (ug/g or ug/ml) for each sample analyzed.
The composition of the fuel, and all SASS train samples (10 + 3 um
particulate, filter + 1 um particulate, XAD-2 resin, first impinger, and
second and third impingers) are noted.
The tables labeled "concentration" give the calculated flue gas
concentrations (ug/dscm) of each element corresponding to each SASS train
sample, and the SASS train sum (labeled "stack gas").
The tables labeled "mass/heat input" give element flowrates in ng/0 heat
input. The tables labeled "mass flow" give corresponding flowrates in ug/s.
Element flowrates in the fuel input and each component of the flue gas SASS
train sample are noted.
The final table, labeled "boiler mass balance," summarizes the total
input and output for each element and notes the ratio of the two as a measure
of mass balance closure.
Symbols appearing in the tables include:
DSCM Dry standard cubic meter at 1 atm and 20°C
MCG Microgram
PPM Part per million by weight
B-l
-------
< Less than
> Greater than
N Element not analyzed
Trace elements having concentrations less than the detectable limit or
having a blank value greater than the sample value were given an arbitrary
concentration of zero. Values in the form A < x < B were determined by
letting elements reported as less than some concentration be represented by a
concentration of zero for the low value and the reported (less than)
concentration as the high value.
Detectability limits for the various SASS, liquid, and solid stream
samples were the following:
o 10 + 3 urn particulate -- 0.1 ug/g
« Filter + 1 um paticulate — 0.2 ug/g
« XAD-2 — 0.05 ug/g
o Impinger solutions — 0.001 ug/ml
o Fuel — 0.2 ug/g
The data inputs to the computer code for calculation of trace element
flowrates were the following:
o CMS flowrate 512.5 g/s, dry basis
9 Heating value of CMS = 34.374 MJ/kg, dry basis
» Natural gas fuel flowrate = 3.16 scm/min
o Heating value of natural gas = 36.9 MJ/scm
» Gas volume sampled by SASS = 29.245 dscm
o Calculated flue gas flowrate = 11.40 dscm/s
• SASS 10 + 3 um cyclone catch = 82.5768g
» SASS 1 um cyclone + filter catch = 7.5784g
B-2
-------
e XAD-2 weight = 130g
o SASS impinger 1 final volume = 1,635 ml
o SASS impingers 2 + 3 final volume 1,870 ml
At standard conditions (20°C (68°F) and 1 atm), one gram molecular
weight of an ideal gas occupies 24.04 liters.
B-3
-------
CWS FI.RED
INPUT DATA INDUSTRIAL BOILER
PPM
ELEMENT COAL-WATER SLURRY
ALUMINUM .700E+04
ANTIMONY .200E+01
ARSENIC .100E+01
BARIUM .230E+02
BERYLLIUM .900E+01
BISMUTH .000E+00
BORON .800E+01
BROMINE .800E+01
CADMIUM .008E+00
CALCIUM .270E+03
CERIUM .400E+01
CESIUM .000E-I-00
CHLORINE .610E+03
CHROMIUM .310E+02
COBALT .300E+01
COPPER .800E+01
DYSPROSIUM .000E+00
ERBIUM .000E+00
EUROPIUM .300E+00
FLUORINE .340E+02
GADOLINIUM .000E+00
GALLIUM .300E+01
GERMANIUM .600E+00
GOLD .000E+00
HAFNIUM .000E+00
HOLMIUM .000E+00
IODINE .5eeF+01
IRON .170E+04
LANTHANUM .600E+01
LEAD .300E+01
LITHIUM .500E+02
LUTETIUM .000E+00
MAGNESIUM .200E+03
MANGANESE .600E+01
MERCURY .200E-01
MOLYBDENUM .200E+01
NEODYMIUM .200E+01
NICKEL .300E+-01
NIOBIUM .100E+01
PHOSPHORUS .460E+03
POTASSIUM .800E+02
PRASEODYMIUM .900E+00
RUBIDIUM .200E+01
SAMARIUM .200E+01
SCANDIUM .300E+01
-------
CD
I
on
CWS FIBED
INPUT DATA INDUSTRIAL BOILER
PPM
ELEMENT COAL-WATER SLURRY
SELENIUM .800E+01
SILICON .128E+05
SILVER .000E+00
SODIUM .700E+02
STRONTIUM .170E+02
SULFUR .897E+04
TANTALUM .000E+00
TELLURIUM <.700E+00
TERBIUM .000E+00
THALLIUM .000E+00
THORIUM .400EH-01
THULIUM .000E+00
TIN .500E+00
TITANIUM .400E+03
TUNGSTEN .000E+00
URANIUM .200E+01
VANADIUM .800E+01
YTTERBIUM .000E+00
YTTRIUM .400E+01
ZINC .600E+01
ZIRCONIUM .600E+01
-------
CD
CTl
INPUT DATA
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
GERMANIUM
GOLD
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYM1UM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
CWS FIRED
INDUSTRIAL BOILER
PPM
3 MICRON + 10 MICRON FILTER + 1 MICRON
.919E405
.500E401
.140E402
.330E+03
. 870E+02
.0eeE+0e
.200E+C2
.300E+02
•C.100E+01
.410E+64
.260E+02
.200E+01
.590E+03
.180E+03
.300E+02
.840E+02
.700E+01
.300E-I-01
.100E+01
<.100E+03
.400E+01
.410E+02
.500E+01
.000E+00
.800E+00
.400E+01
.700E401
.225E405
.320E+02
.280E402
.870E402
.200E400
.250E+04
.200E+02
.800E-01
.120E+02
.120E+02
.320E+03
.180E+02
.600E+03
.900E404
.800E+01
.180E+02
.700E+01
.200E+02
.429E+05
.420E+02
.590E+02
.130E+04
.710E+03
.160E402
.890E+02
.820E+02
.300E+01
.520E+04
.120E+03
.700E+01
.400E403
.490E+03
.130E+03
.140E+03
.160E+02
.800E+01
.400E+01
.300E+03
.138E+02
.180E+03
.3B0E+02
.000E+00
.500E+0J
. 10CE-H02
.400E+01
.307E+05
.180E+03
.310E+03
.440E+02
.100E+01
.230E+04
.430E+02
.500E-01
. 120E+02
.320E+02
.770E+83
.270E+02
.680E+03
. 990E404
.250E+02
. 460E+02
. 220E+02
.820E+02
XAD
.000E+00
. 100E+00
.150E+00
.600E+00
.000E+00
.000E+00
.000E+00
.300E+00
.500E-01
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.090E+00
,0a0E-)-00
.000E+00
.000E+00
. 000EH-00
.350E+02
. 000E-f 00
.100E+00
<.500E-01
<.500E-01
.000E-f00
.000E+00
.150E+00
.000E400
.000E400
.200E+00
.000E+00
.000E+08
. 000EH-00
.000E+00
.300E-01
.160E+0I
.000E+00
.000E+00
<.500E-0)
.000E+00
.C00E+00
.000E+00
.250E400
.000E400
.000E400
FIRST IMPINGER 2ND & 3RD IMPINGERS
.240E-01
.300E-02
.200E-02
.260E-01
.000E400
.000E400
.100E-02
.250E-01
.100E-02
.320E400
<.100E-02
<.100E-02
.700E400
.290E402
.300E-01
.999E400
.000E400
.000E400
.000E400
. 186E402
.000E400
.400E-02
<.100E-02
.000E400
.000E400
<.900E-02
.900E-02
.150E403
.000E400
. 100E400
.150E-01
.000E400
.300E400
.400E400
.000E400
.000E400
<.100E-02
.993E400
.400E-02
-600E-01
. 160E400
.000E400
<.100E-02
.000E400
<.100E-02
N.000E+00
.000E400
.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.080E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
.000E400
N.000E400
N.000E400
N.060E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E+00
N.000E400
-------
INPUT DATA
ELEMENT
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
CWS FIRED
INDUSTRIAL1BOILER
PPM
3 MICRON + 16 MICRON FILTER 4 t MICRON
.800E401
.132E+06
.100E401
.880E+e4
.250E403
.640E403
.200E+01
.000E400
.900E+00
.400E400
.130E+02
.500E+00
.200E401
.540E+04
.900E+00
.700E+01
.120E403
.100E+01
.410E+02
.100E403
.450E402
.170E+82
.513E405
.400E401
.540E404
.688E+03
.300E404
.100E401
.100E+01
.400E+01
.100E+02
.910E402
.100E401
.150E402
.570E404
.900E401
.750E402
. 400E403
.110E402
.930E402
. 400E403
. 140E403
XAD
.200E400
.000E400
.000E400
.000E400
.150E400
.000E400
.000E400
.000E400
.000E400
.000E400
<.400E400
.000E400
.500E400
.100E401
.000E400
.000E400
.000E400
.000E400
.000E400
.000E400
.250E400
FIRST IMPINGER 2ND ft 3RD IMPINGERS
.550E-01
.100E401
.400E-02
.380E403
.200E-02
.470E404
<.I00E-02
<.200E-02
.000E400
.000E400
.000E400
.000E400
.000E400
<.800E-02
.400E-02
.000E400
.100E-01
.000E400
<.!00E-02
.690E400
.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
N.000E400
DO
I
-------
CONCENTRATION
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM,
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
m GADOLINIUM
i GALLIUM
0° GERMANIUM
GOLD
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEOOYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
CWS FIljtED
INDUSTRIAL BOILER
MCG/DSCM
MICRON + 10 MICRON FILTER + 1 MICRON
.259E+06
.141E+02
.395E+02
.932E+C3
.246E+03
.eeeE+ee
.565E+02
.847E+02
< .282E+01
.116E+05
.734E+02
.565E+01
.167E+84
.508E+03
.847E+02
.237E+03
.198E+02
.847E+01
.282E+01
< .282E+03
.113E+02
.116E+03
.141E+02
.000E+00
.226E+01
.113E+02
.198E+02
.635E+05
.904E+02
.791E+02
. 246E+03
.565E+00
.706E+04
.565E+02
. 226E+00
.339E+02
.339E+02
.904E+03
.508E+02
.169E+04
.254E+05
.226E+02
.508E+02
.19BE+02
.565E+02
.111E+05
.109E+02
.153E+02
.337E+C3
.184E+03
.415E+01
.231E+02
.212E+02
.777E+00
.135E+04
.311E+02
.181E+01
. 104E+03
.127E+03
.337E+02
.363E+02
.415E+01
.207E+01
.104E+01
.777E+02
.337E+01
.466E+02
.985E401
.000E+00
.130E+01
.259E+01
.104E+01
.796E+04
.466E+02
.803E+02
.114E+02
.259E+00
.596E+03
.111E+02
.130E-01
.311E+01
.829E+01
.200E+03
.700E+01
.155E+03
.257E+04
.648E+01
.119E+02
.570E+01
.212E+02
XAD
.000E+00
.445E+00
.667E+00
.267E+01
.000E+00
.000E+00
.000E+00
.133E+01
. 222E-1-00
.000E+00
.000E+00
.000E+00
.080EH-00
.000E+00
.000E+00
.000E-H00
.000E400
.060E+00
.000E+00
.156E+03
.000E+00
.445E+00
< .222E+00
< .222E+00
.000E+00
.000E+00
.667E+00
.000E+00
.000E+00
.889E+00
.000E+00
.000E+00
.000E+00
.000E+00
.133E+00
.711E+01
.000E+00
.000E+00
< .222E+00
.000E+00
.000E+00
.000E+00
.111E+01
.000E+00
.000E+00
FIRST IMPINGER 2ND ft 3RD IMPINGERS
.134E+01
.168E+00
.112E+00
.145E+01
.000E400
.000E+00
.559E-01
.140E+01
.559E-01
.179E+02
.559E-01
.559E-01
.391E+02
.162E+04
.168E+01
.559E-1-02
.000E+00
.000E+00
.000E+00
.104E404
.000E+00
. 224E+00
< .559E-01
.000E+00
.000E+00
< .503E+00
.503E4-00
.838E+04
.000E-H00
.559E+01
.839E+00
.000E+00
.168E+02
.224E+02
.000E+00
.000E+00
< .559E-01
.555E402
.224E+00
.335E+01
.895E+01
.000E400
< .559E-01
.000E+00
< .559E-01
N
N
N
N
.000E+00
.000E+00
.000E+00
.000E+00
N .000E+00
N .000E+00
N .000E400
N .000E+00
N .000E+00
N .000E+00
N .000E400
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E4-00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
.000E+00
.000E+00
.000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
.000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
-------
ro
i
10
CONCENTRATION
ELEMENT
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
CWS FIRED
INDUSTRIAL BOILER
MCG/DSCM
3 MICRON + 10 MICRON FILTER + 1 MICRON
.226E+02
.372E+06
.282E+01
.248E+05
.706E+03
.181E404
.565E+01
.000E+08
.254E+01
.113E+01
.367E+02
. H1E+01
.565E+01
.152E+05
.254E+01
. 198E+02
.339E+03
.282E+01
. 116E+03
.2B2E+03
.127E+03
.441E+01
.133E+05
. 104E+01
.140E+04
.176E+03
. 777E+03
.259E+00
.259E+00
.164E+01
.259E+01
.236E+02
.259E400
.389E+01
.148E+04
.233E+01
.194E+02
.104E+03
.2B5E+01
.241E+02
.104E+03
.363E+02
XAD FIRST IMPINGER 2ND k 3RD IMPINGERS
.889E+00 .307E+01
.000E+00 .559E+02
.000E+00 .224E+00
.000E+00 .212E+05
.667E+00 .112E+00
.000E+00 .263E+06
.000E+00 < .559E-01
.C00E+00 < .112E+00
.000E+00 .000E+00
.000E+00 .000E+00
< .178E+01 .000E+00
.000E+C0 .000E+00
.222E+01 .000E+00
.445E+01 < .447E+00
.000E+00 .224E+00
.000E+00 .000E+00
.000E+00 .559E+00
.000E+00 .000E+00
.000E+00 < .559E-01
.000E+00 .386E+02
. 111E4-01 .000E+00
N
N
N
N
N
N
N
N
N
N
N
N
N
N
. 000E+00
. 000E+00
.000E+08
. 000E+00
.000E+00
.000E+00
. 000E-I-00
. 000E+00
. 000E+00
. 000E+00
.000E+00
. 000E+00
. 000E+00
. 000E+00
N .000E+00
N .eeeE+ee
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
-------
00
CONCENTRATION
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
GERMANIUM
GOLD
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTET1UM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
CWS FIRED
INDUSTRIAL BOILER
MCG/DSCM
STACK GAS
.271E+06
.256E+02
.556E+02
.127E+04
.430E+03
.415E+01
.796E+02
.109E+03
106E+0KX<.388E+01
.129E+05
.105E+03
.752E+01
.181E+04
.226E+04
.120E+03
.329E+03
.239E+02
.105E+02
.386E+01
.127E+04
-------
CONCENTRATION INDUSTRIAL BOILER
MCG/DSCM
ELEMENT STACK GAS
SELENIUM .310E+02
SILICON .385E+06
SILVER .408E+01
SODIUM .475E+05
STRONTIUM .883E+03
SULFUR .265E+06
TANTALUM .596E+01
TELLURIUM .259E+00
-------
MASS/HEAT INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
-------
CWS FIRED
INDUSTRIAL BOILER
NG/J
ELEMENT 3 MICRON + 10 MICRON FILTER + 1 MICRON
MASS/HEAT INPUT
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
.132E-01
.217E+03
.165E-02
.145E+02
.411E+00
.105E+01
-329E-02
.000E+00
. H8E-02
.658E-03
.214E-01
.823E-03
-329E-02
.889E+01
. 148E-02
.115E-01
.198E+00
.165E-02
.675E-01
.165E+00
.741E-01
.257E-02
.775E+01
.604E-03
.B16E+00
.103E+00
.453E+00
-151E-03
.151E-03
.604E-03
.151E-02
.137E-01
.151E-03
.227E-02
.861E+00
.136E-02
. 113E-01
.604E-8t
. 166E-02
. 140E-01
.604E-01
.211E-01
XAD
.518E-03
.000E+00
.000E+00
. 000E+00
.389E-03
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
: .104E-02
.000E+00
.130E-02
.259E-02
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
. 000E+00
.648E-03
FIRST IMPINGER 2ND fc 3RD IMPINGERS
.179E-02
.326E-01
.130E-03
.124E+02
.652E-04
.153E+03
< .326E-04
< .652E-04
.000E+00
.006E+00
.000E+00
.000E+00
.000E+00
< .261E-03
.130E-03
.000E+00
.326E-03
.000E+00
< .326E-04
.225E-01
.000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+09
.000E+00
N
N
N
.000E+00
.000E+00
N .000E+00
N .000E+00
N .000E-f00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
OJ
-------
CO
I
MASS/HEAT INPUT
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
GERMANIUM
GOLD
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTET1UM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM _
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
CWS FIRED
INDUSTRIAL BOILER
NG/J
COAL-WATER SLURRY STACK GAS
.204E+03 .158E+03
.582E-01 .149E-01
.291E-01 .324E-01
.669E+00 .742E+00
.262E+00 .250E+00
.000E+00 .242E-02
.233E+00 .464E-01
.233E+00 .634E-01
.000E+00 .615E-03
-------
MASS/HEAT INPUT
ELEMENT
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
CWS FIRED
INDUSTRIAL'BOILER
NG/J
COAL-WATER SLURRY STACK GAS
.233E+00 . 180E-01
.372E+03 .225E+03
. 000E+00 . 23BE-02
.204E+01 .277E+02
.495E+00 .515E+00
-261E+03 . 155E+03
. 000E+00 . 348E-02
.204E-01 .151E-03
-------
co
MASS FLOW
ELEMENT
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
GALLIUM
GERMANIUM
GOLD
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
CWS FIRED
INDUSTRIAL BOILER
MCG/SEC
3 MICRON -I- 10 MICRON FILTER + 1 MICRON
.296E407
.161E+03
.451E+03
. 106E+05
. 280E+04
.000E+00
.644E+03
.966E+03
< .322E+02
.132E+06
.B37E+03
.644E+02
.190E+05
.579E+04
. 966E+03
.270E+04
.225E+0J
.966E+C2
.322E+02
< .322E+04
.129E+03
.132E+04
.161E+03
.000E+00
.258E+02
.129E+03
.225E+03
.724E+06
.103E+04
.901£+03
.280E+04
.644E+01
.805E+05
.644E+03
.258E+01
.386E+03
.386E+03
.103E+05
.579E+03
.193E+05
.290E+06
.258E+03
.579E+03
.225E+03
.644E+03
.127E+06
.124E+03
.174E+03
.384E-f04
.210E+04
.473E+02
.263E+03
.242E+03
.886E+01
.154E+05
.355E+03
.207E+02
.118E+04
.145E+04
.384E+03
.414E+03
.473E+02
.236E+02
.118E+02
.886E+03
.384E+02
.532E+03
.112E+03
.000E+00
.148E+02
.295E+02
.118E+02
.907E+05
.532E+03
.916E+03
.130E+03
.295E+01
.680E+04
.127E+03
.148E+00
.355E+02
.945E+02
.227E+04
.798E+02
.177E+04
.292E+05
.739E+02
.136E+03
.650E+02
.242E+03
XAD
.000E+00
.507E+01
.760E+01
.304E+02
.000E+00
.000E+00
.000E+00
.152E+02
.253E+01
.000E+00
.000E-4-00
. 000E+80
.000E+00
.000E+00
.000E+00
.000E-I-00
.000E+00
.000E+00
.000E+00
. 177E+04
.000E+00
.507E+01
< .253E+01
< .253E-f01
.000E+00
.000E+00
.760E+01
.000E+00
.000E+00
.101E+02
.000E+00
.000E+00
.000E+60
.000E+80
.152E+01
.811E+02
.000E+00
.000E+00
< .253E+01
.000E+00
.000E+00
.000E+00
.>27E+02
.000E+00
.000E+00
FIRST IMPINGER 2ND k 3RD IMPINGERS
.153E+02
.191E+01
.127E+01
.166E+02
.000E+00
.000E+00
.637E+00
.159E+02
.637E+00
.204E+03
< .637E+00
< .637E+00
.446E+03
.185E+05
.191E+02
.637E+03
.000E+00
.000E+00
.000E+00
.118E+05
.000E+00
.255E+01
< .637E+00
.000E+00
.000E+00
< .574E+01
.574E+01
.956E+05
.000E+00
.637E+02
.956E+C1
.000E+00
. 191E+03
.255E+03
.000E+00
.000E+00
( .637E+00
.633E+03
.255E+01
.382E+02
.102E+03
.009E+00
< .637E+00
.000E+00
< .637E+00
N
N
N
N
.000E+00
.000E+00
.000E+00
.008E+00
.000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+60
N .000E+00
N . 000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
.000E+00
.000E+00
N .000E+00
N .000E+00
N .000E+60
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
.000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N . 000E-t-00
N .000E+80
N .000E+00
N .000E+e0
N .000E+00
-------
CO
I
MASS FLOW
ELEMENT
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
ZINC
ZIRCONIUM
CWS FIRED
INDUSTRIAL BOILER
MCG/SEC
3 MICRON + 10 MICRON FILTER t 1 MICRON
.258E+03
.424E+07
.322E+02
.283E+06
.805E+04
.206E+05
.644E+02
.000E+00
.290E+02
.129E+02
.419E+03
.161E+02
.644E+02
.174E+06
-290E+02
.225E+03
.386E+04
-322E+02
.132E+04
.322E+04
. 145E+04
.502E+02
.152E+06
.118E+02
.160E+05
.201E+04
.886E+04
.295E+01
.295E+01
.118E+02
.295E+02
.269E+03
.29SE+01
.443E+02
.168E+05
. 266E+02
.222E+03
. 118E+04
.325E+02
. 275E+03
.I18E+04
.414E+03
XAD
. 101E+02
.000E+00
.000E+00
. 000E+00
.760E+01
.000E+00
.000E+00
.000E+00
. 000E+00
.000E+00
< .203E+02
.000E+00
. 253E-I-02
.507E+02
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
.127E+C2
FIRST IMPINGER 2ND tc. 3RD IMPINGERS
.351E+02
.637E+03
.255E+01
.242E+06
.127E+01
.300E+07
< .637E+00
< .127E+01
.000E+00
.000E+00
.000E+00
.000E+00
.000E+00
< .510E+01
.255E+01
.000E+80
.637E+01
.000E+00
< .637E+00
.440E+03
.000E+09
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N .000E+00
N
N
N
N
N
.060E+00
.000E400
.080E+00
.000E-f00
.000E+00
N .000E+00
N .000E400
N .000E+00
N .000E+00
N .000E+00
N .000E+00
-------
CWS FIRED
MASS FLOW INDUSTRIAL BOILER
MCG/SEC
ELEMENT COAL-WATER SLURRY STACK GAS
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
CD GADOLINIUM
,L GALLIUM
CO GERMANIUM
GOLD
HAFNIUM
HOLM1UM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS ~
POTASSIUM —-
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
.359E407 .309E407
.102E+04 .292E403
.512E+03 .634E403
.118E+05 .145E405
.461E404 .490E+04
.000E400 .473E402
.410E+04 .907E403
.410E404 .124E404
.000E400 .120E+02
-------
CWS FIflED
MASS FLOW INDUSTRIAL BOILER
MCG/SEC
ELEMENT COAL-WATER SLURRY STACK GAS
SELENIUM .410E+04 .353E+03
SILICON .656E+07 .439E+07
S I LVER . 000E+00 . 466E+02
SODIUM .359E+05 .541E+06
STRONTIUM .871E+04 .101 £+05
SULFUR .460E+07 .303E+07
TANTALUM .000E+00 .680E+02
TELLURIUM < .359E+03 .295E+0KX<.423E+01
TERBIUM .000E+00 408E+02
THALLIUM .600E+0e .424E+02
THORIUM .205E-f04 .687E+03
-------
ELEMENT
CWS FIRED
INDUSTRIAL BOILER
BOILER MASS BALANCE
INPUT » FUEL(CWS + NATURAL GAS)
TOTAL IN
ALUMINUM
ANTIMONY
ARSENIC
BARIUM
BERYLLIUM
BISMUTH
BORON
BROMINE
CADMIUM
CALCIUM
CERIUM
CESIUM
CHLORINE
CHROMIUM
COBALT
COPPER
DYSPROSIUM
ERBIUM
EUROPIUM
FLUORINE
GADOLINIUM
133 GALLIUM
txj GERMANIUM
o GOLD
HAFNIUM
HOLMIUM
IODINE
IRON
LANTHANUM
LEAD
LITHIUM
LUTETIUM
MAGNESIUM
MANGANESE
MERCURY
MOLYBDENUM
NEODYMIUM
NICKEL
NIOBIUM
PHOSPHORUS
POTASSIUM
PRASEODYMIUM
RUBIDIUM
SAMARIUM
SCANDIUM
.359E+07
. 102E+04
.512E+03
. 118E+05
.461E+04
.410E+04
.410E+04
. 138E+06
.205E+04
.313E+06
.159E+05
. 1 54E+04
.410E+04
.154E+03
.174E+05
. 154E+04
. 307E+03
. 256E+04
.871E+06
. 307E+04
. 1 54E+04
. 256E+05
. 102E+06
.307E+04
.102E+02
. 102E+04
. 102E+04
. 154E+04
.512E+e3
.236E+06
.410E+05
.461E+03
. 102E+04
. 102E+04
. 154E+04
TOTAL OUT
.309E+07
.292E+03
.634E+03
.145E+05
.490E+04
.473E+02
. 907E+03
.124E+04
.120E+02
-------
ELEMENT
SELENIUM
SILICON
SILVER
SODIUM
STRONTIUM
SULFUR
TANTALUM
TELLURIUM
TERBIUM
THALLIUM
THORIUM
THULIUM
TIN
TITANIUM
TUNGSTEN
URANIUM
VANADIUM
YTTERBIUM
YTTRIUM
CO ZINC
i
£ ZIRCONIUM
CWS FIRED
INDUSTRIAL BOILER
BOILER MASS BALANCE
INPUT = FUEL(CWS + NATURAL GAS)
TOTAL IN
410E+04
.656E+07
.359E+05
.871E+04
.460E+07
X<.359E+03
.205E+04
.256E+03
.205E+06
. 102E+04
.410E+04
.205E+04
. 307E+04
.387E+04
TOTAL OUT
.353E+03
.439E+07
.466E+02
.541E+06
.101E+05
.303E+07
.680E+02
.295E+0KX<.423E+01
.408E+02
.424E+02
.687E+03
-------
TECHNICAL REPORT DATA
(Please read luuructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-86-012a
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Environmental Assessment of a Coal/Water Slurry
Fired Industrial Boiler; Volume I. Technical Results
5. REPORT DATE
April 1986
6. PERFORMING ORGANIZATION COOE
7. AUTHOR(S)
D. Van Buren and L. R. Waterland
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
A cur ex Corporation
Energy and Environmental Division
P.O. Box 7555
Mountain View. California 94039
1O. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-3188
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air and Energy Engineering Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 7/83 - 4/85
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES AEERL project officer is Joseph A. McSorley, Mail Drop 65,
919/541-2920. Volume II is a data supplement.
is. ABSTRACT
repOrt gives results of comprehensive emission measurements and
analyses for a 7.6 kg/s (60,000 Ib/hr) watertube industrial boiler firing a coal/water
slurry. Measurements included continuous monitoring of flue gas; quantitation of
semivolatile organics and 73 trace elements; volatile organic sampling train (VOST)
quantitation of volatile organic priority pollutants; EPA Method 5/8 for particulate
and SOx; controlled condensation for SOx; Andersen impactors for particle size dis-
tribution; and grab samples for N2O. Emissions of NOx, SO2, CO, and hydrocarbons
averaged 510, 450, 285, and 1 ppm, corrected to 3% oxygen. Particulate emissions
were 4.3 g/dscm, and particle size was biased to larger size fractions with over
half of particulate mass at 10 micrometers or greater. Over 90% were 3 micro-
meters or greater. Combustible losses were high with over 40% carbon content in
particulate. Total organic emissions were 15 to 17 mg/dscm with half in the Cl to
C6 range. Naphthalene was the only semivolatile detected.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Assessments
Slurries
Coal
Water
Combustion
Water Tube Boilers
Polluation Control
Stationary Sources
Environmental Assess-
ment
13B
14B
11G
21D
07B
21B
13 A
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
85
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
B-22
------- |