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

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