United States
Environmental Protection
Agency
Industrial Environmental
Research Laboratory
Research Triangle Park NC 27711
1
Research and Development
EPA-600/S7-84-055 June 1984
SER& Project Summary
Procedures for Comparing
Combustion Emissions from
Synthetic and Petroleum Fuels:
Phase I
J.K. Arand and S.S. Cherry
An EPA research program to investi-
gate synfuel emissions, including
health effects, was initiated in 1981. It
was planned as a multiphase project to
develop cost-effective procedures for
comparing characteristic emissions
from synfuels and petrof uels that would
be burned in conventional stationary
combustors. Phase I, conducted at
EPA's IERL-RTP combustion laboratory,
was a two-component test program to
evaluate a package boiler and a diesel
engine, each burning fuels designed to
be burned in them.
A total of 25 test runs were completed
using a wide range of fuels including
No. 6 and No. 2 fuel oils, methanol,
EDS. SRC-II, and shale-derived fuel oil.
Replicate runs on several of the fuels
were made to test the repeatability of
the combustion facility and sampling
procedures.
Particulate from the combustion
systems was sampled and conditioned
by a dilution tunnel to simulate airborne
ambient particles. The particulate
samples were trapped on filters through
which the diluted combustion gases
were passed. The undiluted gases were
also sampled, using an organic adsorber
to investigate the organics formed
during combustion.
The samples were analyzed using
Level 1 procedures with the emphasis
on organic constituents. The results
showed that the test and sample collec-
tion procedures yielded inconsistent
sample loadings, with contaminants
that masked the true fuel combustion
products. Corrective procedures were
identified which will be used in subse-
quent test phases.
This Project Summary was developed
by EPA's Industrial Environmental
Research Laboratory, Research Triangle
Park. NC. to announce key findings of
the research project that is fully docu-
mented in a separate report of the same
title (see Project Report ordering
information at back).
Introduction
The objective of the Phase I program
was to initiate the development of cost-
effective procedures which would permit
an accurate comparison of the combustion
emission characteristics of synfuels and
petrofuels from stationary sources. These
characteristics would include gaseous,
organic, and inorganic components from
the combustion of these two basic fuel
types.
A workshop, held at the conclusion of
Phase I, reviewed the procedures and
results obtained. It was attended by
government and industrial researchers
active in synfuel utilization. Recommen-
dations from workshop participants
were considered for subsequent phases of
the program.
The approach adopted to satisfy the
Phase I program objective was influenced,
to a great extent, by its comparative
nature. The testing and analytical proce-
dures would be structured to identify
statistically significant differences between
the emission characteristics of synfuels
and their petrofuel counterparts under
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similar combustion conditions. In this
respect, the ability to determine absolute
levels of emission characteristics would
be of less importance than the ability to
detect differences.
The magnitude of the synfuel supplies
available for Phase I required that the
combustion systems be of a moderate
size. In addition, the combustion systems
were to be representative of the existing
population of industrial steam boilers and
stationary diesel engines, and were to be
operated in a manner consistent with
current industry practice. The moderate
size of the combustion systems would
also allow better control of the synfuel
from spillage and health standpoints.
Phase I was to be a preliminary effort to
burn a wide range of synfuels (from
methanol to heavy coal-derived distillates)
and petrofuels (from light distillate No. 2
to heavy No. 6 fuel oils). During the
combustion of these fuels, sampling
procedures to obtain large particulate
samples for Level 1 analysis and bioassay
evaluation were to be developed. Of
particular interest would be a determina-
tion of the sensitivity to detect signficant
differences in the combustion emissions
from synfuels/petrofuels using the
analytical, chemical, and biological
testing procedures initially proposed.
Many of the foregoing criteria could be
achieved, including the analytical diag-
nostics, using in-house IERL-RTP facilities;
thus. Phase I was performed in its
entirety at IERL-RTP. A presentation of
the planned Phase I work was made at the
Sixth EPA Symposium on Environmental
Aspects of Fuel Conversion Technology,
in Denver in October 1981.
Phase I results have been discussed at
a workshop where the problems encoun-
tered in the Phase I tests were discussed
and recommendations made to revise the
procedures for subsequent Phase II
testing.
The combustion variables examined
during the tests included combustor and
fuel types. Gaseous combustion products
monitored during the tests included stack
oxygen (02), oxides of nitrogen (NOX),
carbon monoxide (CO), carbon dioxide
(C02), total hydrocarbons (THC), and
sulfur dioxide (SO2).
Test Apparatus
The experiments were conducted by
EPA in a commercially available package
boiler and diesel engine at their laboratory
in Research Triangle Park, NC. All were
conducted at a fixed input or output for
each combustion device. In the package
boiler, a heat input rate of 740 kW (2.5 x
106 Btu/hr) was used. For the diesel
engine, an output of 190kW(250hp)was
used. Both units were operated to
produce optimum stack condition; i.e.,
minimal smoke. A 2-hour test was used
for each fuel. During this test, gaseous
samples of the combustion products were
monitored continually for Oz, CO, COz,
NO/NOx and SO2. A modified Method 5
particulate train was used to obtain both
organic and particulate samples. The
modification consisted of adding an XAD-
2 module between the Method 5 filter and
impingers to collect condensible organic
vapors. The particulate samples were
analyzed by Level 1 procedures, with an
emphasis on organics.
The boiler used for the tests was a
commercially available, three-pass fire-
tube boiler manufactured by North
American (NA) and having a thermal
input rating of 740 MW(2.5x 106Btu/hr.)
The boiler, shown schematically in Figure
1, is located at EPA's Environmental
Research Center in Research Triangle
Park, NC.
The diesel engine used in the experi-
ments was a Model D-334 Caterpillar
diesel. The test setup for the diesel
engine is shown in Figure 2.
A dilution tunnel was used with both
combustors to condition the particulate
emissions to simulate organic vapor
condensation on the particles, as might
happen in the atmosphere. Samples of the
particulate emission from the dilution
tunnel were caught on a filter at the exit
of the tunnel. An organic adsorber
module was used in a modified EPA
Method 5 train to obtain samples at the
stack exit. Continuous monitors were
used to sample for gaseous emissons.
Test Fuels
Six petrofuels and four synfuels were
used in the tests. Table 1 summarizes the
fuels used and their nominal physical and
chemical properties.
The test fuels were subjected to some
of the same analytical chemistry methods
that were used on the captured combus-
tion particulate samples. Table 2 compares
organic components and the polynuclear
aromatic hydrocarbon (PAH) contents of
each fuel.
Results
A total of 25 tests were run during the
program. Of these, 20 were run on the
package boiler; however, onlyl 5 produced
particulate samples. Five tests were run
on the diesel engine. Seven replicate
tests were run.
The data of primary interest were the
particulate loadings and organic contents.
If sufficient organic material could be
collected, bioassays using the Arrles
Salmonella typhimurium plate assay
were to be conducted. The test results are
given in Tables 3 through 6, which show
the fuels tested, the particulate loadings,
and the organic weights (after correction
for possible silicone contaminants).
Conclusion
The results showed that the test and
sample collection procedures yielded
inconsistent sample loadings, and con-
taminants which masked the true fuel
combustion products. Corrective proce-
dures were identified which will be
incorporated in subsequent tests.
Due to problems with extracting the
particulate matter from the filters, the
planned bioassays were not performed.
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Heated Sample
I Line
J Sample
(TYVY^oorKv-inrr-Tn
Ports
502 I I NO/
__l L/VO,
Air Shutter
Atomizing Air
I
Exhaust to Atmosphere
Modified Method 5
Opacity
Stack
Filter
Dilution Tunnel
Fan
Ambient Air
Sample
Ports
Condenser
Drum Heaters
Oil Hand/ing Building
Figure 1. The package boiler facility.
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SO2
Heated Sample Line
NO/
NO,
Condenser
CO
CO*
Control
Valve
Diesel
Engine
i— Modified Method 5
Filter
f?
Opacity
T
Dilution Tunnel
L
Fan
Ambient Air
Variable
Test Load
To Stack
Figure 2. The diesel engine facility.
Table 1. Report of Fuel Oil Tests
Marked
Btu/lb'
Gross
Net
Btu/gal.
Gross
Net
Specific gravity ®
60/60°F by pycnometer
Density"® 60°F
API gravity ' 60°F
Density"® 100°F
Density"® 21O°F
Viscosity @ 100°F. cs
Viscosity @ 210°F. cs
Karl Fischer water, wt. %
Ash, wt. %
Carbon, wt. %
Hydrogen, wt. %
Nitrogen, wt. %
Sulfur', wt. %
No. 2
In-House
19,364
-
138.182
-
0.8571"
0.8562
33.6
0.8441
0.8405
2.75
1.14
-
<0.01
87.0
12.5
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Table 2. Fuel TOO, GRA V. and PAH Spot Test Analysis
Fuel
No. 2, In-House
No. 2, In Barrels
No. 6, 1.4% S
No. 6. 2. r% S
No. 6. 2.9% S
No. 6,0.7%N
Methanol
Shale Derived No. 2
EDS Middle Distillate
SRC-II Heavy Distillate
TCO"
Concentration
mg/mL
729
685
433
241
80
40
3.8
753
741
255
GRAV*
Analysis
mg/mL
240
200
646
791
1008
923
0
394
248
892
Total
(TCO +G RAV>
mg/mL
969
885
1079
1032
1088
963
3.8
1147
989
1147
PAH
Spot Test
positive
positive
positive
positive
positive
positive
negative
positive
positive
positive
Concentration
mg/mL
2
20
20
20
200
20
0.2
2000
2OOOO
- 20
- 200
- 200
- 200
-2000
- 200
-
2.0
TCO - Total Chromatographable Organics. Materials having boiling points in the range of 100°C to 3OO"C. See Lentzen, D.E.. et at., "IERL-RTP
Procedures Manual: Level I Environmental Assessment (Second EditionJ," Research Triangle Institute, Research Triangle Park. NC. EPA-600/7-78-
201 (NTIS No. PB 293795). October 1978.
- Gravimetric Analysis. See Reference in footnote "a."
Table 3. Package Boiler Exhaust Gas Paniculate Summary
Modified Method 5 Sample Train
Loading
Run
No.
1R
16
3
9
14
7R
12
8
10R
4R
6
5
11R
13
15
Fuel
No. 2, In-house
No. 2. In-house
No. 2, In Barrels
No. 6. 1.4% S
No. 6. 1.4% S
No. 6. 2. 1% S
No. 6,2.1%S
No. 6. 2.9% S
No. 6, 0.7% N
Methanol
Shale Derived No. 2
EDS Middle Distillate
EDS Middle Distillate
SRC-II Heavy Distillate
SRC-II Heavy Distillate
Probe Wash
mg
3.9
7.1
2.6
2.6
38.6
127.8
210.2
224.9
12.6
2.6
0.5
51.6
5.6
18.4
0.0
Filter
mg
4.3
0.2
6.7
126.9
191.3
746.5
344.8
385.9
52.5
3.6
183.0
366.8
135.4
393.3
12.8
Concentration"
mg/m3
2.81
1.42
3.68
62.9
120.0
367.0
276.0
257.0
32.4
2.18
43.7
146.0
67.1
206.0
6.40
Dilution Tunnel
Loading
mg
78.0
133.0
97.6
3501.2
3314.4
7580.7
11293
6306. 1
686.7
33.1
183.0
95.0
238.6
329.6
305.0
Concentration
mg/m3
1.25
1.06
1.64
58.9
46.0
135.3
219.3
130.0
9.73
0.538
2.98
1.32
5.47
7.31
6.57
"Paniculate concentration includes probe rinse, cyclone, and filter loadings.
Tab/04. Diesel Engine Exhaust Gas Paniculate Summary
Modified Method 5 Sample Train
Loading
"Paniculate concentration includes probe rinse, cyclone, and filter loadings.
Dilution Tunnel
Run
No.
1
5
3
2
4
Fuel
No. 2, In-house
No. 2, In-house
No. 2, In Barrels
Shale Derived No. 2
Shale Derived No. 2
Probe Wash
mg
9.0
3.6
6.8
15.2
38.2
Filter
mg
24.5
44.5
41.6
23.4
21.5
Concentration"
mg/m3
18.5
27.1
27.5
21.7
33.5
Loading
mg
924.0
1464.2
1487.0
969.1
1046. 1
Concentration
mg/m3
17.1
28.2
27.8
19.0
19.6
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Tables.
Corrected* TOO and GRAV Values — Package Boiler
Modified Method 5 Sample Train*
XAD-2 Extract
Dilution Tunnel
Run
No.
1R
16
3
9
14
7R
12
8
10R
4R
6
5
11 Ft
13
15
Fuel
No. 2, In-house
No. 2. In-House
No. 2, In Barrels
No. 6. 1.4% S
No. 6. 1.4%S
No. 6, 2. 1% S
No. 6. 2. 1% S
No. 6. 2.9% S
No. 6, 0.7% N
Methanol
Shale Derived No. 2
EDS Middle Distillate
EDS Middle Distillate
SRC-II Heavy Distillate
SRC-II Heavy Distillate
Percent
Identified
42
56
40
26
10
4.2
3.6
87
.
26
42
19
17
46
97
TOO
mg
1.02
1.45
0.902
1.74
2.69*
1.58
0.361
4.20
(lost)
1.16
1.28
7.50
0.646
4.82
1.41
mg/m3
0.347
0.289
0.355
0.844
1.41"
0.664
0.180
1.80
-
0.407
0.303
2.63
0.308
2.41
0.703
GRAV
mg
1.9
0
0.25
1.8
0
0.27
0
0.82
.
3.8
0.67
2.0
0
0
0
mg/m3
0.67
0
0.10
0.92
0
0.12
0
0.34
-
1.3
0.16
0.71
0
0
0
Percent
Identified
23
231
17
58
303
33
.
22
176
7.9
.
16
65
131
48
TOO
mg
0.294
0.488
0.437
0.576
0.713
0.658
(lost)
0.564
0.595
0.158
(lost)
0.514
0.645
0.586
0.391
mg/m3
0.00472
0.00390
0.00733
0.00968
0.00989
0.0117
-
0.0117
0.00843
0.00256
-
0.00715
0.0148
0.0130
0.00843
GRAV <
mg
3.2
0
13.6
0.58
0
5.5
0
3.4
0
5.2
-
12.6
2.8
0
2.1
mg/m3
0.051
0
0.23
0.0098
0
0.099
0
0.070
0
0.084
-
0.18
0.064
0
0.045
Flue Gas
Organic
Concentration
mg/m3
0.056
0.0039
0.24
0.019
0.0099
0.11
>O
0.082
0.0084
0.087
-
0.19
0.079
0.013
0.053
'Corrections made for contaminants (silicone, phthalate, and solvent) in identified portions of the extracts.
^Includes extracts from XAD-2, probe rinse. RAC train filter, and organic module condensate.
"^Concentrations uncertain. Sample was spilled during preparation.
TableB.
Corrected* TCO and GRAV Values — Diesel Engine
Modified Method 5 Sample Trainb
XAD-2 Extract
Dilution Tunnel
Run
No.
1
5
3
2
4
Fuel
No. 2. In-House
No. 2. In-House
No. 2, In Barrels
Shale Derived No. 2
Shale Derived No. 2
Percent
Identified
79
42
80
65
46
TCO
mg
67.6
19.0
59.0
33.4
19.4
mg/m3
37.4
10.8
33.6
18.8
10.9
GRAV
mg
5.2
2.5
1.5
3.2
3.0
mg/m3
2.9
1.4
0.91
1.8
1.7
Percent
Identified
9.2
4.3
10
20
21
TCO
mg
2.94
2.69
7.00
2.72
3.47
mg/m3
0.0546
0.0518
0.131
0.0535
0.0649
f
(
GRAV Con,
m
64.8
106
118
58.0
69. 1
mg/m3 '
1.2
2.0
2.2
1.1
1.3
'lue gas
Organic
centration
mg/m3
1.3
2.1
2.3
1.2
1.4
'Corrections made for contaminants (silicone, phthalate, and solvent) in identified portions of the extracts.
^Includes extracts from XAD-2, probe rinse, RAC train filter, and organic module condensate.
«USGPO: 1984 — 759-102/10602
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J. K. ArandandS. S. Cherry are with KVB. Inc., Irvine, CA 92714.
Joseph A. McSorley is the EPA Project Officer (see below).
The complete report, entitled "Procedures for Comparing Combustion Emissions
from Synthetic and Petroleum Fuels: Phase I, "(Order No. PB 84-189 687; Cost:
$13.00, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield. VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
United States
Environmental Protection
Agency
Center for Environmental Research
tnformation
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
U
.0604
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