Analysis of Residential Coal
Stove Emissions
Battelle Columbus Div., OH
Prepared for
Industrial Environmental Research Lab,
Research Triangle Park, NC
Dec 83
PB84-130442
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PDo^i- 1301*4^
EPA-600/7-83-060
December 1983
ANALYSIS OF RESIDENTIAL COAL STOVE EMISSIONS
by
Marcus Cooke, Warren E. Bresler, Robert B. Iden,
Timothy L. Hayes, and Sharron E. Rogers
BATTELLE
Columbus Laboratories
SOS King Avenue
Columbus, Ohio 43201
Contract Number 68-02-3169
Work Assignment 29.0
EPA Project Officer:
Michael C. Osborne
Combustion Research Branch
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
Prepared for:
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
Washington. DC 20460
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TECHNICAL REPORT D*TA
fHraic trail lauruetium on Ihr tci crsc before complelintl
REPORT NO
EPA-600/7-83-060
3 RECIPIENT'S ACCESSION NO
13QA42
* TITLE AND SUBTITLE
Analysis of Residential Coal Stove Emissions
5 REPORT DATE
December 1983
6. PERFORMING ORGANIZATION CODE
7 AUTHORISI Marcus Cooke, W. E. Bresler. R.B. Iden.
T. L. Hayes, and S. E. Rogers
8 PERFORMING ORGANIZATION REPORT NO
» PERFORMING ORGANIZATION NAME AND ADDRESS
BatteUe-Columbus Laboratories
505 King Avenue
Columbus. Ohio 43201
1O PROGRAM ELEMENT NO
II CONTRACT/GRANT NO
68-02-3169. Task 29
12 SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 6/82 - 7/83
14. SPONSORING AGENCV CODE
EPA/600/13
is. SUPPLEMENTARY NOTES IERL-RTP project officer is Michael C. Osborne. Mail Drop 65.
919/541-4113.
16 ABSTRACT,Tne report gives results of an evaluation, in cooperation with the State of
Vermont's Agency of Environmental Conservation, of emissions generated by anthra-
cite and bituminous coal used for residential heating. A residential coal stove was
operated with both coals, while comparing high and low burn rate operations. A
second stove, a commercial stove designed for wood burning but modified by the
manufacturer for coal, was also tested with both coals. Combustion gases were col-
lected by two techniques: evacuated glass bulbs and a Modified Method 5 sampling
train. Volatile species were analyzed by direct gas mass spectrometry and by gas
chromatography using selective detectors. Polynuclear aromatic hydrocarbons
(PAHs) were analyzed by high resolution gas chromatography/mass spectrometry.
High levels of participates, total organics. and sulfur dioxide were found in the
emissions from bituminous coal combustion in a residential coal stove. High PAH
emissions were found with both bituminous and anthracite combustion. The stove
converted from wood to coal burning proved to be highly polluting, especially when
used with bituminous coal.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS
Pollution
Coal
Combustion
Stoves
Space Heaters
Analyzing
Pollution Control
Stationary Sources
Wood Stoves
COSATI I if Id'Croup
13B
21D
2 IB
13A
14B
8 DISTRIBUTION STATEMENT
Release to Public
19 SECURITY CLASS ITha RtfOttl
Unclassified
21 NO OF PAGES
35
20 SECURITY CLASS tThilpafrl
Unclassified
EPA Form tttO-l (1-7J)
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
ii
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ABSTRACT
This study was performed in cooperation with the State of Vermont, Agency
of Environmental Conservation. The goal of the program was to evaluate
emissions generated by anthracite and bituminous coal used for residential
heating. A residential coal stove was operated with both coal fuels while
comparing a high burn rate condition, with low burn rate operation. A second
etove, a commercial stove designed for wood burning and modified by the manu-
facturer for coal, was aleo tested with both coal types. Combustion gases
were collected by two techniques: evacuated glass bulbs, and a Modified
Method S sampling train. Volatile species were analyzed by direct gas mass
spectrometry and by gas chromatography using selective detectors. Polynuclear
aromatic hydrocarbons were analyzed by high resolution gas chromatography/mass
spectrometry.
ill
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CONTENTS
Page
ABSTRACT ill
ACKNOWLEDGEMENTS vi
•1.0 INTRODUCTION 1
2.0 RECOMMENDATIONS 3
3.0 EXPERIMENTAL PROCEDURES 4
SAMPLING PROCEDURES 4
ANALYTICAL PROCEDURES 5
QUALITY ASSURANCE 8
4.0 RESULTS 12
REFERENCES 25
Iv
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LIST OF FIGURES
Number Page
1 Particulate and PAH Sampling System 6
2 Gas Chromatogram of PAH Standard Mixture 9
3 Range of Benzo(a)pyrene Emissions from Coal, Oil,
and Natural Gas Heat-Generation Processes 19
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LIST OF TABLES
Page
1
Estimated Repeatability and Reproducibility for
ASTM Ultimate and Proximate Fuel Tests 10
3 Stove and Sampling Parameters 13
4 Fuel Parameters 14
5 Particulate and Condensible Organic Emissions. ...... IS
6 Principal Volatile Emissions—Anthracite Tests 16
7 Principal Volatile Emissions—Bituminous Tests 17
8 Benzo(a)pyrene Concentrations in Vermont Coal Stove
Study 20
9 Polynuclear Aromatic Hydrocarbon Emissions—Anthracite
Tests 21
10 Polynuclear Aromatic Hydrocarbon Emissions—Bituminous
Tests 22
11 Ben*o(a)pyrene Emission from Several Sources in
Standard Units Recommended in Reference 7 23
vi
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ACKNOWLEDGMENTS
The authors would like to express their appreciation for the assistance
and technical help of Cedric R. Sanborn, Air Pollution Control Engineer,
State of Vermont, Agency of Environmental Conservation (Montpelier, Vermont).
In addition to participating in program planning, Sanborn erected the
stoves and operated the residential test appliances throughout the test.
Without his willing and competent contribution, this coal stove study would
not have been possible.
In addition thanks are given to the EFA Task Officer, Michael C.
Osborne, whose technical guidance and supervision of the field sampling
experiments were instrumental in the successful completion of the program.
The participation of several Battelle staff members is gratefully ack-
nowledged; Cheng Chen Chuang for GC/MS data computation, Robert L. Livingston
for gas mass spectral analyses, and Maria B. Dean for secretarial assistance.
Vit
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SECTION 1
INTRODUCTION
This study was a cooperative program with the Vermont Agency of Envi-
ronmental Conservation. Some interest has been shown in the Northeastern
United States about the effects of coal combustion in residential appliances,
especially stoves designed to use wood then retrofitted for coal. These
stoves may not contain the proper engineering criteria for clean operation
when burning coal fuel especially Eastern bituminous coal. The State of
Vermont has instituted a detailed residential research program under the
direction of Cedric R. Sanborn, Air Pollution Control Engineer, to evaluate
impacts of coal combustion in the home. Mr. Sanborn enlisted the partici-
pation of EPA to measure pollutant discharge levels during a series of stove
tests scheduled for the Fall of 1982. The following table gives a summary of
the tests conducted.
TABLE 1. STOVE TESTS
Unit
Converted Coal/Wood Stove
(low burn rate)
Residential Coal Stove
(high burn rate)
Residential Coal Stove
(low burn rate)
Fuel
Bituminous Anthracite
Bituminous Anthracite
Bituminous Anthracite
Residential coal-fired, stoker-fed furnaces were tested in an earlier EPA
program in which Western bituminous and subbituminous coals were used in two
-------
200,000 Btu/hr residential furnaces (1). This study concluded that parti-
culate discharges are a function of organic content (not inorganic ash) in
residential coal combustion. The authors cited the low efficiencies of small
residential combustion systems to explain this effect. Sulfur oxide concen-
trations followed fuel sulfur levels in that study and carbon monoxide levels
were highly variable (0.04 Kg/ton to 12 Kg/ton fuel). Several polynuclear
aromatic hydrocarbons were identified, generally at very high discharge con-
centrations, e.g., fluoranthene at 22 ppm (W/W fuel basis). In an EPA study,
to measure emissions from large commercial coal-fired stoker boilers, much
lower PAH emission levels were observed (2,3). The average fluoranthene
concentration, including methylpyrene isomers, was 1.5 ppb (W/W fuel basis).
Thus, in the Vermont study it was of interest to investigate emissions of
small residential stoves and compare these emissions with those of the larger
systems previously tested.
A primary goal of this study was to investigate the levels of criteria
air pollutants and hazardous organic constituents found in small residential
coal-fired stoves when operated in a manner characteristic of home heating.
The stoves investigated in this program operated from 22,000-57,000 Btu/hr
compared to an average of 200,000 i>tu/hr for the earlier mentioned EPA resi-
dential coal furnace study (4). The stoves tested in the Vermont study are
characteristic of small hand-stoked stoves used in the United States for
residential space heating.
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SECTION 2
RECOMMENDATIONS
High Levels of particular.es, total organics, end sulfur dioxide (502)
were found in the emissions from bituminous coal combustion in a residential
coal stove. The high levels of SOj foond with anthracite combustion nay
indicate that treated fuel such as cleaned coal or coal pelletized with a
sulfur slagging agent such as limestone nay be of interest to reduce SOj
emissions.
High PAH emissions vere found with both bituminous and anthracite com-
bustion. The elevated levels found when, burning bituminous fuel are espe-
cially significant since benzo(e)pyxene, a known mammalian carcinogen, is one
of the PAH compounds that is shown to be emitted.
The stove converted from woodburning to coal use was proved to be highly
polluting especially when used with Bituminous coal. Additional research is
necessary to determine if the constrained air situation and fireboj Jesign of
this stove can be made "clean burning".
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SECTION 3
EXPERIMENTAL PROCEDURES
Emissions samples were collected during combustion tests conducted in
October, 1982, at the residence of Cedric Sanborn in Barre, Vermont. Two
stoves were used in the tests. One of the stoves was designed by the manu-
facturer for coal combustion. This stove was operated in a high burn rate
mode and an air-starved mode which generated a low burn rate. The second
stove was primarily designed for wood combustion but had been modified by the
manufacturer to accommodate coal. The narrow damper on this modified wood
stove constricted combustion air and consequently this stove could only be
tested at low burn rates. Each stove was tested with anthracite and bitu-
minous coal to evaluate the effect of the two fuels on emissions.
Analyses included fixed combustion gases, condensible organics, Method 5
particulates, principal volatile compound screening by gas mass spectrometry
(CMS), and polynuclear aromatic hydrocarbon (PAH) analysis by high resolution
gas chromatography/mass spectrometry (GC/MS).
SAMPLING PROCEDURES
Samples were collected for fixed gas and volatile organics analysis using
evacuated glass bulbs. Three liter glass sampling bulbs were prepared at
Battelle by evacuating to approximately 10~6 torr pressure and heating to
drive off residual moisture. After preparation, the sample bulbs were wrapped
with foam insulation and shipped to the experimental site in Vermont. The gas
samples were taken by inserting a stainless steel probe through a sample port
located approximately 1 foot up the vertical section of the stove exhaust
stack. A sample was collected by opening the stopcock on the evacuated sample
bulb during steady state combustion.
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PAH and particulate sampling was conducted with an EPA Modified Method 5
sampling train. This system, shown in Figure 1, has been used by Battelle on
a wide variety of programs including industrial and residential coal combus-
tion systems.
The Method 5 sampling train separates the sample into a particulate
fraction in the heated probe and filter section, and a senivolatile organics
fraction which collects on the resin. The XAD-2 resin material was extracted
along with the particulate-laden filter in a Soxhlet extractor using methylene
chloride. The filter was re-extracted separately with benzene to remove PAH
compounds not extracted by ^ethylene chloride. The resin-filter extracts were
combined with the extracted aqueous impinger samples to produce a combined
organics sample. The combined extract was analysed by gas chromatography and
gravimetry to determine condensible organics. This extract was also used for
PAH analyses.
ANALYTICAL PROCEDURES
Fuel and Gas Analyses
Fuel analyses were provided by the Vermont Agency of Environmental Con-
servation. Standard ASTM procedures were used to generate elemental analyses
(C-H-N-0-S), ash, volatiles, fixed carbon, moisture and heating value (dry
basis).
Fixed gas analyses were performed on the glass bulb samples. Samples
were analyzed using a combination of mass spectrometry and three gas chromato-
graphic techniques. A Consolidated Electrodynamics Corporation, Model 21-620,
mass spectrometer was used for a general analysis from mass 2 to 100. Since
the mass spectrometer does not separate carbon monoxide and nitrogen, the
carbon monoxide was determined using an Aerograph, Model 202, gas chromato-
graph with a molecular sieve column and a thermal conductivity detector.
Low molecular weight hydrocarbons and sulfur gases were determined using
a Varian, Model 3700, gas chromatograph. A Poropak Q column with a flame
ionization detector was used in the hydrocarbon analyses and a Supelco S
column with a flame photometric detector was used for the sulfur gases.
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TtMrmoctttkaltv
ControlM
Own
InxpioQW Trim
OrBacfcjMlf_ Owck V«hf«
n
."•?•*.. -J
Vacuum UM
FIGURE 1. PARTICULATE AND PAH SAMPLING SYSTEM.
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Condensible Organics Analyaea
Condensible organics were measured by extracting the Method 5 particu-
lates and the XAD-2 resin bed with methylene chloride and performing a gravi-
metric analysis (GRAY) on the extracts. This procedure is described in EPA's
Level 1 manual for characterization of source discharges (5). The gravimetric
analysis measures the mass of extracted material. This analysis does not
measure volatile species, in fact most volatiles are lost by the Method 5
sampling train. The evacuated gas bulbs are useful in estimating principal
volatile organics.
PAH Analyses
The filter/resin extraction yielded two extracts: a methylene chloride
extract which contained most of the organic burden, and a benzene extract
which contained much of the PAH. The combined extracts were reduced to a
convenient volume by a Kuderna-Danish concentrator. The PAH compounds were
then isolated by liquid chromatography using silica gel to remove interfering
species. The column was packed (methylene chloride slurry) with 10 g of 100-
200 mesh silica gel and washed with 40 ml of petroleum ether. A 25 ml frac-
tion of petroleum ether and a 20 ml fraction of 20 percent methylene chloride
in petroleum ether were collected and discarded. The PAH were eluted with
75 ml of 20 percent methylene chloride in petroleum ether, followed by 30 ml
•of 50 percent methylene chloride in petroleum ether. The volume of the PAH
fraction was reduced to about 1 ml by use of a Kuderna-Danish concentrator and
to a final 0.5 ml by directing a gentle stream of nitrogen across the top of
the sample. An internal standard (9-phenylanthracene) was spiked into the
reduced sample.
The analytical scheme involved a glass capillary GC/MS procedure which
separates many PAH isomers (including benro(a)pyrenc and benzo(e)pyrenc) with
only one chromatographic run. A 30 m SE-52 capillary column was directly
coupled to the mass spectrometer via a glass capillary transfer line. The gas
chromatograph was equipped with a Grob-type injector enabling splitless
injection*]. The column was temperature programmed from 160-320°C at 4°C/min.
Injector temperature was 300°C while the transfer line was held at 315°C.
-------
The separation efficiency and high temperature stability of high reso-
lution capillary GC is shown in Figure 2 for a standard mixture of PAH com-
pounds. Compounds such as coronene and dibenzopyrenes with boiling points
above 520°C are eluted as sharp peaks. Close to baseline separation is
achieved for isomeric compounds such as phenanthrene/anthracene, benzo(a)anth-
racene/chrysene and benzo(a)pyrene/benzo(e)pyrene.
Since the coal extracts were heavily loaded with organics, single ion
monitoring was used in the GC/HS analysis to improve sensitivity. The mole-
cular ions of up to three compounds of interest were simultaneously monitored.
Quantification was achieved by ratioing the ion current of the molecular ion
of interest to that of the differences in ionization efficiencies of the
compound and the internal standard. The use of single ion monitoring mini-
mized interferences from fragmentation of extraneous compounds which may not
have been removed during the liquid chromatographic cleanup.
The GC/MS system used for the PAH analyses consisted of a Finnigan Model
9500 biomedical type gas chromatograph coupled with a Finnigan Model 3200 mass
spectrometer. Data collection and processing was handled by a Finnigan Incos
Data System which utilized a Data General Nova 3 computer with 32K of memory.
QUALITY ASSURANCE
Before the sampling and analysis procedures were initiated a quality
assurance plan was submitted to the EPA project officer. This plan addressed
specific elements of quality control applied to this study in addition to
general quality assurance measures that are routinely performed at Battelle to
ensure defensibility of analytical results, e.g., periodic instrument audits,
defined calibration procedures, and unannounced audits by one of Battelle1s QA
officers.
Fuel tests were ASTM procedures. Confidence limits measured for dupli-
cate analyses and single determinations in separate laboratories are provided
in the ASTM methods. Estimates of repeatability and reproducibility for fuel
data supplied by the Vermont Agency of Environmental Conservation are given in
Table 2.
Quality control procedures for the gas bulb analyses involved careful
daily calibration checks using reference gas mixtures. Quality control and
8
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FIGURE 2. GAS CRROMATOGRAN OF PAH STANDARD MIXTURE.
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TABLE 2. ESTIMATED REPEATABILITY AND REPRODUCIBILITY
FOR ASTM ULTIMATE AND PROXIMATE FUEL TEPTS
Test
Btu gross
Btu net
Moisture (Z)
Ash (Z)
Caibon (Z)
Hydrogen (Z)
Nitrogen (Z)
Sulfur (Z)
Method
D240 (ASTM)
D240 (ASTM)
D174A (ASTM)
D482 (ASTM)
Combustion TCD
Combustion TCD
Chemiluminescence in toluene
D129/2622 (ASTM)
Repeatability(a)
+55 Btu/lb
+55 Btu/lb
+11 ppm
+(0.007-0.003)
+"2Z
+2Z
~
0.016 x + 0.006/0.05
times Z S
Reproducibility(b)
+175 Btu/lb
±175 Btu/lb
Not determined
+(0.024-0.005)
+"2Z
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quality assurance procedures are documented in the Battelle Chemistry Depart-
ment's Quality Assurance Plan and daily records were maintained during the
study. These records are kept in bound laboratory record books which are
microfiched at the end of the study and duplicate copies are stored in fire-
proof safes in different locations to prevent accidental loss.
Instruments used in gas bulb analyses were checked daily for response
performance and calibrated before analyses of samples. Argon was analyzed
daily to check the performance of the mass spectrometer, and several standard
gases were run to verify sensitivity and fragmentation patterns.
Performance checks and calibration of gas chromatographs were done using
standard mixtures of appropriate compounds. The Aerograph, Model 202, gas
chromatograph was calibrated with a standard mixture of oxygen, nitrogen,
methane, and carbon monoxide, and recorded in the laboratory record book. The
Varian, Model 3700, gas chromatograph with flame photometric detector, was
standardized with a mixture of hydrogen sulfide, carbonyl sulfide, and carbon
disulfide. A separate standard was used for sulfur dioxide. Calibration of
the flame ionization detector was conducted with a standard mixture of satu-
rated straight chain hydrocarbons (Cj through C^), and a mixture of
unsaturated straight chain hydrocarbons (Cj through €4). All standard checks
were recorded in a laboratory record book.
Quality assurance of GC/MS data included daily tuning and analysis of a
standard mixture of PAH. The reference standard was made fresh in distilled-
in-glass (DIG) benzene using synthetic standards that had been previously
analyzed to establish chemical purity. A recovery standard of dj2-benzo(a)-
pyrene (BaP) was used to estimate method losses. The d^-BaP was administered
to each Soxhlet extractor by. liquid injection of 200 yl of a 200 ug/ml solu-
tion of the standard in DIG benzene. The amount of this 40 ug spike recovered
by quantitative analysis using the 9-phenylanthracene internal standard method
was used to estimate losses in analytical preparation. The reported PAH data
are corrected for BaP and the other PAH are reported as determined without
correction.
11
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SECTION 4
RESULTS
As shown in Che stove operation data provided in Table 3, the burn rates
during the combustion tests varied between 0.6-1.6 kg/hr and typical gas dis-
charge volumes varied between 44-80 m3. The relationship between flue gas per
unit weight of fuel was computed from the following relationship assuming no
residual ash carbon in residue.
Dry Gas (kg)/Fuel(kg) - 11CO? * 80? * 7
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TABLE 3. STOVE AND SAMPLING PARAMETERS
Stove Paraaetera
Fuel per Teat, kg (Ib)
Burn Rate, kg/hr (lb/hr)<*>
Mein Stack Temperature, C(F)
Sampling Tloe, oln
Stack Water, percent
Stack Oxygen, percent^*)
Stack Carbon Dioxide, percent^)
Stack Carbon Monoxide, percent(e)
Method 5 Volume (dry), SCM (SCP)
Total Stack Discharge, q, SCM
(SCF)
Bituminous
Coal Stove
High Burn Rate
2.5 (5.6)
1.3 (2.6)
270 (520)
120
1.8
13
6
0.6
1.8 (64)
64 (2,300)
Anthracite
Coal Stove
High Burn Rate
2.B (6.2)
1.6 (3.1)
250 (480)
120
3.5
10
10
0.6
1.9 (68)
SB (2,050)
Bitbjinoua
Coal Stove
Low Burn Rate
1.7 (3.8)
0.7 (1.7)
220 (420)
150
1.8
17
4
0.2
2.0 (70)
72 (2,500)
Anthracite
Coal Stove
Lew Burn Rate
1.3 (2.9)
0.6 (1.5)
140 (278)
155
1.6
17
3
0.0
2.4 (85)
80 (2,800)
Bituoinoui
Modified
Hood Stove
Low Burn Rate
2.4 (5.4)
1.0 (2.6)
160 (315)
155
1.9
14
6
0.4
2.3 (81)
67 (2,400)
Anthracite
Modified
Wood Stove
Low Burn Rate
1.7 (3.7)
0.7 (1.8)
140 (280)
155
2.3
13
7
0.4
2.5 (87)
44 (1,600)
(a) Averaged over toul teat.
(b) At Method 5 probe.
(c) Approxinate, valuea determined by ORSAT technique.
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TABLE 4. FUEL PARAMETERS
Oltima-e Analyaea
Carbon, percent (W/W dry)
Hydrogen, percent (W/W dry)
Nitrogen, percent (W/H dry)
Oxygen, percent (W/W dry)
Sulfur, percent (W/W dry)
Aah, percent (W/W dry)
Proximate Analyse*
Fixed Carbon, percent (W/W dry)
Volitiles, percent (W/W dry)
Noi*ture, percent (W/W dry)
Beeting, value, dry baaii, ash
free, J/kg (Btu/lb)
Anthracite
(Pea)<*>
85.8
1.9
0.7
0.1
0.4
8.9
as. 6
3.3
2.2
S.SxlO7 (14,900)
Bituainoua
(Rut)<<>
79.1
3.2
1.5
6.9
0.8
3.2
56.5
37.0
3.3
3.5xl07 (15,100)
Bitiminoui
(Stoker)<«>
80.6
5.3
1.6
4.9
0.8
5.5
56.2
37.0
1.3
3.4xl07 (14,400)
(a) Fuels are graded by diameter range to pass a circular me»h aievei Pea Grade •
1.4 en - 2.1 ca; Hut Grade • 3.2 cm - 5.1 en; Stoker Grade • 1.9 cf - 3.2 cm.
14
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TABLE 5. PARTICULATE AND CONDENSIBLE ORGANIC EMISSIONS
Stove
Coal
Coil
Coal
Coal
Wood
Wood
Coal
Bituainaua
Anthracite
Bltiminout
Anthracite
Bituainou*
Anthracite
Burn Rate
(kg/hr)<«>
High (1.3)
High (1.6)
Low (0.7)
Low (0.6)
Moderate (1.0)
Low (0.7)
Pirticulatea-Method 5
(mg/SCN) (ng/J)
458
8
176
6
197
8
1.8>10-1
2.4x10-3
1.1x10-1
4.2x10-3
7.1x10-2
2.5x10-3
Condeniible Organice^)
(g/kg)
6.2
0.08
3.8
0.13
2.2
0.08
(mg/SCM)
98
3
128
2
66
8
(ng/J>
3.9x10-2
9.2x10"*
7.8x10-2
1.4x10-3
2.4x10-2
2.}xlO-3
(g/kg)
1.3
0.03
2.7
0.04
0.7J
0.08
(a) Corrected for aah.
(b) Gravimetric determination of TAD-2 collected organic*.
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TABLE 6. PRINCIPAL VOLATILE EMISSIONS—ANTHRACITE TESTS
(ppm, V/V)
Methane
Ethene
Tthane
Propene
Propane
1-Butene
S02
COS
CS2
H2S
NOX
Coal Stove
High Low
Burn Burn
100 100
1 0.2
1 —
— —
— —
— —
350 290
— —
— 0.2
— —
—
Modified
Wood Stove
630
0.8
2
—
2
—
25
23
—
6
100
— - Not detected.
In tests with bituminous fuel, the coal stove had much higher levels of
methane and ethene than the modified multifuel stove designed primarily for
wood burning. Comparing the sulfur oxide data from this study with results of
earlier EPA coal stove tests is very interesting. The industrial coal stoker
boiler study firing bituminous coal (2) reported SOX levels of 90-490 g/kg
fuel-dry basis (180-970 Ib/ton) with a mean of 227 g/kg (450 Ib/ton) for 21
stokers tested. The stoker fed residential units cited earlier (1) found SOX
levels of 3-15 g/kg (6-30 Ib/ton) for ten tests with a mean of 9.5 g/kg (19
Ib/ton). Bituminous coal was used in both studies and each study showed a
linear relationship between available fuel sulfur and SOX emissions. In this
16
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TABLE 7. PRINCIPAL VOLATILE EMISSIONS—BITUMINOUS TESTS
(ppm, V/V)
Bituminous
Methane
Ethene
Ethane
Propene
1-Butene
S02
COS
CS2
NOX
Coal Stove
High
Burn
210
722
2
2
—
208
—
—
—
Low
Burn
590
1000
—
—
3
300
3
—
—
Modified
Wood Stove
95
61
—
0.4
—
430
1
0.3
160
— - Not detected.
study the three bituminous tests yielded values of 13 g/kg (fuel basis-dry-ash
free) for the high burn rate coal stove, 32 g/kg for the companion low burn
rate test, and 29 g/kg for the modified wood stove burning bituminous coal.
Thus, the residential units tend to produce lower SOX levels than larger
industrial units. These lower levels are probably caused by lower fuel-bed
temperatures which enable the alkali in the coal ash to capture sulfur as
stable sulfates. The temperatures in industrial units are often too high to
capture much sulfur because sulfates are unstable.
Polynuclear aromatic hydrocarbon emissions from, coal combustion sources
were summarized in 1967 in a paper by Hangebrauck, von Lemden, and Meeker (6).
These researchers graphically illustrated relative PAH emissions from several
sources by using BaP as a key indicator compound. They reported BaP concen-
17
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trations as a function of gross heat input to the furnace. Their graphical
presentation of PAH emissions is reproduced in Figure 3. In this figure,
efficiency in coal combustion is shown to reduce BaP levels. Thus, large
utility furnaces with very high bed temperatures, secondary air, and suffi-
cient excess air produce far less BaP per unit of fuel burned than highly
inefficient residential units. Even though Hangebrauck et al. summarized
data from the 1960s, the relationship of PAH emissions to combustion effi-
ciency is still valid and has been verified many times. The Vermont study
provided an opportunity to measure specific PAH compounds including BaP with
modern analytical techniques and good quality control procedures.
Benzo(a)pyrene (BaP) data are given in units of discharge gas, fuel con-
sumed, and thermal output in Table 8. This table also gives thermal input to
the furnace in units of Btu/hr (xlO~4) consistent with the Hangebrauck curve
shown in Figure 3. Referring back to Figure 3, the Vermont bituminous coal
stove data fall on the line for residential units but the anthracite data fall
well outside the coal curve. This deviation is indicative of the observed
reductions in PAH emissions through the use of anthracite fuel. The emission
data for a representative series of PAR compounds are given in Table 9 for
anthracite tests and Table 10 for bituminous tests. The magnitude of PAH
emissions can be compared between sources by using consistent units. An
Electric Power Research Institute study has suggested using weight of analyte
per Joule as a unit for reporting PAH results (7). Several sources including
coal and wood-fired residential units are compared in Table 11 using this unit
as a basis for comparison. Residential coal combustion (using bituminous
coal) shows the highest emissions of BaP relative to other coal-burning com-
bustion systems compared. This observation is consistent with the Hangebrauck
curve. Anthracite fuel was found to generate far lower BaP emissions than
bituminous coal in equivalent appliances. Although coal gasification (9) and
perhaps other coal processes may result in BaP emission levels that are higher
than residential coal combustion, the high levels observed in residential coal
combustion should not be ignored. The magnitude of the BaP and other PAH
discharges found in this study, together with the high particulate and SOX
levels, should be considered in light of the current increased use of bitu-
minous coal for residential space heating. The values reported in this study
13
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Power ?l*nt Outout,
(0 34* Overall Thernal
Efficiency, MW)
1000
< _ EMISSION LESi
THANV»LU€
10
10- 10' 10*
CROSS HEAT INPUT TO FURNACE. St. hr
10-
10-•
FIGURE 3. RANGE OF BENZO(a)PYRENE EMISSIONS FROM COAL, OIL,
AND NATURAL GAS HEAT-GENERATION PROCESSES
(Reproduced from Reference 5).
19
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TABLE 8. BENZO(a)PYRENE CONCENTRATIONS IN VERMONT COAL STOVE STUDY
Eaiision
Caieoue Eaiaiion (wg/SCM)
Pual Baied Enlulon (ppb-dry-eah free)
Thensal Bleed Eaiulon (ng/J)
Thertul Input to Furnace (Btu/hr)
Bltunlnoui
Coal Stove
High Burn
110
2800
8.1*10-2
4.2x10*
Anthracite
Coal Stove
High Burn
0.1
3
7.3x10-3
4.7x10*
Bitiainouf
Coal Stove
Low Burn
$2
1700
5.0x10-2
2.2x10*
Anthracite
Coal Stove
Low Burn
0.08
5
1.5x10-*
1.7x10*
Bitiainoue
Modified
Wood Stove
Low Burn
120
3400
9.8x10-2
3.0x10*
Anthracite
Modified
Wood Stove
Low Burn
0.17
4
1.2x10-*
2.1x10*
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TABLE 9. POLYNUCLEAR AROMATIC HYDROCARBON EMISSIONS—ANTHRACITE TESTS
(ug/SCM)
Coal Stove
High Burn Rate
Naphthalene
Acenaphthene
Acenaphthylene
Fluorene
Phenanthrenc
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(k)£luoranthene
Benzo(e)pyrene
Benzo ( a ) pyrene
Perylene
Indeno( 1 , 2, 3-c, d)perylene
Benzo(gfh,i)perylene
Anthanthrene
Coronene
5.3
0.94
0.99
0.89
11.
1.2
8.7
6.3
5.4
5.9
0.68
0.16
0.10
0.02
0.37
0.31
0.005
0.21
Coal Stove
Low Burn Rate
0.08
0.12
0.12
0.08
0.81
0.08
0.85
0.48
0.12
0.20
0.12
0.04
0.08
0.02
0.04
0.04
0.01
0.01
Modified
Wood Stove
Low Burn Rate
14.U)
0.82
6.3
1.2
9.0
0.9
4.7
3.7
1.1
1.5
1.3
0.30
0.17
0.04
0.17
0.09
0.02
0.13
(a) Saturated.
21
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TABLE 10. POLYNUCLEAR AROMATIC HYDROCARBON EMISSIONS—BITUMINOUS TESTS
(vg/SCM)
Coal Stove
High Burn Rate
Naphthalene
Acenaphthene
Acenaphthylene 1 ,
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chryaene
Benzo(k) f luoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno(l,2,3-c,d)perylene
Benzo(g,h,i)perylene
Anthanthrene
Coronene
830
120
100
210
780
210
360
210
130
ISO
190
100
110
13
14
49
4
60
Coal Stove
Low Burn Rate
210
19
16
90
180
100
76
69
46
37
92
38
52
5
36
24
7
9
Modified
Wood Stove
Moderate
Burn Rate
330<«>
70
330<«>
210
330
160
270
190
170
140
280
85
120
16
150
72
27
42
(a) Saturated.
22
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TABLE 11. BENZO(a)PYRENE EMISSIONS FROM COMPARATIVE COMBUSTION SOURCES (pg/J)
ro
ui
Wood-Fired Bituninous-Fired Anthracite-Fired
Residential Residential Residential Bituminoui-Fired
Heaters<>> lteatera Heaters^) Industrial Boilers^)
Range 8. 3x103-10"* 98-50 0.15-0.07 0.14-0.005
Average 1.8xU>3 76 0.11 0.07
Number of 5 I 3 IS
Testi
Oil-Fired
Utility Boilera(c)
««IO~*
4»10-*
(not given)
(a) Reference 8.
(b) This study.
(c) Reference 7.
-------
represent a very small data base, thus this work should be considered a con-
tribution to the literature in the field instead of a comprehensive evaluation
of these combustion systems.
24
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REFERENCES
(1) DeAngelis, D. G., R. B. Reznik, Source Assessment: Coal-Fired Resi-
dential Combustion Equipment Field Tests, June 1977. EPA-600/2-78-0040,
U.S. Environmental Protection Agency, Research Triangle Park, NC, June
1978. 83 pp. (NTIS No. PB283699).
(2) Emissions and Efficiency Performance of Industrial Coal Stoker Fired
Boilers. DOE/ET/10386 (Vol. 2) (DE8103026S). U.S. Department of Energy,
August 1981. 342 pp.
(3) Burlingame, J. 0., J. E. Gabrielson, P. L. Langsjoen and V. M. Cooke.
Field Tests of Industrial Coal Stoker Fired Boilers for Inorganic Trace
Element and Polynuclear Aromatic Hydrocarbon Emissions. EPA-600/57-81-
167, U.S. Enviroronental Protection Agency, Research Triangle Park, NC,
1982. (NTIS No. PB82230608).
(4) Hugheti, T. W.t and D. G. DeAngelis. Emissions from Coal-Fired Resi-
dential Combustion Equipment. In: Residential Solid Fuels, J. A.
Cooper and D. Malek, eds. Oregon Graduate Center, Beaverton, OR, 1982.
pp. 333-349.
(5) Lent sen, D. E., D. E. Wagoner, E. D. Estes and W. F. Gutknecht, IERL-RTP
Procedures Manual: Level 1 Environmental Assessment (Second Edition).
EPA-600/7-78-201 (NTIS PS 293-795). U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1978. 173 pp.
(6) Hangebrauck, R. P., D. J. von Lehmden, and J. E. Meeker. Sources of
Polynuclear Aromatic Hydrocarbons in the Atmosphere. Public Health
Service Publication No. 999-AP-33, U.S. Department of Health, Education
and Welfare, Cincinnati, OH, 1967. pp 44. (NTIS No. PB174706).
(7) Zelenski, S. G., N. Pangaro, and J. M. Hall-Enos. Inventory of Organic
• Emissions from Fossil Fuel Combustion for Power Generation. EPRI LA-
1394, Electric Power Research Institute, Palo Alto, CA, April 1980.
72 pp.
(8) Cooke, W. M., J. M. Allen, and R. E. Hall. Characterization of Emissions
from Residential Hood Combustion Sources. In: Residential Solid Fuels,
J. A. Cooper and D. Malek, eds. Oregon Graduate Center, Beaverton, OR,
1982. pp. 139-164.
25
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(9) Nichols, D. G., S. K. Gsngwal, and C. M. Sparacino. Analysis and
Assessment of PAH from Coal Combustion and Gasification. In: Chemical
Analysis and Biological Fate: Polynuclear Aromatic Hydrocarbons, U. M.
Cooke and A. J. Dennis, eds. Battelle Press, Columbus, OH, 1981. pp.
397-406.
26
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