MINIPILOT SOLAR SYSTEM:
Design/Operation of System and
Results of Non-Solar Testing at MRI
by
Paul Gorman
Ed Ball
John Jones
Pam Murowchick
Midwest Research Institute
Kansas City, Missouri 64110
EPA Contract No. 68-DO-0137
Work Assignment No. 18
EPA Technical Program Manager
C.C. Lee
Waste Minimization, Destruction & Disposal Research Division
Risk Reduction Engineering Laboratory
Cincinnati, Ohio 45268
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
RISK REDUCTION ENGINEERING LABORATORY
CINCINNATI, OHIO 45268
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DISCLAIMER
This material has been funded wholly or in part by the United States
Environmental Protection Agency under Contract No. 68-DO-0137 to Midwest
Research Institute. It has been subject to the Agency's review, and it has been
approved for publication as an EPA document. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
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FOREWORD
Today's rapidly developing and changing technologies and industrial products
and practices frequently carry with them the increased generation of materials that, if
improperly dealt with, can threaten both public health and the environment. The U.S.
Environmental Protection Agency is charged by Congress with protecting the nation's
land, air, and water resources. Under a mandate of national environmental laws, the
agency strives to formulate and implement actions leading to a compatible balance
between human activities and the ability of natural systems to support and nurture life.
These laws direct the EPA to perform research to define our environmental problems,
measure the impacts, and search for solutions.
The Risk Reduction Engineering Laboratory is responsible for planning,
implementing, and managing research, development, and demonstration programs to
provide an authoritative, defensible engineering basis in support of the policies,
programs, and regulations of the EPA with respect to drinking water, wastewater,
pesticides, toxic substances, solid and hazardous wastes, and Superfund-related
activities. This publication is one of the products of that research and provides a vital
communication link between the researcher and the user community.
This report was prepared to summarize work performed by Midwest Research
Institute (MRI) for the United States Environmental Protection Agency (U.S. EPA),
Risk Reduction Engineering Laboratory (RREL). The work involved design,
construction, and operational testing of a Minipilot Solar System, followed by a series
of non-solar tests at MRI using EPA sampling and analysis methods. The work at MRI
was done to provide an operational system and non-solar test results in preparation
for transporting the system to the National Renewable Energy Laboratory (NREL) and
conducting tests with solar input.
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
in
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ABSTRACT
Prior to this project, MRI had carried out work for the Environmental Protection
Agency (EPA) on the conceptual design of a solar system for solid waste disposal1
and a follow-on project to study the feasibility of bench-scale testing of desorption of
organics from soil with destruction in a solar furnace.2 The feasibility study involved a
two-step process: (1) thermal desorption of organics from soil (non-solar) with
recovery of the organics in liquid form and (2) destruction of the organics in a solar
furnace.
Previous laboratory work by the National Renewable Energy Laboratory (NREL)
and others indicated efficient destruction of organics by solar input at high
temperatures, but the experiments were limited to low concentrations of organic
vapors in air.3 The feasibility study conducted by MRI recommended the important
difference that the organics should be fed to the solar furnace in liquid form, to provide
destruction through combustion and solar photolytic effects.
Based on the feasibility study, EPA directed MRI to proceed with design,
construction, and testing of a Minipilot Solar Reactor System with liquid organic feed.
Testing of the system on this project was intended to be carried out in two parts. The
first part was to be non-solar testing at MRI using a synthetically prepared liquid
organic mixture. The primary purpose of the non-solar testing at MRI was to utilize
EPA sampling and analysis methods and determine if the organic emissions
quantitated by those methods would enable quantitation of the expected significantly
lower emissions when operating with solar input. A secondary purpose of the testing
at MRI was to conduct tests with a UV lamp to determine if this provided any
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significant reduction in emissions. The second part of the project was to carry out
subsequent testing with solar input at NREL.
MR! proceeded with design and construction of the Minipilot System, and
included complete instrumentation with computerized data logging, flame detectors,
automatic shutdowns, and continuous monitors for CO, O2, and THC. NREL staff
contributed valuable advice that aided in the development of the design.
Extensive operational tests were conducted and resulted in some system
design and operational changes that improved the system's overall utility. Operational
techniques were established for this system during the initial operating tests. The
operational performance of the Minipilot System was demonstrated during a series of
10 tests using the EPA-approved sampling and analysis methods. This report
summarizes the results of those tests, as well as the design and construction work
mentioned above.
Results of the 10 tests showed that it should be possible to determine if there is
a significant reduction in emissions (> 3X) when operating with solar input. Such
reduction in the emissions should be determinable for two of the POHCs contained in
the synthetic feed liquid (CCI4 and DCB), for both the volatile and semivoiatile PICs,
and for dioxins and furans. But reductions are probably not determinable for the other
two POHCs (toluene and naphthalene). Results also showed that a three-fold
reduction in volatile PICs occurred in both single-chamber tests when an artificial UV
light was utilized.
The Minipilot System is now fully operational and has been designed to utilize
the full solar capability of the NREL facility (10 kW) with temperature control via
different aperture openings (to vary the radiation heat losses) and/or water injection. It
has already been operated in the non-solar mode over a temperature range of 1400°
'to 2000°F. Further, the baseline levels of the organic emissions have already been
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determined using EPA sampling and analysis methods for two different operating
modes (single- and dual-chamber) and two different flow rates. Thus the system is
ready for the next phase: solar testing at NREL.
Carrying out the tests as planned at NREL is crucial to the overall goal of the
project: to determine if solar input provides a significant reduction in organic
emissions as compared to emissions in the non-solar mode at the same operating
conditions (i.e., temperature and feed rates, etc.). Moreover, the tests at NREL are
intended to provide data on the effect of certain parameters that are very important to
the design of larger pilot- or full-scale systems. Specifically, tests at NREL would:
(1) investigate effects of solar exposure time (over the range of 4 to 8 s), which is
critical to sizing of reactors; and (2) investigate operation at different solar flux levels,
up to 10 kW, to determine the optimum kilowatt input per unit of gas flow rate (scfm),
which is critical to sizing the costly solar collector/concentrator units. Considering the
important goals of the solar tests at NREL, and results of the non-solar tests that have
already been completed at MRI, it is recommended that work proceed on transporting
the Minipiiot System to NREL and testing it with solar input.
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CONTENTS
Foreword . iii
Abstract iv
Figures . . viii
Tables ix
Abbreviations x
Acknowledgments xi
1. Introduction 1
2. Design and Construction of the Minipilot System 3
Minipilot System 4
Reactors ; 8
3. Initial Operation 14
4. Preliminary Testing 17
5. EPA Method Test Results 23
Test Conditions 24
EPA Method Test Results 29
6. Conclusions and Recommendations 46
Conclusions 46
Recommendations 48
7. References 50
Appendices
A. POHC inputs and VOST results with calculation of DREs for
CCI4 and toluene 51
B. MM5 results and calculation of DREs for dichlorobenzene
and naphthalene 58
C. PIC results for VOST and MM5 samples . . 62
D. Tabulation of analysis results for dioxins/furans 77
E. Liquid organic feed analysis results for Cl, ash, and HHV 79
F. O2, CO2, and H2O analysis results for effluent gas in each
run 81
G. Summary of quality assurance results 83
VII
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FIGURES
Number
1 Schematic diagram of the Minipilot Solar System 5
2 Solar detoxification reactor-section view 9
3 Minipilot-Scale Solar Reactor System (shown: overview of the system
operating in the two-chamber-nonsolar mode) 10
4 Minipilot-Scale Reactor System (shown: close-up of the operating solar
detoxification system with computerized data acquisition and control) 11
VIII
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TABLES
Number Page
1 EPA test method results for Runs 17 and 18 19
2 Summary of EPA tests 25
3 Summary of operating data 26
4 Summary of results from Minipilot Solar Reactor Runs 31 through 40 30
5 Comparison of blanks with sample results 32
6 Comparison of replicate runs (single-chamber mode) 35
7 Comparison of non-UV results for different flows and operating modes .... 37
8 Amount of volatile PICs found in a VOST trap pair sample (ng) . 42
9 Amount of semivolatile PICs found in the MM5 samples (jig) . 44
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ABBREVIATIONS
NREL National Renewable Energy Laboratory (Golden, Colorado)
VOST Volatile Organic Sampling Train
VOA Volatile Organic Analysis
MM5 Modified Method 5 sampling train
ORE Destruction and Removal Efficiency (for POHCs)
THC Total Hydrocarbons
OEMs Continuous Emission Monitors
HHV Higher Heating Value
SIM Selective ion monitoring
UV Ultraviolet
POHCs Principal organic hazardous constituents
V-POHCs Volatile POHCs
SV-POHCs Semivolatile POHCs
PICs Products of incomplete combustion
V-PICs Volatile PICs
SV-PICs Semivolatile PICs
QAP Quality Assurance Plan
CCI4 Carbon tetrachloride
DCB 1,2-Dichlorobenzene
GC/ECD Gas chromatography/electron capture detector
GC/MS Gas chromatography/mass spectrometry
D/F Dioxins/Furans
RRF Relative Response Factor
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ACKNOWLEDGMENTS
Dr. C. C. Lee and Mr. George Huffman of EPA/RREL contributed much to this
project. Their help and support is gratefully acknowledged.
Throughout the work at MRI, NREL staff (Drs. Greg Glatzmaier and Mark Bonn)
provided valuable assistance in the design of the reactors and the rest of the system,
as well as assisting in the preparation of work plans and many other aspects of the
project. MRI and NREL staff also participated in quarterly technical review meetings
held under the Tri-Agency Agreement (EPA/DOD/DOE) on solar soil detoxification.
XI
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SECTION 1
INTRODUCTION
Prior to this project on the Minipilot Solar System, MRI carried out related work
for EPA on "Conceptual Designs of Solar Systems for Solid Waste Destruction"1 and a
"Feasibility Study for Bench-Scale Testing of Desorption of Organics from Soil with
Destruction in a Solar Furnace."2 A major conclusion of that previous work was that
the most feasible concept for solar soil detoxification would:
1. Use available conventional processes for low temperature thermal
desorption of soil with recovery of desorbed organics in liquid form.
2. Feed the recovered organic liquid to a solar reactor for destruction of the
organic components.
The above concept was believed to provide the most feasible system for
several reasons. First, it separates the soil desorption process (non-solar) from the
solar destruction system so that desorption can be done continuously, and is not
dependent on solar availability or the need for rapid shutdown capability if solar input
is interrupted. It also avoids the need for large amounts of solar energy that would be
necessary for thermal treatment of large amounts of soil. Second, the solar destructor
for the recovered organic liquid can be relatively small (approximately 1/1,400th of the
size needed if fed gaseous contaminants directly from the soil desorption process).
Design of the solar destructor would be based on the availability of solar input, but
may or may not be based on the desorption rate of organics from the soil, depending
on whether the destructor is located on-site or at a separate off-site processing facility.
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Third, the solar reactor combines destruction of the organics by both combustion and
photolytic reactions. Fourth, a solar destructor, with liquid feed only, can be rapidly
shut down if solar input is interrupted.
The above concept was the basis for the subsequent project to be carried out
by MRI for EPA, which consisted of two parts:
Part I — Design, construction, and non-solar testing of a minipilot-scale
liquid feed solar reactor system at MRI.
Part II — Operation and testing of the minipilot-scale liquid feed solar
reactor system at NREL with solar input.
The objective of this report is to summarize the Part I work on the project,
which has been completed. Associated with the work are three other documents:
• Test Plan for Testing to Be Done at MRI (dated March 20, 1992)
• Test Plan for Testing to Be Done at NREL (dated April 2, 1992)
• Quality Assurance Project Plan for Testing of the Minipilot-Scale Solar
Reactor (dated March 20, 1992)
Subsequent sections of this report are organized as follows:
Section 2 Design and Construction of the Minipilot System
Section 3 Initial Operation
Section 4 Preliminary Testing
Section 5 EPA Method Test Results
• Test conditions
• EPA method test results
Section 6 Conclusions and Recommendations
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SECTION 2
DESIGN AND CONSTRUCTION OF THE MINIPILOT SYSTEM
Design of the solar reactors and the rest of the Minipilot System was based on
the size of the solar collector/concentrator furnace at NREL and information provided
by NREL on their previous testing done with a small quartz reactor.
The solar collector/concentrator can provide about 10 kW of heat (34,000 Btu/h)
in a 4-in diameter beam. This thermal heat input is capable of heating about 10 scfm
of flue gas (mostly air) to 2000°F. The flow rate of flue gas (approximately 10 scfm of
air) was considered to be a maximum value, and was used to estimate the reactor
volume necessary to provide a residence time of 2 to 3 s in the temperature range of
1400° to 2000°F. NREL suggested a length-to-diameter ratio of 3:1. On this basis,
the reactor's internal dimensions are 10 1/2 in i.d. x 36 in long.
The airflow rate of 10 scfm also was used to estimate the feed rate of a liquid
organic, assuming that one-half the oxygen available in an air feed of 10 scfm was
consumed in the combustion of an organic liquid (i.e., 100% excess air). Further, it
was estimated that the liquid organic, recovered from soil desorption, would have a
heating value on the order of 12,000 Btu/lb. On this basis, the system was designed
to provide a liquid organic feed rate of 1.5 Ib/h (11 g/min).
The above air feed rate, liquid feed rate, and solar thermal input rate provided
the basic design criteria from which other system components were specified. These
design criteria also provided necessary information that served as input for heat
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transfer calculations used to determine the thickness of the reactor's internal and
external insulation. Design of the system and the reactor are discussed in the
following two subsections.
MINIPILOT SYSTEM
A schematic diagram of the solar reactor system is shown in Figure.1.
Important points about this process design are discussed below.
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1. Dual Reactors—Some concern was expressed by NREL that the flame
associated with combustion of the liquid organic might decrease the
effectiveness of the solar input for photolytic destruction of organic
components and/or products of incomplete combustion (PICs). For that
reason, a dual-chamber system was designed, so that the solar beam
could be input to the second chamber, after combustion in the first
chamber. However, the system could also be operated in a single-
chamber mode, with combustion and solar input in the same chamber.
2. Auxiliary Fuel—The system was designed to use propane as an auxiliary
fuel to provide a continuous pilot flame (for safety reasons) and to
provide initial heatup of the reactors prior to introduction of any liquid
organic feed. It was also designed to fire fuel oil as an auxiliary fuel and
for baseline testing with a liquid feed that does not contain any chlorine
(Cl) or hazardous organic constituents.
3. Water Feed—When the liquid organic feed undergoes combustion, the
heat released by this combustion, combined with the solar thermal input,
produces excessive temperature (> 2000°F). The temperature could be
controlled by removal of external insulation from the reactor or by
different size apertures on the quartz window to regulate radiant heat
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losses through the window. However, these are physical changes to the
system that are somewhat difficult to make and do not provide
temperature "control" capability. Therefore, the system was designed to
provide water injection for temperature control.
It was suggested that H2O injection might affect photolytic destruction
reactions, but it was not known if this effect would cause an increase or
decrease in effectiveness of destruction (or no effect at all). Thus the
system was designed to be able to provide H2O injection for temperature
control, with the intent to perform tests to ascertain if it had any
significant effect on destruction of the organics. (Subsequent non-solar
tests at MRI indicated no detrimental effect from H2O injection, but the
tests could be repeated later at NREL with solar input.)
4. Compressed Air—Compressed air (- 90 psig) is supplied to the system
for atomization of liquid feeds and serves as the source of combustion
air. The use of compressed air facilitates flow monitoring and control.
Most of the compressed air (referred to as "secondary air") is introduced
tangentially into the reactor in order to swirl the gases and maximize
turbulence. "Primary air," a small fraction of the total air fed to the
reactor, enters as air premixed with pilot fuel (propane). A very small
amount of air is also used for atomization of any liquid feeds.
5. Reactor Exit Piping—Reactor exit piping was constructed of 40 ft of 2-in
stainless steel tubing. Two 2-in tees were provided near the inlet to the
final cooler for EPA-method sampling. Sections of removable insulation
were installed, as needed, to maintain the temperature at the sampling
points in the range of 250° to 400°F.
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6. Final Cooler—The final cooler was designed for removal of 30,000 Btu/h
in order to cool the exit gases to < 100°F, which is necessary for
condensation of H2O produced by combustion and any H2O injected for
temperature control. It was designed to provide the heat transfer duty
using coolant available at NREL, which has a flow limit of 8 gal/min. The
material of construction for the final cooler was type 304 stainless steel.
Although the final cooler has not failed (leaked), there is evidence of
corrosion. Replacement with a heat exchanger constructed of Hasteloy C-22
is being considered for better corrosion resistance (combustion gases contain
up to 8,000 ppm HCI).
7. Gas Cleanup—Final gas cleanup is accomplished in three 6-in Plexiglas
vessels. The first vessel is a water separator. The second vessel
contains a packed bed of AI2O3 pellets impregnated with NaOH for HCI
removal. Originally it was intended that the third vessel contain a bed of
activated carbon for adsorption of any residual hydrocarbons. This
carbon bed was replaced with the AI2O3 pellets to maximize HCI
removal, since the THC monitor indicated low THC levels during
operation (i.e., usually below 1 ppm). However, it is planned to install a
carbon canister in the effluent gas discharge line from the vacuum pump.
8. Vacuum Pump—The final vacuum pump enables operation of the
reactors below atmospheric pressure (-1 to -5 in of H2O). Pressure
drop through the system, especially the final effluent flowmeter, limits
capacity of the system to near 10 scfm. Contributing to that pressure
drop were cartridge filters that had to be installed to protect the pump
from very fine particulate matter and HCI mist.
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9. CEMs—Continuous emission monitors were installed for CO, O2, and
THC. The sampling location for these extractive-type monitors was
originally intended to be in the 2-in tubing near the inlet to the final
cooler. However, it quickly became obvious that the high HCI
concentration at that location was severely detrimental to the monitors.
Therefore, the sampling location for the CO and O2 monitors was
changed to the exit from the first bed of AI2O3 pellets. The sampling
location for the THC monitors was moved to the exit of the H2O
separator, since it was not known if the pellets might be removing some
of the hydrocarbons.
10. UV Light—A UV light was purchased and an air-cooling chamber built
that could be installed in front of the quartz window whenever needed.
This UV light is a Hanovia high intensity, medium pressure mercury arc
lamp operating at 300 W/in with a 6-in bulb. Approximately 300 W of the
lamp's total output is in the ultraviolet range (240 to 365 nm).
Tests were subsequently carried out at MRI to assess the effect of UV light
on destruction of organics. It should be noted that heat losses through the
quartz window (with or without UV light) caused significant cooling of the
gases (e.g., from 1400° to 1060°F).
REACTORS
Two identical reactors were constructed so that testing could be carried out with
only one reactor, or with the two reactors connected in series (dual chamber mode),
for the reason discussed earlier. A diagram of the reactor is given in Figure 2 and is
shown in the photographs in Figures 3 and 4.
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The reactors were constructed of 330 stainless steel for maximum temperature
capability. The stainless steel shell is insulated with a nominal 4-in thickness of
alumina-silica ceramic fiber blanket (Zircar). The internal insulation includes
approximately 3 in of the alumina-silica ceramic fiber blanket, with a solid 1/£-in-thick
alumina insulating cylinder forming the inner chamber. The alumina insulating cylinder
temperature rating is 3000°F. Dimensions of the chamber are 101/a in inside diameter
x 36 in long.
A flange assembly was designed at one end of the reactor for installation of the
13.875-in diameter x 0.50-in-thick quartz window for solar or UV input. Graphite
gaskets (Grafoil) were used to seal the quartz window, as well as all the other reactor
flanges. Design of the reactors included various size aperture openings (type 330
stainless steel with 1.0 in of insulation) inside the quartz window. These aperture
openings can be used to change the radiant heat losses through the quartz window,
thus providing some control on temperature of the exit gases.
There is a small opening in the top for installation of a "flame rod" for detection
of the propane pilot flame. A 1-in diameter pipe was also designed, aimed at the
center propane burner, for installation of a flickering infrared flame detector.
As mentioned earlier, a tangential air entry port was provided in the design.
Several other flange openings were designed into the system that are used for quartz
obseivation windows or can be used for other purposes. Also, a Vz-ln connection in
the reactor exit pipe provides access for a thermocouple to monitor and control exit
gas temperature.
Each reactor was designed to provide insertion of up to five 1-in diameter,
water-cooled nozzles, as follows:
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• Propane burner (center)
• Liquid organic nozzle
• Fuel oil nozzle
• Water nozzle
• Spare nozzle port
Only two types of water-cooled nozzles were designed and built for the
reactors. The first type consists of an internal 0.5-in tube with a flame stabilizer on the
end. Propane and air are fed to this nozzle to provide a pilot flame. The second type
of water-cooled nozzle is an MRI design that provides air atomization of the fluid
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(liquid organic, fuel oil, or water) with only a very small flow rate of atomizing air.
Originally, the 1-in outer tube of the nozzles, which contains the cooling water,
was constructed of 316 stainless steel. After several hours of operation, it was found
that the portion of the 1-in tubes inside the reactor's internal insulation was severely
corroded, apparently due to condensation of H2O and associated absorption of HCI
from the combustion gases in contact with the cool metal surface. New nozzles were
built using Hasteloy C-22 tubing to better resist this corrosion.
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SECTION 3
INITIAL OPERATION
Work proceeded on assembly of the reactor and the rest of the system, and
initial operation began on February 16, 1992, using propane and fuel oil only. These
initial tests went well, with good performance of the air atomized nozzle for the fuel oil.
Some changes were made in the system to improve operability. It was during
this period that some problems were found with the flame rod flame detection system
and the high-voltage spark igniter. The flame rod detector was found to be
temperamental. It activated the automatic flame failure shutdown, even though flame
was present. For that reason, it was later supplemented with a flickering infrared
flame detector system. The high-voltage spark igniter was also a problem, because it
required careful adjustment and also sometimes caused electrical interferences and
shutdown of the computer control system; Therefore, the electric igniter system was
eliminated. Instead, the propane is manually lighted with a small H2/air torch, which
provides a reliable ignition flame, eliminating uncertainties associated with the spark
igniter.
Part of the initial operating tests included determination of the maximum
temperature achievable when operating in the single-chamber mode. The maximum
temperature achieved in this mode at a "high-flow rate" condition (8.8 to 10.0 scfm of
air input) was 2000°F. However, after the quartz window was installed in the
chamber, this maximum was reduced to 1690°F. Likewise, the maximum temperature
with the quartz window at "low flow" (5 scfm of air input) was 1505°F. These
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maximum temperatures were produced by increasing the feed rate of auxiliary fuel
until the O2 concentration in the effluent gas was reduced to 3.0% to 4.0%, since
3.0% was considered to be a reasonable minimum operating level (shutdown occurs
at 2.0%).
Another part of the initial operating tests was directed to assessing the
accuracy of the thermocouple (T/C) located in the reactor effluent pipe. This T/C is
the primary measure of the reactor temperature and was initially based on a !4-in
diameter shielded T/C. At the suggestion of NREL, an aspirating T/C was also used
to measure the temperature, which indicated a reading 50° to 80°F higher than the
shielded T/C. Also, an exposed bead T/C (i.e., unshielded) was tested and showed
good agreement with the aspirating T/C. The exposed bead T/C was used in
subsequent testing to avoid the problems associated with the aspirating T/C system,
caused by the high HCI concentrations.
During the initial operating period, a Tri-Agency meeting was held that included
selection of the composition of the synthetic liquid organic that would be used
throughout the non-solar tests at MRI and the first phases of subsequent testing at
NREL. The composition selected by the Tri-Agency group was:
Component Wt (%)
No. 2 fuel oil 40
o-Dichlorobenzene 40
Carbon tetrachloride 10
Naphthalene 5
Toluene " 5
Total 100
MRI purchased the above components and blended them together to prepare a
single 150-gal batch of the mixture, which should be sufficient for all the tests, using
this synthetic liquid organic at MRI and at NREL. As discussed in the next section,
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this mixture was used as feed to the Minipilot System after the initial tests with
propane and fuel oil.
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SECTION 4
PRELIMINARY TESTING
Preliminary testing of the Minipilot Solar System emissions was carried out
using an on-line GC/ECD, but also included two tests using EPA methods (VOST per
SW-846 Method 0030 and MM5 per SW-846 Method 0010 with GC/MS analysis).
The on-line GC/ECD involved continuously extracting a small flow of the reactor
effluent gas (- 50 mL/min) through a heated Teflon line and through the autosampling
valve of the GC/ECD. About every 30 to 40 min the autosampling valve was activated
to inject a 1-mL gas sample into the GC system. Output from the GC/ECD was
intended to provide data on the concentration of CCI4 and dichlorobenzene (DCB) in
the reactor effluent gas, for calculation of DREs.
The original purpose of the preliminary testing with the GC/ECD was to carry
out tests over a range of temperatures for each operating mode to identify the
temperature (or other operating conditions) that provided a DRE at or near 99.99% for
one or both of the volatile POHCs. Once that was accomplished, subsequent testing
would be done at the 99.99% DRE conditions, using EPA methods, to ascertain DRE
for all POHCs and to semiquantitate the concentration of volatile and semivolatile PICs
in the reactor effluent gas. Thereafter, it was planned to conduct tests at NREL, at
those same conditions but with solar input, to assess the effect of solar input on the
DREs and PIC emissions.
A very important aspect of the non-solar tests at MRI was to evaluate the
POHC and PIC concentrations relative to the detection limits of the EPA sampling and
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analysis methods and relative to their amounts in blank samples. That is, the
sampling and analysis methods needed to be capable of quantitating a significant
decrease in POHC and/or PIC emissions that might be provided by solar input. If the
results of non-solar tests at MRI exhibited POHC/PIC concentrations at or near the
detection limits of the sampling and analysis methods, or concentrations at or near
those in sample blanks, it would not be possible, using those methods, to show any
decrease that might be provided by solar input.
Operation of the Minipilot System at a ORE near 99.99%, as opposed to higher
DREs, would be well above the detection limits of the EPA methods, thus enabling the
determination of any significant improvement in ORE with solar input. Also, it would
seem to be likely that the same would be true for PIC emissions, assuming that PIC
emissions associated with a ORE of 99.99% would be greater than those at higher
DREs. Partly for that reason, the preliminary testing with the GC/ECD was directed to
identifying the temperature, or other operating conditions, that provided ORE near
99.99%.
MRI proceeded with the preliminary testing with the GC/ECD, yielding results
that indicated relatively low emissions of CCI4 (> 99.99%) but higher levels for DCB,
near the desired DRE of 99.99. However, to confirm those results, two tests were
carried out using the EPA methods (referred to as Runs 17 and 18). Results from the
two EPA tests did not agree with the GC/ECD data. In fact, the EPA results showed
much lower levels of DCB.
Data for the EPA tests from Runs 17 and 18 are summarized in Table 1. As
can be seen in this table, the lowest DRE for DCB (Run 18) was > 99.99983% at a
concentration of < 23 |ig/dscm as determined by the EPA method using the MM5
train. In contrast, the concentration result for the GC/ECD was much higher, at near
3,000 u.g/dscm. Results for CCI4 were considerably better in comparison (i.e.,
10.9 ng/L for VOST versus 30 ng/L by GC/ECD), but showed DREs well above
99.99% (i.e., 99.99969%).
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TABLE 1. EPA TEST METHOD RESULTS FOR RUNS 17 AND 18
CCI4
Toluene
D ichlorobenzene
Naphthalene
Run 17 (low flow)
Single chamber with quartz
window
Low gas flow rate (3.6 scfm)
Low waste feed rate (4.7
g/min)
Chamber exit temperature =
1321°-1365°F
Cone.
ORE
6.4 ng/L
24 ng/L
99.99986
99.9989
< 5.5 u.g/dscm > 99.999970
< 5.5 jj.g/dscm > 99.99976
Cone.
Total volatile PICs 283 ng/L
Total SV-PICs 1,181 u.g/dscm
Run 18 (high flow)
Single chamber with quartz
window
High gas flow rate (8.3 scfm)
High waste feed rate (14
g/min)
Chamber exit temperature =
1612°-1616°F
Cone.
10.9 ng/L
7.6 ng/L
153 ng/L
6,886 ng/dscm
DRE
99.99969
99.99957
< 23 ng/dscm > 99.99983
< 23 ug/dscm > 99.9987
Cone.
19
-------
The large difference in results for DCB (i.e., 23 u.g/dscm for the EPA method
versus 3000 (ig/dscm by GC/ECD) was of great concern and required considerable
investigation. This investigation led to the conclusion that the GC/ECD results for
DCB were incorrect and, further, that valid results for DCB could not be provided by
the on-line GC/ECD sampling and analysis system (even with the replacement
GC/ECD instrument that was found to be necessary). As a consequence, all
subsequent preliminary testing with the replacement GC/ECD relied on CCI4 results
rather than DCB results, since these were in much better agreement (i.e., 10.9 ng/L
for VOST versus 30 ng/L by GC/ECD).
Additional preliminary tests were carried out at different temperatures in an
attempt to identify operating conditions that provided DRE near 99.99% for CCI4.
Temperatures were varied over a range of 1330° to 1900°F, but all indicated DREs
were above 99.999% (near the detection limit of the GC/ECD).
Further tests were carried out at other conditions in an attempt to "degrade"
performance of the Minipilot System to DRE near 99.99%, including the following:
1. Lower atomization air pressure
2. Atomization using N2 instead of air
3. Non-tangential entry of secondary air
4. Change in composition of liquid organic feed
5. H2O injection
1. Lowering of the atomization air pressure, at a temperature near 1300°F,
did decrease DRE (to 99.9927%), but it also resulted in carbon particles
(soot) that caused plugging of the sampling system and concern for
downstream equipment, especially the effluent pump. It also caused CO
levels of near 300 ppm, which is not a realistic operating condition.
Surprisingly, this did not seem to affect THC levels.
20
-------
2. Atomization of the liquid organic feed using N2 instead of air at
temperatures near 1400°F had no significant effect on ORE for CCI4.
Again, lowering the atomization pressure resulted in soot formation.
3. Testing of the Minipilot System was normally carried out using the
tangential entry of secondary air. Tangential air entry was designed into
the system to maximize turbulence, since the Reynolds Number (NRe)
calculated for this system was low (230). In an effort to decrease ORE
by reducing turbulence, the tangential air entry was changed to introduce
combustion air through one of the spare nozzle connections (i.e.,
horizontal air entry). Results indicated that ORE for CCI4 was still near
99.999%.
4. NREL suggested that a preliminary test be conducted using a different
composition of liquid organic feed having higher concentrations of two
POHCs. At this suggestion, MRI prepared a special feed mixture
containing 80% DCB and 20% CCl4.
Even though this special feed mixture had a heating value of only about
7,000 Btu/lb, compared to the normal feed of near 12,000 Btu/ib, it
appeared to burn well. Test results did not indicate any significant
increase in CCI4 emissions (i.e., decrease in ORE) for this special waste
feed.
5. As discussed previously, the Minipilot System was designed with H2O
injection capability for temperature control during solar operation. This
raised some concern that H2O injection might affect ORE. In order to
address that concern, at least in part, one of the preliminary tests
included water injection to assess its effect on ORE (in the non-solar
mode).
21
-------
During one preliminary test when the temperature of the reactor effluent
was at 1897°F, water was injected to lower the temperature to 1504°F.
GC/ECD results for CCI4 clearly showed that the H2O injection did not
decrease the ORE. It may have actually increased the ORE from
99.9995% to 99.9999%, but this is somewhat uncertain considering the
low concentration level (i.e., 16 ng/L versus 4 ng/L).
None of the above changes in operating conditions identified any practical
means of achieving ORE near the desired level of 99.99%. It was therefore decided
to suspend preliminary testing and proceed with tests using the EPA methods,
carrying out all tests at the relatively low temperature of 1400°F to produce the lowest
achievable ORE (but likely not as low as 99.99%).
22
-------
SECTION 5
EPA METHOD TEST RESULTS
The primary purpose of conducting non-solar tests on the Minipilot System,
using EPA sampling and analysis methods, was to determine if the POHC and PIC
emission levels were sufficiently above the detection limits of the methods, and
sufficiently above blank levels, to enable determination of significantly lower levels in
subsequent testing with solar input. This purpose became even more critical in view
of the fact that the non-solar tests would necessarily have to be done at DREs above
99.99%. '
Non-solar testing consisted of 10 runs conducted over the period of May 29 to
June 16, 1992. Each run covered 2 h of sampling by VOST and MM5 per EPA
Methods 0030 and 0010 in SW-846. The only exception to the methods was that the
MM5 was limited to single-point sampling due to the small 2-in diameter sampling
location (near the inlet to the final gas cooler). All analysis was by GC/MS. Full scan
analysis was used for quantitation of POHCs and PICs in the samples. MM5 extracts
were also analyzed by SIM in order to provide lower detection limits for the two SV-
POHCs. Dioxin/furan analysis was also done on some MM5 samples. Samples of
each batch of liquid organic feed used in the tests were taken to confirm the expected
POHC concentrations and were also analyzed for HHV and Cl content.
The following subsection summarizes the operating conditions during each of
the 10 runs. Then, the next subsection summarizes the analysis results for the
10 runs, based on the more detailed analysis results contained in Appendices A
23
-------
through F, along with the summary of quality assurance results contained in
Appendix G.
TEST CONDITIONS
The series of 10 tests involved operation in both single-chamber and dual
chamber modes at two different waste feed and secondary airflow rates (referred to as
"low flow" and "high flow"). Some tests were done with UV light, and some tests
included analysis for dioxins/furans (D/F).
Ail tests were done at essentially the same temperature of 1400°F. For the
dual-chamber tests, the preliminary testing had shown that the gas temperature fell
about 300°F in the second chamber, even if preheated. Although later solar tests
would be done without any flame in the second chamber, it was assumed that it would
be best to carry them out at the same temperature as the first chamber, without the
300°F temperature drop (i.e., 1400°F). Therefore, except for the last test (Run 40),
the dual-chamber tests at MRI were conducted while firing propane in the second
chamber to maintain the gas at 1400°F. However, the last dual chamber test was
done without firing propane, allowing the 300°F temperature decrease across the
second chamber.
The basic conditions for the 10 tests, in the order in which they were done, are
shown in Table 2. Notations indicate duplicate runs and those runs that were selected
to include analysis of MM5 samples for D/F. A summary of the process operating
conditions monitored during each run is provided in Table 3.
24
-------
TABLE 2. SUMMARY OF EPA TESTS
Run No. Conditions
Notations
: : Single chamber tesis
31
32
33
34
35
36
37
38
39
40
Low flow3
High flow3
High flow
Low flow
High flow
with UV light
Duplicate of Run 34
Duplicate of Run 33
Duplicate of Run 32,
D/Fb
Duplicate of Run 31,
D/Fb
Low flow with UV light
(Firing propane
High flow
Low flow
High flow
High flow
Dual chamber tests
in second chamber, except Run 40)
with UV light
with UV light
D/Fb
D/Fb
D/Fb
a Based on waste feed and secondary airflow rates.
b D/F indicates runs which also included analysis for dioxins and furans.
25
-------
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Residence time was calculated for each run based on the temperature of the
gas at the exit of each chamber, air feed rate, and liquid organic feed rate, as well as
other fixed input rates. These calculated residence times are as follows:
Residence Time (seconds)
:'•'•' .-'.-; '•• ';'v:%:, - Single chimiberfriode ': •••;.•• ::/:. ' :" %>:
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7.1
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Run 34 Run 36
7.0 6.8
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Run 32
4.0
Run 33
4.2
Run 35
4.0
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(total residence time for both chambers}
Low flow
Run
38
13.3
High flow
Run 37 Run 39
7.8 7.8
Run 40
8.9
Some important items to note about the operating conditions shown in Table 3
are as follows:
1. All runs were carried out at essentially the same temperature of 1400°F.
Thus the heat loss is relatively constant for each mode (except in tests
with UV light where there was increased heat loss through the quartz
window). As a consequence, the low-flow conditions required a
somewhat higher ratio of heat input to combustion air feed than the ratio
at the high-flow conditions, in order to maintain the same temperature.
Therefore, the O2 levels were lower at the low-flow condition than the
high-flow condition for each operating mode.
2. Heat loss was, of course, greater in the dual-chamber mode, and
propane was fired in the second chamber to maintain the 1400°F
operating temperature. As a consequence of this, the O2 levels were
27
-------
lower in the dual-chamber mode than the single-chamber mode at each
of the two flow conditions. Thus the lowest average O2 level of 4.2%
was associated with the dual-chamber, low-flow test (Run 38) (excluding
tests with the UV light).
3. In the single-chamber tests with UV light, the higher heat loss (through
the quartz window) was compensated for by firing of fuel oil (in a
separate nozzle) to maintain the 1400°F temperature. This reduced the
O2 content of the effluent gas for each flow condition.
Because of the above, the lowest average O2 level (3.2%) occurred in
the low-flow, single-chamber test with UV light (Run 36). Since this was
considered the minimum allowable O2 level, it was not possible to
conduct any low-flow, dual-chamber tests with UV light, at the 1400°F
-temperature.
4. As noted above, fuel oil was fired in the single-chamber tests with UV
light in order to maintain the 1400°F temperature. However, no fuel oil
was fired in the dual-chamber tests. Instead, propane was fired in the
second chamber to maintain the temperature at 1400°F.
5. Average THC levels were low in all tests, near 1 ppm. CO levels were
also low (0 to 3 ppm) in most tests, with the exception of the two high-
flow tests in the single-chamber mode (Runs 32 and 33), which averaged
37 ppm and 11 ppm, respectively. These higher CO levels did not occur
in the high-flow, single-chamber test with UV light (Run 35), which
included firing of fuel oil with reduced O2 level.
28
-------
EPA METHOD TEST RESULTS
A summary of all the analysis results for the 10 EPA method tests is presented
in Table 4. This table contains a large amount of data, since it includes the following:
V-POHCs (CCI4 and toluene)
V-PICs
• SV-POHCs (dichlorobenzene and naphthalene)
SV-PICs
D/F
• All the above for blank samples
As expected, the DREs were above 99.999% for all four POHCs in all runs.
Several interesting conclusions can be drawn from the data and are discussed in this
report. However, as noted previously, the primary purpose of these non-solar tests
was to determine if the amounts of POHCs and/or PICs were sufficiently above the
detection limits, and above the blank levels, to allow determination of significantly
lower amounts in later tests with solar input. This is the first item discussed below in
terms of each of the POHCs and V- and SV-PICs.
29
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Ability to Determine Significantly Lower PQHC/PIC Emissions
The test data were evaluated in terms of the ability to determine lower levels of
POHCs and PICs in later solar tests, based on the results given in Table 5. In this
evaluation, the test data for runs that included UV light were not considered, since
they were intended for other purposes as will be discussed later. Also, the evaluation
is based on the amounts in samples, rather than concentration, because it is the
amount in the samples that is critical.
Ability to determine lower levels may be limited by detection limits of the
methods or by levels present in blank samples. It was concluded from these tests that
the main factor was the levels present in blank samples. Also, the results show that
the lowest sample value always occurred in the low flow tests for all POHCs, PICs,
and D/F (but the lowest sample value was not always associated with either the
single-chamber mode or dual-chamber mode). Conversely, the highest sample value
did not always occur in the high-flow tests. The fact that the lowest sample value
always occurred in the low-flow tests means that a larger decrease in sample amounts
could be determined for high flow rate conditions than for low flow rate conditions.
Bearing this in mind, the minimum decrease in amount that would be possible to
determine was calculated for each POHC and total V/SV-PICs for both the low-flow
and high-flow conditions. The equation used for this calculation was:
Minimum possible decrease (MPD) _ Lowest sample amount
that could be determined Highest blank amount
If the lowest sample amount found in the non-solar tests were the same as the
highest blank amount (i.e., MPD = 1), there would be considerable uncertainty that
any solar test sample amounts would be found below the blank amount. Conversely,
if the lowest sample amount found in the non-solar tests were much larger than the
blank amount (e.g., MPD = 10), it would indicate that a significant decrease in sample
amount could be determined in solar tests, and still be well above the blank amount.
. 31
-------
TABLE 5. COMPARISON OF BLANKS WITH SAMPLE RESULTS
Item
CCI4
Toluene
V-PICs
DCB
Naphthalene
SV-PICs
Dioxins
Furans
Highest blank
6.5 ng
7.7 ng
85 ng
0.06 ng
4.32 ng
225 ng
0.000618 fig
0.0000776 ng
Sample results (excluding UV tests)
Mode
Single chamber
Dual chamber
Single chamber
Dual chamber
Single chamber
Dual chamber
Single chamber
Dual chamber
Single chamber
Dual chamber
Single chamber
Dual chamber
Single chamber
Dual chamber
Single chamber
Dual chamber
Low flow
21 .9 & 37.2 ng
13.6 ng
5.6 &61.2 ng
15.1 ng
4,685 & 6,862 ng
779 ng
0.22 & 0.36 ng
0.21 ng
3.70 & 7.72 ng
5.55 ng
1 ,560 & 3,248 ng
2,148 ng
O.O0161 ng
0.00871 ng
High flow
46.9 & 124.9 ng
40.9 ng
23.5&41.6ng
22.0 ng
4,824 & 5,827 ng
895 ng
0.68 & 0.86 ng
0.45 ng
7.72 & 8.00 ng
9.09 ng
2,01 4 & 4,01 8 ng
3,579 ng
0.00316 ng
0.00655 ng
0.021 92 ng
0.04470 ng
32
-------
Results of calculations using the MPD equation and the data in Table 5, are as
follows:
CCI4
Toluene
V-PICs
DCB
Naphthalene
SV-PICs
Dioxins
Furans
Minimum possible decrease that could be determined
Low flow
13.6/6.5 = 2.1
5.6/7.7 = 0.7
779/85 = 9.1
0.21/0.06 = 3.5
3.70/4.32 = 0.8
1,560/225 = 6.9
0.00161/0.000618 = 2.6
0.00871/0.0000776 = 112
High flow
40.9/6.5 = 6.3
22.0/7.7 = 2.8
895/85 = 10.5
0.45/0.06 = 7.5
7.72/4.32 = 1.8
2,014/225 = 8.9
0.00316/0.000618 = 5.1
0.02192/0.0000776 = 282
In simplest terms, the above results mean that it would be possible to
determine CCI4 emission levels that are a factor of 2.1 less than the levels found in
the low-flow, non-solar tests at MRI, or a factor of 6.3 less than the levels found in the
high-flow tests. These minimum possible decreases are somewhat conservative,
because they are based on the highest blank value and the lowest sample value found
in single- or dual-chamber modes. The main conclusion from this information is that
a significant decrease (> 3 times) is determinable for both V- and SV-PICs.
A significant decrease (> 3 times) is also determinable for two of the POHCs
(CCI4 and DCB) at the high-flow condition and for DCB at the low-flow condition. On
the other hand, the results indicate that it will not be possible to determine a decrease
for toluene or naphthalene at the low-flow condition, and only a limited decrease at the
high-flow condition.
33
-------
Like CCI4, a significant decrease can be determined for dioxin at the high-flow
condition, but not the low-flow condition. A large decrease can be determined for
furans at both low- and high-flow conditions.
As indicated previously, the decrease that could be determined is always
greater for the high-flow condition. This suggests that future solar tests might best be
carried out at the high-flow condition. However, the effect of solar input may be a
function of residence time (i.e., time the gas is exposed to solar input) so at least
some testing at the low-flow condition may be warranted, or could be done optionally,
dependent on results from high-flow tests. Hopefully, the scoping tests (i.e., Phase I
tests at NREL) will provide preliminary data that can be used to determine if there is
no need to conduct subsequent EPA-method testing at the low-flow condition.
34
-------
Replication of Results
Duplicate tests were carried out in the single-chamber mode at the low-flow
condition (Runs 31 and 34) and high-flow condition (Runs 32 and 33). Results for
these two pair of replicate runs and blanks are shown in Table 6 in concentration units
(as calculated from data in Table 4).
Results in Table 6 show that the duplicates generally agree within a factor of
about 2 or less for the duplicate runs at low-flow and high-flow conditions. Agreement
within a factor of 2 or less was considered to be reasonably good agreement
considering the variability of the test conditions and the sampling/analysis methods.
The only exception is toluene, which was different by a factor of 10 for the low-flow
condition (0.31 ng/L versus 3.26 ng/L). However, the low value for toluene of
0.31 ng/L in Run 31 is very close to the detection limit of 0.2 ng/L
TABLE 6. COMPARISON OF REPLICATE RUNS (SINGLE-CHAMBER MODE)
CC!4 (ng/L)
Toluene (ng/L)
V-PICs (ng/L)
Dichlorobenzene (u.g/dscm)
Naphthalene (ng/dscm)
SV-PICs (ng/dscm)
a Concentrations shown for
and 0.699 dscm for MM5.
Blank3
< 0.2
< 0.2
4.5
0.086
6.18
320
blanks are
Run
1
0
258
0
Low flow
31 Run 34
21 1.98
31 3.26
365
36 0.59
6.00 12.6
2,530
based
5,310
High
Run 32
5.98
1.13
231
1.15
10.7
5,350
on average sample volumes; 19.1 L
flow
Run 33
2.50
2.22
311
0.83
9.47
2,470
for VOST
35
-------
Comparison of Emissions for Different Operating Modes and Flow Conditions
Results for the low-flow and high-flow conditions, in both single- and
dual-chamber modes, are shown in Table 7, excluding tests with UV light.
Comparison of these results is discussed below, bearing in mind that duplicates
generally agreed only within a factor of 2 (per the previous paragraphs).
In the non-UV tests in the dual-chamber mode, the POHCs and PICs are
always higher for the high-flow condition than for the low-flow conditions, but are within
a factor of 2, except for CCI4. In the single-chamber mode, the only emissions that
were consistently higher for the high-flow condition than for the low-flow condition were
CCI4 and DCB.
Dioxins and furans are also higher in the high-flow condition than in the low-flow
condition (single chamber), but not by more than a factor of 2. Interestingly, the
highest concentration of dioxins and furans was found in the dual-chamber, high-flow
condition (Run 37).
The parameter most affected by different chamber modes and flow rates is
residence time. High-flow, single-chamber provides the shortest residence time, and
low-flow, dual-chamber provides the longest residence time. The two intermediate
conditions of low-flow, single-chamber and high-flow, dual-chamber provide approxi-
mately the same residence time. It would be expected that the emissions would
decrease with increasing residence, time (since the operating temperatures were
comparable). Results shown in Table 7 indicate that CC14 and DCB follow this
residence time pattern, but that toluene, naphthalene, and PICs do not follow the
pattern.
36
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It is also interesting to note that the dual-chamber mode tests have significantly
lower concentrations of V-PICs at both flow conditions than did any of the single-
chamber mode tests. But, as noted previously, the dual-chamber mode test had the
highest concentration of dioxins and furans.
These comparisons of results for the two operating modes and two flow
conditions tend to support the previous suggestion that future testing be directed
primarily to the high-flow (lower residence time) condition. They also suggest that
future solar testing with EPA methods might possibly be directed primarily to the
single-chamber mode, but this must be contingent on first determining if dual-chamber
operation is necessary for solar effectiveness (i.e., flame in the single chamber may
interfere with solar photolytic affects).
38
-------
Effect of Artificial UV Light
The series of 10 runs done using the EPA sampling and analysis methods
included four runs with the quartz window in the reactor and an artificial UV light. This
ultraviolet lamp with a parabolic reflector was positioned just outside the quartz
window to direct the UV into the chamber (or into the second chamber for the dual-
chamber mode). The purpose of these tests was to determine if the artificial UV had
any significant effect on the POHC and/or PIC levels, compared to the levels in the
thermal destruction tests done without UV light.
When the quartz window was in place for the UV light tests, the heat losses
from the chamber were considerably higher. To maintain the 1400°F temperature, fuel
oil was fired as an auxiliary fuel in one of the burner guns when operating in the
single-chamber mode with quartz window and UV light (i.e., Runs 36 and 35). When
the two UV light tests were conducted in the dual-chamber mode (Runs 39 and 40),
propane was fired in the second chamber during Run 39 to maintain the 1400°F
temperature. No propane was fired in the second chamber in Run 40, which allowed
the temperature to decrease in the second chamber to 1064°F (even though it had
been preheated to 1400°F). Since the two UV light tests in the single-chamber mode
involved firing fuel oil and the one dual-chamber test with UV light involved firing extra
propane in the second chamber, more oxygen was consumed in these three tests, so
the O2 levels were lower than in the corresponding tests done without UV light.
Results for all the tests, including UV tests, are summarized in Table 4. As
shown in that table, two UV tests were done in the single-chamber mode, with one at
low flow (Run 36) and one at high flow (Run 35). Two UV tests were also done in
dual-chamber mode (Runs 39 and 40), but both were done at high flow, and Run 40
was done without firing of propane in the second chamber. The results for these tests
are discussed below.
39
-------
The V-PICs decrease in the single-chamber UV tests by a factor of at least 3.4
in the low-flow test and a factor of at least 2.6 in the high-flow test. No decrease in
V-PICs is evident for the dual-chamber UV tests, but V-PICs are significantly lower in
all the dual-chamber tests than in the single-chamber tests. The data do not show
any significant decrease in emissions of SV-PICs or POHCs for UV light tests.
As noted previously, the UV light tests involved higher heat losses (through the
quartz window) requiring use of additional fuel oil or propane to maintain the desired
temperatures, which reduced the O2 levels. It has been suggested that the lower O2
levels would increase flame temperatures, even though the final gas temperature
remained the same, which may account for the decrease in V-PIC during the single-
chamber UV tests. However, the fact that the SV-PICs did not decrease makes this
suggestion seem an unlikely explanation of the decrease in V-PIC emissions.
UV light did not generally increase POHC emissions in the single-chamber
tests. CCI4 emissions do, however, increase by a factor of 3 in the high-flow, dual-
chamber tests (Run 39 versus Run 37), and there also is some increase in D/F
emissions.
The UV light test done in the dual-chamber mode, without firing of propane in
the second chamber (Run 40), indicates an increase in emissions for SV-PICs and for
two of the four POHCs—CCI4 and DCB. These increases possibly reflect the effect of
a lower temperature in the second chamber (1064°F) rather than an effect of UV light.
However, it is difficult to explain why the emissions in this dual-chamber test would be
higher than those in single-chamber tests. That is, in Run 40, the first chamber is
operating at conditions similar to those in two of the single-chamber tests (Runs 32
and 33). Reformation of the two POHCs and SV-PICs in the second chamber seems
unlikely, but the effect of the residence time in the second chamber (4.9 s) at the
intermediate temperature (1400° to 1064°F), along with UV light, is unknown.
40
-------
Characteristics of V-PIC and SV-PIC Emissions
The previous sections discuss the total amount of V-PICs and SV-PICs that
represent the sum of several different compounds found in the analysis (e.g., the
10 largest components). These compounds could only be semiquantitated, assuming
a relative response factor (RRF) of 1.0. In several cases the compound could not be
specifically identified. The following two subsections provide some additional
information about the PIC analysis results. More details are contained in Appendix C.
V-PICs—Data presented in Table 4 show that the concentration of V-PICs was
lower than the concentration of SV-PICs by at least a factor of 10, in all runs. A
tabulation of the V-PIC data, given in Table 8, shows considerable diversity in the
V-PICs from run to run. That is, except for benzene, the V-PICs found in samples
from one run are generally not the same as those found in other runs, even for
duplicate runs (e.g., Runs 31 and 34). The reason for this lack of consistency in the
V-PICs is unknown, but it might reflect a variety of components present at low
concentrations.
The volatile PIC data do not include very many chlorinated compounds, which
is somewhat surprising considering the high Cl content of the liquid feed. Likewise,
the SV-PICs do not include any chlorinated compounds (see Table 9).
It should be noted that the V-PIC data presented in Table 8 do not include
several silane-containing constituents that were found in all runs in relatively large
amounts (see Appendix C). These silane-containing PICs were not included in the
summation of V-PICs, because they are believed to have been produced from the
reactor's internal insulation. Thus it did not seem appropriate to include them as
"products of incomplete corfibustion."
41
-------
TABLE 8. AMOUNT OF VOLATILE PICs FOUND IN A VOST TRAP PAIR SAMPLE (ng)
Compound
Unknown
Sulfur dioxide
Unknown
Carbon disulfide
Unknown
Dichlonomethane
C6H12 Hydrocarbon
C6H12 Hydrocarbon
Unknown
C6H10-C7H12 Hydrocarbon
Butanal
Jnknown
2-Butanone
Trichloromethane + unknown
Tetrahydrofuran and chloroform
C6H100
Unknown
C6H12 Hydrocarbon
Benzene
C8H18 Hydrocarbon
Cy-Cg Hydrocarbon
2-Propylfuran
C6H12O (Unknown)
Octene (C8H16)
Octane
Unttnown
C6H120 Aldehyde
Unlcnown
Unknown
1,1,1 -Trichloro-2-propanone
C8H140 (Furan)
Chlorohydrocarbon (chloroalkane)
CyH^O Aldehyde
Hydrocarbon (Cg-C13)
Hydrocarbon (Cg-C13)
Benzaldehyde
Unknown
C12H26 Hydrocarbon
CyH^O-CjjH^O Ketone
C8H12O-C8H16O Aldehyde
C10-C13 Hydrocarbon
Octanal
CgH2O Hydrocarbon
Scan
No.
29
29
31
35
36
38
38
45
48
51
55
55
59
63
63
63
64
71
76
81
82
110
134
166
171
172
199
200
218
224
224
225
266
279
286
307
313
314
318
318
321
322
331
Run No.
Blk
35
50
31
32
3
1,670
19
138
327
1,020
155
42
320
454
463
32
62
21
208
423
726
423
178
201
281
1,550
13
33
359
368
444
1,081
1,010
453
788
93
437
11
409
374
34
74
135
570
1,660
16
563
1,170
20
869
375
346
417
647
35
364
136
165
13
203
315
42
188
376
11
36
35
22
274
50
22
213
176
157
113
166
148
37
13
25
17
91
25
570
141
38
44
141
68
53
41
63
201
78
24
41
25
39
19
14
42
13
213
202
34
15
339
i
109
40
19
19
36
149
19
32
404
18
191
42
-------
Table 8 (continued)
Compound
Dichlorobenzene
Unknown
^10^22"<-'12^24 Hydrocarbon
(alkene)
Unknown
C10H22-C13H28 Hydrocarbon
Unknown
Phenyl alkyl ketone
C9-C15 Aldehyde
Unknown
ClO^cP'Cu^sO
C12-C1S Hydrocarbon
Total Amount
Scan
No.
335
336
341
342
351
351
364
372
389
414
426
Run No.
Blk
85
31
42
4,685
32
268
216
13
223
18
4,824
33
5,827
34
6,862
35
10
1,823
36
1,376
37
13
895
38
"
779
39
48
31
1,079
40
99
32
51
1,069
Note: See Appendix D for data on chlorinated dibenzo dioxins and furans.
43
-------
TABLE 9. AMOUNT OF SEMIVOLATILE PICs FOUND IN THE MM5 SAMPLES (ng)
Compound
Alcohol
C6H100
Alcohol
C6H140
c6Hio°
C6H100
C6H12°2
C8H10 (subst. benzene)
Unknown
C6H100
Unknown ketone
p^jQ
[Unknown
C7H1002
C9H10°
[Benzole acid
| Unknown acid ester
J1 ,3-lsobenzylfurandione
kHioPa
C10H1002
(Unknown
Ci5H3o02
Phthalate, subst.
Unknown acid ester
Unknown acid ester
Unknown
C19H2602
C19H3802
Bis(2-ethylhexyl)
jphthalate
IJTotal Amount
Scan
16
112
122
142
181
202
250
290
301
321
342
396
492
567
640
655
704
791
808
948
955
1099
1209
1223
1235
1268
1347
1359
1610
Run No.
Blk
150
33
42
22
31
308
20
190
18
796
94
16
68
20
30
1,56
32
72
360
960
600
140
128
240
1,120
190
108
100
4,01
33
340
190
440
44
800
78
70
52
2,01
34
380
580
1,200
58
800
86
88
56
3,248
35
360
900
1,380
30
780
72
30
69
33
60
3,714
36
300
189
480
630
75
72
99
246
105
54
84
2,334
37
390
930
660
1,170
84
99
132
45
69
3,579
38
285
249
720
27
540
60
36
27
90
24
36
54
2,148
39
330
330
630
21
780
66
30
36
60
48
2,33
40
1,710
111
165
9,300
660
600
168
1,410
96
51
14,271
Deleted C7H8 (toluene) since it was present in XAD/filter blanks and may be a contaminant in XAD or extractant solvent
(also is a volatile POHC).
Deleted C13H28 (tridecane) and C9H20 (nonane) because these were due to the D/F spiking and were present only in the
(samples analyzed for D/F.
(Note: See Appendix D for data on chlorinated dibenzo dioxins and furans.
44
-------
SV-PICs—Results show that the concentrations of SV-PICs were much higher
than those of the V-PICs. Unlike the V-PICs, the SV-PICs were fewer in number, and
those representing the larger amounts were usually present in all runs. As can be
seen in Table 9, the predominant SV-PICs (in terms of frequency of occurrence and
concentrations) consisted of:
• Alcohol (Scan 122)
C6H10O (Scan 181)
C6H12O2 (Scan 250)
• Benzoic acid (Scan 655)
As noted previously, the total SV-PICs were much higher in Run 40 than in any
other runs. This run contained amounts of additional PICs that were not present in
other runs, including large amounts of C6H10O at Scans 112 and 202.
45
-------
SECTION 6
CONCLUSIONS AND RECOMMENDATIONS
Evaluation of the data from the non-solar tests at MRI leads to the following
conclusions and recommendations.
s
CONCLUSIONS
1. DREs for the four POHCs were all above 99.999%. Naphthalene exhibited the
lowest DRE, ranging from 99.99926% to 99.99966%. The highest DREs were
exhibited by DCB, with all being above 99.99999%. No practical method of
operating the system at reduced DRE, near 99.99%, was possible, at least
within the system's present capabilities and design. Changes could be made in
the system that might provide lower DREs, such as reducing reactor internal
volume or increasing gas flow rates to shorten residence time, but were beyond
the scope of the present project.
2. Preliminary testing did not indicate any detrimental effects of water injection on
DRE. If water injection had decreased the DRE from 99.9995% to 99.9985%
(i.e., increased the CCI4 emissions by a factor of 3), this would have been
clearly discernible.
3. The lowest level of POHCs, PICs, and D/F in the emissions always occurred in
the low-flow rate runs. However, the lowest levels were not always associated
46
-------
with one test mode (single- or dual-chamber). Conversely, the highest level did
not always occur in high-flow rate tests.
4. When on-sun or solar tests are subsequently done using the Minipilot System,
a significant decrease in emissions should be quantifiable for V- and SV-PICs,
ranging from a factor of 6.7 to 6.9 for low-flow rates to 8.9 to 10.5 for high-flow
rates. Also, a significant decrease in emissions should be quantifiable for two
of the POHCs (CCI4 and DCB) at the high-flow rate condition (by a factor of 6.3
and 7.5, respectively). A lesser decrease could be determined for these two
POHCs at the low-flow rate condition (by a factor of 2.1 and 3.5, respectively).
It would not be possible to determine any decrease for the other two POHCs
(toluene and naphthalene) at the low-flow condition, and only a limited decrease
at the high-flow condition (i.e., by a factor of 2.8 and 1.8, respectively). Lastly,
a significant decrease in emissions can be determined for dioxin at the high-
flow condition (by a factor of 5.1). Only a limited decrease (a factor of 2.6) can
be determined at the low-flow condition. A large decrease in emissions can be
determined for furans, at either low- or high-flow conditions.
5. Results from two pairs of duplicate tests showed that they generally agreed
within a factor of 2. The only exception was for toluene in one pair of tests, but
it was near the detection limit in one run.
6. Evaluation of data relative to possible effects on emissions of flow rate and
operating modes did not, in general, indicate any dramatic differences,
considering that replicate runs generally agreed only within a factor of 2. The
only exception to this was V-PICs, which were significantly higher in the single-
chamber tests than in the dual-chamber tests.
7. Tests with artificial UV light indicated a significant decrease for V-PIC emissions
in the single-chamber mode (by a factor of at least 3.4 in the low-.flow test and
47
-------
at least 2.6 in the high-flow test) but no significant decrease for SV-PICs or for
the four POHCs. Excluding Run 40, the UV light tests did not indicate any
significant increase in emissions, except that CCI4 appeared to increase in the
dual-chamber test along with some increase in D/F.
One UV light test (Run 40) was done in the dual-chamber mode without firing
any propane in the second chamber, allowing the temperature in the second
chamber to decrease (to 1064°F). Results from this test showed a significant
increase in emissions of two of the four POHCs and SV-PICs. Even though
this test involved a lower temperature in the second chamber, it is difficult to
understand why these emissions would be higher than those in the correspond-
ing high-flow, single-chamber mode tests without UV light (Runs 32 and 33).
That is, in Run 40 the effluent from the first chamber would be expected to be
essentially the same as in a single chamber test done at the same high flow
rate (Runs 32 and 33). That effluent from the first chamber in Run 40 would
then pass through the second chamber. Thus the emissions from the second
chamber in Run 40 should not be significantly higher than those from the first
chamber (Runs 32 and 33), regardless of the temperature or UV light in the
second chamber.
RECOMMENDATIONS
1. Considering the previous discussion of the data and the conclusions, it is
recommended that work proceed on testing at NREL with solar input. The
testing at NREL should be done at the same temperature and flow rates of
secondary air and liquid organic as the non-solar tests at MRI. Use of these
same conditions and the same EPA sampling and analysis methods is neces-
sary for quantitatively determining the decrease in emissions that should be
provided by solar input (as EPA's and NREL's earlier bench-scale research
would indicate).
48
-------
2. The results of the tests at MR! showed that a greater decrease in emissions
can be determined for the high-flow rate condition than for the low-flow rate
condition. It is, therefore, recommended that EPA-method tests at NREL be
directed primarily to tests at the high-flow condition. However, this recommen-
dation should be implemented only if preliminary solar testing (e.g., Phase I
.scoping tests) indicates that the longer residence time provided by the low-flow
condition is not necessary to produce a significant effect on emissions.
Decreases in emissions will likely depend on the length of time the gases are
exposed to solar input, but may not show any effect on emissions within the
range of residence times associated with the two flow conditions. In fact, those
times may be much longer than what is needed. Such a result would indicate
the need for further testing at considerably higher flow rates to determine the
optimum residence time, so that the size of the solar reactor for larger systems
could be minimized.
3. The evaluation of the data, as previously discussed, suggests that future testing
could be limited to single-chamber mode (as well as limiting them to the high-
flow condition). It is, therefore, recommended that single-chamber mode be
implemented, if preliminary solar testing (e.g., Phase I scoping tests) indicates
that the presence of flame (in the single chamber) does not adversely impact
the effect of solar input on the emissions.
4. Further testing with the artificial UV light at different conditions (i.e.,
temperature, exposure time, lamp configuration, etc.) may be warranted, to
determine if reduction in SV-PICs (or POHCs) can be achieved along with the
indicated reduction in V-PICs that occurred in the single chamber tests.
49
-------
SECTION 7
REFERENCES
1. Conceptual Designs of Solar Systems for Solid Waste Destruction. Draft Final
Report prepared for U.S. Environmental Protection Agency by Midwest
Research Institute. September 28, 1990.
2. Feasibility Study for Bench-scale Testing of Desorption of Organics from Soil
with Destruction in a Solar Furnace. Draft Final Report prepared for U.S.
Environmental Protection Agency by Midwest Research Institute.
September 24, 1991.
3. Graham, John L, et al. "The High Temperature Thermal/Photolytic Oxidation of
Monochlorobenzene." University of Dayton Research Institute. Paper
submitted for publication in the Journal of Photochemistry and Photobiology,
1992.
4. Quality Assurance Project Plan for Testing of the Minipilot-Scale Solar Reactor.
Prepared for U.S. Environmental Protection Agency by Midwest Research
Institute. March 20, 1992.
50
-------
APPENDIX A
POHC INPUTS AND VOST RESULTS WITH
CALCULATION OF DREs FOR CCI4 AND TOLUENE
51
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TABLE A-2. ADJUSTED VOST VOLUMES
Run
31
31
31
32
32
32
33
33
33
34
34
34
35
35
35
36
36
36
37
37
37
38
38
38
39
39
39
40
40
40
Trap
pair
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
Volume
sampled
(L)
18.93
20.84
19.74
21 .72
20.19
22.31
19.82
20.95
20.08
20.04
20.00
20.09
20.14
19.96
20.05
19.86
20.06
19.89
19.99
20.02
19.99
19.94
19.94
19.88
19.85
20.03
20.00
19.93
20.09
19.98
Meter
temp.
(F)
74
73
74
72
71
71
72
73
73
74
74
74
72
72
71
73
73
74
61
59
57
63
61
63
59
59
60
52
51
51
BP
("Hg)
29.60
29.60
29.60
29.60
29.60
29.60
29.16
29.16
29.16
29.00
29.00
29.00
28.96
28.96
28.96
28.96
28.96
28.96
29.10
29.10
29.10
29.16
29.16
29.16
29.00
29.00
29.00
28.93
28.93
28.93
Meter
coef.
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
, 0.9788
0.9788
0.9788
\
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
0.9788
Adjusted
volume
(L)
18.12
19.99
18.90
20.87
19.44
21.48
18.76
19.80
18.98
18.80
18.76
18.85
18.94
18.77
18.89
18.64
18.83
18.63
19.29
19.39
19.44
19.20
19.28
19.15
19.16
19.33
19.27
19.45
19.65
19.54
53
-------
TABLE A-3. VOST ANALYSIS RESULTS
Sample
volume
(L)
Run 31
Field blank pair
Pair 1 18.12
2 19.99
3 18.90
Total 57.01
Run 32
Field blank pair
Pair 1 20.87
2 19.44
3 21 .48
Total 61 .79
Run 33
Field blank pair
Pair 1 18.76
2 19.80
3 18.98
Total 57.54
Run 34
Field blank pair
Pair 1 18.80
2 18.76
3 18.85
Total 56.41
Run 35
Field blank pair
Pair 1 18.94
2 18.77
3 18.89
Total 56.60
Carbon Tetrachloride
Amount found (ng) Avg.
cone
front back (ng/Lj
<2.0
15.6
15.5
16.3
66.2
<2.0
77.8
124.0
124.8
437.2
<2.0
35.5
42.3
73.7
193.5
<2.0
28.0
20.9
17.0
85.7
<2.0
118.8
118.1
67.0
389.8
<2.0
6.3
7.3
5.2
1.16
< 2.0
47,1
28.6
34.9
7.08
<2.0
11.4
10.9
19.7
3.36
<2.0
9.2
6.0
4.6
1.52
<2.0
39.9
28.4
17.6
6.89
Toluene
Amount found (ng)
front
<2.0
2.4
9.0
27.8
49.8
<2.0
14.4
31.6
51.6
110.7
<2.0
37.7
8.1
12.6
67.2
<2.0
58.8
9.9
11.5
87.0
<2.0
15.1
5.0
10.5
38.8
back
<2.0
3.2
<2.0
5.4
<2.0
9.1
<2.0
<2.0
<2.0
3.9
2,3
2.6
3.2
2.4
<2.0
2.4
2.4
4.1
1.9
2.2
Avg. Surrogate
cone. recovery
(ng/L) (%)
91/74
71/126
120/122
141/92
0.874
58/44
122/102
146/95
162/57
1.79
49/68
85/79
74/78
105/72
1.17
66/94
116/92
86/89
129/106
1.54
74/101
101/111
74/101
108/108
0.686
54
-------
TABLE A-3 (continued)
Carbon Tetrachloride
Sample Amount found (ng) Avg.
volume ~™v~
(L)
Run 36
Field blank pair
Pair 1 18.64
2 18.83
3 18.63
Total 56.10
Run 37
Field blank pair
Pair 1 19.29
2 19.39
3 19.44
Total 58.12
Run 38
Field blank pair
Pair 1 , 19.20
2 19.28
3 19.15
Total 57.63
Run 39
Field blank pair
Pair 1 19.16
2 19.33
3 19.27
Total 57.76
Run 40
Field blank pair
Pair 1 19.45
2 19.65
3 19.54
Total 58.64
front back {ng/L)
3.2
17.8
17.1
10.6
62.9
<2.0
27.9
34.1
24.9
114.2
<2.0
10.0
7.0
11.5
39.8
<2.0
73.5
25.4
19.4
191.8
<2.0
172.2
283.0
248.4
970.3
3.3
7.4
6.2
3.8
1.12
< 2.0
13.0
7.3
7.0
1.96
< 2.0
3.6
2.8
4.9
0.691
<2.0
52.3
12.7
8.5
3.32
<2.0
57.8
91.9
117.0
16.5
Toluene
Amount found (ng) Avg.
front back (ng/L)
2.6
22.7
6.3
15.4
51.1
<2.0
10.6
13.2
32.2
72.7
4.2
11.4
4.7
10.2
36.5
4.6
20.8
9.9
16.0
65.7
3.0
10.9
12.1
18.2
51.7
•
3.2
2.7
<2.0
<2.0
0.911
<2.0
11.4
3.3
<2.0
1.25
3.4
3.7
< 2.0
4.5
0.633
3.1
6.8
6.8
5.4
1.14
<2.0
3.8
<2.0
4.7
0.882
Surrogate
recovery
(%)
79/84
80/111
89/112
81/106
38/96
125/113
136/111
140/110
81/81
93/111
96/95
99/109
87/76
90/86
93/106
102/108
94/91
115/112
115/99
107/107
55
-------
TABLE A-4. VOLATILE POHC EMISSIONS
Run 31
Run 32
Run 33
Run 34
Run 35
Run 36
Run 37
Run 38
Run 39
Run 40
Effluent
gas flow
(dscm/min)
0.120
0.221
0.208
0.117
0.211
0.121
0.213
0.119
0.209
0.209
POHC concentration •
(ng/L or ng/dscm)
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
CCI4
Toluene
1.16
0.874
7.08
1.79
3.36
1.17
1.52
1.54
6.89
0.686
1.12
0.911
1.96
1.25
0.691
0.633
3.32
1.14
16.5
0.882
POHC
Carbon tetrachloride
(g/min)
0.000000139
0.000001562
0.000000699
0.000000,178
0.000001454
0.000000136
0.000000418
0.000000083
0.000000694
0.000003448
emissions
Toluene
(g/min)
0.000000105
0.000000395
0.000000243
0.000000181
0.000000145
0.000000110
0.000000266
0.000000076
0.000000238
0.000000184
56
-------
TABLE A-5. DREs FOR VOLATILE POHCs
Carbon tetrachloride
Run 31
Run 32
Run 33
Run 34
Run 35
Run 36
Run 37
Run 38
Run 39
Run 40
Run 31
Run 32
Run 33
Run 34
Run 35
Run 36
Run 37
Run 38
Run 39
Run 40
Input
(g/min)
0.432
0.827
0.785
0.487
0.861
0.445
0.819
0.432
0.810
0.760
Input
(g/min)
0.216
0.414
0.393
0.244
0.430
0.223
0.409
0.216
0.405
0.380
Emissions
(g/min)
0.000000139
0.000001562
0.000000699
0.000000178
0.000001454
0.000000136
0.000000418
0.000000083
0.000000694
0.000003448
Toluene
Emissions
(g/min)
0.000000105
0.000000395
0.000000243
0.000000181
0.000000145
0.000000110
0.000000266
0.000000076
0.000000238
0.000000184
ORE
(%)
99.999968
99.99981 1
99.999911
99.999963
99.999831
99.999970
99.999949
99.999981
99.999914
99.999546
ORE
(%)
99.999951
99.999905
99.999938
99.999926
99.999966
99.999950
99.999935
99.999965
99.999941
99.999952
57
-------
APPENDIX B
MM5 RESULTS AND
CALCULATION OF DREs FOR DICHLOROBENZENE AND NAPHTHALENE
58
-------
TABLE B-1. MM5 SUMMARY DATA
Run 31
Run 32
Run 33
Run 34
Run 35
Run 36
Run 37
Run 38
Run 39
Run 40
Sampling
time
(min)
120
120
120
120
120
120
120
120
120
. 120
Gas
volume
(dscm)
0.617
0.751
0.815
0.612
0.824
0.494
0.726
0.604
0.801
0.802
Orsat analysis
%O2
9.0
12.0
12.0
8.8
8.0
3.4
8.4
5.0
7.0
11.3
% CO2
11.0
6.6
6.4
8.4
9.6
12.4
8.8
10.8
9.6
6.7
Percent
water
7.6
8.7
10.0
11.5
10.6
17.5
10.9
12.2
12.3
8.8
Average
stack
temp
232
304
299
198
302
210
324
221
300
266
% Iso-
kinetic
100.9
99.8
100.5
101.4
100.7
108.2
101.0
102.5
102.5
96.2
59
-------
TABLE B-2. SV-POHC EMISSION RESULTS
Run
31
32
33
34
35
36
37
38
39
40
Blank train
Weight Volume POHC
found sampled concentration ,
(fig) (dscm) (ng/dscm)
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
1 ,2-Dichlorobenzene
Naphthalene
0.22 0.617
3.70
0.86 0.751
8.00
0.68 0.815
7.72
0.36 0.612
7.72
0.30 0.824
7.89
0.36 0.494
6.75
0.45 0.726
9.09
0.21 0.604
5.55
0.15 0.801
5.91
1 .04 0.802
5.75
0.06
4.32
0.357
5.997
1.145
10.652
0.834
9.472
0.588
12.614
0.364
9.575
0.729
13.664
0.620
12.521
0.348
9.189
0.187
7.378
1.297
7.170
-
Stack POHC
flow emission rate
(dscm/m) (g/min)
0.120 0.000000043
0.00000072
0.221 0.000000253
0.00000235
0.208 0.000000174
0.00000197
0.117 O.OOOO00069
0.00000148
0.211 0.000000077
0.00000202
0.121 0.000000088
0.00000165
0.213 0.000000132
0.00000267
0.119 0.000000041
0.00000109
0.209 0.000000039
0.00000154
0.209 0.00000027
0.00000150
_
60
-------
TABLE B-3. DREs FOR SEMIVOLATILE POHCs
1 ,2-Dichlorobenzene
Run 31
Run 32
Run 33
Run 34
Run 35
Run 36
Run 37
Run 38
Run 39
Run 40
Run 31
Run 32
Run 33
Run 34
Run 35
Run 36
Run 37
Run 38
Run 39
Run 40
input3
(g/min)
1.73
3.31
3.14
1.95
3.44
1.78
3.27
1.73
3.24
3.04
Input3
(g/min)
0.216
0.414
0.393
0.244
0.430
0.223
0.409
0.216
0.405
0.380
Emissions
(g/min)
0.000000043
0.000000253
0.000000174
0.000000069
0.000000077
0.000000088
0.000000132
0.000000041
0.000000039
0.00000027
Naphthalene
Emissions
(g/min)
0.00000072
0.00000235
0.00000199
0.00000148
0.00000205
0.00000165
0.00000267
0.00000109
0.00000154
0.00000150
ORE (%)
99.9999975
99.9999924
99.9999945
99.9999965
99.9999978
99.9999950
99.9999960
99.9999976
99.9999988
99.999991 1
DRE(%)
99.99966
99.99943
99.99949
99.99940
99.99952
99.99926
99.99935
99.99949
99.99962
99.99961
a Inputs from Appendix A, Table A-1.
61
-------
APPENDIX C
PIC RESULTS FOR VOST AND MM5 SAMPLES
62
-------
TABLE C-1. AMOUNT OF VOLATILE PICs FOUND IN A VOST TRAP PAIR SAMPLE (rig)
Compound
Jnknown
Sulfur dioxide
Unknown
Carbon disulfide
Unknown
Dichloromethane
C,H12 Hydrocarbon
C8H,2 Hydrocarbon
Unknown
CjHto-CjH,, Hydrocarbon
Butanal
Unknown
2-Butanone
Trichloromethane + unknown
Tetrahydrofuran and chloroform
CSH100
Unknown
C,H12 Hydrocarbon
Benzene
CeH1t Hydrocarbon
Cy-Cj Hydrocarbon
2-Propylfuran
CeH12O (Unknown)
Octene(C,Hl6)
Octane
Unknown
CeH,2O Aldehyde
Unknown
Unknown
1 ,1 ,1-Trichloro-2-propanone
C8H14O (Furan)
Chlorohydrocarbon (chloroalkane)
C7HUO Aldehyde
Hydrocarbon (C8-C)3)
Hydrocarbon (C9-C13)
Benzaldehyde
Unknown
C,2H2e Hydrocarbon
C^O-C^eO Ketone
CeH,2O-C8H,8O Aldehyde
C)0-C,3 Hydrocarbon
Octanal
CjjHjo Hydrocarbon
Scan
No.
29
29
31
35
36
38
38
45
48
51
55
55
59
63
63
63
64
71
76
81
82
110
134
166
171
172
199
200
218
224
224
225
266
279
286
307
313
314
318
318
321
322
331
Run No.
Blk
35
50
31
32
3
1,670
19
138
327
1,020
155
42
320
454
463
32
62
21
208
423
726
423
178
201
281
1,550
13
33
359
368
444
1,081
1,010
453
788
93
437
11
409
374
34
74
135
570
1,660
16
563
1,170
20
869
375
346
417
647
35
364
136
165
13
203
315
42
188
376
11
36
35
22
274
50
22
213
176
157
113
166
148
37
13
25
17
91
25
570
141
38
44
141
68
53
41
63
201
78
24
41
25
39
19
14
42
13
213
202
34
15
339
109
40
19
19
36
149
19
32
404
18
191
63
-------
TABLE C-1 (continued)
Compound
Dichlorobenzene
Unknown
C,0H22-C12H24 Hydrocarbon (alkene)
Unknown
CIOH22-C,3H28 Hydrocarbon
Unknown
Phenyl alkyl ketone
C,-C,S Aldehyde
Unknown
CJ^O-C^O
C12-C15 Hydrocarbon
Total Amount
Scan
No.
335
336
341
342
351
351
364
372
389
414
426
Run No.
Blk
85
31
42
4,685
32
268
216
13
223
18
4,824
33
5,827
34
6,862
35
10
1,823
36
1,376
37
13
895
38
779
39
48
31
1,079
40
99
32
51
1,069
Note: See Appendix D for data on chlorinated dibenzo dioxins and furans.
64
-------
TABLE C-2. AMOUNT OF SEMIVOLATILE PICs FOUND IN THE MM5 SAMPLES (jig)
Compound
Alcohol
C,H1C0
Alcohol
C.H,p
C.H100
C,H100
C«HI202
C,H10 (subst. benzene)
Unknown
CsHtoO
Unknown ketone
C7H120
Unknown
C7H,002
C,H100
Benzole acid
Unknown acid ester
1 ,3-lsobenzylfurandione
CSH,002
C10H,002
Unknown
C15H3002
Phthalate, subsL
Unknown acid ester
Unknown acid ester
Unknown
C18HM02
C,,HM02
Bis(2-ethylhexyl)
phthalate
Total Amount
Scan
16
112
122
142
181
202
250
290
301
321
342
396
492
567
640
655
704
791
808
948
955
1099
1209
1223
1235
1268
1347
1359
1610
Run No.
Blk
150
33
42
225
31
308
20
190
18
796
94
16
68
20
30
1,560
32
72
360
960
600
140
128
240
1,120
190
108
100
4,018
33
340
190
440
44
800
78
70
52
2,014
34
380
580
1,200
58
800
86
88
56
3,248
35
360
900
1,380
30
780
72
30
69
33
60
3,714
36
300
189
480
630
75
72
99
246
105
54
84
2,334
37
390
930
660
1,170
84
99
132
45
69
3,579
38
285
249
720
27
540
60
36
27
90
24
36
54
2,148
39
330
330
630
21
780
66
30
36
60
48
2,331
40
1,710
111
165
9,300
660
600
168
1,410
96
51
14,271
Deleted C7H, (toluene) since it was present in XAD/filter blanks and may be a contaminant in XAD or extractant solvent
(also is a volatile POHC).
Deleted C^Ha, (tridecane) and C,Hm (nonane) because these were due to the D/F spiking and were present only in the
samples analyzed for D/F.
Note: See Appendix D for data on chlorinated dibenzo dioxins and furans.
65
-------
TABLE C-3. POHCs AND PICs IN VOST AND MMS BUNKS
Amount (ng)
Scan (on field blank pair
Compound No. from Run 31)
Volatile POHCs
Carbon tetrachloride - < 4.0
Toluene - < 4 0
Volatile PICs
Benzene
CSH,8 Trimethyl pentane
Q!l«*«M .•.«.•.•..:.»:_._ — — * * ^
Total Vol PICs (ng) =
76
81
464-
360-
377-
.
35
50
8-
5-
4-
85
Amount (ug)
Scan (in blank MMS
Compound No. train)
Semivolatile POHCs
Dichlorobenzene - 0.06
Naphthalene - 4.32
Semivolatile PICs
C,H12O2 250 150
Phthalate, subst 1209 33
Bis(2-ethylhexyl) phthalate 1610 42
Total SV PICs (ug) = 225
Note: Silane compounds have not been included in totals, because they
were likely produced from the reactor's internal insulation and were
therefore not considered to be 'products of incomplete combustion."
66
-------
TABLE C-4. RUN 31 POHCs AND PICs
Compound
Volatile POHCs
Carbon tetrachloride
Toluene
Volatile PICs
CS2 (carbon disulfide)
Dichloromethane
Unknown
Silane/methy ethyl ketone
Tetrahydrofuran and chloroform
2-Propylfuran
Hydrocarbon (C9-C13)
Hydrocarbon (C,-C13)
Benzaldehyde
C,2HM Hydrocarbon
Hydrocarbon (C,,-CI3)
Cs,H20 hydrocarbon
Phenyl alkyi ketone
Siljnp
Silgno
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Total Vol PICs (ng) =
Compound
Semivolatile POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
Alcohol
C,H,00
CeH1202
C7H1002
Benzoic Acid
1 ,3-lsobenzylfurandione
C8H,002
C,0H,002
Unknown
Bis(2-ethylhexyl) phthalate
Total SV PICs (ng) =
Scan
No.
-
-
36
38
55
59
63
110
279
286
307
314
321
331
364
247-
442-
484-
364-
377-
484-
386-
378-
Scan
No.
-
-
122
181
250
567
655
791
808
948
1268
1610
Amount (ng)
(on one trap pair)
21.9
5.6
32
3
1,670
19
138
327
1,020
155
42
320
454
463
42
459-
443-
4,640
14,700
8r430-
223-
466-
48-
4,685
Amount (ug)
(in MM5 train)
0.22
3.70
308
20
190
18
796
94
16
68
20
30
1,560
Note: Silane compounds have not been included in totals, because they were likely produced
from the reactor's internal insulation and were therefore not considered to be "products
of incomplete combustion.'
67
-------
TABLE C-5. RUN 32 POHCs AND PICs
Compound
Scan
No.
Amount (ng)
(on one trap pair)
Volatile POHCs
Carbon tetrachloride
Toluene
Volatile PICs
Carbon cfisulfide
Dichloromethane
Butanal
C,H,2 Hydrocarbon
Benzene
C,H1t Hydrocarbon
C,HI40 (Furan)
C7HM0 Aldehyde
Unknown
Unknown
Octanal
Unknown
Unknown
C9-C1S Aldehyde
Unknown
C12-CIS Hydrocarbon
Silano containing
35
38
55
70
76
80
224
266
313
321
322
336
351
372
389
426
442-
485-
124.9
23.5
62
21
208
423
726
423
178
201
281
1,550
13
268
216
13
223
18
Silano containing oontaminanto
no containing i
Silano containing oontaminanto
Silano containing oontaminanto
382-
483-
288-
Total Vol PICs (ng)
6,610
15 TOO
13 300
330-
286-
35-
4,824
Compound
Scan
No.
Amount (ng)
(in MM5 train)
Semivolatile POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
0.86
8.00
Alcohol
Alcohol
C,H100
C,H1202
C,H100
Unknown (ketone)
C,H100
Benzole Acid
Unknown (acid ester)
1 ,3-lsobenzylfurandione
Unknown (acid ester)
Total SV PICs (ng) =
16
122
181
250
321
342
640
655
704
791
1235
72
360
960
600
140
128
240
1,120
190
108
100
4,018
Note: Silane compounds have not been included in totals, because they were likely
produced from the reactor's internal insulation and were therefore not
considered to be 'products of incomplete combustion.*
68
-------
TABLE C-6. RUN 33 POHCs AND PICs
Compound
Volatile POHCs
Carbon tetrachioride
Toluene
Volatile PICs
Unknown
Unknown
Carbon disulfide
Dichloromethane
C8H,Z Hydrocarbon
Trichloromethane + unknown
C7-Ct Hydrocarbon
Benzene
Cj-C, Hydrocarbon
C,H12O (Unknown)
C7HM (aldehyde)
C10-C13 Hydrocarbon
Total Vol PICs (ng) =
Compound
Semivolatile POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
Alcohol
C,H100
C.H.A
C,H100
Benzole acid
1 ,3-lsobenzylfurandione
Unknown (acid ester)
Bis(2-ethylhexyl) phthalate
Total SV PICs (jig) =
Scan
No.
29
31
36
38
44
63
69
76
82
134
265
320
494-
302-
380-
484-
360-
OQ-l...
Scan
No.
122
181
250
321
655
791
1235
1610
Amount (ng)
(on one trap pair)
46.9
41.6
359
368
444
1,081
1,010
453
788
93
437
11
409
374
790-
11 300
o]l40
477-
447-
445-
5,827
Amount (ug)
(in MM5 train)
0.68
7.72
340
190
440
44
800
78
70
52
2,014
Note: Silane compounds have not been included in totals, because they were
likely produced from the reactor's internal insulation and were therefore not
considered to be 'products of incomplete combustion.'
69
-------
TABLE C-7. RUN 34 POHCs AND PICs
Compound
Volatile POHCs
Carbon tetrachioride
Toluene
Volatile PICs
Carbon disulfide
Dichloromethane
CSH,2 Hydrocarbon
C,H12 Hydrocarbon
Butanal
C8H100
CeH12 Hydrocarbon
Benzene
C7-C, Hydrocarbon
Octene (C,H,«)
Octane
Unknown
C10-C)3 Hydrocarbon
Silnno
Total Vol PICs (ng) =
Compound
Semivolatile POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
Alcohol
C,H100
C.H.A
C,H100
Benzoic acid
1 ,3-lsobenzylfurandione
Unknown (acid ester)
Bis(2-ethylhexyl) phthalate
Total SV PICs (>ig) =
Scan
No.
36
38
38
45
54
63
70
76
84
166
171
218
320
442-
494-
384-
484-
360-
378-
Scan
No.
122
181
250
321
655
791
1235
1610
Amount (ng)
(on one trap pair)
37.2
61.2
74
135
570
1,660
16
563
1,170
20
869
375
346
417
647
1 450
1-4- 500
12 200
458-
407-
34-
6,862
Amount (jig)
(in MM5 train)
0.36
7.72
380
580
1,200
58
800
86
88
56
3,248
Note: Silane compounds have not been included in totals, because they were
likely produced from the reactor's internal insulation and were therefore
not considered to be "products of incomplete combustion."
70
-------
TABLE C-8. RUN 35 POHCs AND PICs
Compound
Scan
No.
Amount (ng)
(on one trap pair)
Volatile POHGs
Carbon tetrachloride
Toluene
Volatile PICs
C,H12 Hydrocarbon
Unknown
C,H10 - C7H12 Hydrocarbon
Butanal
Trichloromethane
CeH12 Hydrocarbon
Benzene
Cy-C, Hydrocarbon
C,H,4O aldehyde
Octanal
Silano unknown
Silano containing oontaminanto
Silono containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Total Vol PICs (ng)
45
48
51
54
64
71
76
84
265
322
414
442-
484-
886-
378-
484-
299-
377-
158.7
19.2
364
136
165
13
203
315
42
188
376
11
10
1,470
356-
13,600
10,000
47-
427-
435-
1,823
Compound
Scan
No.
Amount (fig)
(in MM5 train)
Senwolatfle POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
0.30
7.89
Alcohol
C,HI00
C8H,Z02
C,HI00
Benzoic acid
1 ,3-lsobenzylfurandione
Unknown (acid ester)
Unknown (acid ester)
CtAA
Bis(2-ethylhexyl) phthalate
Total SV PICs (ug) =
122
181
250
321
655
791
1223
1235
1347
1610
360
900
1,380
30
780
72
30
69
33
60
3,714
Note: Silane compounds have not been included in totals,
because they were likely produced from the reactor's
internal insulation and were therefore not considered to be
'products of incomplete combustion.'
71
-------
TABLE C-9. RUN 36 POHCs AND PICs
Scan Amount (ng)
Compound No. (on one trap pair)
Volatile POHCs
Carbon tetrachloride - 25.2
Toluene - 25.4
Volatile PICs
Sulfur dioxide 29 35
Carbon cfisulfide 35 22
C,H,j Hydrocarbon 45 274
Unknown 47 50
2-Butanone 59 22
Unknown 64 213
C,H,2 Hydrocarbon 71 176
C7-C, Hydrocarbon 84 157
C12HM Hydrocarbon 315 113
C,0-C13 Hydrocarbon 321 166
CjHjo-C^Ha Hydrocarbon 331 148
Silano unknown 442- 924-
Silano containing contaminants 494-
i containing oontaminanto 363-
378 -|Q 6QQ
Silano unknown 443- 74-
Silano containing oontaminanto 494- 48-
i containing oontaminanto 300 413
I oontaminanto 378- 344-
Total Vol PICs (ng) = 1,376
Scan Amount (ng)
Compound No. (in MM5 train)
Semivolatile POHCs
Dichlorobenzene - 0.36
Naphthalene - 6.75
Semivolatile PICs
Alcohol
C6H100
C9H1202
Benzoic acid
1 ,3-lsobenzylfurandione
C,*H*,02
Unknown (acid ester)
Unknown (acid ester)
C18HM02
C.oH^O,
Bis(2-ethylhexyl) phthalate
Total SV PICs (ug) =
122
181
250
655
791
1099
1223
1235
1347
1359
1610
300
189
480
630
75
72
99
246
105
54
84
2,334
Note: Silane compounds have not been included in totals, because they were
likely produced from the reactor's internal insulation and were therefore not
considered to be 'products of incomplete combustion.'
72
-------
TABLE C-10. RUN 37 POHCs AND PICs
Compound
Scan
No.
Amount (ng)
(on one trap pair)
Volatile POHCs
Carbon tetrachloride
Toluene
Volatile PICs
Sulfur dioxide
2-Butanone
Tetrahydrofuran
C6H,2 Hydrocarbon
Benzene
C7H14O aldehyde
C7H14O-C,H,,O ketone
Unknown
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano containing contaminanto
Silano containing contominanto
Silano containing contaminants)
Sib no
44
60
65
71
78
265
318
342
322-
336-
462-
443-
442-
462-
426-
494-
Silnno
Silano containing oontaminanto
Silano containing contaminants
Silano containing oontaminanto
Total Vol PICs (ng) =
364-
442-
482-
482-
485-
366-
378-
40.9
22.0
13
25
17
91
25
570
141
13
c(9O"
467-
453-
82-
7 Q10
67-
46-
386-
•|Q "7QQ
^•« 3QQ
'448-
66-
44-
27-
326-
664-
895
Compound
Scan
No.
Amount (ng)
(in MM5 train)
Semivolatile POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
0.45
9.09
Alcohol
C.H100
C,H1202
Benzoic acid
1 ,3-lsobenzylfurandione
Unknown
Unknown (acid ester)
ClsHgoOj
Bis(2-ethylhexyl) phthalate
Total SV PICs (ng) =
122
181
250
655
791
955
1235
1359
1610
390
930
660
1,170
84
99
132
45
69
3,579
Note: Silane compounds have not been included in totals, because they were likely
produced from the reactor's internal insulation and were therefore not
considered to be "products of incomplete combustion.'
73
-------
TABLE C-11. RUN 38 POHCs AND PICs
Compound
Scan
No.
Amount (ng)
(on one trap pair)
Volatile POHCs
Carbon tetrachloride
Toluene
Volatile PICs
13.6
15.1
Unknown
Sulfure dioxide
Unknown
2-Butanone
THF (tetrahydrofuran)
Unknown
C,H12 Hydrocarbon
Benzene
Unknown
C7HMO Aldehyde
C10-C1S Hydrocarbon
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Total Vol PICs (ng) =
Compound
29
35
36
57
64
64
71
76
200
266
320
318
462-
443-
462-
4S4-
362-
377^-
442-
462-
494-
464-
OQQ
37?-
Scan
No.
44
141
68
53
41
63
201
78
24
41
25
74-
50-
3 50Q
65-
479-
3 2 "900"'
•"13-QQQ-
'364-
472-
75-
64-
283-
779
Amount (ug)
(in MM5 train)
Semivolatile POHCs
Dichiorobenzene
Naphthalene
Semivolatile PICs
0.21
5.55
Alcohol
C,H100
C,H,A
C7H,20
Benzoic acid
1 ,3-lsobenzylf urandione
Unknown (acid ester)
Unknown (acid ester)
Unknown
C, H O2
Phthalate, subst.
Bis(2-ethylhexyl) phthalate
Total SV PICs (ug) =
122
181
250
396
655 .
791
1223
1235
1268
1347 '
1209
1610
285
249
720
27
540
60
27
90
24
36
36
54
2,148
Note: Silane compounds have not been included in totals, because they were likely
produced from the reactor's internal insulation and were therefore not
considered to be 'products of incomplete combustion.'
74
-------
TABLE C-12. RUN 39 POHCs AND PICa
Compound
Scan
No.
Amount (ng)
(on one trap pair)
Volatile POHCs
Carbon tetrachioride
Toluene
Volatile PICs
Carbon disulfide
2-Butanone
Trichloromethane
C4H8O Tetrahydrofuran + chloroform
C,H,2 Hydrocarbon
Benzene
Unknown
1,1,1-trichloro-2-propanone
C7H120 Aldehyde
C,H120-C,H,,0 Aldehyde
CH>Hz2-C12H24 Hydrocarbon (alkene)
C^Hjj-C^Hj, Hydrocarbon
Silano unknown
Silano unknown
Silano unknown
Silano containing oontaminanto
containing oontaminanto
containing
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Total Vol PICs (ng) =
36
59
64
64
71
77
172
224
265
318
341
351
336-
,462-
444-
494-
364-
377-
364-
125.8
27.6
19
14
42
13
213
202
34
15
339
109
48
31
43-
66-
4€5-
11 400
462-
494-
494-
377-
469-
468-
463-
66-
39-
362-
767-
1,079
Compound
Scan
No.
Amount (ug)
(in MM5 train)
Semivolatile POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
0.15
5.91
Alcohol
C,H100
C,H1202
Unknown
Benzoic acid
1 ,3-lsobenzylf urandione
C10H10O2
Unknown
Unknown (acid ester)
Bis(2-ethylhexyl) phthalate
Total SV PICs (fig) =
122
181
250
492
655
791
948
955
1235
1610
330
330
630
21
780
66
30
36
60
48
2,331
Note: Silane compounds have not been included in totals, because they were likely
produced from the reactor's internal insulation and were therefore not
considered to be "products of incomplete combustion."
75
-------
TABLE C-13. RUN 40 POHCs AND PICs
Compound
Scan
No.
Amount (ng)
(on one trap pair)
Volatile POHCs
Carbon tetrachloride
Toluene
Volatile PICs
Sulfur dioxide
2-Butanone
Trichloromethane + unknown
Benzene
CeH12O Aldehyde
Chlorohydrocarbon (chloroalkane)
C^p Aldehyde
Benzaldehyde
C,0-C,3 Hydrocarbon
Dichlorobenzene
Unknown
C.H1.0-C10HM0 Aldehyde
Silano unknown
Silano unknown
Silano unknown
Silano unknown
Silano containing oontaminanto
Silano containing oontaminonto
Silano containing oontaminanto
Silano unknown
Silano unknown
Silano unknown
Silano containing oontaminanto
Silano containing oontaminanto
Silano containing oontaminanto
Total Vol PICs (ng) =
41
59
65
77
199
225
256
306
321
335
341
342
402-
442-
466-
462-
496-
303-
379-
442-
462-
494-
494-
279-
377-
230.0
14.7
19
19
36
149
19
32
404
18
191
99
32
51
74-
2,310
37-
46-
234-
-«j4 QQQ
-)3 400
357-
252-
23-
24-
382-
1,069
Compound
Scan
No.
Amount (pg)
(in MM5 train)
Semivolatile POHCs
Dichlorobenzene
Naphthalene
Semivolatile PICs
1.04
5.75
C,H100
Alcohol
CSH140
C,H100
CSH12O2
Unknown
Unknown '
Benzoic acid
1 ,3-lsobenzylfurandione
Unknown (acid ester)
Total SV PICs (pg) =
112
122
142
202
250
301
492
655
791
1235
1,710
111
165
9,300
660
600
168
1,410
96
51
14,271
Note: Silane compounds have not been included in totals, because they were likely
produced from the reactor's internal insulation and were therefore not
considered to be "products of incomplete combustion."
76
-------
APPENDIX D
TABULATION OF ANALYSIS RESULTS FOR DIOXINS/FURANS
77
-------
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78
-------
APPENDIX E
LIQUID ORGANIC FEED ANALYSIS RESULTS
FOR Cl, ASH, AND HHV
79
-------
TABLE E-1. LIQUID ORGANIC FEED ANALYSIS RESULTS
Run 31
Run 33
Run 35
Run 35 duplicate
Total organic
chlorine (%)
28.27
28.43
28.33
28.20
% Ash
< 0.006
< 0.006
< 0.006
Higher heating
value (Btu/lb)
13,064
12,830
12,871
12,954
TABLE E-2,. SUMMARY OF GALBRAITH AUDIT SAMPLE RESULTS
Higher heating value (Btu/lb)
Sample 30001
Sample 30002
Sample 30003
Prepared value
11,906
Prepared value
1.03
Prepared value
24.29
Reported value
11,772
% Ash
Reported value
0.93
Organic chlorine (%)
Reported value
26.20
% Accuracy
99%
% Accuracy
90%
% Accuracy
108
80
-------
APPENDIX F
O2, CO2, AND H2O ANALYSIS RESULTS
FOR EFFLUENT GAS IN EACH RUN
81
-------
TABLE F-1. O2, CO2, AND WATER ANALYSIS RESULTS
Run 31
Run 32
Run 33
Run 34
Run 35
Run 36
Run 37
Run 38
Run 39
Run 40
GEM
average
%O2
(dry basis)
9.3
12.3
11.9
9.0
7.9
3.2
8.7
4.2
6.7
11.8
Orsat analysis
%O2
9.0
12.0
12.0
8.8
8.0
3.4
8.4
5.0
7.0
11.3
% CO2
11.0
6.6
6.4
8.4
9.6
12.4
8.8
10.8
9.6
6.7
Percent3
moisture
7.6
8.7
10.0
11.5
10.6
17.5
10.9
12.2
12.3
8.8
a Percent moisture (by volume) determined from MM5
sampling train.
82
-------
APPENDIX G
SUMMARY OF QUALITY ASSURANCE RESULTS
83
-------
SUMMARY OF QUALITY ASSURANCE RESULTS
Several quality assurance procedures were used as part of the 10 tests done
with the EPA sampling and analysis methods. These included:
• QA audit samples
• Surrogates spiked into all VOST and MM5 samples
• Analysis of a blank MM5 train and blank VOST traps
• Analysis of POHCs in liquid organic feed
• Calibration of CEMs
• Calibration of sampling equipment
QA AUDIT SAMPLES
The following audit results were all within QA objectives for accuracy, except for
one determination (naphthalene check standard).4
Description
Simulated liquid
organic feed (spiked
POHCs in fuel oil)
Semivolatile check
standard
VOST/VOA water
check standard
Identification
04797
04801
04796
Analyte
o-Dichlorobenzene
Carbon tetrachloride
Naphthalene
Toluene
o-Dichlorobenzene
Naphthalene
Carbon tetrachloride
Toluene
Spike
level
43.0% w/w
12.24%
2.23%
5.47%
29.5 ng/mL
67.6 ng/mL
87 u.g/mL
113 ng/mL
Found
level
48.1%
12.8%
2.3%
5.2%
30.3 ng/mL
94.1 pg/mL
66.8 )ig/mL
86.1 ng/mL
Accuracy
112%
105%
103%
95%
103%
139%'
77%
76%
a Value is outside QAP accuracy objective of 75% to 125%, However, standard calibrating data were validated
using another independent standard solution (agreement of 109%).
84
------- |