PB84-189851
Controlled Air Incineration of Pentachloropbenol-Treated Wood
Los Alamos National Lab., Ml
Prepared for
Industrial Environmental Research Lab.
Cincinnati, OH
May 84
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
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EPA-600/2-84-089
May 1984
CONTROLLED AIR INCINERATION
OF PENTACHLOROPHENOL- TREATED WOOD
L. A. Stretz and J. S. Vavruska
. Waste Management Group H-7
Los Alamos National Laboratory
P. 0. Box 1663, MS E517
Los Alamos, New Mexico 87545
USEPA Interagency Agreement
A D-89-F- 1-539-0
Project Officer
Richard A. Carnes
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
This study was conducted in cooperation with and with partial support from
• '. -
.Defense Property Disposal Service
Defense Logistics Agency
Federal Center '
Battle Creek, Michigan 49061
US Environmental Protection Agency
Industrial Environmental Research Laboratory
Incineration Research Branch
Cincinnati, Ohio 45268
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-84-089
2.
3. RECIPI
T'S ACCESSION-NO. I
ft 189851
4. TITLE AND SUBTITLE
Controlled Air Incineration of Pentachloro-
Phenol-Treated Wood
6. REPORT DATE
May 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
L. A. Stretz and J. S. Vavruska
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Los Alamos National Laboratory
P.O. Box 163, MS E517
Los Alamos, New Mexico 87545
10. PROGRAM ELEMENT NO.
D 109
11. CONTRACT/GRANT NO.
IAG AD-89-F-1-539-0
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory—Cinn, OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
13. TYPE OF REPORT AND PERIOD COVERED
Research
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This research was initiated to determine the operating conditions necessary to effect
complete thermal destruction (greater than 99.99J) of pentachlorophenol (PCP)-treated
wood in a controlled air incinerator (CAI) and to provide a basis for evaluating the
applicability of other incineration systems to the destruction of PCP-treated wood.
The treated wood in question was scrap from used ammunition crates in Korea. It has
been proposed that a substantial amount of such wood be disposed of by incineration
in a unit located in that country. A major concern in such incineration is the
potential formation of such toxic compounds as chlorinated dibenzo-p-dioxins and
dibenzofurans.
Test results showed a combustion efficiency of >99.9X and a destruction efficiency
of >99.99i for PCP in the primary chamber under test conditions with no detectable
production of tetrachlorodibenzo-p-dioxin (TCDD) or tetrachlorodibenzofuran (TCDF)
at detection limits in sample extracts of 1 and 5 ppb, respectively.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Pentachlorophenol
Controlled Air Incineration
Destruction and Removal Efficiency
PCP
Dibenzodioxins
Dibenzofurans
GC/MS
Chemistry
Engineering
Environment
18. DISTRIBUTION STATEMENT
IB. SECURITY CLASS (ThisReport/
21. NO. OF PAGES
tio
20. SECURITY CLASS (Thispage)
22. PRICE
EPA Form 2220-1 (9-73)
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NOTICE
THIS DOCUM.ENT HAS BEEN REPRODUCED
FROM THE BEST COPY FURNISHED US BY
THE SPONSORING AGENCY. ALTHOUGH IT
IS RECOGNIZED THAT CERTAIN PORTIONS
ARE ILLEGIBLE, IT IS BEING RELEASED
IN THE INTEREST OF MAKING AVAILABLE
AS MUCH INFORMATION AS POSSIBLE.
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
11
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FOREWORD
When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on
our health often require that new and increasingly more efficient pollution
control methods be used. The Industrial Environmental Research Laboratory-
Cincinnati (lERL-Ci) assists in developing and demonstrating new and
improved methodologies that will meet these needs both efficiently and
economically.
This report describes the results of the experimental evaluation of the
thermal destruction of pentachlorophenol (PCP)-treated wood in a controlled
air incinerator at the Los Alamos National Laboratory. The disposal of wood
treated with PCP has become a significant problem for the US Department of
Defense, particularly in Korea, where the sale or burial of treated-wood
ammunition crates is prohibited. The purpose of this study was to provide the
Department of Defense with information on the destruction efficiency of PCP
as a component on wood as a function of various conditions of incinerator
operation. This information is to be used to enable an evaluation of whether
incinerators in Korea could be used to destroy this material.
This report will also be of interest to those concerned with the incineration
of PCP materials in general. Further information on hazardous material
! research may be obtained through the Incineration Research Branch of the
i Energy Pollution Control Division of lERL-Ci.
David G. Stephen
Director
Industrial Environmental Research Laboratory
Cincinnati
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ABSTRACT
This research was initiated to determine the operating conditions necessary
to effect complete thermal destruction (greater than 99.99%) of pen-
tachlorophenol (PCP)-treated wood in a controlled air incinerator (CAI) and
to provide a basis for evaluating the applicability of other incineration systems
to the destruction of PCP-treated wood. The treated wood in question was
scrap from used ammunition crates in Korea. It has been proposed that a
substantial amount of such wood be disposed of by incineration in a unit
located in that country. A major concern in such incineration is the potential
formation of such toxic compounds as chlorinated dibenzo-p-dioxins and
dibenzofurans.
A production-scale CAI at the Los Alamos National Laboratory was used to
evaluate the destruction efficiency for PC P as a component on treated-wood
feed material. This incineration system was originally designed for volume
reduction of combustible radioactive wastes. Components of the system
include a dual chamber CAI, a water spray quench column, a high-energy
venturi scrubber, and a packed-column acid gas absorber followed by an
offgas condenser, reheater, high-efficiency particulate air filters, and an
activated carbon adsorber.
Test results showed a combustion efficiency of >99.9% and a destruction
efficiency of >99.99% for PCP in the primary chamber under test conditions
with no detectable production of tetrachlorodibenzo-p-dioxin (TCDD) or
tetrachlorodibenzofuran (TCDP) at detection limits in sample extracts of 1
and 5 ppb, respectively.
This report was submitted under the terms of US Environmental Protection
Agency interagency Agreement AD-89-F-1-539-0 and covers the period
February 1,1981, to February 1,1982. The work was performed at Los Alamos
under the US Department of Energy Contract W-7405-ENG-36.
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CONTENTS
Disclaimer ii
Foreword Hi
Abstract iv
Figures ; vii
Tables vji
Abbreviations and Symbols viil
Acknowledgments x
I 1. Introduction 1
1 2. Conclusions 2
| 3. Recommendations 3
4. Facility Description .'. 4
: Incineration 6
i Offgas Cleaning 6
Scrub Solution Recycling :...'. 8
Ash Removal 9
j Control and Instrumentation 9
: Auxiliary Equipment 10-
'•. Incineration System Dimensions 11
' Safety Analysis and Environmental Assessment 12
5. Sampling and Sampling Locations 13
PCP-Treated Wood Samples 15
Ash Samples 15
Gas Sampling '.... 15
Offgas Cleanup Water Samples ; 17
Miscellaneous Samples 17
6. Test Plan ,: ..'. .18
Procedural Requirements T. ,.; 18
Contaminated Wood Supply , 18
Operating Conditions ...; 18
Test Schedule ...../ 19
7. Test Run '. 25
Offgas System Control Settings 25
Incinerator 25
System Startup 25
Test Phase 1, Period 1 26
Test Phase 1, Period 2 26
Interim Between Test Phases 27
Phase 2, Period 1 27
Phase 2, Period 2 < 28
Phase 2, Period 3 29
Phase 2, Period 4 30
Test Run Summary 31
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8. Procedures and Analytical Results 32
Sample Preparation 32
Analytical Procedures 33
Analytical Results 37
9. Discussion of Results 39
References .. 40
Appendixes 41
• A. Quality Assurance 41
• B. Combustion, Residence Time, and Sample Requirements Calculations 43
C. Destruction Efficiency Calculations 50
D. Field Data Summary 52
E. Combustion Efficiency and Offgas Composition Data 65
! F. Sample and Flow-Calculations Summary : 75
G. Report on Sample Analysis from Southwest Research Institute .. 77
VI
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FIGURES
Number - Page
1 Simplified line drawing of controlled air incineration process ,. 4
2 Offgas cleaning subsystem :. 5
;
3 Basic controlled air incinerator ; — 5
4 Scrub solution recycling subsystem 8
5 Building ventilation zoned for containment > 11
, •
6 Incineration sample points 13
7 Offgas system sample points
8 Hot-zone traverse points (primary chamber outlet)
9 Hot crossover duct traverse points (afterburner outlet)
10 Average operating conditions during test interval abc ,
14
16
17
31
TABLES
4
Number % . . Page
1 Conceptual Test Schedule: PCP-Treated Wood Run 1 • • 20
. ' • ' ' . i •
2 Planned Operating Conditions — ..21
3 PCP Run Chronology
4 Analysis of PCP Test Samples
. 22
. 38
vu
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LIST OF ABBREVIATIONS AND SYMBOLS
ACFM — actual cubic feet per minute
avg — average
BSA — N, 0-Bis-(trimethylsilyl)-acrylamide
Btu — British thermal unit
C — centigrade
CAI — controlled air incinerator
CE — combustion efficiency
DE — destruction efficiency
DOD — Department of Defense
DOE — Department of Energy
DOP — dioctylphthalate
DPDS — Defense Property Disposal Service
DRE — destruction and removal efficiency
ECD — electron capture detection
EPA — Environmental Protection Agency
F — Fahrenheit
FSAR — Final Safety Analysis Report
ft — foot, feet
ft2 — square feet
ft3 — cubic feet
GADOS — gravity ash dropout system
GC — gas chromatography
h — hour, hours
HEPA — high-efficiency particulate air
HPLC — high-performance liquid chromatography
HZ — hot zone
IAG — interagency agreement
i.d. —. inside diameter -
ID — induced draft
in. — inch, inches
in. Hg — inches of mercury (pressure) ,
kg — kilograms
kJ — kilojoules
kPa — kiiopascals
L — liters
Ib — pounds
m — meters
m3 — cubic meters
max — maximum
m/e — mass to charge ratio
min. — minimum
min — minutes
ml — milliliters
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mm — millimeters
mol — moles
MS — mass spectrometry
ng — nanograms
OG — offgas
POP — pentachlorophenol
PIC — product of incomplete combustion
POHC — primary organic hazardous constituent
ppb — parts per billion
P-P-I — phase - period - interval
ppm — parts per million
psi — pounds per square inch
psia — pounds per square inch absolute
QA — quality assurance
R — Rankine
s — seconds
SCF — standard cubic feet
SCFM — standard cubic feet per minute
SIM — selected ion monitor
SWRI — Southwest Research Institute
T — tons
TCDD — tetrachlorodibenzo-p-dioxln
TCDF — tetrachlorodlbenzofuran
TIC — total ion current
TMCS — trimethylchlorosilane
TRU — transuranic
TSIM — N-trimethyl-silyl-imidazole
W.Q. — water gauge
wt — weight
AP — pressure differential
ng —'micrograms
nL — microllters
urn — micrometers
IX
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ACKNOWLEDGMENTS
This study was performed at the Los Alamos National Laboratory, which is
operated for the US Department of Energy by the University of California
under contract number W-7405-ENG-36.
| The efforts of the staff and technical members of Los Alamos National
i Laboratory Waste Management Group H-7 in performing the experimental
work and the Industrial Hygiene Group H-5 in analytical support are gratefully
acknowledged.
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SECTION 1
INTRODUCTION
Incineration under inadequate conditions or open burning of wood which has been treated
with pentachlorophenol (PCP) can generate toxic products of incomplete combustion (PICs).
Various chlorinated organic compounds can occur in combustion products from burning PCP-
treated wood, including chlorinated dibenzofurans and chlorinated dibenzodioxins such as 2,
3, 7, 8 tetrachlorodibenzo-p-dioxin (TCDD).1"4 The controlled air incinerator (CAI) at the Los
Alamos National Laboratory is capable of incinerating the treated wood safely while combus-
tion products are studied and required operating conditions and procedures are established to
\ avoid production of secondary hazardous materials.
i •
|,
j i The safe disposal of wood treated with PCP has become a significant problem for the US
| i Department of Defense (DOD), particularly in Korea. Wooden ammunition crates are treated
j; with PCP to prevent decomposition of wood due to termite or other insect/borer Infestation
11 during transportation and storage. Disposal of the empty crates by sale or burial is prohibited
in Korea. The volume of wood involved is so large that shipment back to the United States is an
expensive and unattractive option. Incineration of the crates in Korea has been proposed as
: the most cost effective and environmentally acceptable solution.
l| ' ' • •'••'.
Ij The Korean government has asked for evidence that incineration of the material will not
i create an additional, perhaps more severe, problem than the PCP-treated wood Itself presents.
: DOD, through the Defense Property Disposal Service (DPDS), is seeking operating data on
j. PCP-treated wood incineration to demonstrate that an existing incinerator in Korea could
i safely destruct the material. .
]
; In response to discussions with Environmental Protection Agency (EPA) staff and represen-
I tatives of the DPDS, an experimental evaluation of the thermal destruction of PCP on wood was
j performed at Los Alamos National Laboratory by Waste Management Group H-7. The purpose
i of the evaluation was to determine the destruction efficiency for PCP fed as a component on
| treated wood while simulating conditions obtainable in a potential disposal incinerator in
] Korea. •
l
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SECTION 2
CONCLUSIONS
i PCP-treated wood can be incinerated in the Los Alamos CAI unit with a destruction
I efficiency (DE) greater than 99.99%. Testing showed no evidence of TCDD at a detection limit of
i 1 ppb or of tetrachlorodibenzofuran (TCDF) at a detection limit of 5 ppb using gas chromato-
graphy/electron capture detection. The DE is greater than 99.99% for the primary chamber
alone, indicating that such DE can be accomplished in a single-chamber unit if proper
conditions are maintained.
j Uncontrolled burning which occurred during upset conditions yielded some evidence of
• unburned hydrocarbons, although these could not be verified as POP. This result indicates that
such conditions could yield low DEs and/or generation of unwanted PICs. The specific.
conditions were low temperature [<800°C (1480°F)] and insufficient oxygen (substol-
chiometric). Avoiding these conditions should result in the desired 99.99% DE or >99.9%
^combustion efficiency (CE).
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SECTION 3
RECOMMENDATIONS
Incineration is a disposal method for PCP-treated wood which can achieve >99.9% CE
(>99.99% DE) for POP if operating conditions are maintained above acceptable minimums and
the feed rate is low enough to allow complete combustion of the wood. Test results using the
Los Alamos CAI system indicate that a single-chamber incinerator should provide >99.9% CE
(>99.99% DE) if the following conditions are maintained:
• minimum combustion chamber temperature >980°C (1800°F),
• retention time (gas phase) >2.5 s,
• excess air >20% (oxygen >3% in offgas),
• adequate time between feed cycles for ash burnout, and
• avoidance of overfeeding that could cause low instantaneous oxygen level and smoke
formation. .
If maintaining the given conditions at the nominal feed rate for a proposed incinerator is not
possible, the unit should be adjusted to a feed rate at which the conditions can be met.
Sampling the offgas, scrubber effluent, and ash as part of any disposal operation Is also
recommended to verify that satisfactory destruction is occurring and that toxic materials are
not present in the secondary waste streams. This sampling is essential, at least until successful
operation of the subject incinerator is verified, since different incinerator configurations can
have different combustion characteristics at "identical" operating conditions.
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SECTION 4
FACILITY DESCRIPTION
The Los Alamos CAI is a system which has been developed through careful modification and
integration of commercially available equipment. The system was designed and constructed to
demonstrate technology for the combustion of transuranic (TRU) contaminated waste (alpha-
bearing radioactive waste). As a result, the system is equipped with sophisticated containment,
safety, and off gas cleanup systems which make It suited to hazardous material incineration
studies.
: The basis of the Los Alamos CAI is an Environmental Control Products. (Charlotte, North
Carolina) model 500-T incinerator. Many operational modifications made at Los Alamos are
now available as standard options on the basic unit. Such modifications include .fully
modulated burners, gravity ash removal, steam injection capability, and improved mixing of
secondary air with primary chamber effluent. Many other modifications to the standard unit
have been made. The basic incinerator and associated offgas cleaning equipment are available
on the commercial market.
The more prominent features of the Los Alamos CAI system are shown in simplified line
drawings (Figures 1-3) and a discussion of the incineration system is given in this section. A
more detailed facility and process description is given In the facility Final Safety Analysis
Report (FSAR).6 .
RADIOACTIVE
WASTE
FEED
PREPARATION
t
COMBUSTIBLES
ATMOSPHERE
INCINERATION
OFFGAS^
OFFGAS
CLEANUP
NON- COMBUSTIBLES
ASH
TO LLW DISPOSAL
OR TRU WASTE STORAGE
SCRUB SOLUTION
JL L
TO LIQUID WASTE
TREATMENT FACILITY
Figure 1. Simplified line drawing of controlled air incineration process.
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OFFGAS CONDENSER
FROM
INCINERATOR
TO EXHAUSTER
OFFGAS
REHEATER
DEMISTER:
PACKED COLUMN
CARBON BED
ADSORBER-s
LJJ
-VENTURI SCRUBBER
QUENCH COLUMN
•PROCESS HEPA FILTER PLENUM
Figure 2. Offgas cleaning subsystem.
COMBUSTION
CHAMBERS
OFFGAS TO TREATMENT
OMBUSTION FUEL/
AIR SUPPLY GLOVEBOX
ASH
DISPOSAL
SIDE RAM. FEEDER
Figure 3. Basic controlled air incinerator.
5
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4.1 INCINERATION
The incinerator is a conventional design, dual chamber, controlled air, solid waste system
which has been modified to provide physical containment barriers at all pathways between the
incinerator interior and the process area. These modifications have been made to enhance
safety and containment when incinerating radioactive materials and also to increase the level of
protection for operators and the surrounding area when incinerating other hazardous
materials.
The standard unit has a nominal capacity of 170 kg (374 lb)/h of Type-O waste at sea level
and is also rated for waste Types 1-4 and Public Health Service type waste. The Los Alamos
unit has been derated due to the lower atmospheric pressure [2225-m (7300-ft)] elevation of
the site and has been demonstrated at 45.4 kg (100 lb)/h of a waste containing a mixture of 35%
cellulosics, 23% polyethylene, 12% polyvinylchloride, and 30% rubber (primarily polyisoprene,
latex, and neoprene) and having a heating value of 30.5 kJ/g.
The primary chamber is a refractory-lined cylinder with an inside diameter of 1.46 m (4.8 ft)
and a length of 1.83 m (6 ft). The secondary chamber is 1.17-m (3.8-ft) i.d. and 1.83 m (6 ft)
long. The crossover duct to the offgas cleanup system is also refractory lined and maintains the
offgas at near the secondary chamber temperature, thus acting as an extension of the
chamber. This duct has an inside diameter of 0.51 m (1.7 ft) and an overall length of 4.14 m
(13.6 ft). The resulting effective chamber volumes are 3.06 m3 (107 ft3) for the primary chamber
and 1.97 m3 (68 ft3) for the secondary chamber (afterburner excluding the duct). Burners in the
primary and secondary chambers are both fully modulated for temperature control. Maximum-
operating temperatures are nominally 1370°C (2500°F) in both chambers. Constraints on the
glovebox ventilation system limit the temperature achievable to 1230°C (2250°F) in the current
configuration.
Incineration temperature is controlled.by feedback loops on both combustion chambers.
The temperature sensor on the primary chamber is located in the transition duct at the
chamber exit. Secondary chamber temperature is measured in the offgas duct just down-
stream of the chamber outlet. Additional thermocouples are located at the refractory surface in
both chambers and at the end of the hot offgas duct upstream of the quench*column. .,
Operation of the unit with solid waste is a quasi-continuous process with waste charged
through the main ram controlled by an interval timer. The timer is set as a function of desired
feed rate and waste density. For example, waste packaged in 0.06-m3 (2-ff) boxes with a
density of 160 kg (352 lb)/m3 to be fed at a nominal rate of 45.4 kg (100 lb)/h would be fed at 12-
min intervals with the ram automatically activated by the cycle timer. Ash can also be removed
on-line by manual activation of the gravity ash dropout system (GADOS). This is normally done
only when the ash pile becomes excessive.
Underfire and secondary combustion air rates are independently controlled and can be
adjusted to give the desired 02 concentration in the gas effluent stream.
4.2 OFFGAS CLEANING
Exhaust from the CAI upper chamber contains both particles and mineral acids which result
from combustion of the feed material. These chemical pollutants and particles are removed by
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the offgas cleaning system, which consists of a quench tower, a high-energy venturi scrubber,
a packed-column absorption tower, a condenser, a mist eliminator, a reheater, high-efficiency
paniculate air (HEPA) filters, an activated carbon adsorber, and an induced-draft (ID) blower
(Figure 2).
The quench tower is divided into an upper contacting section and a lower separating section.
Combustion gases are cooled from the incinerator exit temperature to approximately 70°C
(160°F) by evaporation of recycled scrub solution. Excess solution collects in the separator
while the saturated gas phase is routed to the inlet of the venturi scrubber.
The variable-throat venturi scrubber, located between the quench tower and the absorption
tower, provides high-efficiency removal of the offgas particles. The venturi assembly consists
of converging and diverging cones with a clamp valve throat to allow the pressure drop to be
controlled. Venturi pressure drop is normally controlled to 14.9 kPa (60 in. W.G.). Scrub
solution is injected through a nozzle located upstream of the throat.
Residual mineral acids are removed from the gas phase by countercurrent contact with
process condensate, recycled scrub solution, or makeup water in the packed-column ab$orp-
tion tower.
The condenser, mist eliminator, and reheater are included to condition the process exhaust
gases before final HEPA filtration. The condenser lowers the offgas temperature to approx-
imately 45°C (110°F), removing most of the water vapor from the scrubbed gas stream. The
offgas is then reheated approximately 17°C (30°F) above the saturation temperature to about-
| 62°C (144°F), to avoid condensation and attendant plugging of the HEPA filters and corrosion
| of the plenum, carbon adsorber, exit ducting, and offgas blowers. The functional parts of each
i of these subsystem components are commercial equipment, housed in enclosures .specially
designed to withstand the 24.8-kPa (100-in. W.G.) pressure differential between the process
and ambient conditions.
HEPA filtration is required for final removal of particles in radioactive service. The HEPA
filters remain in use for hazardous waste testing. The filter module houses two frames in series,
the first consisting of a prefliter and two HEPA filters, the second being similar but without the
prefilter. The filter housing is designed to withstand the 29.8-kPa (120-in. W.G.) pressure
differential capability of the process and is fitted with hatches to access the bagout doors and
in-place filter testing ports. The filters are tested with dioctylphthalate (DOP), and performance
is better than 99.97% removal of 0.3-fim particles. •
An activated carbon .adsorber on the full offgas flow is located downstream of. the HEPA
filters. This adsorber provides additional protection against release of organics through the
process stack. The bed provides a 0.5-s residence time at a superficial velocity of 0.25 m/s (50
ft/min) for maximum offgas flow and approximately 2 s at normal offgas flow rates.
The ID blower is capable of producing 57.2-kPa (230-in. W.G.) static pressure absolute at
53.8 m3 (188 ft3)/min with a discharge pressure of 78.0 kPa (314 in. W.G.) absolute to
accommodate the 2225-m (7300-ft) elevation at Los Alamos.
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COOLING TOWERS
FROM
CONDENSER
CAUSTIC
ADDITION
PROCESS
SUMP
TANK
TO ABSORBER
TOWER
TO QUENCH
TOWER WEIR
-€7
TO QUENCH TOWER
SPRAY LINES
PUMP
SLOWDOWN ON
TANK LEVEL
OR SOLUTION
SPECIFIC GRAVITY
TO VENTURI
SCRUBBER
Figure 4. Scrub solution recycling subsystem.
4.3 SCRUB SOLUTION RECYCLING
A scrub solution recycle system is used to minimize liquid blowdown (waste to liquid
treatment) from the oftgas cleaning system (Figure 4). This system consists of full-flow
cartridge liquid filters, a graphite heat exchanger, two evaporative cooling towers, a scrub
solution receiver tank, a condensate receiver tank, and a caustic (20% NaOH) makeup tank.
Quench tower liquid effluent combines with scrub solution and venturi blowdown from the base
of the packed-column absorber tower. This solution is pumped through 100-nm cartridge
filters and a primary heat exchanger to the receiver tank. Liquid requirements for the quench
tower, venturi scrubber, and absorption tower are satisfied by recycle from the receiver tank.
Solution recycling through the quench tower is filtered to remove particles down to 20 nm.
! The graphite heat exchanger cools recycling solution from 85°C to 50°C (185°F to 120°F).
; The process (tube) side is operated at a lower pressure than the coolant (shell) side to
guarantee in-leakage in the event of tube failure. The shell side fluid from the primary heat
exchanger is cooled by the secondary heat exchange loop, providing isolation from the
environment.
To control scrub solution acidity, 20% caustic (NaOH) solution is added at the receiver tank
inlet. The addition rate is controlled by a pH sensor on the outlet of the receiver tank, and pH is
controlled within the range of 8-9. Condensate from the condenser/mist eliminator drains into
a condensate receiver tank. The level in this tank is maintained by addition of fresh water. The
solution is then pumped either to the top of the packed-column scrubber or to the receiver
tank.
8
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The blowdown rate from the scrub solution receiver tank is controlled by liquid level and
specific gravity. If the specific gravity of the scrub solution exceeds a specified value (currently
11.05) or if the liquid level becomes excessive, the rate of blowdown which is sent to the liquid
'waste treatment plant is increased.
4.4 ASH REMOVAL
Ash removal from the CAI is accomplished through one of two paths. A GADOS is used for
ash removal during operation and a vacuum ash removal system is used for thorough cleanout
of both chambers of the incinerator during shutdowns.
The GADOS consists of a refractory-lined pit and door in the floor of the primary chamber of
the CAI located at the end of the hearth opposite the ram feeder. As new waste is fed to the
incinerator, the ash is pushed down the hearth until It drops into the ash removal pit.
Periodically, the dropout door is opened for a brief time to allow the ash to fall through a grate
and delumper wheel into a collection hopper. The ash is then vacuumed from the GADOS
hopper and collected by a high-energy cyclone and sintered metal filter system into a second
hopper for removal at the ash packaging station.
The vacuum system, which is capable of producing up to 20.8-kPa (84-in. W.G.) suction, is
also used for vacuum ash cleanout during shutdowns. This cleanout is achieved by manipulat-
ing a vacuum hose in the incinerator chambers through the access doors and gloveboxes on
the ends of the chambers.
The ash packaging station consists of a glovebox where ash is removed from the collection
hopper through an interlocked isolation chamber. The chamber is first opened to the ash
hopper and allowed to fill, then isolated from the hopper and opened to drop the ash into a
collection bag. , .
The ash is then packaged and stored for future studies or immobilization.
4.5 CONTROL AND INSTRUMENTATION
Design and specification of the CAI process control system received priority throughout the
planning and construction phase. As the "nerve center" for the
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feedback from oxygen analyzers located at the exit of each chamber. The pressure differential
between the incinerator interior and the operating area is maintained by a valve immediately
upstream of the ID fan. Flow measuring elements and recorders monitor air, natural gas, and
steam introduction rates for energy and material balance purposes.
For offgas cleanup, conditioning, and filtration equipment downstream of the incinerator, the
controlled variables are (1) venturi scrubber liquid feed rate and pressure drop; (2) absorber
tower liquid feed rate; (3) condenser gas-phase temperature decrease; and (4) reheater gas-
phase temperature increase. The pressure drop and nominal temperature of each component
are also monitored as an indication of normal versus deteriorating performance.
In the scrub solution recycle subsystem, a pH feedback arrangement controls neutralization
of the liquid effluent from the primary offgas scrubbing components. Differential pressure is
monitored across each liquid filter, while process side temperatures are controlled in the
graphite heat exchanger. Liquid level and specific gravity are controlled in the scrub solution
receiver tank.
Primary variables, and many secondary variables and parameters, are controlled arfd/or
j recorded at a central station. Variables considered critical to process operation and safety are
I tied into an alarm panel which positively identifies the off-range variable as an aid to
I troubleshooting. Off-range variables identified as vital to process safety will activate one of
three automatic shutdown modes—controlled, fast, or emergency. Less critical alarmed
| variables require only operator response to correct off-range behavior.
A data acquisition system automatically records the many variable and parameter values
generated during experimental CAI process runs. .
A more detailed description of the safety and automatic shutdown systems is given in the
FSAR.5
4.6 AUXILIARY EQUIPMENT
| ' «
1 Backup utilities provide required services for an ortjerly process shutdown under abnormal
: circumstances. A diesel-powered generator with automatic switchgear is kept running during
: all incinerator operations. The unit supplies standby power to high-consumption equipment
| and vital motor-driven equipment such as the ID fans to permit safe operation and shutdown in
case of a main power failure. An on-line, floating battery system provides electrical power for
' process controls and data collection, averting potential momentary power interruptions which
could result in control relay dropout. A 2-h auxiliary cooling water supply is stored in a
pressurized container for release to the quenching system in the event of a recirculation pump
failure which otherwise would present a threat of damage to process equipment. A back-up air
compressor and compressed nitrogen are available to supplement normal instrument air
supply if required. Pneumatic actuators are designed to "fail safe" on loss of air pressure.
, Snuffing steam can be injected into the primary chamber to extinguish burning waste in the
event of a fast shutdown at high temperature. This capability prevents^uncontrolled burning
arid inefficient combustion, which can clog the offgas cleaning system with soot and heavy tars
and lead to release of toxic contaminants.
__.. 10
-------
Containment for the building is maintained by physical barriers and by four separate
ventilation zones. The pressure of each zone is regulated so that ventilation air moves from the
highest pressure zone (atmospheric) toward the lowest pressure zone (the volume internal to
the process). The interface between each zone is controlled by physical enclosures. The zone
ventilation system is shown in Figure 5.
4.7 INCINERATION SYSTEM DIMENSIONS
Dimensions of the incineration system components through the absorption column are
primary chamber 1.46-m i.d. x 1.83 m long (4.8 ft x 6 ft),
transition duct 0.31-m x 0.91-m i.d. x 0.61 m long (1 ft x 3 ft x 2 ft),
1.17-m i.d. x 1.83 m long (3.8 ft x 6 ft),
0.51-m i.d. x 4.14 m long (1.7 ft x 13.6 ft),
0.61-m i.d. x 1.83-m contact length (2 ft x 6 ft),
variable throat x 1.22-m (4-ft) overall length, and
0.61-m i.d. x 3.05-m (2-ft x 10-ft) contact length.
secondary chamber
hot offgas duct
quench column
venturi scrubber
absorption column
COLO MECHANICAL
EQUIPMENT ROOM
COVERED
SHIPPING-
RECEIVING
8 STORAGE
DOCK
PROCESS AREAS-,'.
HZONE i HZONE in
gzoNE H HZONE iv
...... .. .. ^ .......
Figure 5. Building ventilation zoned for containment.
11
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4.8 SAFETY ANALYSIS AND ENVIRONMENTAL ASSESSMENT
The facility housing the Los Alamos CAI has been subjected to a detailed safety analysis,6
including environmental assessment for operation with plutonium-bearing waste. Though
many hazardous waste concerns are similar to those for radioactive waste, the FSAR has been
reviewed to assure that the work force, public, and environment are adequately protected.
12
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SECTION 5
SAMPLING AND SAMPLING LOCATIONS
Sampling and analysis of all streams are essential during testing to evaluate incinerator
performance, to evaluate offgas system performance, and to detect and quantify products of
incomplete combustion or chemical reactions. Figures 6 and 7 show the location of sampling
points and data collection related to process conditions. Samples of the wood material were
subjected to POP analysis to determine the PCP content in the Incinerator feed material.
Appendix A discusses quality assurance (QA) measures taken to validate the testing.
| The configuration of the incinerator and offgas system does not allow isokinetic sampling
! upstream of the quench and scrub system. Nonisokinetic samples were taken from the hot-
zone interchamber and from the hot flue-gas duct upstream of the quench column. Sampling
trains on the hot-zone and hot flue-gas sample points were modified EPA-Method 5 {rains,
including a column of solid sorbent polymer (XAD-2*). Each sample train was used to collect
samples for a 4-h period based on preliminary estimates of detection limits, conversions, and
feed concentrations. A second 4-h sample was collected at each point before modifying the
combustion conditions. The preliminary calculations which led to selection of a 4-h sample
WASTE
- COMBUSTION AIR
i— NATURAL GAS -
S SOLID SAMPLE
G GAS SAMPLE TRAIN
T TEMPERATURE MEASUREMENT
°2
Cn ION-LINE
"2 ANALYZER
CO J
TO OFFGAS CLEANING SYSTEM
UNDERFIRE
AIR
TO PLANT
VENTILATION
SYSTEM
Figure 6. Incineration sample points.
13
-------
F FLOW MEASUREMENT
L LIQUID SAMPLE
G GAS SAMPLE TRAIN
£° JON-LINE
tuz (ANALYZERS
NO,)
FROM
INCINERATOR
CARBON BED
ADSORBER
DEMISTER
PACKED COLUMN
-VENTURI SCRUBBER
QUENCH COLUMN
PROCESS HEPA FILTER PLENUM
Figure 7. Offgas system sample points.
period are shown in Appendix B along with recalculations based on actual run data. Gas
samples were also taken downstream of the HEPA filters and downstream of the carbon bed
adsorber prior to discharge through the facility stack. These samples were passed through a
XAD-2® column for organics collection, and the final sample was passed through NaOH
solution for HCI determination.
Solid samples of the feed material and bottom ash were taken to provide data oh the quantity
of PCP fed to the incinerator that remained uncombusted in the ash. The feed sample was used
to identify the principal organic hazardous constituents (POHCs) as required in the EPA
incinerator standards published in the January 23, 1981, Federal Register." The bottom ash
samples were collected at the ash packaging station following discharge from the incinerator
and conveying to the collection system. Ash samples were collected after each transfer and
retained in separate containers.
Post-run samples were taken of the scrub liquid filters. No material was present on the HEPA
filters.
; In addition to the usual incinerator control instrumentation, on-stream instrumentation
included combustibles/02 analysis on the incinerator interchamber and on the secondary
chamber discharge, CO and C02 analysis at the secondary chamber discharge and the
absorber tower discharge, and final flow measurement on the HEPA filter plenum discharge.
The combustibles/02 analyzer is used primarily for 02 analysis. As a safety feature, the
instrument also indicates when excess fuel (as total hydrocarbons) is present. Auxiliary fuel gas
flow is controlled on temperature, and burner combustion air flows are controlled on ratio to
14
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fuel gas. Auxiliary fuel gas, burner air, underfire air, secondary air, and final offgas flows are all
measured and recorded.
Samples were analyzed at Los Alamos facilities and at Southwest Research Institute (SWRI),
San Antonio, Texas. Gas analyses were done with gas chromatography (GC) and/or systems
with various detectors Including a GC-mass spectrometer system (MS) with ^computerized
data base for species identification and quantification. More details on analytical procedures
are provided in Sec. 8. Detailed sampling Information is given in the following subsections. .
5.1 POP-TREATED WOOD SAMPLES
Samples of PCP-treated wood were collected at random from the more than 2 T of smashed
ammunition crates supplied by DPDS for the test burn. The wood samples were Soxhlet
extracted with toluene at 102°C for 24 h and the extract analyzed as detailed In Sec. 8 to
determine the POP content of the feed material. These samples determined POHCs In the feed
material as required by the EPA incinerator standards published in the Federal Register.*
Chlorine content of the feed material was found to be less than 0.08 wt%. •
5.2 ASH SAMPLES
Samples of ash were collected during ash transfer from the incinerator and held in separate
containers. The incinerator primary chamber was vacuumed between the untreated wood and.
PCP-treated wood phases of the test to assure that the treated-wood ash was not diluted.
[ A portion of each ash sample was Soxhlet extracted with toluene at 102°C and the extract
1 subjected to analysis as detailed in Sec. 8.
5.3 GAS SAMPLING
| Four locations were selected for gas/particulate sampling in the incineration and offgas
systems. System configuration1 and radioactive contamination from previous testing limited
sampling capabilities. However, adequate sampling was achieved by following the procedures
detailed below for each sample location.
5.3.1 Hot-Zone Sample
Hot-zone samples were collected from the connecting duct between the primary and
secondary incineration chambers. The duct is rectangular in cross section with dimensions as
shown in Figure 8. The sampling train used at this location was a modified EPA-Method 5 train
with a high-temperature probe. The probe was stainless steel with water jacket cooling. The
filter holder and filter were omitted from this train and the particulate collected in the cyclone
separator and impingers. The first impinger contained 250 ml of toluene and was followed by
two impingers containing 250 mL each iso-octane (2, 2, 4 trimethyl pentane). A column
containing solid XAD-2® sorbent was included between the third and fourth impingers to collect
any trace organics not captured in the solvent impingers. The fourth impinger contained 200 g
15
-------
t
g
2
i
I
• oid nt
tJSZ CM — «|
aai CM -«•
•-
SAMPIi
PORT
Figure 8. Hot-zone traverse points (primary chamber outlet).
(7 oz) of indicating silica gel to collect moisture from the gas sample upstream of the pump,
gauges, and dry gas meter. All impingers were cooled by immersion in an ice bath.
The sampling probe was limited to a single sample plane as shown in Figure 8, and each 4-h
sample included 20 min at each of 12 traverse points in the duct.
5.3.2 Hot Offgas Sample
The hot offgas samples were collected from the offgas duct upstream of the quench column.
i The duct dimensions and sample location are shown in Figure 9.
The sampling train was similar to the train described in Sec. 5.3.1 except that the probe was
i stainless steel with a tantalum nozzle. The probe was limited to a single plane, and samples
| were taken at equal intervals during each 4-h sample period at the 10 traverse points shown in
I Fig. 9. Nominal sample flow was% 14.2 L (3.7 gal)/min at standard, conditions. •>
i • ' • -
i 5.3.3 Downstream Gas Samples
Two sample locations were downstream of the incinerator offgas cleanup system. The offgas
system includes not only the quench high-energy scrubber absorber system but three stages
of HEPA filters and an activated carbon adsorber. The HEPA filters, which are nuclear grade,
have been tested with dioctylpnthalate to pass a minimum efficiency criterion of 99.97% of 0.3-
nm particles. .
The first downstream sample point followed two banks of these filters and the second
followed the full-flow carbon bed adsorber and a third bank of HEPA filters. These samples
were of a homogeneous gas phase with essentially no particles. Therefore, the sample trains at
these locations did not require a sample probe and traverse. Samples were withdrawn through
a tube open to the gas stream, the collection train at both locations consisted of a single
impinger containing 250 mL of iso-octane followed by a XAD-2® trap and sample monitoring,
controlling, and pumping equipment. Desired sample flow was 14.2 L (3.7 gal)/min at standard
conditions.
16
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SAMPLE
PORT
* 1.27 CM
4.06 CM
7.37 CM
11.43 CM
17.27 CM
50.80 CM
Figure 9. Hot crossover duct traverse points (afterburner outlet).'1
5.4 OFFGAS CLEANUP WATER SAMPLES
• i
Samples of the offgas stream scrub solution were taken during each sample period and were
extracted with toluene to capture TCDD or other chlorinated organics from the solution. The
organic fraction was separated and saved for analysis as described in Sec. 8.
Sample locations for scrubber liquid included the quench column sump, absorber column
sump, and recycle solution. An additional sample was taken of the condensate from the offgas
condenser.
5.5 MISCELLANEOUS SAMPLES
: Other samples were taken whenever operating events occurred that could potentially
remove material of interest from the system. Such events included changing scrub solution
filters during the run and inspecting HEPA filters after the run.
17 .
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SECTION 6
TEST PLAN
The purpose of the testing was to determine the destruction efficiency for PCP-treated wood
as a feed component to the Los Alamos CAI simulating conditions obtainable in a proposed
disposal incinerator in Korea. Potential existed for studying the effects of feed rate, incinerator
temperature, and excess air (and, indirectly, residence time) on the destruction efficiency (DE)
for PCP. Operating conditions included those which would best model the incinerator
proposed for final disposal of the subject feed material.
Available information on the proposed incinerator indicates that It is a single-chamber, oil-
fired, forced-draft unit. Waste is manually fed to the combustion chamber, which operates at
variable temperatures up to a maximum of 1200°C (2192°F). These conditions could be
modeled best by operating the Los Alamos unit and sampling between the primary and
secondary chambers to evaluate the effectiveness of a single chamber. Information on
temperature profiles, feed rates, and offgas flow rates for the proposed disposal incinerator
was not available; therefore, the testing was designed to evaluate performance at several
temperature/residence time values which should be obtainable in the proposed unit.
6.1 PROCEDURAL REQUIREMENTS
Before conducting test burns, several procedural steps were necessary. Since the facilities
at Los Alamos are operated for the US Department of Energy (DOE), an Interagency
Agreement (IAG) between DOE and EPA was required before testing could begin. This
agreement was secured as IAG No. AD-89-F-1 -539-0.
6.2 CONTAMINATED WOOD SUPPLY
PCP-treated wood for testing was as similar as possible to the treated wood for which
disposal options were being evaluated. Actual ammunition crate wood was supplied for use in
the test runs by DPDS, a co-sponsor of this program.
The ram feeder system on the CAI is designed to load 0.31-m x 0.31-m x 0.62-m (1-ft x 1-ft x
2-ft) boxes or bundles of waste. Slightly larger loading configurations are possible, but
modification of the system to alter the feed configuration significantly did not appear to be
warranted. Therefore, the wood was packaged in the standard boxes at a density of 160.2
kg/m3 (10 Ib/ft3) or 9.08 kg (20 lb)/box and fed through the existing feed train.
6.3 OPERATING CONDITIONS
The test plan was designed to provide combustion data over a range of conditions to qualify
a proposed incinerator for PCP-treated wood disposal. Input from the DPDS and EPA was
.18
-------
requested for use in establishing initial test operating conditions to produce the maximum of
useful data. The CAI can be operated at a wide variety of conditions utilizing temperature
control on chambers with combustion and secondary air control to establish desired levels of
excess air. Operating the system at a variety of conditions seemed desirable to provide
parametric data as well as to model the proposed Korean incinerator. The run was separated
into two phases: Phase 1 with untreated wood and Phase 2 with PCP-treated wood. The second
phase consisted of four test periods at various operating conditions.
6.4 TEST SCHEDULE
i
; The first phase involved system startup and operation with untreated wood to verify that the
system was functioning properly with no major problems related to complete combustion of the
wood. This phase was also to be used to obtain baseline (blank) samples for analysis. The
second phase involved testing with PCP-treated wood at conditions specified to simulate the
candidate system and to study the combustion characteristics of the PCP-treated wood. Table
i 1 gives the planned basic test schedule and Table 2 gives the planned operating conditions
(experimental design). •
| The actual test run was about 1 day longer than planned due to several operational problems
during the test period. A run chronology is given In Table 3. Problems which may have
impacted sample results and deviations from the experimental design are discussed in Sec. 7.
19
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TABLE 1. CONCEPTUAL TEST SCHEDULE: PCP-TREATED WOOD RUN 1
Test day Time
Activity
1 0815 Begin startup.
0915 Fire lower chamber burner.
Fire upper chamber burner as needed.
Heatup at 38° C (100°F)/h.
2 0515 Lower chamber at 925°C (1700°F).
0715 Upper chamber at 1010°C (1850° F)
0730 Collect liquid samples and blanks from particulate and offgas sample
trains.
0830 Begin untreated wood feed [45.4 kg (100 lb)/h], period 1.
Begin offgas sample collection.
1230 Collect samples.
1800 Begin second sample interval.
1900 Collect samples.
1930 Adjust operating conditions.
2100 Begin phase 1, period 2 sampling.
3 0100 Collect samples.
0230 Begin second period.
0630 Collect samples.
0730 Begin cooldown.
4 Continue cooldown.
5 0200 Open lower chamber to vacuum ash from hearth. Collect ash sample.
0600 Relight burners, begin heatup for PCP-treated wood phase.
6 1400 Verify operation of all sampling, analysis, offgas cleanup, and safety'
systems. Unit at 927°C (1700°F) lower, 1204°C (2200°F) upper.
1430 Start PCP-treated wood feed at 27.2-kg (60-lb)/h rate, operating
conditions as given in phase 2, period 1, of Table 2.
1830 Collect samples.
1930 Begin second sample interval, period 1.
2330 Collect samples.
7 0100 Increase feed to 45.4 kg (100 lb)/h; adjust conditions given for phase
2, peripd 2, in Table 3. «> s
0500 Collect samples.
0630 Begin second sample interval, period 2.
1030 Collect samples.
1100 Adjust operating conditions.
1200 Begin phase 2, period 3.
1600 Collect samples.
1730 Begin second sample interval, period 3.
2130 Collect samples.
2200 Adjust operating conditions.
2300 Begin phase 2, period 4.
8 0300 Collect samples.
0530 Begin second sample interval, period 4.
0930 Collect samples.
1030 Begin cooldown.
9 1200 Complete shutdown.
10 0900 Open lower chamber, clean and collect additional ash samples.
20
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TABLE 2. PLANNED OPERATING CONDITIONS
OFFGAS SYSTEM CONTROL SETTINGS
Venturi AP
Venturi solution flow
Absorber solution flow
Quench liquid flow
Solution pH (absorber, quench, and venturi)
Condenser gas-phase temperature decrease
Superheater temperature increase
HEPA filter AP
14.9 kPa (60 in. W.G.)
30.3 L/min (8 gal/min)
18.7 L/min (5 gal/min)
60.6 L/min (15.7 gal/min)
8 to 9
17°C (30°F) normal*
17°C (30°F)
0.02 to 0.42 kPa (0.005 to 0.1 in. W.G.)
normal*
• Normal values - not controlled.
INCINERATOR
Lower chamber pressure 0.49 kPa below ambient (-2 in. W.G.)
Steam to lower chamber 2.3 kg (5 lb)/h (for cooling steam nozzles)
Phase 1: Baseline with untreated wood
Period 1: Feed 45.4 kg (100 lb)/h
Upper chamber temp 1010°C (1850°F) 02
Lower chamber temp 927°C (1700°F) 02
Period 2: Feed 45.4 kg/h
Upper chamber temp 1093°C (2000°F) O2
Lower chamber temp 1010°C (1850°F) 0,
Phase 2: Variation of temperature, treated wood, feed rate,
excess air
Period 1: Feed 27.2 kg (60 lb)/h *>
Upper chamber temp 1204°C (2200° F)
Lower chamber temp 927°C (1700°F)
Period 2: Feed 45.4 kg (100 lb)/h . ,
Upper chamber temp 1204°C (2200°F)
Lower chamber temp 1038°C (1900°F)
Period 3: Feed 45.4 kg (100 lb)/h
Upper chamber temp 1204°C (2200°F)
Lower chamber temp 927°C (1700°F)
Period 4: Feed 45.4 kg (100 lb)/h
Upper chamber temp 1093°C (2000°F)
Lower chamber temp 927°C (1700°F)
02
0,
10%
5% min.
10%
5% min.
10%
5% min.
10%
2% min.
10%
0%
10%
5% min.
21
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TABLE 3. PCP RUN CHRONOLOGY
Test day Time
Event
1
0815
0915
1000
1430
1635
1755
2000
2030
2100
0100
0200
0930
1030
1105
1445
1815
2330
0250
0125
0215
0218
0220
0230
0330
Began startup.
Auxiliary generator - 400.8 h, fuel tank 11,355 L (1000 gal) (full).
Lost probe tip from interchamber probe into lower chamber
(quartz liner and tip).
Replaced caps on sample probe ports.
Programmable set point malfunctioned. Pen was hanging up on
drum.
Lost lower burner several times. Relit.
Programmable set point pen hanging up.
Lower burner flame out when secondary air blower started up.
Combustion air to gas ratio controller setting changed to 475.
Both burners off on ID blower shutdown. Relit. Reset program-
mable set point.
Lost lower burner several times. Reset ratio controller to 325.
Tempering steam on at 2.8 kg (6.2 lb)/h. Programmable set
point not tracking. Went to manual control of heatup.
Inserted interchamber sampling probe. Turned on cooling
water at 8 L (2 gal)/min after inserting probe. Quartz tube broke
from thermal shock.
Interchamber probe broken. Undetermined amount of water
flowed into lower chamber.
Cycled ash door to remove broken glass from probes. Noted
water in GADOS. Water was drained and contained. No spread
of contamination. Absorber liquid flow valve on manual.
Absorber sump high-level alarm. While draining absorber
sump, venturi pressure drop cycled erratically. Lower chamber
high-pressure alarm caused a controlled shutdown. Positive
incinerator pressure necessitated shutdown of burners. Fast
shutdown probably initiated by low HEPA filter pressure drop.
Reduced liquid flow to absorber tower; changed liquid filters.
Recovered system. "
Relit lower burner. Back on manual heatup.
Absorber sump high-level alarm. Reduced absorber flow. Low-
level alarm. Increased flow. ,
Tested interchamber sampler. Water was drawn into impingers
showing that glass liner in probe had broken. Began replace-
ment of glass tube with SS tube.
New probe liner installed.
Fed first box of untreated wood, period 1 of phase 1.
Started first sample period.
Second box fed as load timer was set to zero. Burners shut
down due to low HEPA pressure drop. Recovered system.
Lowered feed rate to 27.2 kg (60 lb)/h. Dropped lower chamber
temperature controller to 900°C (1652°F).
Raised lower chamber temperature controller to 927°C
(1700°F).
22
-------
TABLE 3. (cont)
Test day Time
Event
0600
0618
1055
1300
1303
1700
1900
2040
0040
0440
0900
0945
1345
2030
2130
0055
0330
1800
2000
1005
1025
1125
1300
1545
1825
2225
2245
2250
0100
0200
0340
0430
0510
0540
Guillotine door stuck in up position during charging cycle. Main
ram cycled. Lowered door by manually operating relays. Cycled
ram several times without problems.
Finished sample period.
Cycled ram four times. No problems.
Loaded box.
Started second sample period, phase 1, period 1.
Finished second sample period, phase 1, period 1.
Transferred ash. Large amount of water mixed with ash after
transfer due to earlier probe failures.
Fast shutdown caused by high chamber pressure while trying to
obtain 10% O2 in upper chamber. Decided to run at lower O2
level.
Started first sample period, phase 1, period 2.
Ended first sample period, phase 1, period 2. *
Changed quench filters.
Started second sample period, phase 1, period 2.
Finished second sample period, phase 1, period 2. Started
cooldown.
Shut off lower burner.
Shut off upper burner.
Shut off secondary air blower.
Changed one sample pump arid gauges on the carbon bed
sample system. .
Opened lower chamber door. Little ash present. Took photo-
graphs. Vacuumed out all ash with wand.
Ash transferred, lower chamber buttoned up. Began startup.
Fed first box, phase 2, period 4. Burner flame out due to burner
being at high fire when charging. Raised underfire air to 75.
Feed rate increased to 36.3 kg (80 lb)/h. ' .,
Started first sample, phase 2, period 1.
Box stuck inside ram; ram hung up on a piece of wood from box.
Box burnt in ram with guillotine door in up position. Subsequent
feed cycles satisfactory. » .
Finished first gas sample, phase 2, period 1.
Started second gas sample, phase 2, period 1.
Finished second sample, phase 2, period 1.
Low fuel level light on at auxiliary generator.
Auxiliary generator down.
Auxiliary generator fuel arrived.
Fuel oil transfer pump impeller damaged (apparently broken
up). Replaced pump.
Found caustic pump leaking.
Replaced caustic pump.
Resumed feed at 27.2 kg (60 lb)/h.
Burner flame out on first two feed cycles. Lower burner placed
on manual control.
23
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TABLE 3. (cont)
Test day Time Event
8 0550 Started first sample, phase 2, period 2.
0950 Finished first sample, phase 2, period 2.
1100 Started second sample, phase 2, period 2.
1500 Finished second sample, phase 2, period 2.
- 1530 Transferred ash.
1600 Started first sample, phase 2, period 3.
1720 Alarm indicated high lower chamber temperature.
1750 Reset lower chamber high-temperature switch.
1830 Switched to east bank of quench filters. Changed out west bank.
2000 Finished first sample, phase 2, period 3.
2240 Started second sample, phase 2, period 3.
9 0040 Lower burner flame out. Relit.
0130 Additional loss of flame on lower burner when minimum stop
was reduced.
0240 Finished second gas sample, phase 2, period 3.
• 0550 Replaced sample line for interchamber probe.
0600 Started first sample, phase 2, period 4.
1000 Finished first sample, phase 2, period 4.
1200 Started second sample, phase 2, period 4.
1340 Fast shutdown caused by high lower chamber temperature
indication. Chart did not show rise in temperature.
1430 Fast shutdown, same problem. Secured thermocouple leads
; which solved problem.
1600 Finished second sample, phase 2, period 4. Began shutdown.
24
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. I
SECTION 7
TEST RUN
The test run, as completed, differed from both the conceptual test schedule (Table 1) and
from the experimental design. The deviations, reasons for the deviations, and impact of the
deviations are discussed in the following subsections.
7.1 OFFGAS SYSTEM CONTROL SETTINGS
No major problems were experienced with the offgas system operation or control during the
test run.
•
A minor problem with the absorber liquid flow indicator resulted in lower than planned liquid
flow to the absorber. The flow was maintained at 15.9 L (4 gal)/min through phase 1 of the test
and 17.4 L (4.5 gal)/min through phase 2. _._ ...
| A problem with the caustic addition pump following the phase 1 test resulted in a process
liquid pH of approximately 6.5 during period 1 of phase 2 tests. The pump was replaced and pH
I returned to the 8-9 range for the duration of the run.
i . '' • • .
i
| All other offgas system parameters remained normal throughout the run, and no impacts
were expected from the minor deviations noted,
7.2 INCINERATOR
': The incinerator operated at a nominal pressure of 0.49 kPa below ambient (-2 In. W.G.)
throughout the run except for normal upsets during, waste charging operations. Negative*'
pressure is required to assure containment of hazardous materials within the process. Some
deviation was also noted with operation at 1205°C (2200°F) in the upper chamber but was not
.less than 0.37 kPa below ambient (-1.5 in. W.G.) during normal operation. This deviation was
caused by loading the offgas system to capacity, which was a test objective. No adverse impact
on sample data was expected from this deviation.
Other incineration conditions are discussed in the subsections dealing with individual test
periods.
7.3 SYSTEM STARTUP
: During startup of the incineration system, problems were discovered with the EPA-Method 5
sample probe in the hot-zone (interchamber) sample port. The probe was water jacketed and
quartz glass lined with a quartz glass tip. Leakage occurred from the water jacket around the
liner at the tip end of the probe. This leak resulted in thermal shock which fractured the quartz
• . 25
-------
glass tip. Several attempts to correct the problem failed. The probe liner was replaced with a
stainless steel tube and probe tip. No problems with the probe were encountered following the
change.
7.4 TEST PHASE 1, PERIOD 1
Test phase 1, period 1 was initiated at 0218 h on test day 4. Shortly after the start of the initial
sampling interval, a fast feed cycle caused a shutdown of both burners. Both burners were relit
without incident. The feed rate was lowered from 45.4 kg (100 lb)/h to 27.2 kg (60 lb)/h to keep
the lower chamber at the desired temperature. Feed was interrupted at 0600 h due to a
malfunction in the guillotine door on the incinerator feed ram. Because of this problem, the
lower chamber temperature fell to 705°C (1300°F). The problem was resolved at 0605 h and
feed was resumed. The first sample interval was concluded at 0618 h. Sample interval
conditions were
Planned
Actual
Feed Rate
Lower Chamber Temp
Afterburner Temp
Lower Chamber 02
Afterburner 02
45.4 kg/h (100 Ib/h)
927°C (1700°F)
1010°C(1850°F)
5% min.
10%
27.2 kg/h (60 Ib/h)
704°C min., 993°C max, 916°C avg*
(1300°F min., 1820°F max, 1680°F avg)
860°C min.,** 1054°C max, 1010°C avg
(1580°F min., 1930°F max, 1850°F avg)
6% avg
11% avg
•Does not include period following guillotine door failure.
"Due to temp drop on initial burner failure.
The second sample interval of phase 1, period 1, began at 1303 h and proceeded without
incident concluding at 1700 h. Sample interval conditions were
Planned
Actual
Feed Rate
Lower Chamber Temp
Afterburner Temp
Lower Chamber O2
Afterburner 0,
45.4 kg/h (100 Ib/h)
927°C (1700°F)
1010°C (1850°F)
5% min.
10%
27.2 kg/h (60 Ib/h)
849°C min., 971 °C max, 927°C avg
(1560°F min., 1780°F max, 1700°F avg)
1000°C min., 1038°C max, 1010°C avg
(1832°F min., 1900°F max, 1850°F avg)
6% avg
9% avg
7.5 TEST PHASE 1, PERIOD 2
Following completion of period 1, variables were adjusted in preparation for the second set
of operating conditions planned for phase 1 of the test. Sampling in the first interval was
initiated on day 5 at 0040 h. During the course of the interval, the lower burner went out several
times, but it was relit each time without difficulty. The main effect of burner failures is the
entrainment of participates in the off gas during relights. Temperature loss is minimal because
26
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sufficient heat is released by the burning wood. The sample interval concluded at 0440 h.
Operating conditions were
Planned Actual
Feed Rate 45.4 kg/h (100 Ib/h) 45.5 kg/h (100 Ib/h)
Lower Chamber Temp 1010°C (1850°F) 954°C min., 1054°C max, 1004°C avg
\ (1750°F min., 1930°F max, 1840°F avg)
Afterburner Temp 1093°C (2000°F) 1071°C min., 1127°C max, 1093°C avg
(1960°F min., 2060°F max, 2000°F avg)
Lower Chamber 02 5% min. 6% avg
Afterburner 02 10% 8% avg
The lower than planned 02 content of the afterburner effluent was due to loading of the
offgas system and resulting limitation on secondary air input.
The second sample interval of phase 1, period 2, was started at 0945 h on day 5 and
continued through 1345 h. Other than several flame failures on the lower burner, due to
problems with the air/fuel-gas ratio control, no problems were encountered with incinerator
operation in this interval. Conditions were as follows.
Planned Actual
Feed Rate 45.4 kg/h (100 Ib/h) 38.6 kg/h (8 5 Ib/h)
Lower Chamber Temp 1010°C (1850°F) 954°C min., 1043°C max, 1000°C avg
(1750°F min., 1910°F max, 1832°F avg)
Afterburner Temp 1093°C (2000°F) 1077°C min., 1121 °C max, 1093°C avg
(1970°F min., 2050°F max, 2000°F avg)
Lower Chamber O2 5% min. 6% avg
Afterburner 02 10% 8% avg
7.6 INTERIM BETWEEN TEST PHASES
^
At the conclusion of phase 1,"period 2, the incinerator was put into a controlled shutdown to
cool the unit and to remove ash resulting from burning the untreated wood. During the
downtime, adjustments and repairs were made to facilitate phase 2 operations. Shutdown and
restart proceeded smoothly. »
7.7 PHASE 2, PERIOD 1
This test was originally scheduled as phase 2, period 4. The schedule was changed to
provide a more orderly progression in temperatures. This rescheduling also delayed period 3
until the end of the test. This shift was desirable because period 3 had the most potential for
fouling equipment, sample trains, and lines.
Phase 2, period 1, was initiated on day 7 at 1125 h. Operations were normal until
approximately 1300 h. At that time, a feed box jammed in the side ram and tore open as it
entered the main feed ram housing. The main ram was blocked by a piece of loose wood, and
the box ignited in the ram housing with the incinerator guillotine door open. This resulted in a
27
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lower burner shutdown and a significant decrease in lower chamber temperature. Underfire air
was also reduced automatically. Several manually initiated cycles of the feed system cleared
the problem, and operation returned to normal at 1330 h, although the lower chamber
temperature remained low until 1345 h. The impact of this problem, if any, would be reflected in
the Method 5 probe hot-zone sample for this interval. The net result of the problem was low
temperature and low excess air in the lower chamber for a prolonged period, causing low
destruction efficiency for POP and related compounds. The sample interval concluded at 1545
h. ' \
The afterburner functioned normally throughout the disruption so that adverse effects were
not expected in the hot offgas sample.
Nominal conditions, including the upset period, for this sample interval were
Planned Actual
Feed Rate 45.4 kg/h (100 Ib/h) 36.3 kg/h (80 Ib/h)
Lower Chamber Temp 927°C (1700°F) 788°C min.,* 1000°C max, 918°C avg*
(1450°F min., 1832°F max, 1648°F avg)-
Afterburner Temp 1093°C (2000°F) 1077°C min., 1121 °C max, 1099°C avg'
(1970°F min., 2050°F max, 2010°F avg)
Lower Chamber 02 5% min. i 4% avg*
Afterburner 02 10% . • 8% avg
•Includes upset period.
The second sample interval of phase 2, period 1, began at 1825 h on day 7 and was
completed at 2225 h with no operational problems. An error in interpreting the run-plan change
resulted in a high lower chamber temperature. Interval conditions were
Planned Actual
Feed Rate 45.4 kg/h (100 Ib/h) 40.9 kg/h (90 Ib/h)
Lower Chamber Temp 927°C (1700°F) 927°C min., 1060°C max, 1002°C avg
(1700°F min., 1940°F max, 1836°F avg)
Afterburner Temp 1093°C (2000°F) 1027°C min., 1138°C max, 1104°C avg '
(1880°F min., 2080°F max, 2020°F avg)
Lower Chamber 0, 5% min. 5% avg
Afterburner 02 10% , 7.8% avg
The afterburner oxygen content continued to be low as a result of limitations on secondary
air input due to loading on the offgas system.
7.8 PHASE 2, PERIOD 2
Phase 2, period 2, was originally scheduled as phase 2, period 1. The first sample interval
was started on day 8 at 0550 h. The interval was completed without problems at 0950 h.
Operating conditions during the interval were
28
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Planned Actual
Feed Rate 27.2 kg/h (60 Ib/h) 29.5 kg/h (65 Ib/h)
Lower Chamber Temp 927°C (1700°F) 871 °C min., 993°C max, 927°C avg
(1600°F min., 1820°F max, 1700°F avg)
Afterburner Temp 1204°C (2200°F) 1188°C min., 1227°C max, 1202°C avg
(2170°F min., 2240°F max, 2196°F avg)
Lower Chamber 0, 5% min. 5% avg
Afterburner 0, 10% 7.5% avg
| The second sample interval ran with no problems from 1100 h to 1500 h on day 8. Interval
! operating conditions were
• Planned Actual
Feed Rate 27.2 kg/h (60 Ib/h) 31.8 kg/h (70 Ib/h)
Lower Chamber Temp 927°C (1700°F) 871 °C min., 1010°C max, 938°C avg
I (1600°Fmin.,1850°Fmax, 1720°Favg)
Afterburner Temp 1204°C (2200°F) 1199°C min., 1232°C max, 1210°C avg
(2190°F min., 2250°F max, 2210°F avg)
Lower Chamber O2 5% min. 6% avg
| Afterburner 02 10% 7.0% avg
7.9 PHASE 2, PERIOD 3
Phase 2, period 3, was originally scheduled as phase 2, period 2. The first sample interval
was started at 1600 h on day 8 and continued with no problems until 2000 h. Interval operating
conditions were
• ' Planned Actual
Feed Rate 45.4 kg/h (100 Ib/h) 40.9 kg/h (90 Ib/h)
; Lower Chamber Temp 1038°C (1900°F) 927°C min., 1071 °C max, 1027°C avq
! • T.1700°F min., 1960°F max, 1880°Favg)
Afterburner Temp 1204°C (2200°F) 1188°C min., 1238°C max, 1204°C avg
; (2170°F min., 2260°F max, 2200°F avg)
Lower Chamber 0, 5% min. , 5% avg
Afterburner 02 10% 6.5% avg
The second sample interval ran from 2240 h on day 8 to 0240 h on day 9. The only abnormal
occurrences were three flame failures on the lower burner. Since the wood feed rate was
; adequate to supply the required heat to the lower chamber, no impact on sample results was
expected. Conditions during the sample interval were
29
-------
Peed Rate
Lower Chamber Temp
Afterburner Temp
Lower Chamber 02
Afterburner O2
Planned
45.4 kg/h (100 Ib/h)
1038°C (1900°F)
1204°C (2200°F)
5% min.
10%
Actual
38.6 kg/h (85 Ib/h)
927°C min., 1088°C max, 1032°C avg*
(1700°F min., 1990°F max, 1890°F avg)
1193°C min., 1239°C max, 1204°C avg
(2180°F min., 2262°F max, 2200°F avg)
5% avg
6% avg
•Includes minor upset time.
7.10 PHASE 2, PERIOD 4
Phase 2, period 4, was originally scheduled as phase 2, period 3. This set of planned
conditions was likely to result in the poorest combustion conditions and a high potential for
fouled equipment and plugged sample lines; therefore, it was delayed to the last. The first
sample interval was started at 0600 h on day 9 and was completed at 1000 h. No operational
problems were encountered. Conditions during the first sample interval were
Planned
Actual
Feed Rate
Lower Chamber Temp
Afterburner Temp.
Lower Chamber 02
Afterburner 02
45.4 kg/h (100 Ib/h)
927°C (1700°F)
1204°C (2200°F)
0%
10%
29.5 kg/h (65 Ib/h)
904°C min., 1027°C max, 954°C avg
(1660°F min., 1880°F max, 1750°F avg)
1199°C min., 1232°C max, 1210°C avg
(2190°F min., 2250°F max, 2210°F avg)
1% avg
7.5% avg
The second sample interval'ran from 1200 h to 1600 h on day 9. At 1340 h, a false lower
chamber temperature high alarm automatically initiated a fast shutdown. This problem
recurred at 1430 h. The effect of these shutdowns was to increase the amount of uncombusted
material carried out with the off gas and, therefore, icito the samples. The sample results are
conservative for nominal test conditions. Conditions, including the upsets, during the final
sample interval were
Planned
Actual
Feed Rate
Lower Chamber Temp
Afterburner Temp
Lower Chamber 02
Afterburner 0,
45.4 kg/h (100 Ib/h)
927°C (1700°F)
1204°C (2200°F)
0%
10%
27.2 kg/h (60 Ib/h)
827°C min.,* 1000°C max, 916°C avg*
(1520°F min., 1832°F max, 1680°F avg)
1021 °C min.,* 1227°C max, 1174°C avg*
(1870°F min., 2240°F max, 2150°F avg)
0.5% avg
8.0% avg
'Includes upset time.
30
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7.11 TEST RUN SUMMARY
A summary of the actual operating conditions for all sample intervals is given in Figure 10.
Calculations and data summaries include combustion and residence time calculations in
Appendix B, destruction efficiency calculations In Appendix C, field data summaries in
Appendix D, combustion efficiency calculations and off gas composition data In Appendix E,
and sample and offgas flow calculations in Appendix F.
UJ
UJ
9
8
7
12
8
4
0
50
UJ
30
I
SECONDARY CHAMBER
PRIMARY CHAMBER
III 112 121 122 211 212 221 222 231 232 241 242
Figure 10. Average operating conditions during test interval dbc (a = test phase, b - test period, C = *•
sample interval).
. 31
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SECTION 8
PROCEDURES AND ANALYTICAL RESULTS
This section details procedures for sample preparation, analytical procedures used by Los
Alamos and SWRI, and results of analyses. The procedures were developed or modified for
use in this program through consideration of special requirements and accepted prac-
tices.1"1 7-13
8.1 SAMPLE PREPARATION
; After completion of each sample Interval during the PCP-treated wood test burn, the
samples were prepared for analysis using procedures that depended on the sample type. All
samples were refrigerated when not being analyzed.
8.1.1 Impinger Solvents
i . • - '
' Impinger solvents were separated from moisture condensed in the sample trains. Water.
; content was measured and recorded and the water discarded. The Impinger catch and probe
wash solvents were combined for a single sample from each train.
' Analyses at Los Alamos were performed on "as received" and concentrated samples.
Sample concentration was performed by vacuum drying a 25-mL sample at 40°C (105°F) and
taking up the residue in 500 nL of 1:1 iso-octane:toluene containing 25 ppm 1-fluoro-2, 4
dinitrobenzene as an internal standard. Triplicate spiked samples (1 ppm POP) were
simultaneously concentrated by the above method with an average recovery of 70%.
! *
Analyses at SWRI were done on sample concentrates prepared by reducing 30-mL samples
to 0.5 ml by evaporation under a gentle stream of chromatographic-grade nitrogen and adding
dB-naphthalene, d,0-anthracene, and d,2-chrysene as internal standards. Final concentrations
contained 51, 44, and 39 ng/jiL of internal standards, respectively.
8.1.2 Sorbent Traps
Sorbent traps (XAD-2*) from the offgas sample trains were labeled and capped immediately
after removal from the system. In preparation for analysis, the sorbent material was transferred
to a Soxhlet extractor and extracted with 200 mL toluene for 20 h achieving a minimum of 80
cycles. The extract was then submitted for analysis.
6.1.3 Silica Gel
Silica gel from the moisture traps was weighed to determine moisture content and then
stored. No additional analysis is planned.
32
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8.1.4 Aqueous Scrub Solutions and Filters
Samples of the aqueous scrub solutions were extracted with toluene in three contacts using
fresh solvent in each step. Extracts were combined prior to submitting the material to the
laboratory. Scrub liquid filters did not have sufficient particles on them to provide a meaningful
sample.
8.1.5 Ash
Ash samples were bagged in individual packages after phase 1 and after each period of
phase 2 of the test. A measured quantity of ash was placed In a Soxhlet extractor and extracted
with 200 mL toluene for 20 h achieving a minimum of 80 cycles. The solvent was then collected
and submitted for anlaysis.
8.1.6 Wood
I Samples of wood were taken at random from each packing case of shredded ammunition
crates. The wood was reduced to splinters, blended, and divided into two samples. *Each
'. sample of the wood was placed in a Soxhlet extractor and extracted with toluene at 1026C for
24 h. These extracts were then analyzed to provide Information on the POP content (0.106 wt%)
| of the feed. These extracts were also analyzed for the target compounds listed in Appendix G,
Table 1. None of these compounds, including TCDDs and TCDFs, were detected.
8.2. ANALYTICAL PROCEDURES
I • •
When submitted for analysis, all samples consisted of a solvent with unknown amounts of the
target compounds in solution. The solvent was either toluene or a toluene: iso-octane mixture.
The primary target compounds were pentachlorphenol, 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin,
and 2, 3, 7, 8-tetrachlorodibenzofuran.
Analyses were performed by the Los Alamos National Laboratory Industrial Hygiene Group
H-5 Analytical Section with some sample splits analyzed by SWRI. The following subsections
discuss procedures used by both laboratories in performing the analyses.
8.2.1. Los Alamos Procedures •
Samples were analyzed in both the "as received" and concentrated conditions using several
procedures. The "as received" samples were filtered to remove any particles entrained in the
solvents. Concentrations were obtained by evaporating 25-mL samples at 40°C (104°F) under
vacuum and taking up the residue in 500 uL of 1:1 toluene:iso-octane containing 25 ppm
1-fluoro-2, 4-dinitrobenzene as an internal standard.
i Three techniques were used in analytical work at Los Alamos. They were gas chromato-
graphy/mass spectrometry (GC/MS), gas chromatography/electrqn capture detection
(GC/ECD), and high-performance liquid chromatography (HPLC).
33
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8.2.1.1 Qualitative Analysis by GC/MS—
Filtered samples were analyzed on a Hewlett-Packard 5992 GC/MS Data System adapted
with a splitless capillary injection system and capillary restriction interface. This procedure is a
combination of a high-resolution GC and a low-resolution MS. The column was a 30-m (98-ft)
WCOT SE-54 fused silica capillary. Helium carrier gas at 165.5 kPa (24 psi) produced a
1.2-mL/min flow. The column oven was temperature programmed from 100°C (212°F) to
250°C (480°F) at 16°C (60°F)/min and held at 250°C (480°F) for a total of 60 min. Injector
temperature was 270°C (520°F). The instrument was tuned daily by the Hewlett-Packard
AUJOTUNE® program. Total ion signal over the range 20 to 600 amu was scanned at 380
amu/s. Simultaneously, the selected ion signal at 266 amu, corresponding to the most intense
ion in the mass spectrum of PGP, was monitored.
Under these conditions and for a 2-nL injection volume and a 30-s injection time, the 95%
confidence detection limit for PCP was 20 ppm.
8.2.1.2 Quantitative analysis by HPLC—
•
A Micrometritics 7000B HPLC was used with a 30-cm PARTISIL® PXCS 10/25 ODS-2
column. It was operated with constant carrier solvent composition at 1.5 mL/min with a solvent
of 99% cyclohexane, 0.97% acetic acid, and 0.03% acetic anhydride. The UV detector was set
at a wavelength of 300 nm to minimize absorption by the toluene solvent. The injection volume
was 90 nL. The internal standard used was 1-fluoro-2, 4-dinitrobenzene.
For this system under these conditions, the 95% confidence detection limit was 0.5 ppm
PCP, but only 10 ppm TCDD or TCDF. In the X50 concentrated samples, the 10-ppm detection
limit corresponds to 0.2 ppm in the original samples.
The HPLC method was developed for back-up use due to early problems encountered with
GC/ECD methods. It is discussed here only for information. The results were used for
preliminary evaluation of the test, but HPLC was not the primary technique for analysis.
8.2.1.3 Quantitative Analysis by GC/ECD— «
GC using an ECD was the method chosen for quantitative analysis of the test burn samples.
However, a great deal of difficulty was encountered in developing suitable procedures.
»
Three different GCs were used in attempts to develop a satisfactory analytical procedure.
The first was a Perkin-Elmer 900 GC with a Tracer "Ni ECD. The second was a Hewlett-
Packard 5710 with a Valco Model 140B wide-range ECD. The third was a Varian 2800 GC with
the same Valco ECD. The Perkin-Elmer and Varian chromatographs are set up to take only
packed columns, whereas the Hewlett-Packard will take only capillary columns.
A large number of columns and conditions were tried in an attempt to obtain a satisfactory
separation of the components of the samples. Among the columns tried were
3% OV-1 on Supelcoport;.
3% OV-101 on Supelcoport;
3% OV-101+1 H3P04 on Supelcoport;
3% OV-225 on Chromosorb G AW DMCS;
1% SP-1240 DA on Supelcoport;
34 . . •
-------
1% DEGS-PS on Supelcoport;
Tenax GC;
SE-54 WCOT capillary;
Superpack-20M
Chromosorb 102;
i Porapak P;
5% Dexil 300 on Anakrom ABS;
; 3% OV-17 on Chromosorb G AW DMCS;
| 3% SE-30 on Saraport 30; and
| 0.3% SP10000 + 0.3%H3PO«onCarbopakA.
i . •
i With most columns, the POP peak was extremely broad, even at the maximum .operating
temperatures of the column. Such broad peaks led to long analysis time, poor resolutions, and
1 poor detection limits.
i
Pentachlorophenol is a highly acidic, low-volatility compound which tends to decompose
| near its boiling point. This high acidity, combined with the high temperatures necessary to
! vaporize the compound and get it through a column, caused rapid degradation of the columns.
In some cases, a column would appear to give acceptable results initially, but after the first few
j injections of standards, the results would deteriorate rapidly to become totally unsatisfactory.
I In other cases, the POP would decompose or react to give more than one peak for standards
I which gave a single, sharp peak of the appropriate size when examined by HPLC.
i To cut down on the acidity and increase the volatility of the analyte, attempts were made at
I derivatizatjon of the POP. The derivatizing agents trimethylchlorosilane (TMCS), N, 0-Bis-
\ (trimethylsilyl)-acrylamide (BSA), and N-trimethyl-silyl-imidazole (TSIM) were all tried.14
i Chromatographic results indicated that either the derivatization did not occur or the derivative
was not stable under the Chromatographic conditions.
I The literature was not very, helpful when it came to POP analysis. A few recommended
columns were found, but examples given were for 1000 to 2000 ppm PCP, and the methods
would fail when tried at the 1 to 10 ppm levels.
i .' '
The most successful analysis using GC/ECD during early efforts was with a Varian 2800 GC
: and a Valco Model 140B wide-range ECD. The 15-m x 0.3-cm (50-ft x l/8-in.-o.d.) stainless
; steel column was packed with Tenax GC (60/80 mesh). Column temperature required was
; 280°C (540°F), at which point evidence of PCP decomposition was seen. Carrier gas flow was
'. 38 mL/min 9:1 argon:.methane. A 2^L injection gave a detection limit of 0.5 ppm PCP. After a
period of successful operation, this column also failed.
In preparing a new column, an attempt was made to improve performance by blocking
; adsorption sites via treatment with silanizing agents. The new column was a Supelco silane
1 treated glass column, and the packing material was Supelco SP 1240 DA. The column was
. mounted in the Hewlett-Packard 5736 GC and thoroughly purged with carrier gas. It was then
i attached to the 83Ni ECD. instrument conditions for good determination of PCP with this system
j were subsequently found to be
35
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Argon-Methane Carrier Flow Rate 40 mL/min
Injection Temperature 250°C (480°F)
Column Oven Temperature 170°C (340°F)
Detector Temperature 300°C (570°F)
Chromatograph Attenuation 2
POP standards were prepared with a 10-ppm sample purchased from Regis Chemical
Company* and by successive dilutions with toluene. Standard samples were prepared
containing 1.0, 0.10, and 0.01 ppm PCP. The detection limit was 0.015 ppm fora 2-nL injection
and the standard curve is reasonably linear to at least 10 ppm. Detection limits for TCDD and
TCDF were determined to be 1 ppb and 5 ppb, respectively.
8.2.2. Southwest Research Institute Procedures
Samples were reduced in volume from 30 mL to 0.5 mL under a gentle stream of
chromatographic-grade nitrogen. The internal standards de-chrysene were added to the
concentrated extracts prior to injection; the final concentrations of the internal standards were
51,44, and 39 ng/nL, respectively. ' '
: The instrument used for these analyses was a Finnigan 3623 quadrapole MS equipped with
an INCOS® data system and a Tracor 560 GC. The fused silica capillary column is threaded
through a heated conduit into the MS ion source.
Extracted ion current profiling was used to search for the following compounds in each total-
ion current (TIC) run: .
chlorophenols—mono through pentachloro;
chlorobenzenes—di through hexachloro;
chlorodibenzodioxins—mono through octachloro; and
chlorodibenzofurans—mono through octachloro.
The following instrument operating conditions were used for the TIC runs.
' GC s ' ,
Column 15-m (49-rt) x 0.25-mm (0.01-in.) fused silica capillary
Phase SE-54; 1.0 film
Carrier gas He at 40 cm (16 in.)/s ,
Temperature program 64°C (147°F) for 1 min then +10°C (50°F)/min up to 300°C (572°F)
Injector temperature 280°C (540°F)
Splitless injection
MS
Electron energy 70 eV
Scan rate 1 s/scan
Mass resolution 0.3 m/e
•Regis Chemical Co., 8210 Austin Ave., Morton Grove, IL 60053.
36
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Extracts were re-analyzed with the MS in the selected ion monitor (SIM) mode; target
compounds were pentachlorophenol (m/e 266, 268) tetrachlorodibenzodioxin (m/e 320, 322),
and tetrachlorodibenzofuran (m/e 304, 306). Other instrument operating conditions were
identical to those listed for the TIC runs.
Detection limits for the target compounds are given in Table 1 of Appendix G (note: the
reference to MID in Table 1 Is an old nomenclature for SIM). The limits given are in micrograms
per sample. The samples sent to SWRI were 30 ml each. Calculating the detection limits for the
primary target compounds gives 0.17 ppm for PCP and 17 ppb for TCDD and TCDF.
8.3 ANALYTICAL RESULTS
Duplicate extracts from samples of the PCP-treated wood were analyzed at Los Alamos and
found to contain 0.103% and 0.106% by weight of PCP to yield a chlorine content of 0.069 wt%,
well below the 0.5 wt% level requiring chlorine scrubbing at 99% efficiency. The measured PCP
I content is the basis for the destruction efficiency calculation shown in Appendix C and the
sample requirements calculations shown in Appendix B.
Results from analytical work on samples from the hot zone between the incinerator
chambers and from the secondary chamber offgas are given in Table 4. These samples were
the samples of primary interest in the test burn and were analyzed by both Los Alamos and
SWRI. Variations in reported amounts of PCP in the samples by HPLC and GC/ECD are
probably due to better component separation with the GC techniques.
No evidence of PCP, TCDD, or TCDF was found by Los Alamos in any scrub solution or ash
extracts. The detection limits were 15 ppb for PCP, 1 ppb for TCDD, and 5 ppb for TCDF.
Samples taken downstream of the offgas system both before and after the carbon bed showed
no evidence of the target compounds. Criteria for detection included a 0.1-min retention time
window with a response at 4 times noise level for PCP and a 0.05-min retention time window
with 4 times noise level response for TCDD and TCDF.
«
Analysis by SWRI revealed no evidence of PCP, TCDD, or TCDF in the gas stream samples
from the primary or secondary chambers or in extracts from the ash. Detection criteria'
concerning retention time window and signal-to-noise ratio for all target compounds were in
accordance with EPA Method 625, Part 14, Qualitative and Quantitative Determinations.
37
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TABLE 4. ANALYSIS OF PCP TEST SAMPLES
Results* (in sample)
Sample from
Sample** Phase Period Interval
HZ 1 1 1
HZ 1 1 2
HZ 1 2 1
HZ 1 2 2
HZ 2 1 1
HZ 2 1 2
HZ 2 2 1
HZ 2 2 2
HZ 23 1
HZ 2 32
HZ 241
HZ 2 4 2
HZ individual samples from
all test intervals
Ash individual samples from
phase 1 and each
phase 2 period
Scrub composite of all
liquids phase 2 periods
HZ XAD-2 2 2 1
OG XAD-2 2 2 1
HZ XAD-2 2 4 1
OG XAD-2 2 41
HZ XAD-2 24 2
OG XAD-2 24 2
HZ XAD-2 composite of other phase 2
OG XAD-2 composite of other phase 2
•GC/ECD and HPLC by Los Alamos.
GC/MS by Southwest Research Institute.
by GC/ECD
PCP
NDt
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
TCDD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
TCDF
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
>
by HPLC
PCP
ND
ND
ND
ND
1.64 ppm
ND
ND
ND
ND
ND
0.41 ppm
5.09 ppm
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
by GC/MS
PCP
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
— tt '
...
—
...
—
—
...
—
—
TCDD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
...
...
. ...
—
—
...
—
...
...
TCDF
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
...
—
.—
—
—
—
—
...
•,
"Sample HZ = Hot zone between primary and secondary chambers;
OG = Ortgas (secondary chamber effluent);
XAD-2 = Sorbent polymer extracts.
»
tNO = Below detection limits which are:
! 15 ppb for PCP by CG/ECD (Los Alamos), ,
1 ppb for TCDD by GC/ECD (Los Alamos),
5 ppb TCDF by GC/ECD (Los Alamos),
10 ppb for PCP by HPLC (Los Alamos),
170 ppb for PCP by GC/MS (Southwest Research Institute),
i 17 ppb tor TCDD and TCDF by GC/MS (Southwest Research Institute).
ft— indicates not analyzed.
-------
SECTION 9
DISCUSSION OF RESULTS
In the results of offgas sample analyses shown In Table 4, an apparent discrepancy exists
between the results by HPLC and by GC/ECD techniques. This difference is most likely due to
a non-PCP compound with a similar retention time in the HPLC system being reported as PCP.
The HPLC work was done to provide preliminary data while problems with the GC/ECD
procedure and equipment were resolved. No evidence of TCDF or TCDD was found in any
sample by any of the analytical methods. The SWRI results, attached as Appendix G, show
evidence in major peaks of some hydrocarbon components typical of wood burning. These
peaks are not quantified.
•
The DE for PCP in the primary chamber was greater than 99.99% in all cases, based oh the
Los Alamos GC/ECD analytical data on concentrated samples. A sample DE calculation and
results for all sample intervals are given in Appendix C. The actual DE for PCP during normal
operation is expected to be much better than 99.99%, but the low concentration of PCP on the
feed material and the difficult analysis for low levels of PCP in the offgas have precluded
verification of a higher efficiency.
I Results indicate that PCP-treated wood can be incinerated at controlled conditions so as to
', achieve >99.9% CE (>99.99% DE) without producing detectable Jevels of TCDD or TCDF. To
achieve this, conditions in the primary chamber varied between approximately 910°C (1670°F)
and 1025°C (1877°F) with oxygen concentrations in the chamber between 0.5% and 6.0%.
Retention time for the gas phase in the primary chamber varied between 2.5 and 3.5 s based on
effective use of 66.6% of the primary (lower) chamber volume. The remainder of the volume is
considered ineffective because the burning waste pile extends about one-third of the hearth
length. ,
«,
s
It is the authors' judgement that proper operation of a single-chamber incinerator should
also allow destruction of PCP-treated wood to the 99.99% DE level for PCP. Recommendations
for such proper operation include:
• minimum chamber temperature >980°C.(1800°F),
• gas retention time >2.5 s,
• avoidance of overfeeding that causes excessive smoking or low Instantaneous excess
oxygen levels, •
• excess air >20% (oxygen >3% in offgas), and
• adequate time for ash burnout before adding fresh feed.
Any incinerator proposed for use should maintain these conditions to assure 99.99% DE of
the PCP in the feed and to avoid formation of TCDD and TCDF.
39
-------
REFERENCES
1. Lusten, Houwer, K. Olie, and 0. Hutzinger, Chlorinated Dibenzo-P-Dioxins and Related
Compounds in Incinerator Effluents. Chemosphere 9:501-522,1980.
2. Ahling, B. and L. Johansson. Combustion Experiments Using Pentachlorophenol on a Pilot
Scale and Full Scale. Chemosphere 7:425-436,1977.
3. Rappe, C. and S. Marklund. Formation of Polychlorinated Dibenzo-P-Dioxins (PCDDs) and
Dibenzofurans (PCDFs) By Burning or Heating Chlorophenates. Chemosphere 3:269-281,
1978.
4. The American Society of Mechanical Engineers Research Committee on Industrial and
Municipal Wastes. Study on State-of-the-Art of Dioxin From Combustion Sources. New
York. NY, 1981, 78 pp.
•
5. Warner, C. L., Ed. Final Safety Analysis Report for the Transuranic Contaminated Solid
Waste Treatment Development Facility. Report LA-7971-MS, Los Alamos Scientific Labo-
ratory, Los Alamos, NM, 1979.
6. Federal Register, January 23,1981, pp. 7666-7690.
7. Hall, J. et al. Evaluation of PCP Destruction Efficiency in an Industrial Boiler. GCA
Corporation, Technology Division, Bedford, MA, 1980,19 pp.
8. Sano, T. L., D. R. Moore, and D. G. Ackerman. Emissions Testing During Incineration of
PCBs at Rollins Environmental Services, Inc., Deer Park, Texas. TRW Incorporated,
Environmental Engineering Division, Redondo Beach, CA, 1981,130 pp.
9. Cavallaro, A. et al. Sampling Occurrence and Evaluation of PCDDs and PCDFs From
Incinerated Solid Urban Waste. Chemosphere 9:611-621,1980. ' s
10. Ivanov, Z. and R. J. Magee, The Determinations of Trace Amounts of Chlorophenols by
High-Performance Liquid Chromatography. Microchemical Journal 25:543-547,1980.
»
11. diDomenico, L. et al. Analytical Techniques for 2, 3, 7, 8-Tetrachlorodibenzo-p-dioxin
Detection in Environmental Samples after the Industrial Accident at Seveso. Analytical
Chemistry 51(6): 735-740, 1979.
12. Nestrick, J., L. L. Lamparski, and R. H. Stehl. Synthesis and Identification of the 22
Tetrachlorodibenzo-p-dioxin Isomers by High Performance Liquid Chromatography and
Gas Chromatography. Analytical Chemistry 51(13): 2273-2281, 1979.
13. McKinney, J. D., Ed. Environmental Health Chemistry, The Chemistry of Environmental
Agents as Potential Human Hazards. Ann Arbor Science Publishers, Inc., Ann Arbor, Ml,
1981,656pp.
14. The Regis Chemical Company. Regis Derivatization Guide. Morton Grove, IL, 1981.
40
-------
APPENDIX A
QUALITY ASSURANCE
During this study efforts were made to validate all procedures and to provide assurance that
the data obtained in the POP test burn were reliable. Details of the QA considerations are given
; in the following sections.
j
A.1 METHOD 5 TRAINS
i
| Calibration data were available for sample train pitot tubes and gas meters. Pitot and probe
tips were carefully examined before each sample period to note any damage or other
1 problems. ;
: A. 1.2 Glassware
! All glassware was carefully cleaned by washing with soap and water followed by sequential
: rinses with de-ionized water, acetone, methanol, and methylene chloride before each use.
Organic rinse materials were collected and checked for residues by the same methods used for
normal samples.
i _ _.-.'' ' .
i Ground glass fittings were lightly greased only on outside edges to facilitate sealing and to
' avoid sample contamination.
A. 1.3 Sample Bottles and Traps
All sample bottles were amber glass or foil-wrapped glass with TEFLON® seals in the lids.
Sample traps (XAD-2® columns) were wrapped with aluminum foil to avoid UV exposure. •>
»
A.1.4 Reagents
All reagents used in sample collection and glassware rinsirfg after sample transfer were
distilled-in-glass materials.
A.2 MONITORING EQUIPMENT
The incineration and offgas systems are equipped with extensive monitoring and control
devices. Critical elements are checked regularly and calibrated to assure operability and
reliability.
A
Prior to the run, on-line monitors, including analyzers for 02, C02, and CO, were zeroed and
calibrated using appropriate techniques. CO-CQ2 monitors were calibrated with a zero gas,
full-span gas, and a mid-range gas and the calibration was checked daily during the burning of
test materials.
: 41
-------
A.3 SAMPLE LABELING AND CONTROL
All samples were identified by source, date, time, and collector. A unique sample identifi-
cation number was assigned and a chain of custody was established for all samples when they
were collected.
A.4 ANALYTICAL PROCEDURES
Assurance of the adequacy and reliability of analytical procedures is recognized as a major
portion of the overall test program. A comprehensive program utilizing blanks and standards
was developed to provide such assurance.
A.4.1 Blanks
* Blanks were established for all types of samples and were included in sample sets subjected
: to analysis for the test run. Typical blanks for the PCP test run included
i (a) ash from untreated wood burning, ' '
i (b) impinger solutions (unused solvents), and
i (c) scrub solution makeup water.
Such blanks were given a sample identification number and were included with regular
samples from the run.
i
A.4.2 Standards •
Standards of chemicals of primary interest were obtained and used to spike samples for
procedure verification. Standards were also used to calibrate analytical instruments, i.e., the
GC/MS and GC/ECD systems. On the Los Alamos GC/ECD system, standards were run twice
daily. Standard frequency at SWRI on the GC/MS was at least once and usually two or three
times daily.
A.4.3 Duplicate Samples
*
The test plan included provisions for two sample periods at each set of operating conditions.
While this did not provide a true duplicate sample, it did provide back-up samples in case
some samples were lost or spoiled during analysis. Selected samples were split and, after the
samples were shown to be free of radioactive contamination, they were sent to SWRI for
analysis.
A.5 RECORDS
Sample records are maintained in a bound pre-numbered notebook. The record consists of
the unique sample identification number, the sample type (impinger solution, ash, etc.), sample
j location, date, time, and initials of the operator who collected the sample. Analytical results
' were entered in the notebook when received.
I Records accompanying each sample include only the sample identification number and
. type. Information such as sample location, operating conditions, time, etc., did not accompany
the samples.
42 ' .
-------
APPENDIX B
: COMBUSTION, RESIDENCE TIME,
AND SAMPLE REQUIREMENTS CALCULATIONS
i
The following preliminary calculations were performed prior to testing to predict offgas
1 flows, residence times, and sampling time needed to verify a 99.99% destruction and removal
efficiency for POP and to detect TCDDs and TCDFs in the offgas stream. Actual residence time
i and flow calculations, based on operating data, are also included. Calculations are shown in
I the original units. Only the final results have been converted to metric units.
B.1 PRELIMINARY COMBUSTION CALCULATIONS
The PCP-treated wood is essentially pine with trace amounts of POP added. For the purpose
of the preliminary combustion calculations, the composition was assumed to be that of
cellulose.
Heating value (pine, 12% moisture): 7960 Btu/lb .
Higher heating value (dry basis): et (l-O.I^Tb-dry =9066 Btu/lb
Lower heating value (cellulose) at 60°F:
9066 Btu / 5 mole H,0 ' 18 Ib H,O 1060 Btu mole wood
Ib ~ ^ mole wood x mole H2O x Ib H,O x 162 Ib wood
Assumptions: 1. Lower chamber temperature is £000°F.
2. Pine is equivalent to cellulose. -
3. Feed rate is 100 Ib/h.
4. Heat loss from the incinerator surface is 600 Btu/ft2-h.
5. Excess air is 50%. '
6. Gas pilot contributes 10 000 Btu/h.
Reaction at stoichiometric air input: •
C6H1005 + 602 + 22.8N2-*6C02 -f 5H,0 + 22.8N2 .
Reaction at 50% excess air:
C6H1006 + 902 + 34.1 N2— 6C02 + 5H20 + 14.37 air + 22.7N-, .
Mass and energy balance (per Ib-mole wood feed):
43
-------
Component
C02
H20
Air
N2
Total
Heat required:
803 602 Btu/lb-mole
Ib-moles Product
6
5
14.37
22.73
48.10
- AQRn K Rtn/IK utnnrl
mol wt
44.01
18.02
28.84
28.00
AHjooo.8,,
(Btu/lb)
552.3
1047.2
530.2
540.0
Heat Req.
(Btu)
145 840
94 353
219 731
343678
803 602
162 Ib/lb-mole
Heat release at 100 Ib/h feed rate:
8477 Btu/lb x100 Ib/h =
Heat duty'to gases: 4960.5 Btu/lb wood x 100 Ib wood/h
Surface loss: 600 Btu/tt2-h x 437 ft2 surface =
Input from natural gas pilot:
Steam bleed (for nozzle cooling): 5 Ib/h x 962.7 Btu/lb =
Total:
847 700 Btu/h.
-496 050
-262 200
+10000
-4813
94 637 Btu/h
Therefore, the 100 Ib/h feed rate will load the incinerator (10% overload is within expected
errors in assumptions).
B.2 PRELIMINARY RESIDENCE TIME CALCULATIONS
»
Offgas flow: (at 100 Ib/h feed, 50% excess air, 200l)°F lower chamber temp).
(a) from burner pilot (methane):
t
10 OOP Btu/h Ib-mole n _,, .. __,_/h .
21 520 Btu/lb x 16.04 Ib = °'03 lb-mole/h •
(b) from combustion products including excess air:
48.1 Ib-mole prod. Ib-mole wood 100 Ib
Ib-mole wood
(c) from steam bleed:
5 Ib steam Ib-mole
h x 18 Ib
162 Ib
= 0.28 lb-mole/h .
= 29.66 lb-mole/h ;
44
-------
Total: 29.97 Ib-mole/h .
Temperature = 2200°F, chamber pressure = -2 in. W.G.
jsi.ft3 \
jJV_/_RT\ / dn\ \ Ib-mole.oR /
dt \ P
10.73 psi.ft3 \ (246QOR) / 29.97 Ib-mole
dt / (11.3-2/27.07 psi)(60 min/h)
1174 ACFM (actual ft3 per minute) .
i Volume of lower chamber: 108.1 ft3.
Effective volume of lower chamber (due to waste burning on first one-third of hearth):
108.1 ft3 x 0.66 = 72.0 ft3.
Predicted residence time:
(72.0 ft3)(60 s/min)
1174 ACFM 3'68 s'
B.3 SAMPLE REQUIREMENT CALCULATIONS
B.3.1 PCP Detection
Assumptions: 1. 100 Ib/h feed.
2. 250 SCFM offgas from lower chamber.
3. 0.5 SCFM sample rate.
4. 1-L sample from impinger catch.
5. 100% recovery of PCP in sample.
6. 0.5-ppm detection limit for sample.
Given: PCP concentration on wood = 0.106 wt% (based on an arithmetic average of two
i: concentrations, one from each random wood sample). v
j Density of toluene solvent = 0.8 g/mL.
PCP feed rate: 100 Ib/.h x 0.00106 Ib PCP/lb = 0.106 Ib PCP/lj.
PCP in offgas at 99.99% ORE: 0.106 Ib PCP/h x 0.0001 = 1.06 x 1Q-6 Ib/h.
Fraction total PCP in sample: 250 SCFM off a r t = °-002-
Rate into sample catch:
i , 1.06 x10~6 Ib/h x 0.002 = 2.12 x10-*lbPCP/h (9.62 x 10-8 g/h) .
Mass of PCP required in sample with 50x concentration:
- j
i 1000 ml 0.8 g 0.5 ng „
~cn - - r- - -
50 ml g
45
-------
Sampling time required: =0.83 h .
B.3.2. TCDD/TCDF Detection
Assumptions as in Sec. B.3.1 except
1. 95% ORE for POP.
2. 0.1% of remaining PCP is converted to TCDD or TCDF.
3. 100% of TCDD or TCDF goes to offgas..
Resulting TCDD or TCDF in offgas:
0.106 Ib PCP/h x 5% remaining x 0.001 conversion = 5.35 x 10~* Ib/h .
Rate into sample catch:
•
5.3 x 10-" Ib/h x 0.002 sample fraction = 1.06 x 1Q-8 Ib/h (4.81 ng/h).
Assuming the same detection limit, required sampling time is
Bug i RR h
4.81 Mg/h=1-66h-
Sample time selected was twice the required time rounded up to a whole hour:
1.66 hx 2 = 3.33 h.
Therefore, use 4-h sample period.
B.4. ACTUAL RESIDENCE TIME CALCULATIONS
Basis: Operating conditions from test phase 2, period 3, interval 1, during which the highest
feed rate and lowest expected residence time were used for the actual residence time
calculations. Oxygen content of the offgas was assumed correct as indicated by the
on-stream continuous analyzers.
»
Data: Chamber pressure 11.23psia
Lower chamber temperature 1880°F avg
Lower chamber oxygen 5.0% avg
Lower burner fuel-gas flow 5 SCFM
Lower burner combustion air flow 45 SCFM
Underfire air flow 92 SCFM
Upper chamber temperature 2200°F avg
Upper chamber oxygen 6.5% avg
Upper burner fuel-gas flow 20.6 SCFM
Upper burner combustion air flow 185 SCFM
Secondary air flow 380 SCFM
Wood feed rate 90 Ib/h :
46
-------
B.4.1 Lower (Primary) Chamber Flow Calculations
Measured total air = 45 SCFM burner + 92 SCFM underfire = 137 SCFM.
Let P = % excess air/100 and assume wood feed has composition of cellulose; then
CeH,005 + (1 + P)602 + (1 + P)22.6N2-+6C02 + 5H20 + P602 + (1 + P)22.6N2 .
Fuel gas flow to lower chamber = 5 SCFM (0.837 Ib-mole/h).
Wood feed = 90 Ib/h + 162 Ib/lb-mole = 0.555 Ib-mole/h.
Mole fraction of fuels:
fwood = 0.555/(0.555 + 0.837) = 0.399 . .
f,.. = 1 - 0.399 = 0.601 .
Average fuel formula (wood + gas): C2.gB5H63g4O1.9B5 .
Molwt: 74.254 . '
General reaction per mole of feed:
'C,J«HMM01Ji.+ 3.596 (1 + P)02+13.528 (1 + P)N2-* .
2.995C02+3.197H20 + (3.596P)02+13.528 (1 + P)N2 .
I Solving for P, which corresponds to 5% oxygen in the offgas from the lower chamber, gives
! »
! P = 36.7% excess air in lower chamber. „ . ' *•
Oxygen input to the lower chamber to meet 36.7% excess air was 6.84 Ib-mole/h but
measured flow was only 4.806 Ib-mole/h; therefore in-leakage accounted for 2.042 Ib-mole/h
of the oxygen input.
The final offgas composition (leaving the lower chamber) was
Component Ib-moles/h Mole Fraction
C02
HjO from combustion
H,0 from steam
oz
N2
Total
4.172
4.453
0.555
1.839
25.736
36.782
0.113
0.136
0.050
0.700
47
-------
The resulting flowrate from the lower chamber is
dV RT dn (10.73 psi.ft3/°R.lb-mole)(2340°R)(36.8 Ib-mole/h) ,.„ .__,,
"dT= ~F -dT= ' (11.23psia)(60min/h) : — = 1370 ACFM .
Residence time:
Assumes effective volume = 2/3 of lower chamber volume = 72 ft3.
V, (72.0 ft3)(60 s/min) ,
I l""~Q~ 1370 ft3/min o-'os.
B.4.2 Upper Chamber Flow Calculations
! Assumptions: 1. negligible combustibles in offgas from lower chamber.
2. air input = measured flow minus 25 SCFM for the ram door, sightglass
; purges, etc. .
3. no air in-leakage to upper chamber.
; 4. fuel gas is methane.
i
Combustible feed to upper chamber is then fuel gas only at the rate of 20.6 SCFM (3.441 Ib-
mole/h). . .
: The combustion reaction formula for fuel gas with P% excess air is
i .
'! CH4 + (1 + P)202 + (1 + P)(3.29)2N2-*C02 + 2H2O + 2(P)02 + 6.58(1 + P)N2 .
Solving for P, which corresponds to 6.5% O2 in the offgas,. gives
', P = 62.1% excess air.
; 02 input from all sources to result in the 62.1% excess was 11.156 Ib-mote/h, which carried
with it 41.97 Ib-mole/h N2. • " '.•.*"
; The resulting offgas flow from the upper chamber was then
i »
Component Lower Chamber Upper Chamber Total Mole Fraction
C02
HjO
02
N2
4.172
5.008
1.839
25.763
3.441
6.882
4.270
41.970
7.613
11.890
6.110
67.730
0.082
0.127
0.066
0.725
Total 93.343
Flowrate is then
dV RT dn _ (10.73 psi.ft3/°R.lb-mole)(2660°R)(93.34 Ib-mole/h)
dt = "P~ W (11.23 psia)(60 min/h) '. 9M ° '
48
-------
Residence time, based on effective total volume (98.8 ft3) of upper chamber (69.13 ft3) plus hot
duct (29.7 ft3), is
t- _V (98.8 ft3)(60 s/min) . ,
"" Q= 3954ft3/min = '
49
-------
APPENDIX C
DESTRUCTION EFFICIENCY CALCULATIONS
The following calculations were used to evaluate the DE for POP during the test burn:
nt- PCP input - POP emitted ,„
DE-= PCP input X10°-
PCP input = 0.106% (PCP on wood) x feed rate x sample duration.
PCP emitted = detection limit (since none was detected) back calculated to content in the
offgas as follows:
•
solvent weight (g) x detection limit (g/g solvent) = potential content in sample (g).
From Appendix F:
sample gas volume (ft3)
fraction of offgas sampled
offgas flow (ftVmin) x sample duration (min) '
potential content of offgas (g) = potential content from sample (g)
K » \»/ fraction sampled
The potential content of the offgas is then assumed to be the PCP emitted.
Sample calculation: Test phase 2, period 4, interval 2. Hot-zone sample (lower chamber
offgas)
*
solvent weight 704 g. *
detection limit 15 x I0~9g/g solvent
sample gas volume 68.6 SCF
offgas flow 317.0 SCFM
sample duration 240 min '
wood feed rate 27.2 kg/h
PCP input = 27.2 x 103g/hx 0.106% PCP x4h = 115.328 g .
DnD 0 .„ . 15 x10-9g/(g solvent) x 704 (g solvent) __....,
PCP emitted = 68.6 SCF/(317.0 SC>M x240 min) = °'0117 9 '
DEpcp . 115.328-^0117
50
-------
The DE calculation was performed for all hot-zone samples as a measure of the effectiveness
of a single-chamber incineration step for the disposal of PCP-treated wood (to model the
proposed use of a single-chamber Korean incinerator for the disposal of such wood). The
resulting DE values are included in the tabulation below. The detection limit used in these
calculations was 15 ppb POP in the original sample solvent by GC/ECD at Los Alamos.
TABLE C-1. DESTRUCTION EFFICIENCY SUMMARY
Test
P-P-I*
2-1-1
2-1-2
2-2-1
2-2-2
2-3-1
2-3-2
2-4-1
2-4-2
Solvent
(9)
640
688
. 600
648
688
704
688
704
Sample
Volume
(SCF)
65
79
91
97
89
61
86
69
Offgas
Flow
(SCFM)
296
290
286
298
290
283
281
317
Sample
Duration
(min)
240
240
240
240
240
240
240
240
Wood
Feed Rate
(kg/h)
36.3
40.9
29.5
31.8
40.9
38.6
29.5
27.2
DE
99.993
99.995
99.995
99.995
99.995
99.993
99.994
99.990
•P-P-I = test Phase, Period, Interval.
51
-------
APPENDIX D
FIELD DATA SUMMARY
The following data are a summary of the field data from the sample train control boxes and
impingers used to calculate sample volumes and offgas flow rates. The data are given only in
the original units.
Test Phase 1, Period 1, Interval 1
Barometric Pressure 22.03 In. Hg
Sample Zone Pressure 22.93 in. Hg
Ambient Temperature 112°F
Sample Location: HZ
Water Catch
Silica Gel
Impinger
gross
tare
net
#1
#2
#3
252.8 g
200.0 g
52.B mL
15.6 ml
7.0 mL
1.0 mL
Traverse
Point
1
2
3
4
5
6
7
8
9
10
11
12
End
Dry Gas Pilot
Meter AP
(ft') (in. W.G.)
324.2 0.004
0.004
0.003
0.003
0.004
0.003
0.004
0.003
0.004
0.004
0.003
0.002
428.5
Cyclone
Total Water
Sample Zone
Temp
(•F)
1640
1590
1630
1615
1615
1690
1710
1700
1720
* 1630
1650
1660
Meter
Inlet
(°F)
75
70
62
61
65
62
60
62
60*
61
62
62
2.0 mL
i 78.6 mL
Temperature
Outlet
(°F)
70
74
72
80
82
80
89
87
89 „
91
91
91
52
-------
Test Phase 1, Period 1, Interval 2
Sample Location: HZ
Barometric Pressure 23.09 in. Hg
Sample Zone Pressure 22.95 in. Hg
Ambient Temperature 115°F
Dry Gas
Traverse Meter
Point (ft3)
1 429.7
2
3
4
5
6
7
8
9
10
11
12
End 530.0
Pilot
AP
(in. W.G.)
0.005
0.005
0.005
0.005
0.004
0.004
0.004
0.004
0.004
0.004
0.004
0.004
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1675
1770
1790
1810
1800
1830
1870
1830
1820
1820
1800
1800
gross 250.3 g
tare 200.0 g
net
#1
#2
#3
50.3 mL
25.0 ml
4.0 mL
-mL
-mL
79.3 mL
Meter Temperature
Inlet
<°F)
70
75
85
90
100
95
100
90
90
95
100
105
Outlet
(°F)
70
70
80
85
90
90.
95.
90
90
95
100
105
Test Phase 1, Period 2, Interval 1
Sample Location: HZ
Barometric Pressure 23.09 in. Hg
Sample Zone Pressure 22.95 in. Hg
Ambient Temperature
Traverse
Point
1
2
.3
4
5
6
I 7
j ' '8
. 9
10
! 11
12
End
115°F
'
Dry Gas
Meter
(IP)
530.6
637.9
Pitot
AP
(in. W.G.)
0.005
0.005
0.005
0.005
0.006
0.004
0.006
0.006
0.005
0.005
0.005
0.005
Water Catch
Silica Gel
Impinger
„ Cyclone
Total Water
Sample Zone
Temp '
(°F)
1780
1840
1860
1847
1855
1839
1872
1826
1846
1852
1861
1823
gross 252.5 g
tare 200,0 g
net
#1
#2
#3
52.5 mL
5.2 mL
5.0 mL
-mL
15.0 mL
77.7 mL
Meter Temperature
Inlet
(°F)
82
86
89
91
93
94
94
96
.95
96
95
95
Outlet
(°F)
77
83
84
88
89
91
91
90
92
92
90
89
53
-------
Test Phase 1, Period 2, Interval 2
Sample Location: HZ
Barometric Pressure 23.07 in. Hg
Sample Zone Pressure 22.93 in. Hg
Ambient Temperature 111°F
Dry Gas
Traverse Meter
Point (ft3)
1 639.2
2
3
4
5
6
7
8
9
10
11
12
End 750.6
Pitot
AP
(in. W.G.)
0.005
0.004
0.004
0.004
0.005
0.004
0.005
0.004
0.005
0.004
0.005
0.004
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
<°F)
1760
1775
1900
1820
1915
1810
1800
1850
1875
1875
1850
1835
gross 248.3 g
tare 200.0 g
net
#1
#2
#3
48.3 mL
20.1 ml
-mL
-mL
15.2 mL
83.6 mL
Meter Temperature
Inlet
(°F)
80
82
83
85
86
86
88
89
91
90
89
89
Outlet
(°F)
75
76
78
80
81
81 .
83'
83
84
85
85
85
Test Phase 2, Period 1, Interval 1
Sample Location: HZ
Barometric Pressure 23.05 in. Hg
Sample Zone Pressure 22.91 in. Hg
Ambient Temperature 116°F
.
*
Dry Gas
Traverse Meter
Point (ft3)
1 759.5
2
3
4
5
6
7
8
9
10
11
12
End 847.2
Pitot
AP
(in. W.G.)
0.005
0.005
0.004
0.004
0.005
0.005
0.006
0.004
0.005
0.005
0.005
0.005
Water Catch
Silica Gel
Impinger
* Cyclone
Total Water
Sample Zone
Temp '
(°F)
1660
1675
1700
1780
1750
1780
1700
1750
1675
1725
1700
1655
gross 242.5 g
tare 200.0 g
net
#1
#2
#3
42.5 mL
13.3 mL
-mL
-mL
12.7 rrtL
68.5 mL
Meter Temperature
Inlet
(°F)
75
82
88
91
93
94
94
96
,95
95
95
95
Outlet
(°F)
71
79
82
83
85
85
86
87
87
87
87
87
54
-------
Test Phase 2, Period 1, Interval 2
Sample Location: HZ
Barometric Pressure 23.05 in. Hg
Sample Zone Pressure 22.91 in. Hg
Ambient Temperature 125°F
Dry Gas
Traverse Meter
Point (ft3)
1 848.3
2
3
4
5
6
7
8
9
10
11
12
End 953.7
'
Pitot
AP
(in. W.G.)
0.004
0.005
0.005
0.006
0.005
0.005
0.004
0.005
0.005
0.004
0.004
0.004
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1620
1705
1815
1750
1710
1785
1820
1790
1805
1780
1690
1670
gross 242.5 g
tare 200.0 g
net
#1
#2
#3
42.5 mL
10.0 mL
7.6 mL
-mL
3.0 mL
63.1 mL
Meter Temperature
Inlet
(°F)
81
84
85
91
93
93
94
95
93
92
91
91
Outlet
(°F)
76
79
81
81
83.
83.
84
85
86
87
86
87
'
Test Phase 2, Period 2, Interval 1
Sample Location: HZ
Barometric Pressure 23.09 in. Hg
Sample Zone Pressure 22.95 in. Hg
Ambient Temperature 118°F
. Dry Gas
Traverse Meter
Point (ft3)
1 851.7
2
3
4
5
6
7
8
9
10
11
12
End 972.2
Pitot
AP
(in. W.G.)
0.004
0.004
0.003
0.004
0.005
0.006
0.005
0.005
0.005
0.004
0.004
0.004
Water Catch
Silica Gel
Impinger
>
Cyclone
Total Water
Sample Zone •
Temp
(°F)
1680
1809
1810
1710
1760
1780
1695
1725
1750
1690
1735
1680
gross 209.3 g .
tare 200.0 g
net
#1
#2
#3
9.3 mL
22.6 mL
5.3 mL
-mL
14.7 mL
51.9 mL
Meter Temperature
Inlet
(°F)
81
84
86
88
91
93
92
.92
93
93
95
95
Outlet
<°F)
77
77
79
82
83
85
87
87
87
86
86
86
55
-------
Test Phase 2, Period 2, Interval 2
Sample Location: HZ
Barometric Pressure 23.07 in. Hg
Sample Zone Pressure 22.93 in. Hg
Ambient Temperature 127°F
Dry Gas
Traverse Meter
Point (ft5)
1 972.7
2
3
4
5
6
7
8
9
10
11
12
End 1103.5
Pitot
AP
(in. W.G.)
0.005
0.004
0.005
0.005
0.006
0.006
0.005
0.005
0.004
0.004
0.005
0.006
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1625
1700
1850
1800
1755
1810
1850
1800
1775
1750
1750
1695
gross 253.8 g
tare 200.0 g
net
#1
#2
#3
53.8 ml
20.2 mL
1.8 mL
-mL
30.0 mL
105.8 mL
Meter Temperature
Inlet
(°F)
82
83
88
91
93
93
95
94
94
94
95
95
Outlet
(°F)
78
81
84
86
87
86.
88.
89
91
92
92
92
Test Phase 2, Period 3, Interval 1
Sample Location: HZ
Barometric Pressure 22.03 in. Hg
Sample Zone Pressure 22.89 in. Hg
Ambient Temperature 130°F
•
»
Dry Gas
Traverse Meter
Point (ft3)
1 103.7
2
3
4
5
6
7
8
9
10
11
12
End 224.1
Pitot
AP
(in. W.G.)
0.005
0.005
0.005
0.005
0.004
0.004
0.005
0.005
0.006
0.006
0.005
0.004
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp ,
(•F)
1775
1840
1900
1880
1920
1885
1910
1875
1885
1895
1850
1815
gross 242.5 g
tare 200.0 g
net
#1
#2
#3
42.5 mL
21.7 mL
6.2 mL
-mL
12.5 reL
62.9 mL
Meter Temperature
Inlet
(°F)
75
84
89
93
96
97
97
98
99
100
100
99
Outlet
(°F)
77
83
86
91
92
96
95
96
96
96
95
95
56
-------
Test Phase 2, Period 3, Interval 2
Sample Location: HZ
Barometric Pressure 23.04 in. Hg
Sample Zone Pressure 22.91 in. Hg
Ambient Temperature 125°F
Dry Gas
Traverse Meter
Point (ft1)
1 224.7
2
3
4
5
6
7
8
9
10
11
12
End 305.6
Pitot
AP
(in. W.G.)
0.005
0.005
0.004
0.004
0.004
0.005
0.006
0.007
0.005
0.004
0.004
0.003
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1840
1880
1910
1885
1845
1915
1855
1835
1870
1865
1890
1805
gross 227.9 g
tare 200.0 g
net
#1
#2
#3
27.9 mL
12.2.mL
5.0 mL
-mL
11.6 mL
56.7 mL
Meter Temperature
Inlet
(°F)
71
75
79
82
85
88
89
88
89
89
90
90
Outlet
<°F)
73
74
78
81
82
83T
83'
83
84
84
85
86
Test Phase 2, Period 4, Interval 1
Sample Location: HZ
Barometric Pressure 22.13 In. Hg
Sample Zone Pressure 22.99 in. Hg
Ambient Temperature
Traverse
Point
1
2
3
4
5
6
7
8
9
10
11
12
End
123°F
*
Dry Gas
Meter
(IP)
305.7
421.9
Pitot
AP
(in. W.G.)
0.006
0.005
0.004
0.004
0.004
0.004
0.004
0.005
0.005
0.005
0.005
0.004
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone ,
Temp
(°F)
1680
1740
1720*
1790
1785
1825
1705
1785
1800
1785
1775
1695
gross 243.3 g
tare 200.0 g
net
#1
#2
#3 ".
43.3 mL
47.8 mL
12.3 mL
1.5 roL
27,1 mL
132.0 mL
Meter Temperature
Inlet
(Of)
81
82
85
91
94
97
101
103
103
104
104
104
Outlet
(°F)
76
81
82
88
91
95
99
100
100
100
101
101
.57
-------
Test Phase 2, Period 4, Interval 2
Sample Location: HZ
Barometric Pressure 23.07 in. Hg
Sample Zone Pressure 22.93 In. Hg
Ambient Temperature 123°F
*
Dry Gas
Traverse Meter
Point (ft3)
1 422.3
2
3
4
5
6
7
8
9
10
11
12
End 513.7
Pitot
AP
(in. W.G.)
0.005
0.004
0.006
0.006
0.005
0.006
0.007
0.007
0.006
0.005
0.005
0.005
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1695
1748
1810
1795
1641
1695
1705
1638
1695
1710
1655
1630
gross 226.9 g
tare 200.0 g
net
#1
#2
#3
26.9 ml
24.3 mL
12.1 mL
1.0 mL
14.6 mL
78.9 mL
Meter Temperature
Inlet
(°F)
81
84
85
88
91
89
91
92
88
89
91
91
Outlet
(°F)
75
77
79
80
83
83.
ss;
85
82
82
83
82
Test Phase 1, Period 1, Interval 1
Sample Location: OG
Barometric Pressure 23.09 in. Hg
Sample Zone Pressure 22.95 in. Hg
Ambient Temperature 112°F
•
4
Dry Gas
Traverse Meter
Point (ft3)
1 490.1
2
3
4
5
6
7
8
9
10
End 613.6
Pitot
AP
(in. W.G.)
0.07
0.07
0.08
0.09
0.08
0.07
0.07
0.07
0.07
0.07
Water Catch
Silica Gel
Impinger
«> Cyclone
Total Water
Sample Zone
Temp »
(°F)
1605
1686
1710
1711
1727
1718
1703
1696
1699
1701
gross 252.2 g
tare 200.0 g
net
#1
#2
#3
52.2 mL
25.5 mL
7.2 mL
-mL
20.3 mL
105.2 mL
Meter Temperature
Inlet
(°F)
88
91
97
98
100
101
101
100
.100
100
Outlet
(°F)
85
84
84
87
89
90
89
89
89
89
58
-------
Test Phase 1, Period 1, Interval 2
Barometric Pressure 23.07 in. Hg
Sample Location: OG
Sample Zone Pressure 22.93 in. Hg
Ambient Temperature 115°F
Dry Gas
Traverse Meter
Point (ft1)
1 613.9
2
3
4
• 5
6
7
8
9
10
End 713.2
Silica Gel
gross 245.3 g
tare 200.0 g
Pitot
AP
(in. W.G.)
0.06
0.06
0.06
0.05
0.06
0.06
0.05
0.06
0.06
0.06
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°P)
1631
1633
1664
1681
1670
1669
1677
1700
1678
1673
net
#1
#2
#3
Meter
Inlet
<°F)
73
79
88
94
97
99
100
101
102
101
45.3 mL
28.3 mL
2.5 mL
-mL
15.2 mL
91.3 mL
Temperature
Outlet
(°F)
71
76
84
91
95
97
98 r
99'
101
100
Test Phase 1, Period 2, Interval 1
Barometric Pressure 23.09 in. Hg
Sample Zone Pressure 22.95 in. Hg
Ambient Temperature 115°F
Sample Location: OG
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
gross
tare
net
#1
#2
#3 .
223:3 g
200.0 g
23.3 mL
7.7 mL
1.1 mL
-mL
-mL
32.1 mL
Traverse
Point
1
2
3
4
5
6
7
8
9
10
End
Dry Gas ' Pitot
Meter AP
(ft') (in. W.G.)
774.1 0.07
0.08
0:07
0.07
0.07
0.08
0.08
0.07
0.07
0.07
795.4
Sample Zone
Temp
1718 »
1816
1804
1831
1810
1818
1810
1850
1865
1843
Meter Temperature
Inlet
71
75
80
86
88
89
89
89
88
88
Outlet
(CF)
70
75
80
84
85
85
85
85
84
83
59
-------
Test Phase 1, Period 2, Interval 2
Barometric Pressure 23.07 in. Hg
Sample Location: OG
Water Catch
Sample Zone Pressure 22.93 in. Hg
Ambient Temperature 1 1 1 °F
Dry Gas
Traverse Meter
Point (ft3)
1 796.9
2
3
4
5
6
7
8
9
10
End 923.1
Test Phase 2, Period 1 , Interval 1
Barometric Pressure 23.05 in. Hg
Sample Zone Pressure 22.91 in. Hg
Ambient Temperature 1 16°F
Dry Gas
Traverse Meter
Point (ft3)
1 923.3
2
3
4
5
6
7
8
9
10
End 1006.1
Pitot
AP
(in. W.G.)
0.08
0.07
0.08
0.08
0.09
0.09
0.08
0.07
0.08
0.07
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1755
1790
1857
1805
1846
1846
1821
1797
1802
1812
gross .254.5 g
tare 200.0 g
net
#1
#2
#3 .
54.5 mL
20.3 mL
6.5 mL
-mL
8.2 mL
89.5 mL
Meter Temperature
Inlet
(°F)
74
91
102
108
112
116
116
116
119
122
Outlet
(°F)
65
76
86
93
98
101.
103
104
106
108
Sample Location: OG
Pitot
AP
(in. W.G.)
0.08
0.09
0.09
0.10
0.08
O.OB
0.09
0.08
0.08
0.07
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
s
Sample Zone
Temp
(°F)
1747 »
1800
' 1855
1910
1864
1905
1850
1891
1852
1863
gross 254.9 g
tare 200.0 g
net
#1
-#2
#3
,
54.9 mL
33.9 mL
1.3 mL
. -mL
37,4 mL
127.5 mL
Meter Temperature
Inlet
(°F)
65
90
103
110
114
117
119
121
121
122
^ •
Outlet
(°F)
62
75
88
95
101
104
105
107
107
109
60
-------
Test Phase 2, Period 1, Interval 2
Sample Location: OG
Barometric Pressure 23.05 in. Hg
Sample Zone Pressure 22.91 in. Hg
Ambient Temperature 125°F
Dry Gas
Traverse Meter
Point (ft1)
1 7.7
2
3
4
5
6
7
8
9
10
End 121.1
Pitot
AP
(in. W.G.)
0.08
0.08
0.09
0.09
0.09
0.08
0.08
0.07
0.07
0.08
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone '
Temp
(°F)
1780
1805
1890
1889
1852
1837
1831
1864
1886
1855
gross 256.0 g
tare 200.0 g
net
#1
#2
#3
56.0 mL
21.4 mL
0.9 mL
-mL
28.7 mL
107.0 mL
Meter Temperature
Inlet
(°F)
82
103
113
118
119
119
120
120
120
119
Outlet
(°F)
75
88
98
104
105
107:
107'
107
106
106
Test Phase 2, Period 2, Interval 1
Sample Location: OG
Barometric Pressure 23.09 in. Hg
Sample Zone Pressure 22.95 in. Hg
Ambient Temperature
Traverse
Point
1
2
3
4
5
. 6
7
8
9
10
End
118°F
Dry Gas
Meter
(ft1)
121.9
252.0
Pitot
AP
(in. W.G.)
0.09
0.09
0.09
0.09
0.085
0.095
0.085
0.095
0.09
0.09
Water Catch
Silica Gel
Impinger
Cyclone
% Total Water
Sample Zone
Temp
\ / t
1829
1847
1908
1982
1991
1987
1982
1984
1966
1973
gross 253.3 g
tare 200.0 g
net
#1
#2
#3
53.3 mL
29.7 mL
17.9 mL
1.0 mL
42.4 mL
144.3 raL
Meter Temperature
Inlet
(°F)
80
96
110
113
116
117
119
120
119
120
Outlet
(°F)
70
80
94
98
103
104
105
107
106
107
61
-------
Test Phase 2, Period 2, Interval 2
Sample Location: OG
Barometric Pressure 23.07 in. Hg
Sample Zone Pressure 22.93 in. Hg
Ambient Temperature 127°F
Dry Gas
Traverse Meter
Point (ft3)
1 252.4
2
3
4
5
6
7
8
9
10
End 355.9
Pilot
AP
(in. W.G.)
0.09
0.09
0.10
0.09
0.10
0.09
0.09
0.08
0.09
0.08
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1886
1914
1998
1947
1968
1995
1985
1992
1989
1992
gross 252.8 g
tare 200.0 g
net
#1
#2
#3
52.8 mL
16.7 mL
-mL
-mL
48.3 mL
117.8 mL
Meter Temperature
Inlet
(°F)
89
93
97
99
98
99
101
102
101
103
Outlet
(°F)
83
87
103
107
106
106>
109*
112
111
105
Test Phase 2, Period 3, Interval 1
Sample Location: OG
Barometric Pressure 23.03 in. Hg
Sample Zone Pressure 22.89 in. Hg
Ambient Temperature
Traverse
Point
1
2
3
4
5
6
7
8
9
10
End
130°F
Dry Gas
Meter
(tt')
356.7
473.6
Pitot
AP
(in. W.G.)
0.09
0.09
0.09
0.09
0.09
0.08
0.08
0.08
0.08
0.07
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
s •
Sample Zone
Temp
(°F)
1874 '
2000
1999
2000
2010
2000
2010
2010
1965
1953
gross 254.0 g
tare 200.0 g
net
#1
#2
#3-
54.0 mL
37.4 mL
11.6 mL
3.8 mL
91.2 mL
198.0 mL
fc
Meter Temperature
Inlet
(8F)
100
103
104
105
104
104
105
106
106
107
'
Outlet
(°F)
106
111
106
104
103
105
106
103
103
105
62
-------
Test Phase 2, Period 3, Interval 2
Sample Location: OG
Barometric Pressure 23.05 in. Hg
Sample Zone Pressure 22.91 in. Hg
Ambient Temperature
Traverse
Point
1
2
3
4
5
6
7
8
9
10
End
125°F
Dry Gas
Meter
(«')
479.0
627.4
Pitot
AP
(in. W.G.)
0.08
0.09
0.09
0.09
0.08
0.09
0.08
0.08
0.08
0.07
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1899
1965
2000
2000
1998
1996
2000
2000
2000
1986
gross 254.2 g
tare 200.0 g
net
#1
#2
#3
54.2 mL
36.7 mL
31.3 mL
6.6 mL
93.4 mL
222.2 mL
Meter Temperature
Inlet
(°F)
96
109
113
115
114
114
114
113
112
115
Outlet
(°F)
83
94
100
102
102
101
102*
101*
101
102
' Test Phase 2, Period 4, Interval 1
Sample Location: OG
Barometric Pressure 23.13 in. Hg
Sample Zone Pressure 22.99 in. Hg
Ambient Temperature
Traverse
Point
1
2
3
4
5
6
7
8
9
10
End
123-F
Dry Gas
Meter
(ft3)
629.1
762.0
Pitot
AP
(in. W.G.)
0.08
0.08
0.09
0.09
0.09
0.08
0.09
0.09
0.08
0.08
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
Sample Zone
Temp
(°F)
1870 '
1838
1993
2000
2000
2000
2010
2010
2005
1990
gross 225.6 g
tare 200.0 g
net
#1
#2
#3
,
25.6 mL
43.7 mL
18.4 mL
3.5 mL
92.4 mL
183.6 mL
Meter Temperature
Inlet
(°F)
78
98
105
109
110
109
109
108
108
108
'
Outlet
(°F)
72
83
90
95
96
97
97
96
96
97
63
-------
Test Phase 2, Period 4, Interval 2
Barometric Pressure 23.07 in. Hg
Sample Zone Pressure 22.93 in. Hg
Ambient Temperature 123°F
Sample Location: OG
Water Catch
Silica Gel
Impinger
Cyclone
Total Water
gross 253.9 g
tare 200.0 g
net
#1
#2
#3
53.9 ml
42.0 ml
7.9 mL
-mL
85.1 mL
188.9 mL
Traverse
Point
1
2
3
4
5
6
7
8
9
10
End
Dry Gas Pilot
Meter AP
(ftj) (in. W.G.)
765.5 0.08
0.08
0.09
0.09
0.08
0.09
0.09
0.09
0.08
0.08
889.8
Sample Zone
Temp
(°F)
1900
1872
2000
1995
2010
2000
2010
2005
1920
1924
meier i ei
Inlet
(°F)
88
98
107
112
114
114
113
110
110
108
mperaiure
Outlet
(°F)
70
84
94
100
103
102,
101
98
97
96
64
-------
APPENDIX E
COMBUSTION EFFICIENCY AND OFFGAS COMPOSITION DATA
Carbon dioxide and carbon monoxide readings were tabulated following each incinerator
feed cycle at the point where combustion efficiency (CE) was expected to be lowest. These
values were then used to calculate instantaneous combustion efficiencies from
CE=corrco*100-
The data and calculated combustion efficiencies are tabulated on .the following pages and
summarized in Table E-1.
•
The carbon dioxide and carbon monoxide data were averaged for each sample interval for
use in the offgas and sample flow calculations (Appendix F) and are tabulated on the gas
composition data sheets following the combustion efficiency summary.
65
-------
Test
(P-P-I)*
1-1-1
1-1-2
1-2-1
Feed
Cycle
1
2
3
4
5
6
7 •
8
9
10
11
12
Avg
1
2
3
4
5
6
- 7
8
9
10
11
12
Avg
1
2
3
4 .
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Avg
C02
(%)
4.8
4.9
5.2
5.3
5.4
4.7
4.9
5.4
4.8
4.9
5.1
4.6
5.0
3.7
4.5
5.2
5.0
4.8
4.5
5.0
5.1
4.5
4.7
4.6
4.8
4.7
5.4
4.8
4.7
5.1
4.5
4.8
5.6
5.1
5.3
5.6
4.8
4.6
4.7
5.2
4.8
4.6
5.2
5.2
4.9
CO
(ppm)
36
32
34
27
30
37
32
29
30
27
30
21
30
29
21
39
20
25
30
32
25
18
20
14
30
25
34
30
36
- 27
39
32
37 ,
21
18
30
39
36
34
32
39
27
23
20
31
Combustion
Eff. (%)
99.93
99.93
99.93
99.95
99.94
99.92
99.93
99.95
99.94
99.94
99.94
99.95
99.92
99.95
99.93
99.96
99.95
99.93
99.94
99.95
99.96
99.96
99.97
99.94
99.94
99.94
99.32
99.95
99.91
99.93
99.93
99.96
99.97
99.95
99.92
99.92
99.93
99.94
99.92
99.94
' 99.96
99.96
•p.p-l = Phase-Period-Interval.
66
-------
Test Feed
(P-P-I)* Cycle
1-2-2 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Avg
2-1-1 1
2
3
4
5
6
7
8
9
10
11
12
13«
14
15
16
C02
(%)
3.8
4.8
4.9
4.9
5.2
4.8
5.0
4.9
4.2
4.6
4.8
4.9
4.9
5.0
5.2
4.9
4.8
4.8
4.8
5.4
5.5
5.3
4.9
5.5
5.5
4.8
5.2
5.1
4.8
5.5 .
5.3
5.4
5.4
5.0
CO
(ppm)
25
18
36
32
34
41
32
29
36
43
30
39
25
34
45
32
34
33
32
37
34
25
21
27
32
18
30
37
30
36
27
23
27
29 ,
Combustion
Eff. (%)
99.93
99.96
99.93
99.93
99.93
99.91
99.94
99.94
99.91
99.91
99.94
99.92
99.95
99.93
99.91
99.93
99.93
99.93
99.93
99.94
99.95
99.96
99.95
99.94
99.96
99.94
99.93
99.94
99,93
99.95
99.96
99.95
99.94
Avg 5.1 29
67
-------
Test
(P-P-I)*
2-1-2
2-2-1
Feed
Cycle
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Avg
1
2
3
4
5
6
7
8
9'
10
11
12 .
13
co,
(%)
4.8
5.4
5.8
5.9
5.3
5.0
4.7
5.4
5.1
5.6
5.0
4.9
5.7
5.8
5.5
5.6
5.4
5.8
5.4
5.4
5.0
4.8
5.1
5.5
5.3
4.8
5.0
5.5
5.5
5.3
5.0
5.4
CO
(ppm)
29
21
23
27
18
21
25
29
23
23
29
27
18
20
23
21
18
23
23
32
25
18
20
21
23
29
34
25
23
18
20
21
Combustion
EH. (%)
99.94
99.96
99.96
99.95
99.97
99.96
99.95
99.95
99.95
99.96
99.94
99.94
99.97
99.97
99.96
99.96
99.97
99.96
99.94
99.95
99.96
99.96
99.96
99.96
99.94
99.93
99.95
99.96
99.97
99.96
99.96
Avg 5.2 24
68
-------
Test
(P-P-I)*
2-2-2
2-3-1
Feed
Cycle
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Avg
: 1 I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16'
17
18
C02
(%)
5.4
5.0
5.3
5.2
5.5
5.5
4.8
5.0
5.1
5.3
5.5
4.8
5.4
5.0
5.2
5.2
4.8
4.7
5.1
5.2
4.8
5.2
5.5
4.9
4.7
5.0
5.1
4.9
4.7
5.3
5.4
4.8
4.8
CO
(ppm)
21
27
23
34
36
39
30
25
32
34
37
25
29
21
30
32
29
34
36
27
23
21
27
18
20
29
25
30
29
, 21
18
16
18
Combustion
EH. (%)
99.96
99.95
99.96
99.93
99.93
99.93
99.94
99.95
99.94
99.94
99.93
99.95
99.95
99.96
99.94
99.94
99.93
99.93
99.95
99.95
99.96
99.95
99.96
99.96
99.94
99.95
99.94
99.94
99^96
99.97
99.97
99.96
Avg 5.0 25
69
-------
Test
(P-P-I)*
2-3-2
2-4-1
Feed
Cycle
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Avg
1
2
3
4
5
6
7,
8
9
10
11 •
12
13
co,
(%)
4.7
4.9
5.1
5.3
5.0
4.7
4.5
5.1
4.9
5.3
5.0
4.5
4.8
4.9
5.2
5.1
4.7
4.5
4.9
4.8
5.9
5.5
5.4
5.4
5.8
5.3
5.5
5.6
5.5
5.7
5.4
5.5
5.6
CO
(ppm)
32
30
21
27
29
34
32
37
32
29
23
30
27
32
37
29
25
20
27
29
37
32
21
16
25
30
21
34
37
43
* 29
21
27
Combustion
EH. (%)
99.93
99.94
99.96
99.95
99.94
99.93
99.93
99.93
99.93
99.95
99.95
99.93
99.94
99.93
99.93
99.94
99.95
99.96
99.94
99.94
99.94
99.96
99.97
99.96
99.94
99.96
99.94
99.93
9932
99.95
99.96
99.95
Avg 5.6 29
70
-------
Test Feed C02
(P-P-I)' Cycle (%)
2-4-2 1
2
3
4
5
6
7
8
9
10
11
12
Avg
5.0
5.3
4.9
6.0
5.5
4.8
4.9
5.6
4.8
5.5
5.5
5.3
5.3
CO Combustion
(ppm) Efl. (%)
27
21
23
75
39
29
59
32
21
29
18
16
28
99.95
99.96
99.95
99.86**
99.93
99.94
99.88**
99.94
99.95
99.95
99.97
99.97
"Occurred during fast shutdown transient. __
Gas Compositions (Dry Basis)
Test Phase
Component
1, Period 1, Interval
!. HZ
1
Location
OG
O2 (%) 6.0 11.0
CO (ppm)
C02 (%)
N2 (%)
Test Phase'
Component
02 (%)
CO (ppm)
i C02(%)
— *
—
—
1, Period 1, Interval
! HZ
6.0
...
—
30
5
84.0
2
Location
OG
9.0
25
,4.7
«
Nj (%) — 86.3
Test Phase
Component
• 0, (%)
' CO (ppm)
. C02(%)
N2 (%)
1, Period 2, Interval
HZ
6.0
—
—
—
1
Location
OG
8.0
31
4.9
87.1
•Indicates not measured.
71
-------
Gas Compositions (Dry Basis) (cont)
Test Phase 1, Period 2, Interval 2
Location
Component HZ OG
02 (%) 6.0 8.0
CO (ppm) --- 33
C02 (%) 4.8
N, ~- 87.2
Test Phase 2, Period 1, Interval 1 .
Location
Component • HZ OG
4.0 8.0_
CO (ppm) --- 29
CO, -- 5.1
N2 -. 86.9
Test Phase 2, Period 1, Interval 2
Location
Component | HZ OG
02 (%) 5.0 7.8_
CO (ppm) — 23
CO; (%) • — 5.4_
N2(%) — 86.8
Test Phase 2, Period 2, Interval 1
Location
Component HZ OG
0,(%) 5.0 T£_
CO (ppm) — 2*4
CO; (%) --. 5.2
N2 (%) — 87.3
72
-------
Gas Compositions (Dry Basis) (cont)
Test Phase 2, Period 2, Interval 2
Location
Component HZ OG
02 (%) 6.0 7.0_
CO (ppm) --- 30
C02(%) 5.2_
N2 (%) 87.8
Test Phase 2, Period 3, Interval 1
Location
Component HZ OG
0, (%) 5.0 6.5
2
CO (ppm) — 25
CO, (%) — 5.0
N2 (%) -» 88.5
Test Phase 2, Period 3, Interval 2
Location
Component j HZ OG
02 (%) 5.0 6.0_
CO (ppm) 29
CO2 (%) 4.8
— 89.2
Test Phase 2, Period 4, Interval 1
Location
Component HZ OG
02 (%) 1.0 7.5_
CO (ppm) _-~ 29
C02 (%) . 5.6_
N; (%) ~- 86.9
Test Phase 2, Period 4, Interval 2
Location
: Component HZ OG
0, (%) 0.5. 8.0_
CO (ppm) — 28
' CO; (%) -" 5.3
N; (%) -.- 86.7
73
-------
TABLE E-1. COMBUSTION EFFICIENCY
CALCULATIONS SUMMARY
Sample Interval
1-1-1"
1-1-2
1-2-1
1-2-2
2-1-1
2-1-2
2-2-1
2-2-2
2-3-1
2-3-2
2-4-1
2-4-2
Min. (%)
99.92
99.92
99.91
99.91
99.93
99.94
99.93
99.93
99.93
99.93
99.92
99.86"
Avg (%)
99.939
99.946
99.938
99.931
99.944
99.956
99.954
99.943
99.950
99.941
99.948
99.939
*Test Phase-Test Period-Test Interval.
••Occurred during a fast shutdown transient.
74
-------
APPENDIX F
SAMPLE AND FLOW CALCULATIONS SUMMARY
The field data (Appendix D) and the gas composition data (Appendix E) were used in the
calculation of offgas flows and sample volumes as described below.
Variable definitions:
SA = sample zone flow area (432 in.2 for HZ, 314 in.2 for OG).
Vm = sample volume at meter conditions.
V. = sample volume at standard conditions on dry basis.
Vw = volume of water vapor in sample at standard conditions.
T, = meter inlet temperature. . *
T0 = meter outlet temperature.
Tm = average meter temperature.
V«% = per cent moisture in offgas.
Md = mole fraction dry offgas. -
MWB = molecular weight of offgas.
EA = excess air (%).
T, = temperature of offgas at sample zone'.
; • S . = average (square root of velocity head x T.).
Hw = velocity head (pressure drop on pitot). .
u = offgas velocity in sample zone at sample zone conditions.
Q = volumetric flow of offgas at standard conditions.
]~] = concentration in per cent, i.e., [CO] = per cent CO.
Vm =dry gas meter reading at end of sample interval minus dry gas meter reading at
beginning of sample interval.
*
V-
/n where n is the number of traverse points .
/n .
Tm =[T,(average) + T0(average)]/2 .
: ., 177U pressure at meter
' v.= 1'-'v"-x Tm + 460'
j Vw = 0.0474 x mL water trapped in sample train .
«
, . Vw% =100VW/(VB + VJ .
Md =(100-VWJ/100 .
75
-------
MWg = (0.44[C02] + 0.28[CO] + 0.32[02] + 0.28[N2])Md + 18(1 - Md)
EA =100([02]-[CO]/2)/(0.264[N2]-[CO]/2) .
T.(average) = I V T.(j) | /n .
S=\
vl=1.n
u = 4350 S [1 /(MWg x sample zone pressure)]0-5 .
_Q = 0.123 u SA Md x sample zone pressure/(T, average + 460) .
In the above calculations, n = 12 for hot-zone (HZ) samples and 10 for hot crossover duct (OG)
samples. Results of the calculations are summarized in the following tabulation.
I Test
I (P-P-I)*
1-1-1
1-1-2
1-2-1
1-2-2
2-1-1
2-1-2
2-2-1
2-2-2
2-3-1
2-3-2
2-4-1
2-4-2
1-1-1
1-1-2
1-2-1
1-2-2
, 2-1-1
2-1-2
2-2-1
2-2-2
i 2-3-1
2-3-2
2-4-1
2-4-2
Sample
Zone"
HZ
HZ
HZ
HZ
HZ
HZ
HZ
HZ
HZ
HZ
HZ
HZ
OG
OG
OG
OG
OG
OG
OG
OG
OG
OG
OG
OG
Tm
(°F)
64
90
90
84
87
87
87
89
93
83
94
85
93
92
83
101
102
107
104
102
105
105
98
101
vm
<«3)
104.3
100.3
107.3
111.4
87.7
105.4
120.5
130.8
120.4
80.9
116.2
91.4
123.5
99.3
21.3
126.2
82.9
113.4
130.1
103.5
116.9
148.7
132.9
124.3
v.
(ft3)
81.4
74.7
79.8
83.8
65.4
78.8
91.3
97.4
88.9
60.9
86.0
68.6
91.5
73.5
16.0
92.0
60.3
81.7
94.4
75.4
84.5
107.4
97.7
90.6
EA
(%)
179
34
21
41
'48
30
57
46
32
25
31
65
98
65
53
53'
54
52
48
43
39
34
49
54
U
(ft/min)
454
534
589
544
555
545
530
571
580
564
547
594
«
2140
1889
2206
2274.
2387
2325
2507
2520
2461
2443
2452
2456
i •
Q
(ft'/min)
250
274
298
275
296
290
286
298
290
283
281
317
%
835
743
785
847
830
839
862
857
802
806
822
817
P-P-I = Phase-Period-Interval.
Sample zones were HZ = hot zone (primary chamber offgas)
and OG = hot crossover duct (secondary chamber offgas).
76
-------
APPENDIX G
REPORT ON SAMPLE ANALYSIS FROM
SOUTHWEST RESEARCH INSTITUTE
This report has been reproduced as received from SWRI.
77
-------
SOUTHWEST RESEARCH INSTITUTE
POST OFFICE DRAWER 2B61O • 6220 CULEBRA ROAD • SAN ANTONIO. TEXAS 78284 • IB12I684-6111
DIVISION OF CHEMISTRY
AND CHEMICAL ENGINEERING
January 12, 1982
; Dr. Larry Stretz
: University of California
; Los Alamos Laboratory
Box 990; Lab SP-2
Los Alamos, New Mexico 97545
Subject: SwRI Project 01-6761-023
Dear Dr. Stretz:
Attached please find the report on the methods and results of the
GC/MS analyses of sample extracts sent to us. If you have any questions or
require further information, please call me.
Very truly yours,
Carter Nulton, Ph.D.
Manager, Mass Spectrometry
! APPROVED:
Donald E. Johnson, Director
Department of Environmental Sciences
CN:bz/L7
Attachments
SAN ANTONIO. TEXAS
78
-------
Methods
Sample extract number 1 was broken on receipt at SwRI.
All extracts were ca. 30 ml. except number 7 which was ca. 23 ml.
Extracts were reduced in volume to 0.5 ml under a gentle stream of
chromatographic grade nitrogen. Th^ internal standards dg-naphthalene,
d,g-anthracene and dj^-chrysene were added to the concentrated extracts
prior to injection; the final concentrations of the internal standards were
51, 44 and 39 ng/yL, respectively.
The instrument used for these analyses was a Finnigan 3623 quadrapole
mass spectrometer equipped with an INCOS data system and a Tracer 560 GC.
The fused silica capillary column is threaded through a heated conduit into
the mass spectrometer ion source.
The following compounds were searched for by extracted ion current.
profiling in each total ion current (TIC) run:
chlorophenols - mono through pentachloro
chlorobenzenes - di through hexachloro
chlorobenzenes. - di through hexachloro
chlorodibenzodioxins - mono through octachloro
chlorodibenzofurans - mono through octachloro
The following instrument operating conditions were used for the TIC
runs:
GC
MS
Col umn
Phase
Carrier gas
Temperature program
Injector temperature
Splitless injection
Electron energy
Scan rate
15 m X 0.25 mm fused silica capil.lary
.SE-54; 1.0 v film
He at 40 cm/sec
65° 1 min|10/min|300°
280*
70 ev
1 sec/scan
Extracts were reanalyzed with the mass spectrometer in the selected
ion -monitor (SIM) mode; the target compounds were pentachlorophenol
; .(m/e 266, 268) tetrachlorodibenzodioxin (m/e 320, 322) and tetrachloro-
79
-------
dibenzofuran (m/e 304, 306). Other instrument operating conditions were
identifical to those listed for the TIC runs.
Selected target compound detection limits for both the TIC and SIM
analyses are given in Table 1.
Results -\_
Target compounds and their concentrations found in the TIC runs are
listed in Table 2.
In Table 3 tentatively identified major peaks are given along with
estimated concentrations (relative to nearest internal standard). The TIC
chromatograms are attached.
Except for the pentachlorophenol found in sample, extract number 113
none of the SIM target compounds were detected in the SIM runs.
80
-------
TABLE 1
SELECTED TARGET COMPOUND DETECTION LIMITS
Total ng in Samplea
TIC
2-Chlorophenol
! 2,4-dichlorophenol
j trich!orophenol
j hexachlorobenzene
I 2-chlorodibenzo-p-dioxin
2,8-dichlorodlbenzofuran
I 2,7-dichlorodibenzo-p-dioxin
: pentachlorophenol
• l,2,4-tr1chlorodibenzo-p-diox1n
1,2,3,4-tetrachl orodi benzo-p-dipxi n
; pctachlorodlbenzo-p-dioxin
octachlorodibenzofuran
i
MID
i pentachlorophenol
I tetrachlorodibenzo-p-dioxl n
i tetrachlorodibenzofuran
1.3
3
6
6
5
5
6
10
8
8
20
20
.5
.5
a - Based on a final sample volume of 0.5 mLs and a 2 yL
injection volume.
81
-------
TABLE 2
TARGET COMPOUNDS DETECTED IN TIC RUNS
Total yg In Sample
Sample 110
1,3-dichlorobenzene tr
1,4-dichlorobenzene tr
1,2-dichlorobenzene tr
2-chlorophenol tr
1,2,4-trichlorobenzene 0.9
1,2,3-trichlorobenzene tr
1,2,3,5 or 1,2,4,5-tetrachlorobenzene tr
1,2,3,4-tetrachlorobenzene tr
pentachlorobenzene tr
Sample 111
1,3-dichlorobenzene tr
1,4-di chlorobenzene tr
1,2-di chlorobenzene tr
1,2,4-trichlorobenzene 0.9
1,2,3-trichlorobenzene . tr
1,2,3,5 or 1,2,4,5-tetrachlorobenzene tr
1,2,3,4-tetrachlorobenzene tr
pentachlorobenzene tr
Sample 112
i 1,4-dichlorobenzene tr
: 1,2,4-trichlorobenzene tr
Sample 113 .
pentachlorophenol 61,000
tetrachlorophenol 16,000
tr = trace, below detection limits
82
-------
TABLE 3
TENTATIVE IDENTIFICATIONS AND RELATIVE CONCENTRATIONS
OF MAJOR PEAKS IN TIC RUNS
Scan
Number
Total ug 1n Sample
Sample 2, 5, 7, 30, 27 had no major peaks
Sample 6
524 naphthalene3
628 naphthalene 2-methyl
705 l.l'-biphenyl
779 acenaphthylene
893 9H-fluorene .
106 phenanthreneb
1163 4H-cyclopenta[def]phenanthrene
1268 fluoranthene
1307 pyrene
1482 benzo[ghi]fluoroanthene or isomer
1519 benzo[ghi]fluoroanthene or isomer
! 1538 b1s(2-ethylhexyl)phtha1ate
1856 benzof1uoroanthene or Isomer
Sample 10 .
526 naphthalene3
629 naphthalene, 2-methyl
707 l.l'-biphenyl
782 acenaphthylene
837 dibenzofuran
895 9H-fluorene
1062 phenanthreneb .
1164 4H-cyclopenta[def]phenanthrene
1269 fluoranthene
1309 pyrene
1446 hexanedioicacid, dioctylester
1483 benzo[ghi]fluoranthene or isomer
1520 benzo[ghi]fluoranthene or isomer
1539 bis(2-ethylhexyl)phthalate
1767 benzofluoranthene or isomer
1859 benzofluoranthene or isomer
Sample 11
366 benzyl alcohol
523 naphthalene3
778 acenaphthylene
1060 phenanthrene^
>2.5
<2.5
<2.5
>2.5
>2.5
<2.5
<2.5
x2.5
<2.5
<2.5
x2.5
<2.5
>2.5
<2.5
<2.5
>2.5
<2.5
<2.5
>2.5
>2.5
>2.5
<2..5
<2.5
<2.5
x2.5
<2.5
<2.5
<2.5
>2.5
x2.5
83
-------
Scan
Number . Total ug In Sample
Sample 22
1266 fluoranthene 1.2.5
1305 pyrene -v2.5
1447 hexandioic acid, b1s(2-ethylhexy1)ester . >2.5
Sample 23
361 benzyl alcohol <2.5
1446 hexanediocacid, bis(2-ethylhexy!Jester >2.5
Sample 26
381 benzene, 1-propynyl or IH-indene <2.5
525 naphthalene9 >2.5
781 acenaphthylene >2.5
I.1061 phenanthrene0 >2.5
j 1268 fluoranthene • x2.5
1306 pyrene 2.5
1446 hexanediocacid, bis(2-ethyl)ester x2.5
Sample 34
369 benzyl alcohol <2.5
781 acenaphthylene <2.5
1435 butyl benzylphthalate <2.5
1449 hexanediocacid, bis(2-ethylhexyl)ester >2.5
1543 bis(2-ethylhexyl)phthalate >2.5
Sample 38
364 benzyl alcohol <2.5
524 naphthalene3 . >2.5
782 acenaphthylene >2.5
1270 fluoranthene -».2.5
1308 pyrene x2.5
1450 hexanediocacid, bis(2-ethylhexyl )ester >2'.5
! • . " •
i Sample 42
j 314 methyl phenol <2.5
i 432 naphthalene3 • >2.5
! 690 acenaphthylene ->,2.5
I 966 phenanthreneb <2.5
: 1167 fluoranthene x2.5
.1204 pyrene x2.5
1345 hexanediocacid, bis(2-ethylhexyl)ester >2.5
i 1434 bis(2-ethylhexyl)phthalate >2.5
84
-------
Scan
Number Total ug 1n Sample
Sample 43
333 benzyl alcohol <2.5
1397 hexanediocacid, b1s(2-ethylhexylJester >2.5
Sample 46
339 naphthalene3 >2.5
564 acenaphthylene -v-2.5
673 9H-fluorene <2.5
832 phenanthreneb >2.5
1037 fluoranthene >2.5
1074 pyrene >2.5
1221 hexanediocacid, bis(2-ethylhexyl)ester >2.5
1310 bis(2-ethylhexyl)phthalate -v2.5
Sample 47
923 aliphatic hydrocarbon <2.5
1401 hexanediocacid, bis(2-ethylhexyl)ester >2.5
Sample 50
325 benzyl alcohol <2.5
484 naphthalene3 . >2.5
603 methyl naphtha!ene <2.5
664 1,1-biphenyl <2.5
734 acenaphthylene -v2.5
848 9H-fluorene <2.5
1011 phenanthrene" >2.5
1216 fluoranthene >2.5
1254 pyrene ' >2.5
1400 hexanediocacid, bis(2-ethylhexyl)ester >2.5
1429 benzo[g,h,i]fluoranthene <2.5
1464 benzofluoroanthene or isomer 1.2.5
1737 benzof 1 uoranthene or isomer "• -»,2.5
Sample 51
329 benzylalcohol , <2.5
| 1398 hexanediocacid, bis(2-ethylhexyl)ester >2.5
i •
j Sample 106
i 325 1-hexanol, 2-ethyl >2.5
i 333 benzylalcohol >2.5
j 522 1,2-benzisothiazole <2.5
! 1488 bis(2-ethylhexyl)phthalate >2.5
85
-------
Scan
Number Total ug in Sample
Sample 110
299 trimethyl benzene <2.5
323 1-hexanol, 2-ethyl -v2.5
485 naphthalene3 >2.5
523 1,2-benzisotMazole <1.5
scans 700-1500 envelope of
incompletely resolved hydrocarbons ^2.5 each
805 trimethyl naphthalene x2.5
1493 bis(2-ethylhexyl)phthalate >2.5
Sample 111
303 trimethyl benzene <2.5
327 1-hexanol, 2-ethyl . t2.5
335 benzyl alcohol %2.5
525 1,2-benzisothiazole <2.5
scans 700-1200 envelope of
incompletely resolved hydrocarbons <2.5 each
712 dimethyl naphthalene <2.5
806 trimethylnaphthalene <2.5
1497 bis(2-ethylhexyl)phthalate >2.5
Sample 112
326 1-hexanol, 2-ethyl <2.5
333 benzyl alcohol <2.5
1500 bis(2-ethyThexyl)phthalate >2.5
branched and/or cyclic hydrocarbons >2.5
i aliphatic hydrocarbon series >2.5
1000 pentachlorophenol (see Table 2)
1504 bis(2-ethylhexyl)phthalate >2.5
a - co-elutes with dg-naphthalene
b - co-elutes with dig~arrtnracene «
86
-------
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