EPA/600/R-95/071
June 1995
OPERATIONS AND RESEARCH AT THE U.S. EPA
INCINERATION RESEARCH FACILITY-
ANNUAL REPORT FOR FY94
By
L. R. Waterland
Acurex Environmental Corporation
Incineration Research Facility
Jefferson, Arkansas 72079
EPA Contract 68-C9-0038
EPA Project Officer: Robert C. Thurnau
Waste Minimization, Destruction, and Disposal Research Division
Risk Reduction Engineering Laboratory
Cincinnati, Ohio 45268
RISK REDUCTION ENGINEERING LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
Printed on Recycled Paper
-------
NOTICE
The information in this document has been funded wholly or in part by the United
States Environmental Protection Agency under Contract 68-C9"-0038 to Acifrex Environmental
Corporation. It has been subjected to the Agency's peer and administrative review, and it has
been approved for publication as an EPA document. Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
-------
FOREWORD
Today's rapidly developing and changing technologies and industrial products and
practices frequently carry with them the increased generation of materials that, if improperly
dealt with, can threaten both public health and the environment. The U.S. Environmental
Protection Agency is charged by Congress with protecting the Nation's land, air, and water
resources. Under a mandate of national environmental laws, the Agency strives to formulate and
implement actions leading to a compatible balance between human activities and the ability of
natural systems to support and nurture life. These laws direct the EPA to perform research to
define our environmental problems, measure the impacts, and search for solutions.
The Risk Reduction Engineering Laboratory is responsible for planning, implementing,
and managing research, development, and demonstration programs to provide an authoritative,'
defensible engineering basis in support of the policies, programs, and regulations of the EPA
with respect to drinking water, wastewater, pesticides, toxic substances, solid and hazardous
wastes, and Superfund-related activities. This publication is one of the products of that research
and provides a vital communication link between the researcher and the user community.
This document reviews the accomplishments at the Incineration Research Facility (IRF)
in Jefferson, Arkansas, during Fiscal Year 1994. In the 12-month period, two major test
programs were completed at the facility and a third carried to near-completion. The major EPA
program supported through test activity was the Superfund site remediation program within the
Office of Emergency and Remedial Response (OERR) as administered by OERR and EPA
Region III, and as supported by the Superfund Innovative Technology Evaluation (SITE)
program. In addition, one of the test programs completed supported the Defense Nuclear
Agency's (DNA's) efforts to supply aid to former Soviet Union states' efforts to eliminate
strategic offensive arms. The report outlines all efforts completed or ongoing at the facility
during FY94.
-------
ABSTRACT
The U.S. Environmental Protection Agency's Incineration Research Facility (IRF) in
Jefferson, Arkansas, is an experimental facility that houses a pilot-scale rotary kiln incineration
system (RKS) and the associated waste handling, emission control, process control, and safety
equipment; as well as onsite laboratory facilities.
During fiscal year 1994 (FY94), two major test programs were completed at the IRF and
a third carried through to near-completion. Incineration testing of fluff waste and contaminated
soil from the M. W. Manufacturing Superfund site in Region III was completed as the first major
test program. Testing to demonstrate that the ballistic missile liquid propellant components
unsymmetrical dimethylhydrazine fuel and nitrogen tetroxide oxidizer can be safely incinerated
while complying with the U.S. environmental regulations, as well as those of the two former
Soviet Union states, the Ukraine and Russia, was the second major test program. The third
major test program underway in FY94 was a Superfund Innovative Technology Evaluation
(SITE) of the pulse combustion burner technology developed by Sonotech, Inc. This test
program was carried through the completion of all but the last few of the planned 12 extensive
tests.
Two bench-scale incineration test programs were also completed in the thermal
treatment unit (TTU) at the facility: an evaluation of the effectiveness of sorbents as additives
for metals capture, and a comparative evaluation of TTU performance in treating contaminated
soil from the M. W. Manufacturing site.
Plans were also developed for a set of bench-scale treatability tests of contaminated
materials from the Southern Shipbuilding Superfund site, and a pilot-scale treatability study of
direct-fired thermal desorption applied to contaminated soils from the Rocky Mountain Arsenal.
This report summarizes all efforts completed or ongoing at the IRF during FY94.
IV
-------
CONTENTS
Page
NOTICE y
FOREWORD . . ] " -
ABSTRACT iv
FIGURES . . . .' viii
TABLES ix
1 INTRODUCTION . . 1
2 EVALUATION OF ROTARY KILN INCINERATOR OPERATION AT LOW
TO MODERATE TEMPERATURES 4
2.1 TEST PROGRAM 5
2.1.1 Test Contaminated Soil . 5
2.1.2 Test Conditions . ' ' . ' ' . . ' ' ' '.'.'.',[[[', 7
2.1.3 Sampling and Analysis 10
2.2 RESULTS AND CONCLUSIONS :...... 12
2.2.1 Organic Decontamination and Compound Boiling Point 13
2.2.2 Organic Decontamination and Solid Temperature 13
2.2.3 Organic Decontamination and Solids Bed Depth 13
2.2.4 Organic Decontamination and Soil Moisture Content 13
2.2.5 Organic Decontamination and Treatment Time and
' Temperature 14
2.2.6 Trace Metal Distributions 17
2.2.7 Trace Metal Leachability , 17
2.2.8 Summary lg
3 TESTING OF FLUFF WASTE AND CONTAMINATED SOIL FROM
THE M. W. MANUFACTURING SUPERFUND SITE 19
3.1 BACKGROUND 19
3.2 TEST PROGRAM '.'.'.'.'.'.'.'.'.'.'.'.'.'. 21
3.2.1 Waste Description 21
3.2.2 Test Conditions 22
-------
CONTENTS (continued)
Section
3.2.3 Sampling and Analysis Procedures .......................... 23
3.3 TEST RESULTS ............ ................................ 24
3.3.1 SVOC Results ...... ................................... 24
3.3.2 VOC Results .......................................... 27
3.3.3 POHC DREs .......................................... 29
3.3.4 Dioxin and Furan Results ................................ 31
3.3.5 Trace Metal and TCLP Results . . ---- . ..................... 36
3.3.6 Particulate and HC1 Emissions ....... . . .................... 38
3.4 CONCLUSIONS ............................................ 41
4 TEST INCINERATION OF BALLISTIC MISSILE PROPELLANT
COMPONENTS ........................ ................. ....... 43
4.1 TEST PROGRAM . ......................................... 44
4.1.1 Environmental Regulations ............................... 44
4.1.2 Test Conditions ........................................ 47
4.1.3 Sampling and Analysis Procedures .......................... 4§
4.2 TEST RESULTS ...... . ---- ................................. 50
4.3 CONCLUSIONS .............. ...... ........................ 58
5 EVALUATION OF THE SONOTECH PULSE COMBUSTION
TECHNOLOGY ............... ........ ---- - - - .................. 60
5.1 DESCRIPTION OF THE TECHNOLOGY ...... ... .............. 60
5.2 DEMONSTRATION OBJECTIVES ............................. 61
5.3 TEST PROGRAM ...... .................................... 62
5.4 PRELIMINARY TEST RESULTS .............................. 64
5.4.1 Incinerator Operating Conditions ........................... 64
5.4.2 CEM Data ............................................ 67
5.5 CURRENT STATUS ........................................ 68
vi
-------
CONTENTS (continued)
Page
6 EVALUATING THE EFFECTIVENESS OF ADDITIVES AS SORBENTS
FOR METAL CAPTURE ............................ . . . . .......... 70
6.1 TEST FACILITY DESCRIPTION ....... ............... 71
6.2 TEST PROGRAM .... ................... ' " .......... 73
6.3 TEST RESULTS ..... . ....... . _______ ...... ['," ........ ••-... ^
6.4 CONCLUSIONS ......... ....... ..-.' ____ ....... '.'. . '. . .' ',['.', ' " ' ] 79
7 TREATABILITY TESTING OF THE M. W. MANUFACTURING
SUPERFUND SITE CONTAMINATED SOIL IN THE TTU ............. . . . 83
7.1 TEST PROGRAM ..................... .... 83
7.2 TEST RESULTS ........ . ..... .......... " ' ....... 85
7.3 CONCLUSIONS ............. . ......... ... ..... •..'.'.'.•'.'.','.'.'.'.'.'. 87
8 BENCH-SCALE TREATABILITY TESTING OF CONTAMINATED
MATERIALS FROM THE SOUTHERN SHIPBUILDING SUPERFUND
SITE ..................... . ..... ........................ ...... 88
8.1 TEST PROGRAM ................. . . 89
8.2 CURRENT STATUS ............ . ........ . . ....... ;.'.'.'.'.'.'.'.'.'. 89
9 DIRECT-FIRED THERMAL DESORPTION TREATABILITY STUDY
ON ROCKY MOUNTAIN ARSENAL SOILS ... .......... . . ____ . ...... 91
9.1 BACKGROUND ....... . ____ . ____ ____ ....... . . ........... 91
9.2 PLANNED TEST PROGRAM . . ....... ......... ...7. ... . ..... 92
9.3 SAMPLING AND ANALYSIS PROCEDURES ..... ...... 93
9.4 CURRENT STATUS . . .......... ........... ............ . ____ [ 96
10 EXTERNAL COMMUNICATIONS ........ ". ...... . . . . ....... ____ ... 97
11 PLANNED EFFORTS FOR FY95 ...... ..... ..... ____ ............. 102
12 REFERENCES ........ ........... ...... ..... . . ..... . ........... 104
vu
-------
FIGURES
Number
1 Schematic of the IRF rotary kiln incineration system 6
2 Organic compound decontamination effectiveness versus the differences in
solid bed temperature and compound boiling point 15
3 Effect of cumulative treatment time and achieved solid temperature
(adjusted for compound boiling point) on organic decontamination 16
4
5
6
7
8
Test sampling locations 49
The IRF TTU 72
Schematic of bed thermocouple arrangement (a), and typical sample
run (b)
77
Average soil bed temperature history for the RKS and TTU test program 86
Test sampling locations • 94
VJUl
-------
TABLES
Number , page
1 Organic constituents in the synthetic contaminated soil . 8
2 Trace metal constituents in the synthetic contaminated soil . . 9
3 Target test conditions .. 9
4 Actual test operating conditions 11
5 M. W. Manufacturing site characterization sample analysis results 21
6 Test matrix , . 23'
7 APCS operating conditions . , 24
8 Semivolatile organic contaminant analysis results . , 25
9 Volatile organic contaminant analysis results 1 28
10 POHC DREs 30
11 Dioxin and furan analysis results 32
12 Ratio of discharged dioxins and furans to fed amounts , ; 34
13 Trace metal analysis results . 37
14 TCLP leachate analysis results 39
15 Particulate and HC1 emissions 40
16 Russian Federation environmental regulations for UDMH incineration 45
17 European hazardous waste incinerator emission limits 46
18 Test operating conditions for UDMH tests 50
19 Test operating conditions for N2O4 tests .. 51
IX
-------
TABLES (continued)
Number
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
CEM data for the UDMH tests 52
CEM data for the N2O4 tests . L 54
N204 DREs 55
Flue gas hazardous constituent concentrations for the UDMH Set 1
tests
Flue gas hazardous constituent concentrations for the UDMH Set 2
tests
56
57
Scrubber exit flue gas PCDD/PCDF concentrations 57
Flue gas trace metal concentration method detection limits 58
Test waste composition 63
Test program sampling and analysis matrix 64
Test condition operating data 65
Continuous emissions monitor data • • 67
Test matrix '^
- Metal spike solution concentrations 76
Test program metal dispersion concentrations 76
Trace metal ash fractions 78
TCLP fractional teachabilities 80
Comparison of treatment chamber characteristics: TTU and rotary kiln 84
-------
Number
37
38
39
40
41
42
TABLES (continued)
Approximate bed temperature history in the RKS tests of the M. W.
Manufacturing site soil ............. .
Comparison of test data from the RKS and TTU testing of M. W.
Manufacturing site soil ............................... .
Planned test program measurements ........ .................. ...... 90
Tentative test matrix conditions for each soil . ............ ....... . ..... 93
IRF program reports and presentations in FY94 ................ ....... 98
Visitors to the IRF .......... ............ ____ ..................... 99
XI
-------
-------
SECTION 1
INTRODUCTION
The U.S. Environmental Protection Agency (EPA) Incineration Research Facility (IRF)
in Jefferson, Arkansas, is an experimental facility that currently houses a pilot-scale rotary kiln
incineration system (RKS) and its associated waste handling, emission control, process control,
and safety equipment, and a bench-scale thermal treatment unit (TTU) for performing thermal
treatability studies on a smaller scale. The IRF also has onsite laboratory facilities for waste
characterization and analysis of process performance samples.
The objective of research projects conducted at the IRF have been and continue to be
as follows:
• To develop technical information on the performance capabilities of the hazardous
waste incineration process to assist EPA Regional Offices and state environmental
agencies in the review, assessment, and issuance of reasonable and responsible
permits for regulated hazardous waste incineration facilities, and to assist waste
generators and incinerator operators in the preparation of permit applications
• To develop incinerator system performance data for regulated hazardous wastes
to support current Resource Conservation and Recovery Act (RCRA) incinerator
regulations and performance standards, and to provide a sound technical basis for
any necessary future standards
• To promote an understanding of the hazardous waste incineration process and
develop methods to predict the performance of incinerators of varying scale and
design for the major classes of incinerable hazardous wastes as a function of key
process operating variables
• To develop methods of improving reliability and control of the incineration
process
• To provide a means of conducting specialized thermal treatment tests (particularly
for high-hazard and special waste materials such as Superfund site wastes) in
support of specific Regional Office permitting or enforcement actions and
Regional Office or private party Superfund site remediation efforts
• To test the performance of new and advanced incinerator components and
subsystems, and emission control and measurement devices
-------
Fiscal year 1994 (FY94, October 1, 1993 through September 30, 1994) saw the
continuation of incineration research testing efforts at the IRF. During the year, two major
pilot-scale programs were completed and a third carried to near-completion, and two bench-scale
test programs of lesser scope were completed. In addition, plans to continue uninterrupted
testing into FY95 with an additional two test programs were developed.
The major EPA program supported through test activities in FY93 was the Superfund
site remediation program with the Office of Emergency and Remedial Response (OERR). One
major test program to evaluate incineration as a treatment option for fluff waste and
contaminated soil from the M. W. Manufacturing Superfund site in Region III was completed.
Another test program, a Superfund Innovative Technology Evaluation (SITE) of an innovative
pulse combustion burner technology developed by Sonotech, Inc., was initiated and nearly
completed.
The third major test program underway during FY94 directly supported the Defense
Nuclear Agency's (DNA's) efforts to assist two former Soviet Union (FSU) states comply with
strategic offensive arms elimination schedules negotiated in the Strategic Arms Reduction Treaty
(START). This test program established that the two ballistic missile liquid propellant
components, unsymmetrical dimethylhydrazine (UDMH) fuel and nitrogen tetroxide oxidizer
could be separately destroyed in an incinerator safely, and with flue gas emissions that would
meet U.S. environmental regulations as well as those of the Ukraine and Russia. This test
program served as the basis for setting the specifications for transportable incinerators to be
procured for shipment to one or both FSU states for use in destroying the propellants from
missiles decommissioned in accordance with START. During the performance of this test
program, the IRF hosted visits of high level delegations from both the Ukraine and Russia,
accompanied by DNA officials, to witness safe and effective propellant destruction.
In addition to these three major programs, two bench-scale test programs accomplished
in the thermal treatment unit (TTU) were completed in FY94. The first was an extensive
evaluation of the effectiveness of several additives employed as sorbents for metal capture during
incineration. The second was a series of tests that fed contaminated soil from the M. W.
Manufacturing site to the TTU to evaluate its performance in duplicating the findings of the
pilot-scale incineration tests in the RKS.
In other FY94 efforts, the results of an extensive set of tests to evaluate the rotary kiln
operation at low to moderate temperature were assembled and submitted.
Activities completed during FY94 are discussed in more detail in the following sections.
Section 2 discusses the results of the low to moderate temperature kiln operation tests. Section
3 discusses the RKS test program to evaluate the incinerability of fluff waste and contaminated
soil from the M. W. Manufacturing Superfund site. Section 4 discusses the incineration test
program with ballistic missile liquid propellant components for DNA. Section 5 covers the
demonstration of the Sonotech SITE pulse combustion burner technology. Section 6 presents
the results of the series of tests in the TTU to evaluate the effectiveness of candidate additives
as trace metal sorbents. Section 7 describes the brief series of TTU tests with the contaminated
soil from the M. W. Manufacturing site. Section 8 details the plans for the START tests of the
contaminated materials from the Southern Shipbuilding site in the TTU. Section 10 discusses
external communication activities associated with the facility and its operation.
-------
Finally, planning efforts were initiated for the first major test program for FY95, a pilot-
scale direct-fired thermal desorption (DFTD) treatability study on contaminated soils from the
Rocky Mountain Arsenal (RMA), to be performed in the RKS. This project will be a third-party
test program funded by the Department of Energy's Argonne National Laboratory (ANL).
Section 9 outlines the plans for this study. Planning efforts were also completed for a bench-
scale incineration treatability study of contaminated materials from the Southern Shipbuilding
Superfund site in Region VI. This study will support the Risk Reduction Engineering
Laboratory's (RREL's) Superfund Technical Assistance Response Team (START). An outline
of plans for activities to be completed in FY95 is given in Section 11.
-------
SECTION 2
EVALUATION OF ROTARY KILN INCINERATOR OPERATION
AT LOW TO MODERATE TEMPERATURES
As part of the EPA's efforts to remediate Superfund sites, several remediation
technologies can be candidates for consideration. One of the more frequently used technologies
to decontaminate soils contaminated with organic hazardous constituents is incineration. High-
temperature incineration, while effective in destroying organic compounds, may not be necessary
for some soils that need treatment, such as soils contaminated with volatile organic compounds
(VOCs). Also, in soils contaminated with toxic trace metals, high-temperature incineration may
increase the volatilization of some metals into the combustion flue gas. The presence of elevated
levels of volatile trace metals in the flue gas can pose increased challenges to an APCS.
Another thermal treatment technology, thermal desorption, may be an attractive
alternative to incineration. When successful in decontaminating soils to the necessary degree,
thermal desorption treatment of soils offers the benefits of lower fuel consumption, avoidance
of slag formation, reduced metals volatilization, and reduced APCS demands.
Most conventional rotary kiln incinerators can be easily operated at temperatures below
those typically employed for incineration treatment. Thus, the following question arises: how
effective is the treatment of contaminated soils by a rotary kiln incinerator operated at the low
to moderate temperatures?
To address this question, a series of tests was conducted in the IRF RKS with the kiln
of the RKS operated at low to moderate temperatures. The test program consisted of 12 tests
under 11 different kiln operating conditions; one test condition was tested in duplicate.
The objective of the test program was to study the global effects of five parameters
believed to be of primary importance in the treatment effectiveness of soil decontamination and
the fate of contaminant metals. These parameters were soil moisture content, treatment
temperature, treatment time, solids bed depth, and degree of solids agitation.
The results obtained from the test program were intended to yield the following
information:
• The relationship between compound boiling point (vapor pressure) and the extent
of decontamination for each organic contaminant
• How the solids bed temperature affects decontamination
-------
• The differences in organic constituent decontamination for beds of different
depths, when the same bed temperatures were reached
• How the presence and the amount of moisture affect organic decontamination
effectiveness '.
• The relationship between treatment time, treatment temperature, and organic
constituent decontamination effectiveness
• The distribution of trace metals in process discharges when a metal-contaminated
soil is treated by thermal desorption
• Whether thermal desorption treatment conditions affect a metal's leachability
from the treated soil
While the tests were completed during FY93, sample analysis efforts extended into
1994,with data evaluation and reporting becoming significant FY94 efforts.
2.1
TEST PROGRAM
All tests were performed in the IRF RKS. The RKS was configured as shown in
Figure 1, with the exception that the baghouse system with the flue gas reheater indicated in the
figure was not in place. The venturi/packed-column scrubber system shown in the figure served
as the primary APCS for these tests. ,
2.1.1 Test Contaminated Soil
A synthetic contaminated soil was prepared for testing in the program. This synthetic
soil was prepared by mixing a locally obtained topsoil with an attapulgite clay oil sorbent in a 1:1
weight ratio. This clay additive was required to allow the test mixture to be reliably fed
continuously to the kiln of the RKS using a screw feeder. The local topsoil without the clay
additive readily bridged in the feed hopper, preventing reliable feed.
The test soil/clay mixture was spiked to contain contaminants reflecting contamination
by gasoline, volatile organic solvents, semivolatile organic compounds associated with coal tar,
and trace metals. Benzene, n-heptane, and n-octane represented gasoline components; benzene,
toluene, tetrachloroethene, and chlorobenzene represented volatile organic solvents; and
naphthalene, phenanthrene, and pyrene represented coal tar constituents. Spiking levels ranged
from 2,000 to 4,800 mg/kg in the final synthetic contaminated soil mixture for the volatile
organic compounds (VOCs) added, and from 200 to 600 mg/kg for the semivolatile organic
compounds (SVOCs) added. The test soil/clay mixture was also spiked to contain commonly
encountered hazardous constituent trace metal contaminants. The trace metals spiked were
arsenic, barium, cadmium, chromium, lead, and mercury. Spiking levels ranged from 10 to
200 mg/kg in the final synthetic contaminated soil mixture.
The soil/clay mixtures were prepared in two 3.5-ft3 (100-L) cement mixers via the
addition of weighed quantities of each mixture component into a mixer. The organic
contaminants were added to the soil/clay mixtures as a combined organic solution. Trace metal
-------
-------
contaminants were added in an aqueous solution. After spiking, the moisture content of the
spiked soil/clay mixture was adjusted to one of two test program targets of 10 to 20 percent by
adding additional water, if needed. The final soil mixtures were tumbled to uniform appearance,
then transferred to 55-gal (208-L) drums that were then sealed. Contaminated soil mixtures
were allowed to age between 7 and 14 days before use in a test.
Table 1 summarizes the organic solution composition used to spike the test mixtures.
The organic contaminant mixture was added to the soil/clay mixtures in the ratio of 0.02 kg
organic liquid per kg final soil mixture. Resulting contaminated soil organic constituent
concentrations are also noted in Table 1. The composition of the concentrated aqueous solution
of trace metals added is summarized in Table 2. All metal constituents were added as soluble
nitrate salts except arsenic, which was added as As2O3 dissolved into an acid nitrate spike
solution. The metals spike solution was added to the soil/clay mixtures in the ratio of 0.05 kg
spike solution per kg of final contaminated soil mixture. Resulting contaminated soil trace metal
concentrations, neglecting native soil/clay metal concentrations, are also noted in Table 2.
2.1.2 Test Conditions
As noted above, the test program consisted of 12 tests under 11 different combinations
of the test variables, with one test performed in duplicate. The test parameters were soil
moisture content, treatment temperature, treatment time, solids bed depth, and degree of solids
agitation. Soil moisture content was directly varied, at 10 and 20 percent, respectively, as noted
in earlier discussion. Changes in the other test parameters were caused by changing the RKS
operating conditions. The operating conditions varied from test condition to test condition were:
kiln exit gas temperature, contaminated soil feedrate, and kiln rotation rate. Three target kiln
exit gas temperatures were tested, 320°, 480°, and 650°C (600°, 900°, and 1,200°F). Two target
feedrates were tested, 70 and 210 kg/hr (150 and 470 Ib/hr).. Three target rotation rates were
tested, 0.2, 0.5, and 1.5 rpm.
Kiln exit gas temperature primarily affected peak solids bed temperature. Peak solids
bed temperatures corresponding to the above kiln exit gas temperatures were about 120°, 260°,
and 430°C (250°, 500°, and 800°F), respectively. Kiln rotation rate affected both degree of
agitation and solids residence time in the kiln, or maximum treatment time. Total kiln solids
residence times corresponding to the above rotation rates were 60, 40, and 30 minutes,
respectively. The combination of feedrate and kiln rotation rate affected solids bed depth.
Total treatment times were changed by varying kiln rotation rates, as noted above.
However, to allow for the evaluation of treatment effectiveness at partial treatment times for
each test condition, samples of the solids bed material were taken at four axial locations along
the kiln for each test in addition to a solids discharge sample. These additional samples
corresponded to four different treatment times at each test condition.
A summary of the target test operating conditions and soil moisture contents for each
of the specified 12 tests is given in Table 3. The "center point" of the test matrix is represented
by Test 2, with soil feedrate at 70 kg/hr (150 Ib/hr), kiln exit gas temperature of 480°C (900°F),
kiln rotation rate of 0.2 rpm, and soil moisture content of 10 percent. This test condition was
tested in duplicate (Test 12). From this "center point," kiln temperature was varied (Tests 1
and 3), soil moisture content was varied (Test 5), kiln rotation rate was varied (Test 7), and soil
-------
d
o
CO
Q
S
<|
pj
|
H
O
U
o
N
s
H
>•<
C/2
33
3
to
7
a
p
•-<
I
1
O
S
•
•x}
1
H
'o
w
.S
a
ncentratio:
a
13
*3
.sr
u
1
O
•B
*3 ^
W ri
(U CM U)
o'-g S
s g
03 cq
«
01 O
£* •*•(
1 I?
'as
s
^
.s
P
cf0
m
o
M
jf
o
Cw
bflO
« °
1
gj tw.
"0 ^
CO* &
If
M S3
Is
•a
3
Q
1
§, o o o o
o o o o
P-. °~ °°~ C-J.
v> T) «n •* T)
T-H T— 1 rH CM rH
S 29 '-| '-' vo
00 0\ T-H CM CN
T-H l/"l CS1 l^*-
o\ o\ r^ ^^
VO i t i i
oo oo t-~ co o
oq vq oq vq t-;
O O O rH O
*"} C3 t*: o\ co
OO C3 CO if) -^
F- r-l 0\ vo T-H
U
c
42
•4— »
U
O
-------
TABLE 2. TRACE METAL CONSTITUENTS IN THE SYNTHETIC CONTAMINATED
SOIL
Aqueous spike solution
Metal
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Metal
concentration,
g/L.
0.50
4.0
0.20
0.50
0.80
0.20
Compound
AS203
Ba(N03)2
Cd(NO3)2 - 4H2O
Cr(NO3)3 - 9H2O
Pb(NO3)2
Hg(N03)2 '
Compound
concentration3,
g/L
0.67
7.61
0.55
3.8
1.28
0.32
> Resulting soil
feed metal
concentration1*,
mg/kg
25
200
10
25
40
10
Sufficient HNO3 added to maintain lead arsenate compounds in solution.
bNegligible soil metal concentrations and a ratio of 0.05 kg of spike solution per kg of
organic/soil/spike solution mixture assumed.
TABLE 3. TARGET TEST CONDITIONS
Test
1
2
3
4
5
6
7
8
9
10
11
12
Kiln exit gas
temperature,
°C (°F)
320 (600)
480 (900)
650 (1,200)
320 (600)
480 (900)
650 (1,200)
480 (900)
480 (900)
480 (900)
480 (900)
480 (900)
480 (900)
Expected peak
solids bed
temperature,
°C (°F)
120 (250)
270 (520)
430 (800)
120(250)
270 (520)
430 (800)
270 (520)
270 (520)
270 (520)
270 (520)
270 (520)
270 (520)
Kiln rotation
rate, rpm
0.2
0.2
0.2
; 0.2
0.2
0.2
0.5
0.5
1.5
0.2
0.2
0.2
Soil feedrate,
kg/hr (Ib/hr)
70 (150)
70 (150)
70 (150)
70 (150)
70(150)
70 (150)
70 (150)
70 (150)
70 (150)
210 (470)
210 (470)
70 (150)
Soil
moisture
content,
%
10
10
10
20
20
20
10
20
20
10
20
10
-------
feedrate was varied (Test 10). Additional test combinations were performed for the high
moisture soil at the base feedrate and rotation rate (Tests 4 and 6), at the high feedrate and
base rotation rate (Test 11), and at the base feedrate and increased rotation rate (Test 8). The
highest rotation rate was tested at high feedrate with the high moisture soil (Test 9).
For all tests, the afterburner was operated at 1,090 °C (2,000 °F) to ensure satisfactory
burnout of all volatilized organic compounds. The scrubber system was operated under its
nominal design conditions to achieve typical scrubber performance. The scrubber was operated
at near total recycle, so there was minimum blowdown. The synthetic contaminated soil was fed
continuously until all flue gas sampling was completed. Treated soil was continuously removed
from the kiln ash hopper via an ash auger transfer system, and deposited in clean 55-gal (208-L)
drums. After the completion of each test (all flue gas sampling completed) the system continued
to operate at the specified test conditions, without soil feed, until all treated soil was cleared
from the kiln. The weight of treated soil collected was monitored continuously throughout the
test; the resulting data allowed the calculation of total kiln solids residence times.
A summary of the actual test conditions in effect for each test is given in Table 4. As
shown, average kiln exit gas temperature targets were closely met for all tests. Solids bed
temperatures were measured at four locations along the kiln axis: 0.6, 1.1, 1.5, and 2.0 m (2.0,
3.5,5.0, and 6.5 ft) from the kiln feed face. Measurements were made with a specially-fabricated
probe that allowed the immersing of four thermocouples in the solids bed at the respective axial
locations. Solids bed temperatures measured for the tests are also given in Table 4.
2.13 Sampling and Analysis
For all tests, the sampling protocol consisted of:
• Obtaining a composite sample of the contaminated soil feed material mixture
• Obtaining composite samples of the treated soil in the kiln chamber at four axial
locations corresponding to the solids bed temperature measurements: 0.6,1.1,1.5,
and 2.0 m (2.0, 3.5, 5.5, and 8.6 ft) from the kiln feed face
• Obtaining a composite sample of the treated soil discharge from the discharge
collection drum
• Obtaining composite pre-test and post-test scrubber liquor samples
• Sampling flue gas for trace metals using an EPA multiple metals train at the
venturi/packed-column scrubber exit
• Sampling flue gas for mercury using a Method 101A train at the venturi/packed-
column scrubber exit
• Continuously monitoring O2, CO, and total unburned hydrocarbon (TUHC) levels
in the kiln exit flue gas
• Continuously monitoring O2 in the afterburner exit flue gas
10
-------
en
%
8
O
W
O
B
"
a
s s
8
•5
i
II
§ e
oS
CO 00
•s-l.
o ^^
IS M§
S C 3d)'
a
S
s d;
I
rH fsl
R5?
s s
u
i
si
"0
o
C3
2
3
U
tn
VO
ov
-------
• Continuously monitoring O2 and CO2 downstream of the venturi/packed-column
scrubber
• Continuously monitoring O2 and CO in the stack downstream of the secondary
APCS (carbon bed/HEPA filter)
• Sampling the stack gas for particulate, and HC1, and C12 using Method 50
As noted in Section 2.1.1, contaminated soil feed was prepared, placed into 55-gal
(208-L) drums, and allowed to age between 7 and 14 days prior to use in a test. Just prior to
a test, the drums of soil to support the test were opened and sampled. Drum contents were then
transferred to the screw feeder hopper for feeding.
Four composite kiln solids bed samples were also collected for each test. One sample
was collected using a custom-fabricated quartz scoop at each of the four axial locations where
solids bed temperature was measured. Each of these samples represented a different treatment
time under the set of other test conditions established for each test. A sample of the final
treated soil discharge was also collected from the discharge collection drum after the completion
of each test.
Test program samples were analyzed as follows. Unspiked soil/clay absorbent mixture,
each test's feed mixture, and all treated soil samples were analyzed for the spiked VOC and
SVOC contaminants and the spiked trace metals. A composite of the Test 1, 2, and 3 soil feed,
and the final treated soil discharge samples for each of these tests, were analyzed for
polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) by
Method 8290.
Toxicity characteristic leaching procedure (TCLP) leachates of two composite soil feed
samples and of all treated soil samples were prepared and analyzed for the test trace metals.
Specifically, leachates were digested by EPA Method 3010 and analyzed for barium, cadmium,
chromium, and lead by inductively coupled argon plasma (ICAP) spectroscopy by Method 6010;
leachates were digested and analyzed for arsenic by Method 7060; and leachates were digested
and analyzed for mercury by Method 7470.
All pre-test and post-test scrubber liquor samples were analyzed for the test trace metals
by the same methods employed for the TCLP leachate samples. In addition, one composite pre-
test scrubber liquor and all post-test scrubber liquor samples were analyzed for the spiked
volatile and semivolatile organic soil contaminants.
Finally, all multiple metals train samples were analyzed for the non-mercury test trace
metals, and the Method 101A sampling train samples were analyzed for mercury.
23,
RESULTS AND CONCLUSIONS
The quantity of test data collected during this program was extremely large and required
a significant effort to accumulate and evaluate. Given the extent of the test program data base,
a fuH discussion of test program results would be beyond the scope of the summary-type
information reported in an IRF research program annual report such as this. Accordingly, the
12
-------
following summarizes only major test program findings. The test program results and
conclusions are summarized according to the information points listed at the close of the
introduction to Section 2. A published final report will be available from EPA during FY95.
2.2.1 Organic Decontamination and Compound Boiling Point
The test program data clearly demonstrate that lower-boiling compounds (more volatile)
can be driven out of the test soil nearly quantitatively (to non-detectable levels) and rapidly (in
less than 20 minutes). In contrast, higher-boiling-point compounds remain in the soil, and
require higher treatment temperatures (greater than 480°C (900°F) kiln exit gas temperature)
and longer treatment times (longer than 30 minutes) for effective soil decontamination.
Treatment at gas temperatures less than 480 °C (900 °F) can result in very poor decontamination
of the high-boiling-point organic compounds tested.
222 Organic Decontamination and Solid Temperature
The test
decontamination.
program data demonstrate that elevated solid temperature favors
In particular, elevated temperature is essential for satisfactory
decontamination of high-boiling-point compounds. However, while solid temperature appears
to be correlatable to the degree of organic decontamination, it is not, by itself, a sufficient
predictive indicator of decontamination level. Other parameters, such as the presence of
moisture or the degree of solids bed agitation, can enhance the decontamination process under
the right combination of conditions. i
223 Organic Decontamination and Solids Bed Depth
Solids bed depth was altered in the test program by changing soil feedrate and kiln
rotation speed. However, the solid bed depth measurement was not sufficiently precise to allow
direct correlations between bed depth and decontamination levels. While it is possible to use
calculated kiln hold-up solid weights to infer bed depth, the method by which bed depth was
altered also resulted in significant changes in solid mixing and solid heat up behavior. The
presence of these mixing and temperature variations made it difficult to draw meaningful
conclusions concerning bed depth effects on organic decontamination. Test data need further
evaluation before firm conclusions can be drawn regarding the effects of solids bed depth on
organic decontamination.
22A Organic Decontamination and Soil Moisture Content
The test program data obtained are difficult to interpret with respect to evaluating the
effects of soil moisture content on organic compound decontamination effectiveness. Competing
phenomena are likely involved. Three possible explanations for the test observations are
developed as follows:
Increases in moisture content reduces solid heat-up rates due to the higher thermal mass
(specific heat and latent heat of vaporization). This tends to reduce the rate of organic
compound decontamination.
13
-------
Inferences based on kiln solid hold-up weights and kiln solids residence times suggest
that increased moisture in the test soils within the tested range increased the solids bed agitation
when the kiln was rotated at 0.5 rpm or faster. This increase in agitation led to faster heat
absorption and reduced mass transfer resistance, but shorter solids residence times. Faster heat
absorption increases the driving force for volatilization. Reduced mass transfer resistance
increases decontamination rate. Shorter residence times lower the achievable decontamination
extent of an organic constituent, if the decontamination rate for that constituent is slow.
Increased moisture content may enhance the decontamination rates for the less volatile
organic compounds through steam stripping, provided that the additional moisture, with its
higher specific heat and latent heat of vaporization, does not prevent the solids from reaching
temperatures that are necessary for effective stripping of the volatile organic contaminants.
2.2.5 Organic Decontamination and Treatment Time and Temperature
The extent of organic compound decontamination increases with solids residence time
and also increases with treatment temperature. However, the relationship between these
variables is not straightforward. An attempt to summarize all the test program data is illustrated
in Figures 2 and 3. The figures include all test program data collected in the range of treatment
times from 7 to 67 minutes, with the difference between solid bed temperature and compound
boiling points ranging from -333° to +371°C (-599° to +668°F).
Figure 2 includes 432 data points (4 locations per test, 9 compounds per test and a total
of 12 tests for the test program) and is a plot of the extent decontamination achieved versus the
difference between solid temperature and compound boiling point. The extent of
decontamination achieved is represented by the expression C/C0, where C is the final
contaminant concentration in the treated soil and C0 is the feed soil contaminant concentration.
The difference between solid temperature and compound boiling point is represented by (Tsoud-
Tj, _ ) where Tsoi;
-------
S6-81003V
I
1
•a
-------
S6-/10 03V
o
•a
I
I
4)
I
9
£
1
M
1
I
«§
T3 -S
•1
-
"-> S
II
i
«« a
W
(°0/0)Bo|-
16
-------
Trace Metal Distributions
Overall average metals mass balance closures achieved in the test program ranged from
96 to 113 percent. Individual metal mass balance closures achieved ranged from 38 to
181 percent at the temperatures tested. On average, arsenic, barium, cadmium, chromium, and
lead were not volatile and remained in the soil. With the exception of mercury, the extent of
metal volatilization from the treated soil was not significantly affected by any of the test
variables. No significant reductions in the fractions recovered in the treated soil occurred with
increased treatment time.
Mercury was the volatile metal, as expected, tending to be equally distributed between
the treated soil and the scrubber exit flue gas. At the highest soil treatment temperature tested,
the extent of mercury volatilization increased with increasing treatment time.
22.7 Trace Metal reachability
The effects of thermal treatment on metals teachabilities varied from metal to metal.
Among the test variables, the most influential one was treatment temperature. The behavior of
the metals'leachabilities are summarized in the following:
2.2.7.1 Lead and Barium
Lead and barium leachabilities were not affected by any of the test variables.
22.72 Arsenic
Leachable fractions of arsenic from the untreated soil ranged from 16 to 37 percent, with
an average of 26 percent over the 12 tests. Arsenic leachabilities in the TCLP did not change
significantly at low treatment temperatures [solids temperatures below 123 °C (254°F)]. At
maximum soil temperatures ranging from 228° to 277°C (443° to 531°F), arsenic teachability
decreased to about 15 percent. At yet higher soil temperatures [400° to 451°C (753° to 844°F)],
arsenic leachability decreased further, to about 10 percent.
While effects of feedrate and rotation speed were apparent, these effects may be
attributable to the different maximum solid temperatures that resulted from the changes in
feedrate and rotation speed. Overall, the test data suggest that a minimum soil treatment
temperature of 228°C (442°F) is required to reduce arsenic leachability from the synthetic soil
tested. Soil moisture content, within the tested range, had no effect on arsenic leachability.
2.2.7.3 Cadmium
At the highest soil temperatures reached, above 300°C (572°F), the soil contained a
smaller leachable cadmium fraction, at about 2 percent, compared to about 13 to 16 percent
leachable from the feed. It is possible that cadmium leachability in the TCLP may be further
reduced at higher soil temperatures.
17
-------
2.2.7.4 Chromium
The chromium in the feed soil was barely leachable, at about 1 percent or less. The data
show that soil temperature affects chromium mobility in the treated soil. A dramatic increase
in the leachable fraction of chromium, from less than 1 percent to more than 15 percent, was
observed when soil treatment temperature was increased from 225°C (437°F) to 275°C (527°F).
At higher treatment temperatures and increased kiln rotation rates, the onset of the observed
leachability increase occurred at shorter treatment times.
2.2.7.5 Mercury
The mercury leachability data suggest behavior comparable to that of chromium. When
heated to temperatures of 200° to 275°C (392° to 527°F), the treated soil gave TCLP leachate
mercury concentrations two or three times those from the feed samples. These corresponded
to leachable fractions of 5 to 62 percent. Unlike chromium, however, when heated above 300 °C
(572 °F), the treated soil TCLP leachate mercury concentrations returned to levels similar to
corresponding feed TCLP concentrations.
2.2.8 Summary
In summary, operating an incinerator at low-to-moderate temperatures can, under the
right conditions, effectively decontaminate soils containing organic contaminants, including high-
boiling-point compounds. The principal parameters that affect decontamination effectiveness
are compound boiling point, achieved solids temperature, and soil moisture content. Agitation
can affect decontamination effectiveness, most likely by increasing the rate at which heat is
absorbed into the solid, and by decreasing the average mass transfer resistance. As for the
effects of solids bed depth, the methods of varying bed depth also resulted in changes in agitation
and solids heating rates. Therefore, the test data did not permit the effects of solid bed depth
to be separated from those caused by variations in agitation and solids heating rates.
Except for mercury, trace metal constituents were not volatile under low-to-moderate
temperature incineration conditions. The leachability of arsenic, cadmium, and chromium in the
TCLP can be affected by treatment temperature.
Results of the test program were documented in the test report:
• J. Lee, D. J. Fournier, Jr., C. King, S. Venkatesh, and C. Goldman, "Evaluation
of Rotary Kiln Incinerator Operation at Low to Moderate Temperature
Conditions," Draft, September 1994.
18
-------
SECTIONS
TESTING OF FLUFF WASTE AND CONTAMINATED SOIL
FROM THE M. W. MANUFACTURING SUPERFUND SITE
One of the IRF's primary missions is to support Regional Offices in evaluations of the
potential of incineration as a treatment option for wastes and other contaminated materials at
Superfund sites. One priority site is the M. W. Manufacturing site in Danville, Pennsylvania.
EPA Region HI (B. Khona, Remedial Project Manager) and the U.S. Army Corps of Engineers
(USAGE) (H. Santiago, Project Manager) requested that a pilot-scale test program be conducted
at the IRF to support evaluations of the suitability of incineration as a treatment technology for
wastes and contaminated soil at the site. FY94 efforts in support of this test program are
discussed in this section.
3.1
BACKGROUND
The M. W. Manufacturing site began operation in 1966. M. W. Manufacturing
Corporation reclaimed copper from scrap wire using both mechanical and chemical processes.
Reclamation activities began in 1969 and continued until 1972 when M. W. Manufacturing filed
for bankruptcy. The chemical recovery processes used by M. W. Manufacturing led to site
contamination with volatile organic solvents. Warehouse 81, Inc., acquired the site in 1976 and
began mechanical recovery operations from the existing waste piles onsite. The mechanical
recovery operations generated large volumes of waste material, termed fluff.
The fluff waste produced by the mechanical stripping process consists of fibrous
insulation material mixed with plastic. Phthalate esters, copper, and lead are the major
contaminants in this material. The chemical recovery process used by M. W. Manufacturing was
a two-step process. The first step involved the use of a hot oil bath to melt the plastic insulation
away from the metal in the scrap wire. Residual oils were removed from the separated copper
in the second step through the use of chlorinated solvents, including trichloroethene and
tetrachloroethene. Thus, these solvents are waste and soil contaminants at the site.
The June 1990 record of decision (ROD) document for the site identified five wastes
and contaminated materials for remedial treatment:
• Fluff waste piles
• Organic- and trace-metals-contaminated surface soils
• Organic- and trace-metals-contaminated subsurface soils
19
-------
• Lagoon water
• Contents of drums and tanks
Onsite incineration was identified as the selected treatment for the fluff and the soil. The
remedy includes possible stabilization of the incineration ash prior to landfill disposal.
Region HI requested the pilot-scale test program at the IRF to support the further
progress of the remediation of the site, and specifically to supply data on optimum incineration
conditions for both fluff waste and contamination to the remediation design effort. The specific
objectives of the IRF test program were defined as follows:
• Verify that the fluff waste and the contaminated soil at the site can be incinerated
in compliance with the hazardous waste incinerator performance standards and
permit requirements of:
— 99.99 percent principal organic hazardous constituent (POHC) DRE
— HC1 emissions less than 1 percent of the APCS inlet flowrate or 1.8 kg/hr,
whichever is greater
— CO emissions of less than 100 ppm at 7 percent O2, 1-hour rolling average
and the performance guidance announced in 1993 of:
— Particulate emissions of less than 34 mg/dscm (0.015 gr/dscf) corrected to
7 percent O2
— Total tetra- through octa-PCDD/PCDF emissions of less than 30 ng/dscm
corrected to 7 percent O2
• Measure the effectiveness of incineration treatment in decontaminating fluff and
soil of their organic contaminants and evaluate whether incineration temperature
affects the effectiveness of fluff decontamination
• Measure the distribution of the contaminant trace metals in the fluff and the
contaminated soil among the incineration system discharge streams
• Determine whether the bottom ash residue and the APCS discharges from the
incineration of fluff and contaminated soil will be toxicity characteristic (TC)
hazardous wastes
• Determine whether the bottom ash residue from the incineration of contaminated
soil meets the cleanup levels for soil given in the ROD
20
-------
3.2 TEST PROGRAM
3.2.1 Waste Description
Samples of the fluff waste and surface and subsurface soil from the site were sent to the
IRF for characterization analyses. Results of the analyses are summarized in Table 5. The data
in Table 5 show that the major site contaminants are the two phthalate esters, bis (2-ethylhexyD
phthalate (BEHP) and di-n-octyl phthalate (DNOP). Thus, these compounds would be
considered the POHCs in the site wastes. In addition, Region HI was interested in establishing
that tetrachloroethene, one of two VOCs found in fluff and soil characterization samples is
effectively destroyed by incineration, so tetrachloroethene was also defined to be a POHC. Site
TABLE 5. M. W. MANUFACTURING SITE CHARACTERIZATION SAMPLE ANALYSIS
RESULTS
Sample
Parameter
Fluff Surface soil Subsurface soil
Characterization
Moisture, %
Ash, %
at 550 °C
at 900 °C
Heating value, MJ/kg
(Btu/lb)
Volatile organic constituents, mg/kg
Tetrachloroethene
1,1,2-Trichloroethane
Semivolatile organic constituents, mg/kg
BEHP
DNOP
Trace metals, mg/kg
7.7 18 9.8
41 77 89
14 76 90
6.50 0.07 Will not burn
(2,800) (30)
146 69 18
4.8 1.5 NDa
124,000 47.6 4.62
17,800 1.95 ND
Antimony
Barium
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
230
64
3.5
57
31,000
2,700
6.1
4.0
890
51
60
<0.2
30
8,300
1,800
15
<0.4
76
<5
78
0.93
21
160
180
31
<0.4
62
aND = Not detected.
21
-------
wastes were also highly contaminated with copper and lead, and with lesser, though still
significant amounts of antimony, barium, chromium, nickel, and zinc.
The two semivolatile POHCs in site materials, BEHP and DNOP, are poor candidates
for testing the incineration process with regard to destroying other site waste organic
contaminants because they are ranked as relatively easy to thermally destroy compounds in the
thermal stability based incinerability ranking (Reference 1). This ranking groups the 333
compounds ranked into seven stability classes from most stable, or most difficult to destroy
(Class 1), to least stable or easiest to destroy (Class 7). Both BEHP and DNOP are ranked in
Class 6, or relatively easy to destroy. To present a challenge to the incineration process and
develop data that suggest incineration is capable of achieving sufficient DREs for other site
organic contaminants, the test waste materials were spiked with naphthalene, a Class 1 (most
difficult to destroy) POHC, at 2 percent by weight. In addition, it was decided to spike the
volatile POHC, tetrachloroethene, into test materials at a level of 3,100 mg/kg by weight.
Tetrachloroethene is a Class 2 POHC. Spiking was needed because site material concentrations
of tetrachloroethene, were too low to allow establishing 99.99 percent DRE at achievable flue
gas concentration quantitation limits.
Prior to testing, the contents of the three 55-gal (208-L) drums of fluff shipped to the
IRF for testing were emptied into a 250-gal (946-L) mixing trough where they were manually
mixed with hoes until visually homogeneous. After mixing, the fluff feed was repackaged into
1.5-gal (5.7-L), polyethylene (PE) bag-lined cubical cardboard containers for feeding to the RKS.
Each container was filled with about 1.8 kg (4 Ib) of mixed fluff.
Naphthalene was added to each fluff-filled box as a preweighed amount of solid
naphthalene crystals contained in a 60-mL high-density polyethylene (HDPE) bottle with a
polypropylene screw cap closure. The tetrachloroethene was added in a 4-mL HDPE bottle with
polypropylene screw cap closure. The HDPE bottles containing the naphthalene and
tetrachloroethene spikes were imbedded in the feed box contents, the polyethylene liner was then
closed with a plastic tie, and the box was closed and sealed with paper packaging tape.
Contaminated soil for testing was similarly mixed, packaged into the cubical cardboard
feed containers, and spiked with naphthalene and tetrachloroethene, except that about 4.5-kg
(10-lb) quantities of soil were used to fill each cardboard container.
3.2.2 Test Conditions
The completed test program consisted of seven tests. All tests were conducted in the
RKS at the IRF. The configuration of the RKS shown in Figure 1, including the fabric filter
APCS, was used.
In the test program, two sets of duplicate tests feeding fluff waste alone and one set of
duplicate tests feeding contaminated soil alone were performed. The two sets of fluff feed tests
were conducted at different kiln temperatures. Soil and fluff were separately tested because the
eventual site remediation may treat each material separately for logistical reasons. In addition,
Region IE requested data to determine whether the ash from incinerated soil alone would meet
the cleanup levels given in the ROD. The target test operating conditions were as given in
Table 6.
22
-------
TABLE 6. TEST MATRIX
Test
0
1
2
3
4
5
6
Feed
Packaging container material
Fluff
Duplicate of Test 1
Soil
Duplicate of Test 3
Fluff
Duplicate of Test 5
O ~ -mrMm^mr ^HU *.
drums placed in the RKS ash pit. For the soil tests, kiln ash was continuously removed'" om the
e " ^"^ SSt6m dean
Sampling and Analysis Procedures
For all tests, the sampling matrix entailed:
• Obtaining a composite sample of the test material feed
• Obtaining a composite sample of the kiln ash discharge
• Obtaining a composite sample of the pre-test and post-test scrubber system liquor
23
-------
TABLE 7. APCS OPERATING CONDITIONS
Venturi liquor flowrate 76 L/min (20 gpm)
Venturi pressure drop 6.2 kPa (25 in WC)
Packed tower liquor flowrate 115 L/min (30 gpm)
Scrubber liquor temperature 49 °C (120 °F)
Scrubber blowdown rate 0 L/min (0 gpm) or minimum operable
• Obtaining a composite sample of the baghouse ash
• Continuously measuring O2 concentrations in the kiln exit flue gas; O2, CO2, and
NOX in the afterburner exit flue gas; CO, CO2, NOX, and TUHC concentrations
in the baghouse exit flue gas; and O2 and CO concentrations in the stack gas
• Sampling flue gas at the baghouse exit for trace metals using the EPA multiple
metals train
• Sampling flue gas at the baghouse exit for the waste and spiked semivolatile
POHCs using a Method 0010 train
• Sampling flue gas at the baghouse exit for the waste and spiked VOC
contaminants using Method 0030, the volatile organic sampling train (VOST)
• Sampling the flue gas at the baghouse exit for PCDDs/PCDFs using Method 23
• Sampling the baghouse exit and the stack for particulate and HC1 using Method 5;
the stack sample is needed to comply with the IRF's permit requirements
Test program samples were analyzed for matrix-specific combinations of semivolatile
POHCs, VOC contaminants, semivolatile target compound list (TCL) organic constituents,
volatile TCL organic constituents, PCDDs/PCDFs, contaminant trace metals, and chloride.
33 TEST RESULTS
33.1 SVOC Results
Table 8 summarizes the measured concentrations of the target SVOC analytes in test
program samples collected. For each test performed, the table also indicates the average kiln
exit gas temperature measured over the flue gas sampling period corresponding to each test. As
shown, test average values for this primary operating parameter variable for all tests were quite
close to the corresponding test target values indicated in Table 6.
The data in Table 8 show that the BEHP concentrations in the actual fluff waste fed for
each fluff waste test, at 48,300 to 53,300 mg/kg, were about half the level measured in the pretest
24
-------
Sample
Test 0 (10/27/93), kiln temperature:
871°C (1,599°F)
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
Fluff Waste Tests
Test 1 (11/9/93), kiln temperature:
883°C (1,622°F)
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /jg/dscm
Test 2 (11/16/93), kiln temperature:
876 °C (1,608°F)
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /*g/dscm
Test 5 (11/18/93), kiln temperature:
762°C (1,403°F)
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /tg/dscm
Test 6 (11/23/93), kiln temperature:
767°C C
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
==========--
aSpiked concentration.
BEHP
0.057
6.6
8.4
48,800
<1.3
< 0.013
14.3
7.0
53,300
<1.3
< 0.013
4.5
9.9
48,300
<1.3
<0.013
21.1
9.8
49,000
<1.3
< 0.013
6.6
6.2
DNOP
< 0.004
4.1
<0.9
1,850
<0.4
0.007
9.9
<1.2
2,610
<0.4
< 0.004
2.2
<1.3
2,870
<0.4
< 0.004
13.4
<1.1
2,810
<0.4
< 0.004
4.1
<1.2
Naphthalene
< 0.003
<0.3
<0.8
20,200a
<0.3
< 0.003
<0.3
<0.9
20,200a
<0.3
< 0.003
<0.3
<1.1
20,200a
<0.2
< 0.003
<0.3
<0.9
20,200a
<0.3
< 0.003
<0.3
<1.0
(continued)
25
-------
TABLE 8. (continued)
Concentration
Sample
Soil Feed Tests
Test 3 (12/1/93), lain temperature:
876°C (1,609°F)
Soil feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
Test 4 (12/2/93), kiln temperature:
874°C (1,606°F)
Soil feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /tg/dscm
BEHP
9,810
<1.3
0.016 .
23.5
7.8
9,440
<1.3
<0.013
14.2
7.0
DNOP
580
<0.4
< 0.004
17.0
<1.2
550
<0.4
< 0.004
9.7
<1.2
Naphthalene
20,200a
<0.3
< 0.003
<0.3
<1.0
20,200a
<0.3
< 0.003
<0.3
<1.0
aSpiked concentration.
characterization sample as reported in Table 5. Similarly, the DNOP levels in actual test fluff
waste, at 1,850 to 2,870 mg/kg, were also substantially lower than the 17,800 mg/kg level
measured in the pretest characterization sample. Nevertheless, contamination levels of these two
constituents in the test fluff waste were still significant. The 20,200 mg/kg naphthalene
concentration noted in incinerator feed samples in the table represents the quantity of
naphthalene spike added to feed containers.
The data in Table 8 show that the contaminated soil tested contained 9,440 to
9,810 mg/kg of BEHP and 550 to 580 mg/kg DNOP. These levels are substantially greater than
those measured in the pretest soil characterization samples analyzed. Again, the naphthalene
concentrations in test soil feed samples correspond to spiked amounts.
The data in Table 8 also show that the native and spiked SVOC contaminants were
essentially completely removed from the fluff waste by incineration at both kiln temperatures
tested as evidenced by their absence in the kiln ash discharge for all fluff waste tests at method
detection limits (MDLs) of 0.3 to 1.3 mg/kg. Similarly these contaminants were removed from
the contaminated soil for both soil tests at the single kiln temperature tested for this matrix. No
kiln ash concentration data are given for the blank burn test, Test 0, in Table 8 because no kiln
ash was discharged for this test.
None of the three SVOC contaminants was found in the scrubber liquor for three of the
four fluff waste tests and for one of the two contaminated soil tests at MDLs of 0.003 to
26
-------
0.013 mg/L. A small amount of BEHP, near its MDL, was found in the scrubber liquor from
one soil test. However, a larger, though comparable, level was found in the scrubber liquor from
the blank burn test, Test 0. A small amount of DNOP, again near its MDL, was found in the
scrubber liquor from one fluff waste test.
Naphthalene was absent from the baghouse ash for all tests at an MDL of 0 3 me/kg
However, low levels of both BEHP (6.6 to 23.5 mg/kg) and DNOP (2.2 to 17.0 mg/kg) were
SxT™m ba&ouse ash for all tests, including the blank burn. Neither naphthalene nor
DNOP was present in the baghouse exit flue gas for any test, at MDLs of about 1 ug/dscm
BEHP was found in the baghouse exit flue gas for all tests, including the blank burn at levels
ranging from 6.2 to 9.8/ig/dscm.
332 VOC Results
Table 9 summarizes the measured concentrations of the target VOC analytes in test
program samples collected. As shown, no fluff waste sample contained 1,1,2-triehloroethane at
an MDL of 1 mg/kg. This contaminant was absent from one test soil sample, but found at
30 mg/kg in the other test soil Trichloroethene was not found in three of four fluff feeds at an
M?T of}fms^- II was Present in the fourth fluff feed at 2.4 mg/kg, and in the soil test feeds
at 27 to 45 mg/kg. Tetrachloroethene was not detected in two tests' fluff feed (before spiking)
at an MDL of 4 mg/kg, though it was present at 4.9 and 17 mg/kg in the other two tests' fluff
feed. These levels are substantially lower than the 146 mg/kg found in the pretest fluff feed
characterization sample indicated in Table 5. The contaminated soil tested contained 830 to
1,050 mg/kg of native (before spiking) tetrachloroethene, much higher than the levels in pretest
soil characterization samples. The addition of the tetrachloroethene spike to all test feed
samples raised spiked fluff feed concentrations to 3,100 mg/kg and spiked soil feed
concentrations to the 4,000 mg/kg range as indicated in Table 9.
As was the case for the S VOC contaminants, incineration treatment of the fluff waste
at both temperatures tested and of the contaminated soil at the one temperature tested was
essentially completely effective in decontaminating the feed materials of their native and spiked
VOC contaminants. The kiln ash discharge for all tests contained no detectable VOC
contaminants at MDLs ranging from 1 to 4 mg/kg with the single exception of a 5 6 mg/kg
concentration of trichloroethene in the kiln ash from one low temperature fluff waste test The
fact that the fluff feed for this one test contained no detectable trichloroethene suggests that the
low level of this contaminant measured in the kiln ash arose as an incomplete destruction
product of the spiked tetrachloroethene. In addition, neither the scrubber liquor nor the
baghouse ash from any test contained detectable VOC contaminants at MDLs of 0.004 to
0.15 mg/L in scrubber liquor and 1 to 4 mg/kg in baghouse ash.
The baghouse exit flue gas for all tests, including the blank burn test, contained low
fjr8 °L trichloroethene, at 0.09 to 0.73 pg/dscm, and tetrachloroethene, at 0.14 to
1.57 /ig/dscm. No 1,1,2-trichloroethane was found in the baghouse exit flue gas at MDLs of 0 05
to 0.14 /ig/dscm for the blank burn test, either fluff test at the higher incinerator temperature
one of the two fluff tests at the lower incineration temperature, and one of the two soil feed
tests. This contaminant was found in the baghouse exit flue gas from the two tests detected at
0.23 to 1.27 /ig/dscm.
27
-------
TABLE 9. VOLATILE ORGANIC
Sample
CONTAMINANT ANALYSIS RESULTS
Concentration
Tetrachloro- 1,1,2-Trichloro- Trichloro-
ethene ethane ethene
Test 0 (10/27/93), kiln temperature:
870 °C (1,599 °F)
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /zg/dscm
Fluff Waste Tests
Test 1 (11/9/94), kiln temperature:
883°C (1,622°F)
Huff feed, mg/kg, native
Fluff feed, mg/kg, spiked
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
Test 2 (11/16/93), kiln temperature:
876°C (1,608°F)
Fluff feed, mg/kg, native
Fluff feed, mg/kg, spiked
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
Test 5 (11/18/93), kiln temperature:
762°C (1,403 °F)
Fluff feed, mg/kg, native
Fluff feed, mg/kg, spiked
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /zg/dscm
< 0.015
<4
0.66
<4
3,100
<4
< 0.015
<4
0.68
< 0.004
<0.09
< 0.004
<0.09
< 0.004
0.15
4.9
3,100
<4
< 0.015
<4
0.27
<1
<1
< 0.004
<1
<0.14
2.4
<1
< 0.004
<1
0.16
<4
3,100
<4
<0.015
<4
0.71
<1
<1
< 0.004
<1
<0.09
-------
TABLE 9. (continued)
Concentration
Sample
Tetrachloro- 1,1,2-TrichIoro- Trichloro-
ethene ethane ethene
Test 6 (11/23/93), kiln temperature:
767°C
Fluff feed, mg/kg, native
Fluff feed, mg/kg, spiked
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, jtg/dscm
Soil Feed Tests
Test 3 (12/1/93), kiln temperature:
876°C (1,609°F)
Soil feed, mg/kg, native
Soil feed, ng/kg, spiked
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
Test 4 (12/2/93), kiln temperature:
874 °C (1,606 °F)
Soil feed, mg/kg, native
Soil feed, mg/kg, spiked
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
17
3,100
<4
< 0.015
<4
0.61
1,050
4,200
<4
< 0.015
<4
1.57
830
4,000
<4
< 0.015
<4
0.14
<1 <1
<1 5.6
< 0.004 < 0.004
<1 <1
0.23 0.09
30 45
<1 <1
< 0.004 < 0.004
<1 <1
1.27 0.73
<1 27
<1 <1
< 0.004 < 0.004
<1 <1
<0.05 0.17
POHCDREs
Feed contaminant concentration, feedrate, baghouse exit flue gas contaminant
concentration, and flue gas flowrate data can be combined to calculate contaminants DREs for
each of the tests. Calculated DREs are summarized in Table 10. As shown in the table, the
measured levels of BEHP in the baghouse exit flue gas corresponded to BEHP DREs ranging
from 99.99932 to 99.99962 percent for the fluff waste tests and 99.9974 to 99.9980 percent for
the soil feed tests. Kiln temperature had no apparent affect on BEHP DRE from fluff waste.
Measured baghouse exit flue gas tetrachloroethene concentrations corresponded to
tetrachloroethene DREs of 99.9988 to 99.99990 percent over all tests. Comparable
tetrachloroethene DREs were measured for both fluff and soil, and for fluff treated at both
incineration temperatures. Neither the spiked naphthalene nor the native DNOP contaminants
29
-------
TABLE 10. POHC DREs
Parameter
BEHP DNOP Naphthalene
Tetrachloro-
ethene
Fluff waste test
Test 1 (11/9/93), kiln temperature:
883 °C (1,622°F)
Feed concentration, mg/kg
Feedrate, kg/hr
Baghouse exit flue gas:
Concentration, /ig/dscm
Emission rate, mg/hr
DRE, %
Test 2 (11/16/93), kiln temperature:
876°C (1,608°F)
Feed concentration, mg/kg
Feedrate, kg/hr
Baghouse exit flue gas:
Concentration, /ig/dscm
Emission rate, mg/hr
DRE, %
Test 5 (11/18/93), kiln temperature:
762°C (1,403 °F)
Feed concentration, mg/kg
Feedrate, kg/hr
Baghouse exit flue gas:
Concentration, /xg/dscm
Emission rate, mg/hr
DRE, %
Test 6 (11/23/93), kiln temperature:
767°C (
Feed concentration, mg/kg
Feedrate, kg/hr
Baghouse exit flue gas
Concentration, /xg/dscm
Emission rate, mg/hr
DRE, %
48,800 1,850 20,200
2.93 0.11 1.21
7.0 <1.2 <0.9
11.9 <2.0 <1.5
99.99959 > 99.9982 > 99.99987
53,300 2,610 20,200
3.15 0.15 1.19
9.9 <1.3 <1.1
19.4 <2.5 <2.2
99.99939 > 99.9984 > 99.99982
48,300 2,870 20,200
2.94 0.18 1.23
9.8 <1.1 <0.9
20.1 <2.3 <1.8
99.99932 > 99.9987 > 99.99985
49,000 2,810
2.98 0.17
6.2
11.3
20,200
1.23
<2.2 <1.8
99.99962 > 99.9987 > 99.99985
3,100
0.19
0.27
0.46
99.99975
3,100
0.18
0.71
1.4
99.99924
3,100
0.19
0.68
1.4
99.99926
3,100
0.19
0.61
1.1
99.99941
(continued)
30
-------
TABLE 10. (continued)
- . . II
Parameter
Soil Feed Tests
Test 3 (12/1/93), kiln temperature:
876°C (1,609°F)
Feed concentration, mg/kg
Feedrate, kg/hr
Baghouse exit flue gas:
Concentration, /jg/dscm
Emission rate, mg/hr
DRE, %
Test 4 (12/2/93), kiln temperature:
874 °C (1,606 °F)
Feed concentration, mg/kg
Feedrate, kg/hr
Baghouse exit flue gas:
Concentration, /zg/dscm
Emission rate, mg/hr
DRE, %
BEHP DNOP
9,810 580
0.58 0.034
7.8 <1.2
15.0 <2.3
99.9974 > 99.9933
9,440 550
0.56 0.033
7.0 <1.2
11.3 ' <1.9
99.9980 > 99.9940
Tetrachloro-
Naphthalene ethene
20,200 4,200
1.19 0.25
<1.0 1.57
<1.0 3.0
>99.99984 99.9988
20,200 4,000
1.19 0.24
<1.0 0.14
< 1.6 0.23
> 99.99986 99.99990
were detected m the baghouse exit flue gas for any test. The DREs corresponding to baghouse
exit flue gas MDLs, and noted with the ">" sign in Table 10, were 99.9998.2 to 99 99987 percent
for naphthalene for all tests, 99.9982 to 99.9987 percent for DNOP in the fluff waste tests and
99.9933 to 99.9940 percent for DNOP in the soil feed tests. All DREs demonstrated were
greater than the 99.99 percent level required by the current hazardous waste incinerator
performance standard.
33.4 Dioxin and Furan Results
A summary of the PCDD/PCDF data obtained in this test program is given in Table 11.
While test program samples were analyzed for the total concentration of each homologue
grouping of total tetra-, penta-, hexa-, hepta-, and octa-chlorinated dioxins and furans, as well
as the concentration of each congener chlorinated in the 2,3,7, and 8 positions within each group,
the two summary concentration values given in Table 11 are typically reported. The values given
in the column labeled total PCDD/PCDF in the table represent the sum of the homologue group
total concentrations analyzed. The values in the column labeled TEQ in the table are in terms
of 2,3,7,8-TCDD toxicity equivalents (TEQs). In calculating TEQs, the measured concentration
of each specific 2,3,7,8-chlorinated congener is weighted by a toxicity equivalent factor (TEF).
The TEF is a measure of the congener's toxicity relative to 2,3,7,8-TCDD, which has a TEF of 1.
31
-------
TABLE 11. DIOXIN AND FURAN ANALYSIS RESULTS
Sample
Total PCDD/PCDF
TEQ
Test 0 (10/27/93), loin temperature:
870°C (1,599°F)
Scrubber liquor, pg/L
Baghouse ash, ng/kg
Baghouse exit flue gas ng/dscm at 7% O2
Fluff waste test
Fluff feed, ng/kg
Test 1 (11/9/93), kiln temperature:
883 °C (1,622°F)
KUn ash, ng/kg
Scrubber liquor, pg/L
Baghouse ash, ng/kg
Baghouse exit flue gas, ng/dscm at 1% O2
Test 2 (11/16/93), kiln temperature:
876°C (1,608°F)
Kiln ash, ng/kg
Scrubber liquor, pg/L
Baghouse ash, ng/kg
Baghouse exit flue gas, ng/dscm at 7% O2
Test 5 (11/18/93), kiln temperature:
762°C (1,403 °F)
KUn ash, ng/kg
Scrubber liquor, pg/L
Baghouse ash, ng/kg
Baghouse exit flue gas, ng/dscm at 7% O2
Test 6 (11/23/93), kiln temperature:
767°C
Kiln ash, ng/kg
Scrubber liquor, pg/L
Baghouse ash, ng/kg
Baghouse exit flue gas, ng/dscm at 7% O2
68-170
64
0.21
56,000
65,000
370-380
520
1.3
89,000
730-750
740
1.3
830,000
290
340
0.44
2,700,000
520-540
1,000
0.96
9.7-25
0.94-1.0
0.005-0.017
730
1,200
4.6-12
6.8-7.0
0.048-0.052
2,000
7.0-23
8.9-9.2
0.044-0.049
29,000
17-18
81
0.016-0.027
110,000
6.7-23
22-23
0.038-0.049
(continued)
32
-------
TABLE 11. (continued)
Sample
Total PCDD/PCDF
TEQ
Soil Feed Tests
Soil feed, ng/kg 10)000 210
Test 3 (12/1/93), kiln temperature:
876°C (1,609°F)
Kiln ash, ng/kg 2,400 55
Scrubber liquor, pg/L 2,300-2,400 46-54
Baghouse ash, ng/kg 2,600 39
Baghouse exit flue gas, ng/dscm at 7% O2 0.68 0.025-0.032
Test 4 (12/2/93), kiln temperature:
874°C (1,606°F)
Kiln ash, ng/kg 3;600 98
Scrubber liquor, pg/L 260-280 1.3-15
Baghouse ash, ng/kg 390 8.2-8.4
Baghouse exit flue gas, ng/dscm at 7% O2 0.48 0.018-0.020
The TEFs used to calculate the TEQs in Table 11 were those established by EPA in the rule
regulating hazardous waste destruction in boilers and industrial furnaces (the BIF rule
Reference 2). In many cases, concentrations in Table 11 are reported as ranges. This arises out
of the fact that analyzed concentrations for both homologue group totals and specific congeners
are often reported as being less than an MDL. Thus, in cases where a concentration is listed
as a range in Table 11, the maximum value in the range corresponds to the assumption that
constituents not detected were present at the MDL, and the minimum value in the range
corresponds to the assumption that they were not present, i.e., at zero concentration.
The data in Table 11 show that the fluff feed contained 56 ng/kg of total PCDD/PCDF
?rnn°A73 *$** °n a TEQ basis (1 ^^ often reP°rted as parts per billion, or ppb, equals
1,000 ng/kg, the unit used for solid samples in Table 11; 1 ng/kg is often reported as parts per
trillion, or ppt). Levels in the kiln ash discharge from the higher temperature incineration tests
were somewhat higher at 65 to 89 Mg/kg total, or 1.2 to 2.0 /ig/kg TEQ. Levels in the kiln ash
discharge from the lower temperature incineration tests were substantially higher at 830 to
2,700 ftg/kg total, or 29 to 110 ng/kg TEQ. These data indicate that, not only was incineration
treatment ineffective in destroying contaminant dioxins and furans in the fluff waste in fact
conditions experienced by the noncombustible fraction of the fluff waste during incineration
likely led to PCDD/PCDF formation at the lower temperature.
That PCDD/PCDF formation in the kiln ash discharge occurred, at least for the fluff
waste tests at the lower incineration temperatures, is further substantiated by the data in
Table 12. The total weight of fluff waste or soil fed and the total weight of kiln ash collected for
each test are combined with respective PCDD/PCDF concentrations from Table 11 to ultimately
33
-------
II «i
1
H ^"^ O
II P>< g
Q 2 tS
Q S ^
1 O T3 13
.2 •!
CQ |j "S 53
O If
O 1
8 1
«I g>
H 1
CO j ^w
3 .s
i 1
1
CO
5
o
Q
1
~v
«
0 ^
E-«
S
W
J
o
E"H
fa
it
CM
I
fa M **
Q ~
O -g fa
ir^ w3 ^^
Q « 0
8J3 « OH
« ^ So"
ft* T3 H Q
O
PH
-
CJQ u
•5* WO
5 •**
|.a
H "»
WO ^^
^ S
qjj* C^
CM
&b Qb
0 Q
0 _ 0
CU cs D^
Q" ^ C
O C
CU PH
^
*a
•a*
S -w b
"i
3
«
oo
ON
10
oo
T-l
o •
T-T
^
T— 1
C3
Ol
o
o
o
^
o
CO
Fluff Waste Tests
Test 1 (11/9/93)
, CO •* >O
•st VO >O
1
2 8 S
CM ° §
CO ^ »
S § §
^ ON t-
2- vo" vo"
T-1 TH Tt
ON •* CO
1O C3 t"~
T-H Ol TH
0^ ° °
Ol OI 0)
§ 8 §
°~ °l "~1
T^l T^i TH
o o .0
CO CO CO
o5 0} Q} o
titLi co^tt< coafc cogpu
fZ o ON*5o ON^o ON*JO
cs rss ^^. cd oo ^*** cd co ^^ ^ Ol
|§ s_^g ^^^ g^s^
— . o O4 ^ o ^O ^j o ^ rt °
^M £f} i^j \o ^_i »-3 ^^ *-» r3 ^"^
00 $ °° H ^ H
II
01 '*•
ON ^
2 1
vo *S
e~s ^3
T}" Ol
ol >o
T— 1 IO
O ^S"
rH T-l
O T-H
0 0
0 0
ON ON
of 01
'
00 0
S a
o5 0} s—^
CO 3 o CO +-" o
M O\ cd ON ON TO vo
'to T— 1 W vo Ol jU VO
*a ~^s ® r i ^— • ' ® fl
« CO ^ o ^ ^ ^
^* OT v"j r1^* ^ v/"3 c*^
:| ^ °° E^ °°
CO
34
-------
give the ratios of the amounts of dioxins and furans discharged in the kiln ash to the amounts
introduced in the incinerator feed for each test. The data show that, for the fluff waste tests at
the target 870°C (1,600°F) kiln temperature, the amount of total PCDD/PCDF discharged was
5.9 to 8.3 percent of the amount introduced to the incinerator in the fluff feed. This would
correspond to an effectiveness of dioxin/furan decontamination by incineration at this higher
tested temperature of 91.7 to 94.1 percent. On a TEQ basis, the ratio of discharged-to-fed
dioxins/furans was 8.4 to 14.3 percent, corresponding to incineration decontamination
effectiveness or a TEQ basis of 85.7 to 91.6 percent at the higher incineration temperature.
However, for the fluff waste tests at the 760°C (1,400°F) target kiln temperature the
amount of total PCDD/PCDF discharged was 98.5 to 273 percent of the amount fed In o'ther
words, the quantity of total PCDD/PCDF discharged for the lower kiln temperature fluff tests
was roughly the same to 2.7 times the amount fed to the incinerator. On a TEQ basis the ratios
of discharged to feed dioxins/furans were even larger, at 264 to 855 percent. Clearly, at the
lower incineration temperatures, dioxins/furans were being produced in the noncombustible
fraction of the fluff waste feed ultimately discharged as kiln ash.
This should not be surprising, however. It has become recognized over the past few
years that dioxins and furans arising out of combustion processes result from the formation of
these compounds from precursor organic constituents and a chlorine source, such as HC1, at
relatively low temperatures. The presence of metal-containing solids, such as particulate, appears
to catalyze the process. Copper has specifically been shown to catalyze reactions leading to
dioxin/furan formation. The rate of dioxin/furan formation is highest at temperatures near
300°C (570°F), and this rate decreases as the temperature at which precursors, a chlorine
source, and metal-bearing solids are held is either increased or decreased.
Evidently, the right combination of conditions were in place in the kiln solids bed before,
or shortly after, discharge from the kiln into the ash collection pit of the RKS during the
incineration of the fluff waste at the 760°C (1,400°F) target kiln temperature. Dioxin/furan
precursors were likely present in the near-bed combustion gas, and chlorine, likely in the form
of HC1 from the chloroorganic components of the fluff, was likely in abundance. The fluff waste
tested contained 17 percent by weight chlorine. As discussed below, a major contaminant metal
in the fluff waste was copper, so this likely dioxin-formation catalyst was present. Apparently
kiln solids bed temperatures were sufficiently close to the peak reaction temperature of 300 °C
(570°F) to be within a "dioxin formation" window. The data clearly show that dioxin formation
occurred at the lower incineration temperature tested.
All other dioxin formation conditions would have been in effect for the fluff incineration
tests at the 870 °C (1,600 °F) target kiln temperature. However, at this higher incineration
temperature, kiln solids bed temperatures were apparently above the window associated with
more rapid dioxin formation. Similar results were seen in the soil feed tests, also performed at
the higher, 870 °C (1,600 °F), target kiln temperature. Ratios of discharged to feed
PCDD/PCDFs noted in Table 12 for the soil tests are comparable to those experienced for the
fluff waste tests at the higher incineration temperature.
Returning to the data in Table 11, the scrubber liquor for the fluff waste tests contained
total PCDD/PCDF concentrations in the 290 to 750 pg/L (1 pg/L is often reported as parts per
quadrillion, or ppq). Scrubber liquor concentrations were in the 4.6 to 23 pg/L ranges on a TEQ
35
-------
basis. No apparent .difference in the scrubber liquor concentrations with incineration
temperature was seen. The scrubber liquor concentration measured during the blank burn test
was comparable to those for the fluff waste tests on a TEQ basis, though total PCDD/PCDF
concentrations were slightly lower. Scrubber liquor dioxin/furan concentrations for one of the
two soil feed tests were also comparable to those measured for the fluff waste tests, although
levels measured for the other soil feed test were substantially higher.
Baghouse ash total PCDD/PCDF concentrations ranged from 340 to 1,000 ng/kg (ppt)
for the fluff waste tests, with no apparent change associated with changing incineration
temperature. On a TEQ basis, the measured range was 6.8 to 23 ng/kg. Baghouse ash dioxin
levels were lower for the blank burn test on both bases. As for the scrubber liquor, baghouse
ash dioxin levels for one of the two soil feed tests were comparable to those measured for the
fluff waste tests; they were higher for the other soil feed test.
Baghouse exit flue gas total PCDD/PCDF levels were 0.021 ng/dscm corrected to
7 percent O2 for the blank burn test. Measured levels were increased, at 1.3 ng/dscm at
7 percent O2, for the fluff waste tests at the 870°C (1,600°F) target kiln temperature. Levels
for the fluff waste test at the 760°C (1,400°F) target kiln temperature, at 0.44 to 0.96 ng/dscm
at 7 percent O2, were slightly lower than for the higher temperature tests. Levels for the soil
feed tests were comparable, at 0.48 to 0.68 ng/dscm. All measured levels were significantly lower
than the EPA guidance announced in 1993 of 30 ng/dscm at 7 percent O2.
On a TEQ basis, baghouse exit flue gas dioxin/furan levels were 0.005 to 0.017 ng/dscm
at 7 percent O2 for the blank burn test, increased, at 0.044 to 0.052 ng/dscm at 7 percent O2 for
the fluff waste tests at the 870°C (1,600°F) kiln target temperature. Compared to these latter
levels, comparable to slightly decreased emissions, at 0.016 to 0.049 ng/dscm at 7 percent O2,
were measured for the fluff waste tests at the 760°C (1,400°F) target kiln temperature. Levels
measured for the soil feed tests were also comparable, at 0.018 to 0.032 ng/dscm at 7 percent
O2. The European suggested dioxin emission limit for waste incinerators is 0.1 ng/Nm3 TEQ
corrected to 11 percent O2. Thus, while the TEQ emission levels reported in Table 11 use the
EPA TEFs, which are slightly different than the international TEFs used by the Europeans, the
temperature correction for scm is slightly different than for Nm3, and the O2 correction for the
European standard, at 11 percent O2, differs from the 7 percent O2 used in the Table 11 data,
all emission levels reported in Table 11 will be lower than the suggested European standard.
3.3.5 Trace Metal and TCLP Results
Trace metal concentrations measured in test program samples are summarized in
Table 13. The data in the table clearly show that the major metal contaminants in both the fluff
waste and the contaminated soil were copper and lead. Both of these metals were also present
in the kiln ash discharge for all tests. The presence of high concentrations of these metals,
especially copper, in the kiln ash discharge substantiates that presumed catalysts for the relatively
low temperature reactions in the dioxin formation pathway would be present in the kiln ash so
that dioxin formation in this matrix, especially as noticed for the lower incineration temperature
fluff waste tests, can be understood.
Fluff and soil feed, kiln ash, scrubber liquor, and baghouse ash samples from the test
program were subjected to the TCLP, and resulting TCLP leachates were analyzed for a subset
36
-------
TABLE 13. TRACE METAL ANALYSIS RESULTS
Concentration
Sample
Test 0 (10/27/93), kiln temperature:
870°C (1,599°F)
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Fluff Waste tests
Test 1 (11/9/93), kiln temperature:
883°C (1,622°F)
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /tg/dscm
Test 2 (11/16/93), kiln temperature:
876 °C (1,608 °F)
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, ftg/dscm
Test 5 (11/18/93), kiln temperature:
762°C (1,403 °F)
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
Test 6 (11/23/93), kiln temperature:
767°C (1,412°F)
Fluff feed, mg/kg
Kiln ash, mg/kg
Scrubber liquor, mg/L
Baghouse ash, mg/kg
Baghouse exit flue gas, /ig/dscm
Sb
0.7
120
120
1,100
4.7
830
<21
180
940
3.7
400
<11
90
950
4.7
1,300
<11
100
950
4.9
1,900
<10
Ba
8.5
18
74
270
2.4
38
50
70
220
1.8
22
6
47
240
1.5
35
6
81
250
1.4
19
5
Cr
0.7
510
34
390
1.9
520
<9
38
480
1.4
320
<4
27
460
1.4 •
470
<4
"~"
24
530
1.4
510
<4
Ca
0.6
58
8,800
186,000
210
31,000
85
8,400
142,000
130
14,000
44
8,500
115,000
170
56,000
38
8,400
176,000
180
77,000
26
Pb
18
410
2,400
3,000
789
30,000
1,600
2,400
3,800
490
19,000
130
1,100
5,700
560
28,000
46
900
5,700
610
38,000
38
Zn
6.6
1,800
100
190
19
4,100
26
180
260
11
2,100
18
140
240
12
4,400
13
120
250
12
5,000
44
(continued)
37
-------
TABLE 13. (continued)
Concentration
Sample
Sb
Ba Cr Ca Pb Zn
Soil Feed Tests
Average soil feed, mg/kg 66
Test 3 (12/1/93), kiln temperature:
876°C (1,609°F)
Kiln ash, mg/kg 190
Scrubber liquor, mg/L 1.5
Baghouse ash, mg/kg 1,400
Baghouse exit flue gas, /ig/dscm < 10
Test 4 (12/2/93), kiln temperature:
874°C (1,606°F)
Kiln ash, mg/kg 190
Scrubber liquor, mg/L 1.3
Baghouse ash, mg/kg 950
Baghouse exit flue gas, /ng/dscm < 13
72 74 14,000 3,100 190
120 73 53,000
1.3 0.8 110
29 540 64,000
10 <3 51
91
1.3
19
6
56
1.0
520
<3
35,000
160
52,000
620
4,100
120
48,000
190
320
3
4,200
20
4,100 290
180 4
41,000 2,900
2,030 42
of the TCLP trace metals. Leachate analysis data are summarized in Table 14. The data in the
table show that the fluff waste from two of the four tests would be a lead-contaminated TC
hazardous waste. Further, the lead concentrations in the leachates of the fluff for the other two
tests were very close to the regulatory level for lead. Despite this, no resulting kiln ash discharge
from the incineration of fluff waste would be a TC hazardous waste due to its leachable lead, or
any other metal analyzed, concentration. Similarly, the scrubber liquor from all fluff waste tests
was not TC hazardous. However, the baghouse ash for all fluff waste tests would be a lead-
contaminated TC hazardous waste, and for three of the four tests a cadmium-contaminated TC
hazardous waste.
Although the contaminated soil tested was not a TC hazardous waste, conclusions
regarding the TC status of the residual discharges from its incineration were the same as for the
fluff waste. Namely, neither the kiln ash discharge nor the scrubber liquor resulting from its
incineration under the conditions tested would possess the TC, and the baghouse ash for both
tests performed would be considered both cadmium- and lead-contaminated TC hazardous waste.
33.6 Particulate and HC1 Emissions
The baghouse exit flue gas paniculate and HC1 emission data developed in the test
program are summarized in Table 15. The data show that baghouse exit particulate
concentrations were less than 10 mg/dscm corrected to 7 percent O2 for all but one test for
which they were 14 mg/dscm at 7 percent O2. All measured levels were well below the current
38
-------
TABLE 14. TCLP LEACHATE ANALYSIS RESULTS
Leachate concentration, mg/L
Sample leached
Regulatory level
Fluff Waste tests
Test 1 (11/9/93), kiln temperature:
883 °C (1,622°F)
Fluff feed
Kiln ash
Scrubber liquor
Baghouse ash
Test 2 (11/16/93), kiln temperature:
876°C (1,608°F)
Fluff feed
Kiln ash
Scrubber liquor
Baghouse ash
Test 5 (11/18/93), kiln temperature:
762°C (1,403 °F)
Fluff feed
Kiln ash
Scrubber liquor
Baghouse ash
Test 6 (11/23/93), kiln temperature:
767°C (1,412°F)
Fluff feed ,
Kiln ash
Scrubber liquor
Baghouse ash
As
5
<0.05
<0.05
<0.05
0.20
<0.05
<0.05
<0.05
0.08
<0.05
<0.2
<0.05
<0.2
<0.05
<0.2
<0.05
<0.2
Ba
100
0.25
1.2
0.93
0.23
0.26
1.3
0.76
0.05
0.19
2.2
0.60
0.4
0.55
1.2
0.6
0.6
Cd
1
0.03
< 0.004
0.03
1.4
0.04
< 0.004
0.03
0.9
0.03
< 0.005
0.03
1.8
0.03
< 0.005
0.02
1.8
Cr
5
< 0.007
0.32
0.06
0.29
< 0.007
0.41
0.04
0.20
< 0.007
0.05
0.04
0.13
< 0.007
0.01
0.05
0.2
Pb
5
3.6
0.42
0.52
3,800
5.4
0.09
0.40
1,900
3.7
<0.1
2.2 '
5,200
5.8
0.50
0.6
4,400
Ag
5
< 0.007
< 0.007
0.08
< 0.007
< 0.007
< 0.007
0.09
0.02
< 0.007
< 0.007
0.06
0.02
< 0.007
< 0.007
0.08
0.02
(continued)
39
-------
TABLE 14. (continued)
Leachate concentration, mg/L
Sample leached
Regulatory level
Soil Feed Tests
Average soil feed
Test 3 (12/1/93), kiln temperature:
876°C (1,609°F)
Kiln ash
Scrubber liquor
Baghouse ash
Test 4 (12/2/93), kiln temperature:
874°C (1,606°F)
Kiln ash
Scrubber liquor
Baghouse ash
As Ba
5 100
<0.05 0.91
<0.2 0.26
<0.05 0.16
0.2 0.50
<0.2 0.70
<0.05 0.09
0.24 0.2
Cd Cr
1 5
0.02 < 0.007
< 0.005 0.05
< 0.004 0.04
2.2 0.3
< 0.005 0.03
< 0.004 0.10
1.7 0.3
Pb Ag
5 5
0.67 0.007
<0.1 <0.007
0.08 < 0.007
6,600 0.03
0.2 < 0.007
0.39 0.02
5,700 0.03
TABLE 15. PARTICULATE AND HC1 EMISSIONS
Cl feedrate,
Test kg/hr
Test 0 (10/27/93) 0.28
Fluff waste tests
Test 1 (11/9/93) 9.48
Test 2 (11/16/93) 9.48
Test 5 (11/18/93) 9.48
Test 6 (11/23/93) 9.48
Soil feed tests
Test 3 (12/1/93) 1.1
Test 4 (12/2/93) 1.1
Particulate
concentration,
mg/dscm at 7%
<>2
7
7
4
6
14
5
9
Baghouse exit
HCI emission
rate, g/hr
<0.2
1.7
2.0
2.0
2.3
2.6
0.7
Apparent
system HCI
collection
efficiency, %
> 99.93
99.98
99.98
99.98
99.98
99.76
99.94
40
-------
hazardous waste incinerator performance standard of 180 mg/dscm at 7 percent O2, and even
substantially below the EPA's announced 1993 guidance of 34 mg/dscm at 7 percent O2.
Baghouse exit flue gas HC1 emission rates were at most 2.6 g/hr. Apparent system
collection HC1 efficiencies were greater than 99.9 percent for all except one soil feed test for
which the apparent system HC1 collection efficiency was 99.76 percent.
3.4
CONCLUSIONS
Results of the test program conducted to evaluate the incineration treatment of fluff
waste and contaminated soil from the M. W. Manufacturing Superfund site confirm that
incineration represents an effective treatment option, but several cautions regarding its use need
emphasis. Indeed, incineration of the fluff waste offers several benefits including substantial
waste volume reduction, and effective, near complete, decontamination and destruction of both
the VOC and SVOC contaminants in the waste. While the volume reduction benefit is less
significant in the incineration treatment of the contaminated soil, the benefit of effective and
near complete decontamination and destruction of organic POHC contaminants remains.
Both site materials can be incinerated in compliance with the current hazardous waste
incinerator performance standards in a rotary kiln incineration system of the type in place at the
IRF with an APCS consisting of a wet scrubber for acid gas control and a baghouse for final
particulate control. Specifically:
• Greater than 99.99 percent POHC DREs were uniformly measured
• HC1 emissions were well below 1.8 kg/hr and system HC1 control efficiencies well
above 99 percent
In addition, compliance with the more stringent incinerator emissions guidance announced in
1993 was demonstrated. Specifically:
« Particulate emissions measured were well below 34 mg/dscm corrected to
7 percent O2
9 Total PCDD/PCDF emissions measured were well below 30 ng/dscm at 7 percent
°2
In fact, measured dioxin/furan emissions were well below the suggested European emission limit
of 0.1 ng/Nm3 dry at 11 percent O2.
However, the kiln ash discharge from the incineration of both site materials remains
dioxin-contaminated. The kiln ash discharge from the incineration of contaminated site soil at
a kiln temperature of nominally 870°C (1,600°F) contained total PCDD/PCDF concentrations
of 2.4 to 3.6 j«g/kg. Levels in the kiln ash discharge from the incineration of fluff waste at a
nominal kiln temperature of 870°C (1,600°F) were higher, at 65 to 89 /ig/kg. Levels in the kiln
ash discharge from the incineration of fluff waste at a nominal kiln temperature of 760°C
(1,400°F) were substantially higher, at 830 to 2,700 pg/kg.
4-1
-------
Thus, with respect to fluff waste, incineration offers substantial volume reduction,
however the resulting treated waste discharge (kiln ash) will still need to be managed as a dioxin-
contaminated material. Dioxin contamination levels were decreased at higher incineration
temperatures, but they remained significant nonetheless. Perhaps higher incineration
temperature, with or without the use of an ash water quench system, would give a kiln ash
discharge relatively free of dioxin contamination. However, further tests are needed to
investigate this possibility.
In addition, the flue gas particulate collected as baghouse ash in essentially all tests was
a cadmium- and lead-contaminated TC hazardous waste. So this discharge would need to be
appropriately managed as a hazardous waste.
Test results were documented in the test report:
• J. W. Lee, W. W. Vestal, and S. Venkatesh, "Pilot-Scale Incineration Testing of
Fluff Waste and Contaminated Soil from the M. W. Manufacturing Superfund
Site," Draft, May 1994.
42
-------
SECTION 4
TEST INCINERATION OF BALLISTIC MISSILE PROPELLANT COMPONENTS
The U.S. Department of Defense (DoD) recently concluded agreements with the
Ukraine and the Russian Federation under which the DoD is committed to providing both
former Soviet Union (FSU) states with equipment and other aid for use in eliminating their
strategic offensive arms (SOA) in accordance with schedules negotiated in the Strategic Arms
Reduction Treaty (START). The agreement with the Ukraine specifically includes supplying this
FSU state with mobile and transportable single-trailer incinerators for use in destroying
unsymmetrical dimethylhydrazine (UDMH) and nitrogen tetroxide (N2O4, or NTO), used in
FSU land-based and submarine-launched ballistic missiles. The agreement with the' Russian
Federation requires supplying liquid propellant component treatment or destruction process
equipment, while not specifically requiring the process to be incineration. Nevertheless
incineration may be the process selected. '
The Defense Nuclear Agency (DNA) is responsible for providing the treatment/
destruction process equipment that will be used in carrying out this effort. Should incinerators
be provided, one requirement is that they meet both the U.S. environmental regulatory
requirements, as well as those of the respective FSU states. Thus, to supply the data to
demonstrate that purge media contaminated by either compound or that pure UDMH or N2O4
can be effectively destroyed by incineration while complying with the requisite environmental
regulations, DNA funded a series of incineration tests at the IRF under two interagency cost
reimbursement orders (lACROs), IACRO 93-691, Work Unit 00005, and IACRO 94-7615 (Mai
R. Schultz, Coordinator).
The general objectives of the test program performed were to:
• Demonstrate the U.S. and FSU environmental certifiability of the incineration of
FSU ballistic missile fuel UDMH
• Demonstrate the U.S. and Russian environmental certifiability of the incineration
of FSU ballistic missile oxidizer N2O4
Environmental certifiability was to be established by showing that both UDMH and N2O4 can
be separately destroyed in an incinerator to levels which meet both U.S. and FSU state
environmental regulations, while resulting in emissions of incineration by products considered
acceptable under those regulations.
43
-------
4.1 TEST PROGRAM
The test program was conducted in the IRF RKS. A process schematic of the RKS as
it was configured for these tests is shown in Figure 1. However, because very little flue gas
particulate was expected from the incineration of either component of the ballistic missile liquid
propellant, the baghouse system shown in Figure 1 was bypassed.
4.1.1 Environmental Regulations
As noted above, the objectives of the test program were to establish that UDMH and
N2O4 can be destroyed in an incineration system in a manner that meets U.S. arid FSU state
environmental regulations. The applicable U.S. environmental regulations are the hazardous
waste incinerator performance standards established under RCRA. These standards require that
the incinerator achieve:
• At least 99.99 percent DRE of the POHCs in the waste feed to the incinerator
• HC1 emissions of less than 1 percent of the HC1 entering the incinerator's APCS
or 1.8 kg/hr, whichever is greater
The promulgated regulations require that particulate emissions be no greater than 180 mg/dscm
(0.08 gr/dscf) corrected to 7 percent O2. However, EPA guidance announced in 1993 states that
particulate emissions be limited to 34 mg/dscm (0.015 gr/dscf) corrected to 7 percent O2.
In addition, hazardous waste incinerator permits currently being enforced in the U.S.
require that CO emissions be no greater than a 1-hour rolling average of 100 ppm, corrected to
7 percent O2, and limit hazardous constituent trace metal feedrates to levels designed to prevent
exceeding risk-based ambient levels. The hazardous constituent trace metals are antimony,
arsenic, barium, beryllium, cadmium, chromium, lead, mercury, silver, and thallium. Finally, 1993
guidance states that total tetra- through octa-chlorinated PCDDs/PCDFs be limited to
30 ng/dscm corrected to 7 percent O2.
Discarded or off-specification UDMH to be destroyed or disposed of would be the listed
hazardous waste U098. The POHC for this waste for which an incinerator would need to
achieve 99.99 percent DRE would obviously be UDMH. Discarded or off-specification N2O4
would be listed waste P078. P078 is listed as nitrogen dioxide (NO2). However, N2O4 is the
term used to refer to the equilibrium mixture of N2O4 and NO2 expressed as
N204 * 2N02
(1)
Because neither N2O4 nor NO2 is an organic constituent, showing 99.99 percent N2O4/NO2
DRE would not be required.
The Russian environmental regulations limit the emissions of UDMH and several
potential UDMH PICs from the incineration of UDMH. These limits are summarized in
Table 16. Ukrainian regulations are essentially the same. The limits noted in the table are
44
-------
TABLE 16. RUSSIAN FEDERATION ENVIRONMENTAL REGULATIONS
FOR UDMH INCINERATION
Compound
Maximum permissible
concentration in workplace air,
mg/m3
UDMH
Dimethylamine
N-Nitrosodimethylamine
Hydrogen cyanide (HCN)
1, l,4,4-Tetramethyl-2-tetrazene
Formaldehyde
CO
NO,
0.1
1.0
0.001
0.3
3.0
0.5
20
2.0
occupational exposure limits in terms of maximum permissible concentrations in workplace air
Corresponding ambient air standards for population centers can be a factor of up to 600 lower
Region-specific regulations may further constrain a sources' duration of operation to ensure
maintenance of the ambient standards. For example, in a highly industrialized region with many
CO or NOX sources, a UDMH incinerator may be constrained to operate only a set number of
hours per day or days per week to ensure that ambient CO or NO2 levels from resulting from
the collection of sources in the region are not exceeded. The candidate locations for operating
the transportable incinerators to be supplied to the FSU states are sufficiently remote from
highly industrialized urban areas that no additional region-specific constraints will apply.
European hazardous waste incinerator regulations might also be considered in
addressing the environmental certifiability of missile propellant incineration. A summary of
select European incinerator regulations is given in Table 17. Of the European regulations noted
in Table 17, the German regulations are currently the most stringent. Other European countries
either do not specifically regulate incinerator emissions or have less stringent emission limits
such as the French limits noted in Table 17. Recognizing this, and coupled with the desire to
have a common set of regulations within Europe, the former European Community (EC)
proposed a new directive in 1992, which is also given in Table 16.
With respect to UDMH incineration, the primary requirements that need to be
demonstrated are that 99.99 percent UDMH DRE can be achieved with acceptable CO, NO ,
and other UDMH PIC emissions. For N2O4 incineration, only acceptable CO and NO*
emissions need to be demonstrated. The U.S. incinerator standard of 100 ppm CO 1-hour
rolling average at 7 percent O2, might represent an appropriate target. This equates to
183 mg/dscm at 7 percent O2. Thus, only a 10-fold dilution of stack emissions into ambient air
would be needed to meet the Russian workplace standard of 20 mg/m3. Typical stack to
maximum ambient concentration dilution factors are much larger, generally 100 to several
thousand.
45
-------
TABLE 17. EUROPEAN HAZARDOUS WASTE INCINERATOR EMISSION LIMITS
Pollutant
Particulate
HC1
HF
S02
NOX
CO
Total organic carbon
Heavy metals
Cd + Tl
Hg
Others0
Dioxins and furans,
TEQd
Germany,
17th BImSch V,
mg/Nm3,
11% 02, dry,
daily average
10
10
1
50
200b
50
10
0.05
0.05
0.5
0.1 ng/Nm3
France
Regulation
mg/Nm3,
7% CO2, wet
150
100
a
—
—
—
—
1
I 5 total
J
—
Recent permit
requirements,
mg/Nm3,
7% CO2, wet
30
50
—
—
—
—
—
]
I 5 total
J
—
EC directive,
mg/Nm3, 11%
O2, dry, daily
average
5
5
1
25
—
50
5
0.05
0.05
0.5
0.1 ng/Nm3
a— = No standard.
bAs N02.
°Sb, As, Cr, Co, Pb, Mn, Ni, Sn, and V.
dTEQ = 2,3,7,8 tetrachloro dibenzo-p-dioxin (TCDD) toxicity equivalents.
The U.S. hazardous waste incinerator standards do not address NOX emissions.
However, the new source performance standard (NSPS) for large municipal waste incinerators
(greater than 250 tons/day [227 Mg/day] capacity), established under the Federal Clean Air Act,
is 180 ppm NOX at 7 percent O2. This is comparable to the German standard of 200 mg/Nm3
as NO2 at 11 percent O2, which equates to an emission limit of 136 ppm NOX at 7 percent O2.
A 100-fold dilution of stack emissions of 200 mg/Nm3 would satisfy the Russian workplace
standard for NO2. This is at the lower bound of typical dilution factors, as noted above.
Emissions of particulate, HC1, HF, SO2, heavy metals, and dioxins and furans, regulated
in Germany and proposed for regulation in the former EC, would be expected to be negligible.
Total organic carbon emissions should also be negligible if the CO emission limit is met.
Emission rates of several of these pollutants were measured in the test program, however. In
addition, emission rates of UDMH and the UDMH PICs having Russian occupational exposure
requirements, noted in Table 16, were also measured.
46
-------
In summary, the specific test program objectives were:
• To develop the data to evaluate whether UDMH and N2O4 can be incinerated in
compliance with the U.S. hazardous waste incinerator performance standards and
recent permitting guidance of:
— 99.99 percent UDMH DRE
— HC1 emissions less than the greater of 1 percent of the APCS inlet flowrate
of 1.8 kg/hr
— CO emissions of less than 100 ppm hourly rolling average at 7 percent O2
— Particulate emissions of less than 34 mg/dscm (0.015 gr/dscf) corrected to
7 percent O2
- Total tetra- through octa-PCDD/PCDF emissions of less than 30 ng/dscm
corrected to 7 percent O2
• To develop particulate, HC1, and total organic carbon emission rate data from the
incineration of UDMH and N2O4 for comparison to European limits
• To develop CO and NOX (NO plus NO2) emission rate data from the incineration
of UDMH and N2O4 for comparison to the U.S. hazardous waste incinerator
permit guidance limits and the NSPS for large municipal waste incinerators
• To develop UDMH PIC emission rate data from the incineration of UDMH for
comparison to the emission rate limits corresponding to the Russian occupational
exposure limits
• To develop trace metal emission rate data from the incineration of N2O4 for
comparison to both European limits and the U.S. incinerator performance
standard Tier II limits defined in the BIF rules (Reference 2)
• To develop PCDD/PCDF emission rate data from the incineration of UDMH and
N2O4 for comparison to the 1993 EPA guidance and European target limits
4.1.2 Test Conditions
The test program consisted of nine incineration tests. Three tests (triplicate testing)
were performed under the same incineration system operating conditions feeding each
component of the missile propellant. Two sets of triplicate tests feeding UDMH (six total) were
required to complete all the flue gas sampling procedures planned for the UDMH feed tests, as
noted in Section 4.1.3. Thus, nine tests in total, six feeding UDMH and three feeding N,O,
were performed. z 4'
47
-------
The six UDMH destruction tests were performed at a nominal kiln exit gas temperature
of 980°C (1,800°F). Only UDMH was fed to the kiln along with the required combustion air.
The RKS auxiliary fuel, natural gas, was not fed during actual testing, although natural gas was
used for incinerator heat up, and to maintain incinerator temperatures overnight between tests.
UDMH was fed to the kiln via the liquid waste/fuel nozzle of the kiln's dual fuel burner. The
UDMH was directly pumped and metered from its nitrogen-blanketed storage container to the
burner nozzle via a UDMH feed system custom-fabricated at the IRF for these tests. As a
unique feature of this feed system, nitrogen was used instead of air as the atomizing fluid in the
kiln air-atomized main burner. Substitution of nitrogen for air ensured that no explosive
mixtures of UDMH vapor with air could exit within the burner tip.
The three N2O4 destruction tests were also be performed at kiln exit gas temperature
of 980°C (1,800°F). Diesel fuel served as the material to be oxidized by N2O4 for its
destruction. The diesel fuel was fed to the kiln via the liquid nozzle of the kiln's dual fuel
burner. The N2O4 oxidant was added to the burner primary air supply via an N2O4 feed system,
also custom-fabricated at the IRF for the tests. The key feature of this system was an N2O4
evaporator designed to supply a constant pressure vapor N2O4 stream to the burner primary air
plenum. For all nine tests the RKS afterburner was fired with natural gas to maintain a nominal
afterburner exit gas temperature of 1,090 °C (2,000 °F).
4.13 Sampling and Analysis Procedures
The RKS sampling locations and the scope of the sampling effort are shown in the
process schematic given in Figure 4. For all tests, the sampling matrix defined to meet the test
program objectives listed in Section 4.1.1 included:
• Obtaining a composite sample of the pre-test and post-test scrubber system liquor
• Continuously measuring O2, CO, NOX, and TUHC concentrations in the kiln exit
flue gas; O2, CO2, and NOX concentrations in the afterburner exit flue gas; O2,
CO2, and NOX concentrations in the scrubber exit flue gas; and O2 and CO
concentrations in the stack gas
• Sampling flue gas at the scrubber exit for trace metals using the EPA multiple
metals train
• Sampling flue gas at the scrubber exit for PCDDs/PCDFs using Method 23
• Sampling flue gas at the scrubber exit and the stack for particulate and HC1 using
Method 5; the stack gas sample was needed to comply with the IRF's permit
requirements
Additional sampling procedures were performed for the UDMH incineration tests.
These were:
• Sampling flue gas at the kiln exit, afterburner exit, and scrubber exit for:
48
-------
l6-i6S QS3
i
E
2
0
'I
i
i
§i«
l^i-S
I1!!
(hod Method 0010,
I and semivolatile
iine UDMH PICs
2g|
So
£|0
l|i
"fa
j£
| o
£
}Jj
fill
•0
11
ss H
cT
8"
8
°M
•£> e
11
*a
.S
e
a.
I
"E.
CO
s s si
^ ^ r^ II
>-» *j p it
s's s
S S 3
o
. X
3
•z
r-t
•z
X
XX X
X X
X X
XX XX
X
a
s u>
« " ... J
u> g S e
1 | = 'S
£5 V p p *o
S3 •< tw OT w
>-' r4 m •& irt
•
CO
1
s
•S
1
cs
CO
^4
cS
H
rf
S
.
ss
t> ^>
c/a M
2 1
wT w"
•dll
io-li
5 ^.^
1-H c4
X"V *-> *-i
4< i-J hJ
49
-------
— UDMH and dimethylamine using a variation of the National Institute for
Occupational Safety and Health (NIOSH) Method S143
— N-nitrosodimethylamine and l,l,4,4-tetramethyl-2-tetrazene
(tetramethyltetrazene) using Method 0010
— HCN using a modified California Air Resources Board (CARB) Method 426
— Formaldehyde using Method 0011
Measurements of NOX, UDMH, and UDMH PICs were specified at the three locations
noted, specifically to supply data to allow evaluating the need for a secondary combustion
chamber (afterburner) and/or a wet scrubber APCS in the units to be supplied to the FSU
states. Additional sampling and analyses were also performed for all tests to allow a wider scope
of environmental acceptability to be evaluated. This additional sampling measured particulate,
HC1, trace metal, and PCDD/PCDF emission rates. This additional sampling was performed
in the scrubber exit gas. Pre- and post-test scrubber liquor samples were also taken and analyzed
for UDMH (for UDMH incineration tests), chloride, nitrate, nitrite, and trace metals.
The number of sampling procedures specified for the UDMH tests could not be
performed simultaneously at the IRF due to the unavailability of sampling ports in all the
locations specified. Thus, the UDMH sampling matrix was completed over two sets of tests.
The procedures denoted Ul in Figure 4 were simultaneously completed over one set of three
test days; the procedures denoted U2 were completed during a second set of three test days.
4.2 TEST RESULTS
Table 18 summarizes the RKS operating conditions for the six UDMH tests performed.
Table 19 presents an analogous summary for the N2O4 tests. As shown, incineration conditions
for all nine tests were quite close to the test target temperatures of 980°C (1,800°F) at the kiln
TABLE 18. TEST OPERATING CONDITIONS FOR UDMH TESTS
Average kiln exit
conditions
Average afterburner
exit conditions
Test
No.
1
2
3
4
5
6
UDMH feedrate,
Test date kg/hr (Ib/hr)
(2/1/94)
(2/3/94)
(2/15/94)
(2/23/94)
(2/24/94)
(3/1/94)
47 (104)
47 (103)
44 (96)
41 (91)
42 (92)
44 (97)
Temperature,
°C (°F)
994 (1,821)
992 (1,817)
981 (1,797)
981 (1,797)
982 (1,800)
977 (1,791)
°2,
%
12.6
11.9
11.4
11.1
11.4
11.1
Temperature,
°C (°F)
1,107 (2,024)
1,097 (2,007)
1,097 (2,007)
1,097 (2,007)
1,097 (2,007)
1,097 (2,007)
02,
%
9.1
9.2
9.5
8.7
9.3
9.4
50
-------
Test
N204
Diesel
fuel
1 (3/24/94) 61 (135) 27 (60)
2(3/30/94) 65(142) 33(72)
3(4/5/94) 67(147) 33 (72)
Average kiln
exit conditions
Temperature,
oft /o-r?\
^ \ r J
979 (1,795)
980 (1,796)
985 (1,805)
02,
13.8
13.8
14.2
Average afterburner
exit conditions
Temperature,
°f /°V\
^ V. K)
1,097 (2,007)
1,098 (2,008)
1,098 (2,008)
—^^-" ^— _^
10.8
11.4
11.7
exit and 1 090°C (2000°F) at the afterburner exit. All six UDMH tests destroyed nominally
A °f ^ °f UDMH- ,?Ch °f ^ thrCe N*°* tCStS destr°yed "
r) of N204 using nominally 32 kg/hr (70 Ib/hr) of diesel fuel.
64
rn * ™r CEM data f°r the UDMH tests' As shown *» the table, both
CO and TUHC leve s at the kiln exit were low, at <2 ppm and about 1 ppm, respectively. NO
levels at the kiln exit ranged from 693 to 781 ppm at 7 percent O2, with a six-test average of
733 ppm. Afterburner exit NOX levels were lower, at 414 to 500 ppm at 7 percent O2, with a six-
test average of 462 ppm at 7 percent O2. However, these lower afterburner exit concentrations
can be shown to result from flue gas dilution by the CO2 and N2 added to the flue gas resulting
from the extra auxiliary fuel burned in the afterburner to raise its gas temperature Original
hopes were that some true NOX reduction via reburning mechanisms would occur in the
afterburner. To increase the probability that this would occur, the afterburner burner was fired
as fuel rich as possible Despite this, no true NOX reduction in the afterburner was achieved
In tact, some additional NOX was produced in the afterburner during these tests. However the
additional dilution gas introduced in the afterburner more than compensated for the extra NO
produced, so that NOX concentrations were decreased in the afterburner exit gas.
f ,M t thC scrubber exit were comparable to those at the afterburner exit, ranging
from 449 to 497 ppm at 7 percent O2, with a six-test average of 480 ppm at 7 percent O9
Because essentially all the NOX measured for the UDMH tests was as NO (no difference in NO
monitor reading was observed when going from an NO measurement to a total NO*
measurement), this is as expected. x
All NOX levels measured were substantially greater than the target level of 180 ppm at
7 percent O2. About a 75 percent reduction in the kiln exit NOX levels measured would be
needed to reach the 180 ppm target. The corresponding reduction needed to reach the target
from the afterburner and scrubber exit levels measured is about 60 percent Some low-NO
T^L00™*?15 may. be Capable °f achieving these reduction levels, but their applicability to
UDMH combustion is uncertain given the safety considerations UDMH combustion demands
Non-catalytic NO reduction processes, such as ammonia- or urea injection, might also be
effective though 70 percent NOX reductions are about the limit of effectiveness^ for these
3.pp ro 3.cn cs.
51
-------
ON
co
O CO
ON o\
-3- NO
CO
in
CO
O\
CO
ON
oo
oo
CO OO
CO •<*•
V
CO
O T-l
o\
•*
CO
w in
O CO
ON CO
•<*• t>
CO CO
OO VO
co •<*•
^r o\
T-l 00
CO •<*•
ON
V
CO
CO
co •*
O T-l
CO
ON
CO
VD
OO
e a
0,0,
&, a.
0)
S S
a, o
O. OH
U
O O
o
CO
O O
52
-------
evit rn T 21 surmmarif S thL6 CEM data fr°m the three N2°4 destruction tests. Again, kiln
exit CO levels were low, at less than 2 ppm, for two of the three N2O4 tests. For some unknown^
eSSTOScTe:2ge ^fl^ lGVel f°r J^ ^ W" Substantia4lly higher at 60 ppm S
tSlvS? t t^ J 16 Ppm, were higher for the N2O4 tests than were measured for the
UDMH tests, although even these higher levels are common from industrial combustion sources.
extr,mPI^ ^°XT C°T ntrationsj ™easured at all three flue gas locations for the N2O4 tests were
extremely high. Levels measured ranged from 1.80 to 2.06 percent at 7 percent O, at the kiln
exit, with a three-test average of 1.93 percent; from 1.22 to 1.33 percent at 7 percent ^ to
afterburner exit; and from 1.06 to 1.22 percent at 7 percent O2 aUhe scrubbe? exit. Again he
afterburner exit NOX levels were apparently reduced from those measured at the kiln ex*
However, as was the case for the UDMH tests, and as discussed below, additional NO was
produced in the afterburner; the addition of diluent CO2 and N2 from the afterburner burner
operation more than compensated for the additional NOX produced, so that the afterburner exit
JNOX concentrations were reduced from kiln exit concentrations.
The data in Table 21 further show that a significant fraction of the flue gas NO
at 6 °nS C°UrSe tWs W°Uld be that
H TK, 2
fnr data in Table 21 indicated that about 50 percent of the kiln exit NOX was NO?
for two of the three N2O4 tests; a lower fraction, about 40 percent, was measured for the third
test. N02 fractions at the afterburner exit were lower, at about 35 percent. This would be
expected because the additional NOX formed in the afterburner would be combustion-generated
NO. Thus the afterburner adds NOX in the form of NO to the combustion gas; the NO amount
increases but the NO2 fraction decreases. At the scrubber exit the NO2 fractions were S
oTTe ™' IT, M^erCeAnt- This,Would be ex?ected * the scrubber'system removed soml
of the more soluble NO2. Apparently some removal may have occurred as evidenced by the
scrubber **"** ^^ * ? percent °2> from the afterburner exit to the
Unfortunately, a complete picture of flue gas NOX levels for the N9O4 tests cannot be
discussed, because for two of the three tests performed, one of the three ^.monitors k ^ use
^t ?°TK ' aS," ^ "iT^G 21' °f C°UrSe' 'm retr°SPect PerhaPs this mi^ have been
expected. The extremely high flue gas NOX levels present in the tests presented a severe and
expected^ enVir°nment tO the monito''s used, so that more frequent malfunction might be
. high NOX levels measured in the flue gas for these tests clearly suggests that
Jn2 Tthl£* i™™^ C0mplete' ThC N2°4 DRES achieved for these tests a"e summarized
in Table 22. The DREs given in the table are based on the measured flue gas NO
concentrations only, thus giving "destruction credit" to the partial reduction of NO2 to NO The
nta mtTf tSat the N2°4 (°r N°2> DREs achieved were essentially 90 percent for
all the tests as measured at all three flue gas locations sampled.
The very high levels of NOX measured at aU locations for the N2O4 destruction tests
suggest that meeting a 180 ppm at 7 percent O2 standard when destroying N2O4 cannot be
achieved Measured kiln exit levels would require over 99 percent reduction to meet the
180 ppm level; measured afterburner exit and scrubber exit levels would require greater than
98 percent reduction. The most effective NOX control techniques are selective catalytic reduction
53
-------
TABLE 21. CEM DATA FOR THE N2O4 TESTS
Parameter
Kiln exit
CO, ppm
TUHC, ppm as propane
NOX, ppm
NOX, ppm at 7% O2
NO, ppm
NO2, ppm
N02/ NOX, %
Afterburner exit
NOX, ppm
NOX, ppm at 7% O2
NO, ppm
NO2, ppm
N02/NOX, %
Scrubber exit
NOX, ppm
NOX, ppm at 7% O2.
NO, ppm
NO2, ppm
NO2/NOX, %
Testl
(3/24/94)
<2
15
9,720
18,020
4,220
5,050
54
a
f
—
—
5,880
10,550
4,190
1,690
29
Test 2
(3/30/94)
<2
16
9,860
19,170
4,690
5,170
52
8,390
12,230
5,180
3,110
37
—
—
—
—
Tests
(4/5/94)
60
15
10,010
20,610
6,100
3,910
39
8,800
13,250
5,850
2,950
34
6,860
12,160
4,800
2,060
30
a— = Malfunctioning monitor.
54
-------
TABLE 22. N2O4 DREs
Parameter
Test! Test 2 Test 3
(3/24/94) (3/30/94) (4/5/94)
N2O4 feedrate, kg/hr 61 65
Kiln exit
Flue gas flowrate, dscm/hr 750 770
NO2
Concentration, g/dscm as NO2 9.7 9.9
Emission rate, kg/hr 7.2 76
ORE, % 88 88
Afterburner exit
Flue gas flowrate, dscm/hr 1,060 1,130
NO2
Concentration, g/dscm as NO2 —a 6.0
Emission rate, kg/hr — 6.7
DRE, % •••__, 90
Scrubber exit
Flue gas flowrate, dscm/hr 1,930 1,840
NO2
Concentration, g/dscm as NO2 3.2
Emission rate, kg/hr 6.3
DRE, % 90
67
770
7.5
5.7
91
1,350
5.6
7.6
89
1,770
3.9
7.0
90
a _
= Malfunctioning monitor.
approaches using ammonia. These processes offer no better than 95 percent NOX reductions
Further, they require ammonia addition as a reducing agent, an aspect that would greatly
complicate the operation of a transportable incinerator at a remote FSU operation site.
Table 23 summarizes the test data on the flue gas concentrations of other constituents
of interest measured in the first set of UDMH incineration tests. Data on flue gas
concentrations of UDMH, dimethylamine, and formaldehyde are given in Table 23. As shown
in the table, the concentrations of UDMH and dimethylamine were less than method detection
limits at all three flue gas locations sampled. Some formaldehyde was measured at the
afterburner exit and scrubber exit locations at levels between 9.4 and 8.0 /ig/dscm. A comparable
level at 7.2/jg/dscm was measured for one test at the kiln exit.
The UDMH detection limits can be used to set a lower bound on the UDMH DREs
achieved for the tests. These are also shown in Table 23. As indicated, UDMH DREs achieved
55
-------
TABLE 23. FLUE GAS HAZARDOUS CONSTITUENT CONCENTRATIONS
FOR THE UDMH SET 1 TESTS
Parameter
Test 1
(2/1/94)
Test 2
(2/3/94)
Test3
(2/15/94)
Kiln exit
Concentrations:
UDMH, /ig/dscm
Dimethylamine, /ig/dscm
Formaldehyde, /ig/dscm
UDMH DRE, %
Afterburner exit
Concentrations:
UDMH, /ig/dscm
Dimethylamine, /ig/dscm
Formaldehyde, /ig/dscm
UDMH DRE, %
Scrubber exit
Concentrations:
UDMH, /ig/dscm
Dimethylamine, /ig/dscm
Formaldehyde, /ig/dscm
Particulate, mg/dscm at 7% O2
UDMH DRE, %
<40
<440
7.2
<40
<380
<0.23
<40
<410
> 99.99991 > 99.99993 < 99.99993
<50
<460
6.8
<50
<280
2.4
<40
<410
4.3
> 99.99982 > 99.99988 > 99.99983
<80
<770
6.5
4
<70
<700
8.0
4
<70
<710
8.0
30
> 99.99974 > 99.99976 > 99.99973
were greater than 99.9997 percent in all cases at all locations, well above the 99.99 percent level
required under the current hazardous waste incinerator performance standards.
Table 24 summarizes the flue gas concentrations of other constituents of interest
measured during the second set of UDMH incineration tests. Data on cyanide, N-nitrosodi-
methylamine, and tetramethyltetrazene are given. As shown, none of the three constituents was
found in the flue gas at any sampled location for any test at the method detection limits noted
in the table.
Table 25 summarizes the PCDD/PCDF concentrations measured in the scrubber exit
flue gas for the one UDMH incineration test sampled and for the three N2O4 destruction tests.
As shown, total PCDD/PCDF concentrations for all four tests were comparable and quite low,
in the 0.13 to 0.45 ng/dscm at 7 percent O2 range. These levels are far below the 1993 EPA
guidance target of 30 ng/dscm at 7 percent O2. Or a TEQ basis, measured concentrations were
0.01 to 0.02 ng/dscm at 7 percent O2. These levels would similarly be far below the European
target of 0.1 ng/Nm3 TEQ at 11 percent O2, dry.
56
-------
TABLE 24. FLUE GAS HAZARDOUS CONSTITUENT CONCENTRATIONS
FOR THE UDMH SET 2 TESTS
Parameter
Kiln exit concentrations
Cyanide, ng/dscm
N-nitrosodimethylamine, jtg/dscm
Tetramethyltetrazene, /ig/dscm
Afterburner exit concentrations
Cyanide, /jg/dscm
N-nitrosodimethylamine, /ig/dscm
Tetramethyltetrazene, jig/dscm
Scrubber exit concentrations
Cyanide, ^g/dscm
N-nitrosodimethylamine, /ig/dscm
Tetramethyltetrazene, jig/dscm
Test 4
(2/23/94)
<40
<5
<3
<30
<5
<3
<30
<5
<3
Tests
(2/24/94)
<30
<5
<3
<30
<5
<3
<30
<5
<3
Test 6
(3/1/94)
<30
<5
<3
<30
<5
<3
<30
<5
<3
TABLE 25. SCRUBBER EXIT FLUE GAS PCDD/PCDF CONCENTRATIONS
Parameter
Scrubber exit flue gas PCDD/PCDF
concentration, ng/dscm at 7% O2
Total
TEQ
UDMH
Test 2
(2/3/94)
0.45
0.02
Test 1
(3/24/94)
• - .-
0.27
0.02
N2O4 tests
Test 2
(3/30/94)
0.13
0.01
Test3
(4/5/94)
0.36
0.01
57
-------
Scrubber exit flue gas concentrations of antimony, arsenic, barium, beryllium, cadmium,
chromium, cobalt, lead, manganese, nickel, silver, thallium, tin, and vanadium were measured for
the N2O4 destruction tests. None except lead was found in any test at the method detection
limits given in Table 26. Lead was found in the flue gas for two tests at 17 and 31 /ig/dscm,
respectively.
43 CONCLUSIONS
Test program results show that:
• NOX levels were in the range of 690 to 780 ppm at 7 percent O2 at the primary
combustion chamber exit while incinerating UDMH; these were reduced to 410
to 500 ppm at 7 percent O2 at the secondary combustion chamber exit, largely due
to the dilution that accompanies the addition of the extra fuel and air required to
raise the secondary chamber's temperature. Scrubber exit levels were similar to
afterburner exit levels, at 440 to 500 ppm at 7 percent O2.
NOX levels were quite high for the
N204
tests, at 9,300 to 10,000 ppm
(uncorrected) at the primary chamber exit; 8,400 to 8,800 ppm, lowered again due
to dilution, at the secondary chamber exit; and 5,900 to 7,100 ppm at the scrubber
exit. Approximately 30 to 50 percent of the flue gas NOX was NO2, the lower
fractions corresponding to the scrubber exit location. The lower total NOX levels
and the lower NO2 fractions at the scrubber exit location are likely due to some
removal of NO2 by the wet scrubber.
No UDMH was measured at any flue gas location for any UDMH test; UDMH
destruction and removal efficiencies (DREs) corresponding to the method
detection limits (MDLs) were uniformly greater than 99.9997 percent.
TABLE 26. FLUE GAS TRACE METAL CONCENTRATION
METHOD DETECTION LIMITS
Detection limit, Detection limit,
Metal jtg/dscm Metal /tg/dscm
Sb
As
Ba
Be
Cd
Cr
Co
12
21
1.0
0.1
1.0
3.0
17
Pb
Mn
Ni
Ag
Tl
Sn
V
15
1.0
4.0
3.0
15
89
3.0
58
-------
• No cyanide, dimethylamine, tetramethyltetrazene, or N-nitrosodimethylamine, all
postulated UDMH combustion byproducts, was measured at any flue gas sampling
location for any UDMH test. Corresponding MDLs were 30 ng/dscm for cyanide;
300 to 800/ig/dscm, depending on sampled location, for dimethylamine;
3 ng/dscm for tetramethyltetrazene; and 5 /tg/dscm for N-nitrosodimethylamine!
• Flue gas formaldehyde levels ranged from 2 to 8 ng/dscm at all three sampled
locations for the UDMH tests.
• Total PCDD/PCDF levels measured at the scrubber exit were 0.45 ng/dscm at
7 percent O2 for the one UDMH test for which they were measured; levels
measured for the three N2O4 tests were 0.13 to 0.36 ng/dscm at 7 percent O2.
In terms of toxicity equivalents, the scrubber exit flue gas levels were 0.02 ng/dscm
for the UDMH test, and 0.01 to 0.02 ng/dscm at 7 percent O2 for the three N,(X
tests. . •
• None of the 14 trace metals sought in the N2O4 tests was found in the scrubber
exit flue gas with the exception of low levels (17 to 30 ^g/dscm) of lead.
Test results were documented in the report:
• S. Venkatesh, L. R. Waterland, and C. Goldman, Test Incineration of Ballistic
Missiles Propellant: Phase I Testing," Draft, April 1994, Revised, October 1994.
59
-------
SECTION 5
EVALUATION OF THE SONOTECH PULSE COMBUSTION TECHNOLOGY
Sonotech, Inc., of Atlanta, Georgia, has developed a pulse combustion burner technology
that claims to offer benefits when applied in a variety of combustion processes. The burner
system incorporates a pulse combustor that can be tuned to excite large-amplitude sonic
pulsations inside a combustion chamber such as a boiler or incinerator. These pulsations serve
to increase the rates of heat, mixing (momentum), and mass transfer in the combustion process.
Sonotech claims that these rate increases in heat, mixing, and mass transfer are sufficient to
result in more complete combustion.
Sonotech has targeted waste incineration as a potential application for this technology.
Accordingly, to demonstrate the claimed benefits of the technology within a well-established
forum for providing technically sound and unbiased evaluations, Sonotech proposed a technology
evaluation test series under the Superfund Innovative Technology Evaluation (SITE) program.
The Sonotech proposal was accepted, and the testing portion of the evaluation program was
completed during FY94.
5.1
DESCRIPTION OF THE TECHNOLOGY
A pulse combustor typically consists of an air inlet, a combustor section, and a tailpipe.
In pulse combustion, fuel oxidation and heat release rates vary periodically with time. These
variations produce pulsations in combustor section pressure, temperature, and gas velocities.
The frequency of pulsations is generally close to the resonant frequency of the fundamental
longitudinal acoustic mode of a duct consisting of the combustor section and tailpipe. Thus, by
changing combustor and tailpipe geometry, for example by varying the length of the tailpipe, the
frequency of pulsations can be changed, or tuned. Furthermore, if properly applied, a pulse
combustor can excite large-amplitude (150-dB or higher) resonant pulsations within a cavity
downstream of the pulse combustor tailpipe. This cavity could be the combustion chamber of
a boiler or an incinerator, for example. Thus, with the development of frequency-tunable pulse
combustors, it became possible to apply pulse combustion to a variety of combustion processes
such as boilers, dryers, calciners, and incinerators.. In such applications, the pulse combustor
could be used as the combustion process burner, supplying all of the heat input to the process.
Alternatively, the pulse combustor could be used only as the driver to excite pulsations in the
combustion process. In such applications, most likely retrofit applications, the pulse combustor
would deliver only a fraction, as little as 1 to 10 percent, of the combustion process heat input,
while still exciting resonant pulsations in the process combustor. The remaining heat input would
be supplied via the normal process means, e.g., the process conventional burner.
60
-------
A retrofit application of the Sonotech pulse combustion system was evaluated in this test
program. Specifically, the kiln section of the RKS at the IRF was retrofitted with a pulse
combustion burner capable of delivering up to 73 kW (250,000 Btu/hr) of heat input from
natural gas fuel to the kiln. This corresponds to 15 to 20 percent of the typical heat input to the
kiln. The RKS was configured as shown in Figure 1, with the Sonotech combustion system
retrofitted into the end plate at the ash discharge end of the kiln.
5.2 DEMONSTRATION OBJECTIVES
Sonotech claims that the application of pulse combustion technology to an incineration
system has several significant advantages over conventional (non-pulsating) incineration. Thus,
the general objective of the demonstration test program was to develop the data needed to allow
objective and quantitative evaluation of these claims. Accordingly, the primary test program
objective was to develop test data to allow evaluating whether the Sonotech pulse combustion
technology applied to the IRF RKS, when compared to conventional, non-pulsating combustion,
resulted in:
• Increased incinerator capacity or productivity
• Increased principal organic hazardous constituent (POHC) destruction and
removal efficiency (DRE)
• Decreased flue gas CO emissions
• Decreased flue gas NOX emissions
• Decreased flue gas soot emissions
• Decreased combustion air requirements
• Decreased auxiliary fuel requirements
The secondary test program objective was to develop test data to allow evaluating whether the
application of the Sonotech technology, when compared to conventional, non-pulsating
combustion:
• Reduced the magnitude of transient puffs of CO and total unburned hydrocarbons
(TUHC)
• Allowed reduced incineration costs
« Caused significant changes in:
— The distribution of hazardous constituent trace metals among the
incineration system discharge streams (kiln bottom ash, scrubber liquor,
baghouse flyash, and baghouse exit flue gas)
61
-------
— The teachability of the toxicity characteristic leaching procedure (TCLP)
trace metals from kiln bottom ash, scrubber liquor, and baghouse flyash
This last secondary objective item does not relate to any Sonotech claim, but is of general
interest to the overall IRF research program.
S3 TEST PROGRAM
To address the test program objectives, tests at the following four different incineration
system operating conditions were performed:
• Test Condition 1: Conventional combustion under baseline, typical RKS
operation
• Test Condition 2: Conventional combustion at the maximum RKS waste feedrate
without pulsations
• Test Condition 3: Sonotech pulse combustion at the same feedrate and conditions
as Test Condition 2
• Test Condition 4: Sonotech pulse combustion at the maximum RKS waste
feedrate with pulsations
The test waste feed for all tests was a mixture of contaminated materials from two
manufactured gas plant (MGP) Superfund sites. (The specific components of this feed are
discussed later.) This waste feed was batch fed to the RKS via the system's fiberboard container
ram feed system, which feeds 1.5-gal (5.7-L) fiberboard containers to the kiln at virtually any
specified feed frequency. When a relatively high heat content material is being fed, the
maximum allowable waste feedrate is established based upon the onset of puffs of incompletely
combusted organic constituents (CO and TUHC) that survive the afterburner.
Given this, Test Condition 1 was at a waste feedrate consistent with stable incinerator
operation under conventional combustion, with infrequent spikes of CO and/or TUHC at the
afterburner exit. Test Condition 2 was at an increased waste feedrate that resulted in routine
afterburner CO spikes. This condition could be termed borderline acceptable incinerator
operation under conventional combustion. Test Condition 3 was at the same waste feedrate as
Test Condition 2, but with the Sonotech pulse combustion system in operation. Test Condition
4 was at a further increase in waste feedrate, with the pulse combustor in operation, such that
routine afterburner exit flue gas CO spikes recurred. This condition could be termed borderline
acceptable operation under pulse combustion operation. Three test runs (triplicate testing) at
each test condition were completed to allow the precision of each emission and discharge stream
composition measurement to be assessed.
As indicated above, the test waste feed material for the test program was a mixture of
materials from two MGP Superfund sites. One component of the material was a combination
of pulverized coal and contaminated sludge waste from the Peoples Natural Gas Company
Superfund site in Dubuque, Iowa. This site is an abandoned coal MGP site, and the sludge
waste at the site contains high concentrations of coal tar constituents. The other components
62
-------
of the test feed material were contaminated soil borings and a tar waste from an oil gasification
process, both obtained from an MGP site in the southeastern United States.
The hazardous constituent contaminants of all three test waste components were several
polynuclear aromatic hydrocarbon (PAH) compounds, and the VOCs benzene, toluene,
ethylbenzene, and xylenes (BTEX). The concentrations of each of these contaminants in each
waste component and in the composite test waste mixture are given in Table 27. Although
concentrations of several contaminant compounds were quite high in at least the tar component
of the waste mixture, it was decided that spiking the waste feed with benzene and naphthalene
would be necessary to guarantee meaningful DRE calculations. The data in Table 27 reflect the
spiked amounts of these two constituents.
To address the test program objectives, the composite waste feed, the kiln ash discharge,
the scrubber system liquor, the collected baghouse ash, the afterburner exit flue gas participate,
the afterburner exit flue gas, and the baghouse exit flue gas for each test were sampled and
TABLE 27. TEST WASTE COMPOSITION
Constituent
Coal + Sludge
Concentration, rag/kg
Tar Soil Spike
Composite
PAHs:
Acenaphthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(ghi)perylene
Benzo(a)pyrene
Chrysene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
2-Methylnaphthalene
Naphthalene
Phenanthrene
Pyrene
BTEX:
90
280
320
260
110
230
250
530
300
110
200
330
570
450
2,200
12,000
8,600
5,200
2,200
4,500
6,300
10,200
6,400
1,700
26,700
47,600
27,500
14,800
150
60
130
90
40
90
100
190
120
30
170
130
340
250
250,000
690
3,250
2,390
1,470
630
1,280
1,750
2,910
1,810
480
7,070
13,500
7,470
4,100
Benzene
Toluene
Ethylbenzene
Total xylenes
1.7
2.4
<1
6.6
1,450
1,960
480
1,560
0.3 750,000
0.1
0.3
0.5
9,040
510
130
410
63
-------
analyzed for sample-matrix-specific combinations of PAHs, VOCs, contaminant trace metals,
PCDDs/PCDFs, and TCLP-leachable trace metals. Li addition, the total organic carbon (TOG)
content of the afterburner exit flue gas particulate was determined and used as the measure of
soot emissions. The sampling and analysis matrix for each test is summarized in Table 28. Later
in the test program, measuring the heating value of each test's kiln ash discharge was added as
an indication of waste treatment residue quality.
5.4
PRELIMINARY TEST RESULTS
Installation of the Sonotech system on the RKS was completed in April 1994. System
shakedown and initial scoping tests to establish the specific operating condition settings and
waste feedrates to give the desired four test conditions were completed in May. However,
resolution of several important QA issues delayed the initiation of the actual evaluation testing
until early September. The last test was completed on October 18, just after the close of FY94.
5.4.1 Incinerator Operating Conditions
Table 29 provides a summary of the average incineration system operating conditions
for each of the four program test conditions. Each operating parameter noted in the table was
recorded nominally every 30 seconds over a 4- to 5-hour flue gas sampling period for each test
by the RKS data acquisition system. Test averages were calculated for each parameter. The
data in Table 29 represent the average over the three tests performed for each test condition of
the test average parameter values.
The data in Table 29 show that the kiln exit gas temperature tested for all conditions
averaged close to the test program target of 925°C (1,700°F), and that average afterburner exit
gas temperature was right at the test program target of 1,095 °C (2,000 °F). Afterburner exit flue
gas O2 levels averaged close to 9 percent for all test conditions, although slightly lower average
levels existed for Test Conditions 3 and 4, the two pulse combustion test conditions.
TABLE 28. TEST PROGRAM SAMPLING AND ANALYSIS MATRIX
Sample matrix
TCLP/
PAHs VOCs Metals PCDDs/PCDFs TOC Metals
Feed
Kiln ash
Scrubber liquor
Baghouse ash
Afterburner particulate
Afterburner exit flue gas
Baghouse exit flue gas
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
64
-------
v
1
O
I
I
8
en
ON
U
I
c
^g
•3
§
o
wa
os
e "9
£ 8
-
ij
a I s
01
10
t>
en
en
0
en
en
.0
of
•4-*
cd
0>
,0)
0)
OO OO VO ON 10
»-i in r~ «o en
^^ TH CM •*
o\
en
vo
co
oo
o
en
t~- oo
o\
000
en '-H o
t^ oq^ o
T-T T-T C>f
O\ O
O «O
o\
00
en oo *•"• 01 en o^ ON
3^o5SS vS s
O VO
en
ON
O\
ov o\
o o o
(N t> O
>o »o «o
en vo O\
O\ ON
IX,
o
VO
t-
0
«O
en
T— 1
of
O
O
ON O vo O
ON o\
ON ON oo
VO
O
en
of
-en
vo
O £-•
r? S
0 T-H
o •/—.
C3 O
>0 Ol
oC «
0 r-t
en
o
o
O
O\
U
0*
er
terb
IM
J3
•*-»
S
B
1
"•!-»
I
X
65
-------
The baseline (Test Condition 1) waste feedrate was 27.7 kg/hr (61.0 Ib/hr). This
feedrate was increased to 33.1 kg/hr (72.8 Ib/hr) to give the borderline acceptable operation
associated with Test Condition 2. Test Condition 3, with the pulse combustion system in
operation, was performed at nominally the same (just slightly higher) feedrate as Test
Condition 2, as planned. The Test Condition 3 feedrate was 21 percent greater than the Test
Condition 1 feedrate. A further 13-percent feedrate increase over that for Test Condition 2 was
possible before incinerator operation entered the borderline acceptable regime with the pulse
combustion system in operation. Thus, with respect to the Sonotech claim that increased
incinerator capacity can be realized with pulse combustion, test data show that a capacity
increase in the range of 13 percent (comparing Test Condition 4 to Test Condition 2) to
21 percent (comparing Test Condition 3 to Test Condition 1) can indeed be realized. The
feedrate for Test Condition 4 was 35 percent greater than that for Test Condition 1.
The data in Table 29 further show that the total system heat input needed to maintain
target incineration temperatures was relatively constant for all four test conditions at about
640 kW (2.2 MBtu/hr). Specifically comparing the auxiliary fuel use for Test Condition 3 to that
for Test Condition 2 shows that the auxiliary fuel requirements were nominally the same. Thus,
the Sonotech claim that decreased auxiliary fuel use would be possible with the application of
pulse combustion is not supported by the test data. However, because the waste treated in these
tests had significant heat content, the capacity increase noted above equates to a corresponding
decrease in the auxiliary fuel consumed per unit of waste treated. Comparing the auxiliary fuel
consumption per unit of waste treated for Test Condition 3 to that for Test Condition 1 shows
that the feedrate increase allowed by the Sonotech system yields a corresponding decrease in
auxiliary fuel use per unit of waste treated from 63.4 MJ/kg (27,300 Btu/lb) to 49.9 MJ/kg
(21,500 Btu/lb). Visual observations indicated that the Sonotech system produced improved
mixing in the kiln chamber.
With respect to combustion air requirements, the data in Table 29 show that less
combustion air was required for the two pulse combustion test conditions compared to the
conventional combustion test conditions. Specifically, the combustion air feedrate for Test
Condition 3 was 5 percent lower than that for Test Condition 2.
The kiln ash heating value data shown in Table 29 suggest that incineration residue
quality, as measured by residue (kiln ash) heating value, was improved with pulse combustion.
A decrease in kiln ash heating value from 3.1 MJ/kg (1,320 Btu/lb), for Test Condition 2, to
<1.1 MJ/kg (<500 Btu/lb), for Test Condition 3, at the same nominal feedrate but with pulse
combustion, was seen. The solids bed temperature data shown in the table are consistent with
this decrease. Solids bed temperatures were measured at four axial locations in the kiln during
the tests. The temperature at the location recording the peak temperature for each test was
averaged over the flue gas sampling period for that test. The entries in Table 29 represent the
average of these individual test averages for the three test runs at each test condition. The data
in the table show an increase in average peak solids bed temperature of from 965° (1,770 °F)
(Test Condition 1) to 990°C (1,810°F) (Test Condition 2), for conventional combustion, to
1,020°C (1,870°F) (Test Condition 3) to 1,030°C (1,890°F) (Test Condition 4), for pulse
combustion. Specifically, comparing the data for Test Condition 3 to those for Test Condition 2
shows an increase from 990°C (1,810°F), for conventional combustion, to 1,020°C (1,870°F), for
pulse combustion, at the same waste feedrate and other system operating conditions. These data
suggest that the Sonotech claim of increased heat transfer rates with pulse combustion,
66
-------
specifically to the solids bed, is justified. This increase in heat transfer rate to the solids bed
apparently gives rise to the increased bed temperatures seen and the corresponding decrease in
kiln ash discharge heating value.
5.4.2 CEMData
Table 30 summarizes the continuous emissions monitor (CEM) and soot emissions data
for the test program. As for the operating conditions data, summarized in Table 29, CEM
readings were recorded at nominally 30-second intervals on the RKS data acquisition system.
These readings were averaged over the flue gas sampling period for each test. The CEM entries
in Table 30 represent the average of each test's average for the three tests at each test condition.
The data in Table 30 show that average kiln exit CO levels substantially increased with
pulse combustion, from 68 ppm at 7 percent O2 for the two conventional combustion test
conditions (1 and 2), to 117 ppm at 7 percent O2 for Test Condition 3 and to 153 ppm at 7
percent O2 for Test Condition 4. This increase is consistent with both the kiln solids bed
temperature and the kiln ash residue quality data in Table 29. As discussed above, pulse
combustion caused increased kiln solids bed temperatures, which would, in turn, lead to a greater
degree of waste feed organic content devolatilization into the kiln combustion gas. The
observation that kiln exit CO levels were increased with pulse combustion suggests that the
greater amounts of devolatilized organics were not completely destroyed in the kiln.
Higher kiln exit CO levels should not be viewed as a negative, however. Incineration
systems have afterburners specifically to complete the combustion process and destroy the
incomplete combustion products, such as CO, in the kiln exit combustion gas. Indeed, average
afterburner exit CO levels were decreased to 15 ppm at 7 percent O2, for Test Condition 1, and
to 20 ppm at 7 percent O2 for Test Condition 2. Compared to conventional combustion, pulse
combustion produced slightly lower average afterburner exit CO levels. Comparing Test
TABLE 30. CONTINUOUS EMISSIONS MONITOR DATA
Test condition average (3 tests)
Constituent
Kiln exit:
CO, ppm at 7% O2
Afterburner exit:
CO, ppm at 7% O2
NOX, ppm at 7% O2
Baghouse exit:
NOX, ppm at 7% O2
1: 2: 3: 4:
Conventional Conventional Pulsations Pulsations
baseline max. feed feed as in 2 max. feed
68
15
90
88
68
20
82
85
117
14
77
78
153
17
78
72
67
-------
Condition 3 (pulse combustion) to Test Condition 2 (with conventional combustion), both of
which had the same waste feedrate, shows that pulse combustion resulted in decreased average
afterburner exit CO emissions of 14 ppm at 7 percent O2. Even at the increased waste feedrate
achieved with pulse combustion for Test Condition 4, afterburner exit CO levels were only
marginally increased, to 17 ppm at 7 percent O2 — higher than the Test Condition 3 level, but
still 15 percent lower than the Test Condition 2 level.
CO is the final incomplete combustion product in the series of reactions that converts
the carbon in organic constituents to CO2. Thus, an explanation for why afterburner exit CO
levels under pulse combustion operation were lower than under conventional combustion
operation, while kiln exit levels were higher, may be that organic constituent combustion in the
kiln was more complete under pulse combustion operation. More complete organic constituent
combustion can result in higher CO (the final incomplete combustion product) levels, while other
unburned hydrocarbon levels, including soot, would be decreased. In such cases, the burden on
the afterburner to carry the destruction process to completeness would be lessened, resulting in
lower afterburner exit CO levels.
Afterburner and baghouse exit NOX emissions were comparable from test condition to
test condition and were 90 and 88 ppm at 7 percent O2, respectively, for Test Condition 1, and
a slightly decreased 82 and 85 ppm at 7 percent O2 for Test Condition 2. Levels of afterburner
and baghouse exit NOX were, respectively, 77 and 78 ppm at 7 percent O2, for Test Condition 3
(under pulse combustion), and 78 and 72 ppm at 7 percent O2, for Test Condition 4 (also under
pulse combustion). Although the Sonotech claim that pulse combustion would result in
decreased NOX emissions was confirmed by the test data, the reductions achieved were small,
and from relatively low initial conventional combustion levels.
5.5
CURRENT STATUS
As noted above, the testing phase of the evaluation program was completed just after
the close of FY94. Preliminary test results outlined above allow several vendor claims to be
evaluated as follows:
• Increased incinerator capacity. Application of the Sonotech pulse combustion
system allowed waste feedrate increases of between 13 and 21 percent compared
to corresponding operating conditions under conventional combustion.
• Decreased flue gas CO emissions. Average afterburner exit flue gas CO levels
were indeed reduced, from 20 ppm at 7 percent O2 in a maximum waste feedrate
operating condition under conventional combustion operation, to 14 ppm at
7 percent O2 at the same feedrate with pulse combustion. Pulse combustion
allowed a higher waste feedrate to be achieved, with average afterburner exit CO
emissions of 17 ppm at 7 percent O2, still below the conventional combustion
maximum feedrate condition.
• Decreased flue gas NOX emissions. Both afterburner exit and baghouse exit NOX
emissions were slightly decreased, from 82 and 85 ppm at 7 percent O2,
respectively, in a conventional combustion maximum waste feedrate operating
condition, to 77 and 78 ppm at 7 percent O2 at the same feedrate with pulse
68
-------
combustion. At the higher waste feedrate achievable with pulse combustion, NO
emissions were 78 and 72 ppm at 7 percent O2.
• Decreased combustion air requirement. Required combustion air decreased
slightly with pulse combustion.
• Decreased auxiliary fuel requirements. No measurable change in auxiliary fuel
requirements to establish a given set of combustion conditions was observed.
The analysis of all samples collected in the program to address the other demonstration
objectives will be completed during early FY95, and the test report will be assembled and
submitted by mid FY95.
69
-------
SECTION 6
EVALUATING THE EFFECTIVENESS OF ADDITIVES
AS SORBENTS FOR METAL CAPTURE
There is currently considerable interest in the potential use of mineral-based sorbents
for capturing and retaining hazardous constituent trace metals released during incineration. A
number of fundamental, bench-scale research programs at several universities and research
laboratories have been recently reported on this subject. These studies are investigating the
application of sorbents both in the combustion flue gas and in the solids bed.
Most of the research completed to date has focused on quantifying the effectiveness of
various proposed sorbents for capturing vaporized metals from the flue gas. In such applications,
it is theorized that vaporized metals will react with the sorbent particles at the elevated
incinerator temperatures or heterogeneously condense onto the sorbents as the flue gas cools.
In the absence of available condensation sites, vaporized metals will primarily undergo
homogeneous condensation, forming a fine fume. Thus, the goal of this approach is to make
particles available in the flue gas with which the metals can react or upon which they can
condense. Metals bound to larger sorbent particles will be more effectively collected by APCSs
than metals presented as a fine fume. In addition, studies completed to date suggest that
chemical reaction between the metal and the sorbent dominates over physical adsorption,
offering the additional advantage of reduced potential for metal leaching from collected
particulate.
Other researchers have studied the incorporation of sorbents into the solid feed. This'
approach seeks to capture and bind the metals in the incinerator ash, thereby preventing them
from exiting with the combustion gases. For this approach to be effective, the metal should be
volatilized in the incinerator environment and chemically react with the sorbent material.
The test program described in this section was designed to further investigate the second
approach by screening several minerals for their suitability as sorbent materials. In addition to
capturing the metals, an ideal sorbent would retain them in the ash when disposed, so that a
TCLP leachate of the ash would contain metals concentrations below respective regulatory levels.
Thus, the objective of this test program, completed at the IRF in FY94, was to evaluate several
candidate sorbents with respect to:
• The degree to which they facilitate retention of trace metals in the solid bed that
would be the bottom ash discharge from a rotary kiln incinerator
« The degree to. which they retain trace metals in the solid bed when subjected to
TCLP extraction
70
-------
6.1
TEST FACILITY DESCRIPTION
The screening tests in this program were conducted in the IRF TTU. This unit consists
of a small commercial pathological incinerator that has been modified to allow for continuous
test material feed and treated-material (e.g., ash) removal, for variable and controlled thermal
treatment temperatures, and for expanded process operation monitoring. The TTU is illustrated
in Figure 5.
The combustor portion of the TTU consists of three chambers: the charge chamber, the
retention chamber and the breeching chamber. The charge chamber is designed to accept the
TTU's solid material feed stream. It corresponds to the primary combustion chamber, or kiln
portion, of a waste incinerator. Its inner cross section is 0.66 m (2 ft 2 in) square, its height
1.9 m (6 ft 2 in), and its chamber volume 0.82 m3 (29 ft3). The retention chamber, which directly
follows the charge chamber, is designed to effect complete organic constituent destruction. It
corresponds to the secondary combustion chamber, or afterburner portion, of a waste incinerator.
Its inner cross section is also 0.66 m (2 ft 2 in) square, its height 1.5 m (5 ft), and its chamber
volume 0.67 m (23.5 ft3). The breeching chamber serves as a second-stage afterburner. Its
inner diameter is 0.41 m (1 ft 4 in), its total height 0.76 m (2 ft 6 in), and its chamber volume
0.10 mj (3.5 ft3). All chambers are lined with a 13-cm (5-in) thickness of refractory.
As received from the incinerator vendor, all three chambers were designed to be fired
with natural-gas-fueled burners. The burners installed in the charge and retention chambers are
natural-gas-fired, with 350 kW (1.2 million Btu/hr) capacities and 5-to-l turndowns. Modulating
burner controls allow variable firing rates to control temperatures in each chamber at preset
levels between 260° and 1,090°C (500° and 2,000°F) with variable air-to-fuel ratio. The
breeching chamber has a manually adjustable 220 kW (750,000 Btu/hr) burner.
Test material is fed to the charge chamber via a chain-drive feed system that transports
quartz trays containing the test material. Each quartz tray is 23 cm (9 in) long by 13 cm (5 in)
wide by 5 cm (2 in) deep, and holds up to 2.3 kg (5 Ib) of test material. The variable-speed
chain drive allows trays containing test material to have charge chamber residence times of
between 20 minutes and 1 hour. Multiple trays can be fed in sequence to simulate continuous
feed to a thermal treatment system.
Combustion gas temperatures are recorded using type K or R thermocouples at the
following locations in the system:
• Inside feed door
• Inside discharge door
• Bottom of charge chamber center
• Charge chamber exit gas
• Retention chamber exit gas
71
-------
TEMP INDICATING
CONTROLLER
TEMP INDICATING
CONTROLLER
FEED
CONVEYOR
-3
SAMPLING
PORTS
BREECHING
CHAMBER
RETENTION
CHAMBER
CHARGE
CHAMBER
TEMP INDICATOR
TEMP INDICATOR
a
CO
in
&
BURNERS
BURNER 2
CHART
RECORDER
BURNER 1
ASH
Figures. The IRF TTU.
72
-------
6.2
• Breeching chamber exit gas
• Stack gas
TEST PROGRAM
The test program performed consisted of 50 tests. The test variables were sorbent
material, solid bed temperature, feed chlorine content, and metal form in the feed Sk sorbents
were evaluated in this study. Five of the six, silica, diatomaceous earth, kaolinite, bauxite and
alumina, were selected based on the most promising results from other researchers and comprise
a sorbent material spectrum ranging from pure silica to pure alumina. The attapulgite clay used
in past IRF trace metal studies was tested as the sixth sorbent to serve as a link to the past IRF
studies. e
Three solids bed temperatures were tested: 540°, 700°, and 870°C (1,000°, 1,300° and
1,600 °F). Two feed chlorine contents were tested, 0 and 4 percent by weight. Polyvinyl chloride
(PVC) powder was added to chlorine-containing feed mixtures to provide the desired chlorine
content.
Sorbent behavior in retaining five trace metals in the feed was evaluated in the test
program. The five metals were arsenic, cadmium, chromium, lead, and nickel, two forms of
incorporating the metals into metals/sorbent mixtures for testing will be investigated Past trace
metal tests at the IRF (References 3 and 4) have used aqueous metal spike solutions containing
soluble nitrate salts of the metals, with the exception of arsenic which has been added as As^O,
This form was one of the two used in these tests. The second form of metal spiking used a
metal compound dispersion. The dispersions consisted of metal compound powders suspended
in a liquid carrier analogous to pigments dispersed in paint or ink. The metals dispersion was
a custom-designed proprietary mix prepared for this test program by Marsten-Bentley Inc of
Houston, Texas. J
Table 31 summarizes the .matrix of test variable combinations tested. Combinations of
the test variables resulted in a 48-test matrix. Test condition 36 in Table 31 was performed in
triplicate giving a total of 50 tests.
The composition of the metal spiking solution was as given in Table 32. The appropriate
quantity of the spiking solution was combined with the solid sorbent and PVC (if added) to
result in solid charge metal concentrations approximating those noted in the rightmost column
of Table 32.
The metals dispersion used as the second form of metal spiking, and tested with the
silica and attapulgite clay only, consisted of finely ground (particle size typically between 0.1 and
5 nm) metal compounds in a matrix of fuel oil and vegetable oils. The metal compounds used
to prepare the dispersions had to be friable, so they could be ground to fine powders and
sparingly soluble in water and oil. The compounds chosen by the vendor to make a stable
dispersion were cadmium, chromium, and lead oxides, arsenic sulfide, and nickel carbonate.
Table 33 gives the metal and metal compound concentrations in the dispersion prepared for the
tests. The appropriate quantity of metal dispersion was combined with the solid charge to result
73
-------
TABLE 31. TEST MATRIX
Test Sorbent
1 Crystalline silica (quartz)
2
3
4
5
6
7
8
9
10
11
12
13 Attapulgite clay
14
15
16
17
18
19
20
21
22
23
24
Feed chlorine,
Metal form %
Aqueous nitrates 0
0
0
4
4
4
Metal dispersions 0
0
0
4
4
4
Aqueous nitrates 0
0
0
4
4
4
Metal dispersions 0
0
0
4
4
4
Solids bed
temperature,
°C
540
700
870
540
700
870
540
700
870
540
700
870
540
700
870
540
700
870
540
700
870
540
700
870
(continued)
74
-------
TABLE 31. (continued)
Test Sorbent Metal form
25 Diatomaceous earth Aqueous nitrates
26
27
28
29
30
31 Kaolinite Aqueous nitrates
32
33
34
35
36
37 Alumina Aqueous nitrates
38
39
40
41 ' '
42
43 Bauxite Aqueous nitrates
44
45
46
47
48
Feed chlorine,
%
0
0
0
4
4
4
0
0
0
4
4
4
0
0
0
4
4
4
0
0
o
4
4
4
Solids bed temperature,
°C
540
700
870
540 .
700
870
540
700
870
540
700
870
540
700
870
540
700
870
540
700
870
540
700
75
-------
TABLE 32. METAL SPIKE SOLUTION CONCENTRATIONS
Metal
Arsenic
Cadmium
Chromium
Lead
Nickel
Metal
concentration,
g/L
7.75
1.55
4.65
7.75
4.65
Spike solution
Compound
As2O3
Cd(N03)2-4H20
Cr(N03)3-9H2O
Pb(N03)2
Ni(N03)2-6H20
Compound
concentration3,
g/L
10.2
4.25
35.8
12.4
23.0
Approximate
resulting feed
metal concentration,
mg/kg
250
50
150
250
150
Sufficient HNO3 will be added to maintain lead arsenate compounds in solution.
TABLE 33. TEST PROGRAM METAL DISPERSION CONCENTRATIONS
Metal
concentration,
Metal g/kg
Arsenic
Cadmium
Chromium
Lead
Nickel
Total
7.73
1.49
9.31
7.80
4.50
Dispersion
Compound
As2S3
CdO
Cr2O3
PbO
NiC03
Compound :
concentration,
g/kg
12.7
1.7
13.6
8.4
9.0
45.4
Approximate
resulting feed metal
concentration,
mg/kg
250
50
300
250
140
76
-------
in a mixture with total metal concentrations approximating those noted in the rightmost column
of Table 33.
For each of the tests, the TTU was allowed to reach steady state at the desired
temperature condition before feeding the test tray for the test. The feed tray was fitted with two
thermocouples to measure bed temperatures near the top and the bottom of the bed. The feed
tray was fed to the TTU to start the test, then removed when the feed material had been held
at the target temperature for 20 minutes. To be considered at target temperature, the average
of the top and bottom thermocouple readings was required to be within 5 percent of the target
bed temperature. Figure 6 shows the bed temperature heat-up profile for a typical test run.
Four sample matrices were collected or prepared for the analytical measurements-
unspiked sorbent, TTU feed, TTU residual discharge, and TCLP leachates of TTU feed and
residual discharges. These samples were analyzed for the test trace metals.
63 TEST RESULTS
The primary measures of sorbent performance in retaining metals in the discharge
residue, and in retaining discharged metals in the solid phase when subjected to TCLP
extraction, are the fraction of metal in the TTU feed remaining in the TTU discharge after a
test, and the fraction of metal leached from the TTU discharge in the TCLP. Table 34
Tray: 18.5 cm L X 8.5 cm W X 4 cm D
Bed Temperature TC
"¥
J
(a)
800
O
o
-------
TABLE 34. TRACE METAL ASH FRACTIONS
Bed
Feed chlorine Fraction of metal fed measured in ash, %
temperature, concentration,
Test
1
2
3
4
5
6
13
14
15
16
17
18
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
Sorbent type
Silica
Silica
Silica
Silica
Silica
Silica
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Kaolin
Kaolin
Kaolin
Kaolin
Kaolin
Kaolin
Alumina
Alumina
Alumina
Alumina
Alumina
Alumina
Bauxite
Bauxite
Bauxite
Bauxite
Bauxite
Bauxite
°C
537
700
865
537
696
860
536
717
868
539
697
866
538
692
863
539
703
868
529
689
860
533
695
866
543
684
858
539
693
860
539
689
864
540
693
856
%
0
0
0
4
4
4
0
0
0
4
4
4
0
0
0
4
4
4
0
0
0
4
4
4
0
0
0
4
4
4
0
0
0
4
4
4
Arsenic
82.2
97.1
89.0
82.9
59.0
563
192.6
234.5
169.4
125.2
164.9
1953
110.6
96.1
111.4
93.4
73.4
77.7
100.2
135.2
98.1
97.9
114.2
97.0
116.7
134.7
123.4
81.9
74.1
70.5
96.1
99.1
96.5
70.7
80.8
64.0
Cadmium
933
89.6
90.9
139.5
78.2
29.2
122.2
164.0
99.4
137.4
83.7
14.1
95,6
87.5
99.2
723
46.0
59.1
141.9
181.9
174.1
235.3
134.5
170.0
102.6
120.9
108.7
61.4
35.7
153
155.0
112.4
161.5
64.8
46.1
32.1
Chromium
88.2
82.1
85.9
94.6
95.1
83.7
93.8
149.3
89.2
1003
94.1
111.0
89.7
81.0
87.5
88.3
78.1
95.1
84.5
105.1
92.9
115.2
78.6
75.1
109.7
122.5
104.0
89.4
86.6
86.5
97.0
76.9
913
93.2
89.5
88.3
Lead
76.4
92.8
86.5
44.1
72.0
47.5
70.1
78.3
64.7
117.2
763
69.2
84.5
71.4
78.8
67.3
473
63.6
139.8
1803
143.5
143.2
99.9
123.4
89.3
1173
92.0
62.2
57.2
34.8
76.8
25.4
89.4
50.6
54.4
32.8
Nickel
86.6
88.6
1033
93.5
101.2
117.0
124.7
156.5
1233
95.0
127.0
236.6
87.3
833
90.6
93.6
82.7
115.8
76.7
109.6
102.5
90.5
116.8
114.6
92.8
105.4
105.7
60.8
73.7
61.2
84.8
47.7
90.5
68.8
91.1
89.1
78
-------
summarizes the measured fractions of feed metal retained in the discharge for all tests. Table 35
summarizes the measured fractional teachabilities of the metals from the feed and discharge
samples when subjected to the TCLP. To be considered a good sorbent, retained metal fractions
would be close to 100 percent, and fractional teachabilities would be small, near 0.
Analysis of the data in Table 34 shows that there was not a substantial difference among
the sorbents tested with respect to the volatility of chromium, lead, and nickel The term
volatility is used to indicate loss of the metal from the solid bed; high retention is low volatility
and vice versa. With no feed chlorine present, there was also no substantial difference among
the sorbents with respect to the volatility of arsenic and cadmium. With chlorine present in the
waste feed, arsenic was less volatile from the attapulgite clay and cadmium was less volatile from
kaolin, compared to the other sorbents.
The data in Table 35 show that in nearly every case, metal fractional teachabilities from
the treated samples were less than those from corresponding feed samples. However there were
differences in the measured fractional teachabilities of the metals from metal to metal as well
as variations with test conditions. With no chlorine in the feed, all of the sorbents'showed
comparable fractional teachabilities for cadmium and lead. Similarly, fractional nickel
teachabilities did not vary significantly among the sorbents for tests with chlorine in the feed
With no chlorine present in the feed, alumina, attapulgite clay, bauxite, and kaolin were better
at retaining nickel. Attapulgite clay, bauxite, kaolin and alumina were better for retaining arsenic
with and without feed chlorine present. With feed chlorine present, attapulgite clay kaolin and
diatomaceous earth were better than the other sorbents in retaining cadmium For lead
retention with chlorine in the feed, attapulgite clay, diatomaceous earth, and kaolin were better
than the other sorbents. With the exception of attapulgite clay, all of the sorbents showed
similar chromium factional teachabilities. Notably, chromium was very easily leached from the
thermally treated attapulgite clay samples.
6.4
CONCLUSIONS
Conclusions from the tests with regard to sorbent retention of the metals are
summarized on a metal-by-metal basis as follows:
ar
• Arsenic volatility in the absence of chlorine in the feed was low, and all six
sorbents tested appear to have performed equally well in preventing arsenic
vaporization. Attapulgite clay and kaolin were the most successful in limiting
arsenic vaporization when chlorine was present in the feed.
• Cadmium volatility in the absence of feed chlorine was low with all six sorbents
In the presence of chlorine, kaolin appears to be the most effective in limiting
cadmium volatility.
• Chromium volatility was low with all six sorbents, both with and without feed
chlorine.
• Lead volatility was low with all six sorbents in the absence of feed chlorine With
feed chlorine, lead was significantly more volatile at higher bed temperatures for
all of the sorbents.
79
-------
TABLE 35. TCLP FRACTIONAL LEACHABILITIES
Bed Feed chlorine
Fraction teachable by TCLP, %
temperature, concentration,
Test
Feed
1
2
3
Feed
4
5
6
Feed
13
14
15
Feed
16
17
18
Feed
25
26
27
Feed
28
29
30
Feed
31
32
33
Feed
34
35
^6
Sorbent type
Silica
Silica
Silica
Silica
Silica
Silica
Silica
Silica
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Attapulgite clay
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Diatomaceous earth
Kaolin
Kaolin
Kaolin
Kaolin
Kaolin
Kaolin
Kaolin
Kaolin
°C
20
537
700
865
20
537
696
860
20
536
717
868
20
539
697
866
20
538
692
863
20
539
703
868
20
529
689
860
20
533
695
866
%
0
0
0
0
4
4
4
4
0
0
0
0
4
4
4
4
0
0
0
0
4
4
4
4
0
0
0
0
4
4
4
4
Arsenic
63.0
64.8
36.3
693
68.7
4.1
52.4
59.8
69.8
6.1
10.2
8.8
143.1
8.8
5.6
15.2
84.1
45.9
54.3
34.1
74.1
45.8
44.0
46.5
80.0
4.3
7.4
6.0
70.4
8.5
103
5.2
Cadmium
92.1
46.0
30.8
22.8
198.8
38.9
27.4
28.0
74.6
10.2
2.5
3.7
147.7
22.7
21.7
53
86.7
19.5
11.8
1.8
90.4
10.1
2.3
0.8
151.8
6.7
1.2
0.7
181.0
16.3
2.0
0.8
Chromium
65.6
50.5
10.4
2.0
65.6
7.9
15.4
9.2
23
70.1
72.9
104.3
6.1
48.0
52.8
3.9
48.8
32.0
17.8
03
51.4
16.1
7.6
0.6
25.0
4.0
17.8
13
23.5
5.0
21.8
2.2
Lead
62.1
4.1
6.5
16.7
68.9
28.0
12.4
16.9
5.9
4.8
4.3
4.6
33.6
6.2
8.5
9.4
77.8
3.3
4.1
1.2
81.4
4.1
1.8
1.5
189.4
15.5
8.5
1.7
158.2
1.9
2.1
2.2
Nickel
79.4
29.6
11.3
3.0
83.1
9.8
3.1
1.2
30.7
83
4.5
1.6
58.2
7.2
8.5
0.7
58.9
213
12.7
0.7
61.4
6.6
0.9
1.0
74.3
5.0
1.7
0.9
78.9
3.6
1.6
3.5
(continued)
80
-------
TABLE 35.
Test
Feed
37
38
39
Feed
40
41
42
Feed
43
44
45
Feed
46
47
48
Sorbent type
Alumina
Alumina
Alumina
Alumina
Alumina
Alumina
Alumina
Alumina
Bauxite
Bauxite
Bauxite
Bauxite
Bauxite
Bauxite
Bauxite
Bauxite
Bed
temperature,
°C
20
543
684
858
20
539
693
860
20
539
689
864
20
540
693
856
(continued)
Feed chlorine
concentratio
%
0
0
0
0
4
4
4
4
0
0
0
0
4
4
4
4
«,
Arsenic
77.8
4.0
4.2
14.0
48.0
3.1
11.7
23.4
5.2
3.5
2.3
24.2
4.9
20.4
0.8
31.0
Fraction teachable by TCLP, %
Cadmium
104.8
33.6
21.2
20.8
62.0
71.8
55.2
3.2
135.5
35.3
8.4
5.1
89.7
32.3
5.6
3.7
Chromium
67.5
31.3
29.3
18.0
35.9
3.6
8.4
9.0
3.2-
25.6
5.0
0.6
2.8
0.3
0.5
0.4
Lead
97.1
43
1.8
6.0
81.5
31.6
28.4
183
29.5
4.2
231.4
2.2
33.7
18.6
16.4
3.2
Nickel
96.5
7.7
3.7
0.8
61.6
12.5
1.8
0.7
78.6
13.0
83
0.9
87.0
3.1
0.7
• Nickel volatility was low with all six sorbents under all test conditions except for
one. Nickel appeared to be slightly more volatile from alumina in the presence
of feed chlorine.
Conclusions from the tests with regard to metals leachability in the TCLP are
summarized on a metal-by-metal basis as follows: ,
• The most effective sorbents for limiting arsenic TCLP leachability were kaolin,
attapulgite clay, alumina, and bauxite, both with and without chlorine in the feed!
Based on performance in both limiting arsenic vaporization and reducing its TCLP
leachability, kaolin and attapulgite clay appear to be the most effective sorbents
for arsenic.
« Reduced cadmium TCLP leachability was best with kaolin, diatomaceous earth,
bauxite, and attapulgite clay, both with and without feed chlorine. Based on
performance in both limiting cadmium vaporization and reducing its TCLP
leachability, kaolin appears to be the most effective sorbent for cadmium.
• The leachability of chromium was not significant, except from attapulgite clay.
Chromium was only slightly leachable from the attapulgite clay feed; however, its
leachability increased with increased treatment temperature. Kaolin appears to
81
-------
be slightly more effective than the other sorbents in limiting TCLP teachability in
the case of no feed chlorine and treatment temperature of 530 °C (985 °F).
• In the absence of feed chlorine, all sorbents performed equally well in limiting the
TCLP leachability of lead. In the presence of feed chlorine, kaolin, diatomaceous
earth, and attapulgite clay appear to be more effective in limiting lead leachability.
• With feed chlorine, all sorbents were equally effective in limiting the leachability
of nickel.
Overall, all six sorbents appear to be potentially effective in the retention and
immobilization of the five metals tested under certain combinations of treatment temperature
and feed chlorine concentration. The specific conditions of best effectiveness varied for each
sorbent. For the specific conditions tested, kaolin and attapulgite clay, in that order, appear to
be the most effective universal sorbents.
Test results will be documented in a test report to be completed in early FY95.
82
-------
SECTION 7
TREATABILITY TESTING OF THE M. W. MANUFACTURING
SUPERFUND SITE CONTAMINATED SOIL IN THE TTU
The pilot-scale incineration testing of fluff waste and contaminated soil from the M W
Manufacturing Superfund Site was performed in the IRF RKS in November and December 1993
as discussed in Section 3. In 1992, the capabilities of the IRF were expanded by the addition of
the bench-scale TTU described in Section 6.1. One role of the TTU is to provide economical
screening data to assist in planning for tests in the RKS. Therefore, to evaluate the role of the
TTU as a screening tool for the RKS, tests were conducted in the TTU with the M. W.
Manufacturing site soil under conditions that were representative of the tests with the soil in with
the RKS. The objective of these tests was to develop data to assess whether conclusions
regarding treatment residue composition and characteristics obtained via bench-scale TTU
testing would be substantially the same as those obtained in pilot-scale RKS tests.
A summary of the features of the RKS kiln and the TTU treatment chamber are
presented in Table 36. One key difference between the TTU and RKS is the mode of solid
progression (or lack of it) in the respective treatment chambers. In the RKS the solid undergoes
a tumbling action resulting in the agitation of the solid bed. Entrapment of the solid particles
into the flue gas occurs as a result of the agitation. Entrainment losses of the solid in the RKS
typically range from 10 to 50 percent of the total ash content of the material fed. In the TTU,
the solid bed itself is always stationary and entrainment losses are minimal. Another important
difference between the TTU and the RKS is in the geometry and size of the respective treatment
chambers. As a result of the geometric dissimilarity, the treatment chamber exit gas
temperature, a key incineration operating parameter, is not suitable for explicit comparison
between the two systems. That leaves the solids bed temperature as the key parameter that can
be compared between the two systems. It is reasonable to assume that the temperature of the
solids bed during treatment is critical in affecting changes (such as organic decontamination and
metal vaporization or retention) in the solid. Therefore, the solids bed temperature was
determined to be the critical operational measurement in these TTU tests.
7.1
TEST PROGRAM
The test conditions under which the RKS test program was conducted were outlined in
Section 3. As discussed, two tests were performed with the M. W. Manufacturing site soil under
similar test conditions. The soil was batch fed in cardboard containers to the kiln Each
container-held nominally 4.5 kg (10 Ib) of sort, and a charge rate of one container every
5 minutes was followed, resulting in a feedrate of 55 kg/hr (120 Ib/hr). The soil residence time
in the kiln was approximately 60 minutes. The soil bed temperature was measured along the
length of the kiln at locations of 0.61, 1.1, 1.5, and 2.0 m (2.0, 3.5, 5.0, and 6.5 ft) from the feed
83
-------
TABLE 36. COMPARISON OF TREATMENT CHAMBER CHARACTERISTICS: TTU
AND ROTARY KILN
Features
TTU
Rotary kiln
Treatment chamber
geometry
Treatment chamber
volume
Burner type
Mode of treatment and
solid movement
Typical solid entrainment
level to flue gas
Treatment chamber exit
gas temperature
Typical residence time
characteristics
Charge size
Cubical
0.82 m3 (29 ft3)
Direct fired natural gas burner,
350 kW (1.2 MMBtu/hr)
Semi-continuous/batch process
Solid fed in quartz trays
Solid progression by a
conveyor belt system
1 to 5 percent
Maximum 2,000 °F
Variable
Typical charge size is 0.1 to
0.5 kg/tray (0.2 to 1 Ib/tray)
For the M. W. test program
soil, tray charge weight was
0.23 kg (0.51 Ib)
Cylindrical (Frusto-conical)
1.90 m3 (67.2 ft3)
Direct fired natural gas
burner, 590 kW
(2.0 MMBtu/hr)
Continuous process
Solid progression by kiln
rotation
10 to 50 percent
Typical maximum of 1,800 °F
0.75 to 1 hr at 0.2 rpm kiln
rotation speed, depending
on feedrate and feed type
Typically feedrates vary
from 30 to 230 kg/hr (65 to
5001b/hr). For the M. W.
test program, soil feedrate
was 55 kg/hr (120 lb/hr)
end. The kiln itself is 8.25 m (7.4 ft) long. Based on the soil residence time and the axial
temperature profile, the soil temperature with time profile along the kiln length can be
determined. This average temperature-time history of the soil bed in the RKS tests of the M. W.
Manufacturing site soil is summarized in Table 37.
For tests in the TTU, soil temperature-time profiles can be varied by changing treatment
chamber gas temperatures. Because solids bed temperatures are continuously measured in the
TTU, the full treatment temperature-time history is known.
Three tests under conditions giving the soil temperature-time profiles seen in the RKS
tests were performed in the TTU. Archived soil samples from the RKS test program were used
for these tests. Scoping tests were conducted with local topsoil to determine the burner firing
rates and temperature set-points for the TTU that would achieve the soil bed temperature-time
conditions given in Table 37.
84
-------
TABLE 37. APPROXIMATE BED TEMPERATURE HISTORY IN THE RKS TESTS
OF THE M. W. MANUFACTURING SITE SOIL
Kiln
section
I
n
m
IV
Distance from
feed end,
m(ft)
0.61 (2.0)
1.1 (3.5)
1.1 (5.0)
2.0 (6.5)
Approximate residence
time in section,
min
16
12
12
12
Total residence Bed temperature
time,
min
16
28
40
52
at this location,
°C (°F)
870 (1,600)
870 (1,600)
843 (1,550)
788 (1,450)
For each test, samples of the soil feed and treated soil were taken. These were analyzed
for copper and lead, and TCLP leachates of these samples were prepared and analyzed for
copper and lead.
12. TEST RESULTS
Figure 7 shows the soil bed temperature profiles for the three TTU tests performed.
The temperature profile data for the RKS tests from Table 37 are also shown in the figure. As
indicated, the RKS test data points fall right on the TTU test profiles.
A comparison of the test data obtained from the RKS and TTU tests of the M. W.
Manufacturing site soil is given in Table 38. The data in the table show that, for the RKS tests
performed in December 1993, the weight of kiln ash discharge collected was 52 percent of the
weight of soil fed to the kiln for one test, and 50 percent for the other. Corresponding treated
soil weights for the TTU tests were quite comparable, at 55, 61, and 59 percent of the soil feed
charge for TTU Tests 1, 2, and 3, respectively.
The data in Table 38 also show that the soil feed copper concentrations were slightly
lower for the TTU tests than the RKS tests. Treated soil ash residue copper concentrations for
the TTU tests were also lower then for the RKS tests, such that essentially all the copper fed to
the respective thermal treatment process was discharged in the ash residue.
For lead, the Table 38 data show that TTU test soil concentrations were comparable or
slightly higher than the RKS test soil concentrations. Treated soil concentrations were
comparable or slightly lower for the TTU tests compared to the RKS tests. Again, quite
comparable fractions of the lead fed for each test series are seen, at 46 and 65 percent for the
RKS tests, and 51 to 53 percent for the TTU tests.
Soil feed TCLP leachate concentrations of both copper and lead were substantially
higher, about a factor of 5 for both, for the soil feed samples from the TTU tests compared to
those from the RKS tests. Treated soil TCLP leachate copper concentrations were comparable
or lower for the TTU discharge compared to the RKS discharge. Lead TCLP leachate
concentrations in the treated soil were comparable between the two test series.
85
-------
900
20 40
Treatment Time, min
Figure 7. Average soil bed temperature history for the RKS and TTU test program.
TABLE 38. COMPARISON OF TEST DATA FROM THE RKS AND TTU TESTING OF
M. W. MANUFACTURING SITE SOIL
Parameter
Fraction of feed collected as treatment residue (ash), %
Coppcn
Soil feed concentration, mg/kg
Ash residue concentration, mg/kg
Fraction in ash residue, % of fed amount
Soil feed TCLP leachate concentration, mg/kg
Ash residue TCLP leachate concentration, mg/L
Lead:
Soil feed concentration, mg/kg
Ash residue concentration, mg/kg
Fraction in ash residue, % of fed amount
Soil feed TCLP leachate concentration, mg/kg
Ash residue TCLP leachate concentration, mg/L
RKS
Testl
12/1/93
52
14,100
46,000
115
21
0.25
3,140
4,140
46
0.67
<0.1
tests
Test 2
12/2/93
50
14,100
35,400
126
21
0.20
3,140
4,080
65
0.67
0.2
======
ITU tests
Testl
8/9/94
55
8,300
15,000
99
150
0.03
3,900
3,600
51
3.5
=====
Test 2
8/10/94
61
11,350
22,000
118
150
<0.02
4,100
3,500
52
3.5
<0.1
Test3
8/11/94
59
11,000
22,000
117
150
0.28
4,200
3,800
53
3.5
0.5
86
-------
7J CONCLUSIONS
Test program conclusions are summarized as follows:
o The M. W. Manufacturing site soil could be treated in the TTU at bed
temperature profiles that appeared to duplicate the soil bed temperature profiles
tested in the RKS test program.
• The fraction of treated soil ash residue recovered after treatment from both
combustors were in very good agreement. The average ash residue collected as
a fraction of the soil feed amount in the RKS test was 51 percent. In the TTU
tests, the average fraction of the ash residue as percent of the soil feed was
58 percent.
• The fractions of both copper and lead recovered in the ash residue from both test
units were quite comparable. Essentially all the copper fed to both units was
retained in the treated soa residue. Only about half the lead fed to both units was
retained in the treated soil residue.
• Ash residue TCLP leachate concentrations of both copper and lead from both test
units were quite comparable.
Test results suggest that the TTU well-simulates the RKS in terms of producing quite
comparable ash residue discharge composition and characteristics.
Test results were documented in the brief test report.
• S. Venkatesh and S. King, "Treatability Testing of the M. W, Manufacturing
Superfund Site Contaminated Soil in a Thermal Treatability Unit (TTU} " Draft
September 1994. • ''
87
-------
SECTION 8
BENCH-SCALE TREATABILITY TESTING OF CONTAMINATED MATERIALS
FROM THE SOUTHERN SHIPBUILDING SUPERFUND SITE
The Southern Shipbuilding Corporation (SSC) Superfund site in Slidell, Louisiana, is an
inactive barge/ship manufacturing and repair facility that conducted gas-freeing and barge
cleaning operations between 1917 and 1971. Wastes resulting from these operations were stored
in two primary surface containment pits (the north pit and the south pit) located less than
25 miles from Bayou Bonfouca, a deep water channel that feeds into the largest lake in
Louisiana, Lake Portchartrain. During operations, wastes were initially pumped into the north
pit directly from barges. To avoid overflowing this pit, lighter organics and rainwater were
periodically pumped to the south pit. The south pit was connected to a baffle system.
Wastewater was pumped through this system, which was designed to remove oily materials
before the waste was discharged to Bayou Bonfouca. The discharge to the bayou was regulated
under a National Pollutant Discharge Elimination System (NPDES) permit.
The SSC facility was operated by its current owner since 1957, which reportedly was
reorganized under Chapter 11 bankruptcy in May 1993. All site manufacturing and repair
operations ceased in August 1993 due to owner financial difficulties.
The contaminants of concern in all site materials are various organic constituents
classified as total petroleum hydrocarbons (TPH), target compound list (TCL) VOCs, and TCL
SVOCs. In addition, site materials contain varying levels of hazardous constituent trace metals.
Four candidate remedies for treating one or more site materials are under
consideration: incineration, bioremediation, solidification and stabilization, and soil washing.
A series of bench-scale treatability studies using these candidate remedies was planned to supply
the data to allow choosing the most applicable remedy for site materials. The Superfund START
within EPA's RREL (E. Opatken, E. Bates, RREL coordinators) was asked by Region VI (B.
Griswold, RPM) to administer these treatability studies. The incineration treatability study was
to be performed in the TTU at the IRF, described in Section 6.1.
The objectives of the incineration treatability test program are to:
• Determine the degree of organic contaminant decontamination achieved for
different combinations of incineration treatment temperature and treatment
residence time; degree of decontamination is measured by the decontamination
effectiveness, defined to be: 100 • (1 - (mass of contaminant in treated
waste)/(mass of contaminant in waste))
88
-------
• Determine whether the treatment residue from various combinations of treatment
temperature and treatment residence time are toxicity characteristic (TC)
hazardous wastes because of leachable trace metal content
Treatability data for two site materials are to be developed, with each site material tested at two
treatment temperature/treatment time combinations.
8.1 TEST PROGRAM
The test plan specified that two SSC site materials would be tested: composites of the
contents of each of the south pit and the north pit at the site. Each material would be tested
at two TTU operating conditions as follows:
• Charge chamber gas temperature (i.e., incineration treatment temperature) of
870 °C (1,600 PF) with treatment residence time of 20 minutes
• Charge chamber gas temperature of 980°C (1,800°F) with treatment residence
time of 60 minutes
One 5-gal (19-L) container of each site material was received at the IRF for the test
program. In preparation for the tests, each container's contents were transferred to a 25-gal
(95-L) galvanized container and mixed to produce a homogenous mixture. For the tests, a 1-lb
(0.45 kg) quantity of the mixed material will be placed into each of seven quartz trays for feeding
into the TTU for each test.
For each test, the TTU will be allowed to reach steady state at the desired temperatures
condition. The seven feed trays will then be sequentially fed to the TTU, each remaining in the
charge chamber for the specified residence time. After completion of each test, the contents of
the seven trays will be weighed, mixed with a small shovel in a 2.5-gal (9.5-L) container, then
analyzed. For each test, the measurements listed in Table 39 will be taken.
8.2
CURRENT STATUS
The QAPP for the test program was prepared in July 1994, revised in September, and
approved in early October. The treatability tests were completed in mid-October. Sample
analyses, data evaluation, and test reporting efforts will be completed in early FY95.
89
-------
TABLE 39. PLANNED TEST PROGRAM MEASUREMENTS
Parameter
Process measurements
TTU gas temperatures
Analytical measurements
Feed material concentrations:
Moisture
Ash
Heating value
Oil and grease
Total organic carbon (TOC)
TPH
VOCs
SVOCs
Trace metals
Treatment residue concentrations:
TOC
TPH
VOCs
SVOCs
Trace metals
Feed material and treatment residue TCLP leachate concentrations
Trace metals
90
-------
SECTION 9
DIRECT-FIRED THERMAL DESORPTION TREATABILITY
STUDY ON ROCKY MOUNTAIN ARSENAL SOILS
During FY94, Argonne National Laboratory (ANL) (M. Gowdy, Project Manager) in
support of remediation efforts being planned at the Rocky Mountain Arsenal (RMA) (M
Bessmer, coordinator) in Denver, Colorado, requested an IRF proposal to perform a pilot-scale
treatability study of the performance of direct-fired thermal desorption (DFTD) in
decontaminating pesticide-contaminated RMA soils. The treatability study, to be performed as
a third-party test at the facility, will be designed to evaluate the overall effectiveness of the
DFTD technology on contaminated RMA soils and to provide data upon which future conceptual
design assumptions and cost estimates for a full-scale system can be made. If proven to be a
feasible and effective technology, DFTD will provide RMA with a means of remediating selected
areas onsite, and the test program will provide the Army with valuable information about a
technology that may be used at other contaminated facilities.
9.1
BACKGROUND
Past pesticide manufacturing activities on the grounds of RMA have resulted in
substantial quantities of soil contaminated with pesticide components, other organic constituents,
and inorganic contaminants. Soils from three areas at the site are considered candidates for
remediation using low temperature thermal desorption treatment. Several reasons suggest that
direct-fired thermal desorption may offer improved performance over other approaches. The
overall purpose of the planned study is to develop the data to evaluate this presumption.
The three areas of RMA from which soil will be collected for testing are termed
Basin F, South Plants Central Processing, and Basin A. Approximated 13,600 kg (30,000 Ib) of
Basin F soil contained in 52 55-gal (208-L) polyethylene drums, 11,400 kg (25,000 Ib) of Basin A
soil contained in 42 drums, and 12,300 kg (27,000 Ib) of South Plants soil contained in 45 drums
were excavated at the site. These were shipped to the IRF for eventual during July through
September 1994. The drummed Basin F soil consists of a dark brown sandy clay with a
14 percent moisture content, the drummed Basin A soil is a light brown sandy clay soil with an
average moisture content of 30 percent and the drummed South Plants soil consists of a brown
sandy clay with 15 percent moisture.
All three soils are contaminated with several pesticide compounds, other SVOCs, VOCs,
and several hazardous constituent trace metals.
91
-------
92,
PLANNED TEST PROGRAM
As noted above, the overall purpose of the treatability study to be performed is to
evaluate the effectiveness of DFTD treatment of RMA site soils in achieving effective soil
decontamination. Data on the effect of DFTD treatment process operation on process
performance is also desired. In addition, data on the fate of arsenic, cadmium, lead, mercury
and other contaminant metals during DFTD treatment, and on the effectiveness of a
conventional air pollution control system (APCS) in reducing offgas emission stream pollutant
concentrations to acceptable levels are desired.
Specific test program objectives are to:
• Measure the effectiveness of DFTD treatment in decontaminating RMA soils of
their organic contaminants, and determine the effect of treatment temperature,
treatment residence time, and treatment process feedrate on decontamination
effectiveness
• Measure the distribution of the contaminant trace metals in the soils among the
treatment process discharge streams, including treated soil, APCS discharges, and
final system offgas discharges, and determine the effect of treatment temperature,
residence time, and process feedrate on these distributions
• Determine whether DFTD treatment byproduct compounds such as
PCDDs/PCDFs, other hazardous constituent SVOCs, or hazardous constituent
VOCs are formed and at what concentrations in treatment process discharges,
APCS discharges, or process offgas, and determine whether treatment
temperature, residence time, or process feedrate affect the level of these
byproduct constituents in process discharges
• Determine whether DFTD treatment process discharges, including APCS
discharges, would be TC hazardous wastes
The test program will consist of 12 tests in the RKS at the IRF. The RKS will be
configured as shown in Figure 1. The soil feed system installed for the planned tests will be a
solids screw feeder with a 4-inch (10.2-cm) variable-pitch, full-flight screw, and feed chute
agitators.
In the planned test program, four tests will be performed with each of the three RMA
soils received for testing. DFTD process operating parameters to be varied over the four tests
with each soil are treatment temperature, as measured by the kiln exit solids bed temperature;
treatment time, as measured by the bulk solids residence time in the kiln; and soil feedrate.
Another thermal desorption process operating parameter, kiln fill volume, will not be varied in
this test program, but will be held constant at about 6 percent. The tentative matrix of test
conditions to be tested for each soil is given in Table 40.
Test soil feedrate will be varied by varying screw feeder rotation rate. Kiln solids exit
temperature will be measured (as will solids bed temperature at other kiln axial locations) and
92
-------
TABLE 40. TENTATIVE TEST MATRIX CONDITIONS FOR EACH SOIL,
Test condition
A: Baseline
B: High temperature
C: Low residence time/high feedrate
D: Low temperature
Solids bed exit
Soil feedrate, Solids residence temperature,
kg/hr (Ib/hr) time, min °C (°F)
230 (500)
230(500)
340 (750)
230(500)
35
35
25
35
357(675)
440 (825)
357(675)
274(525)
controlled by varying the firing rate of the natural-gas-fired kiln main burner. Burner firing rate,
in turn, determines kiln combustion gas temperatures. "
For all tests, the RKS afterburner will be operated at an exit gas temperature of 1,090°C
(2,000 °F), with combustion air addition to maintain afterburner exit gas O2 at nominally 8 to
10 percent. The afterburner will serve to destroy organic contaminants desorbed in the kiln by
the DFTD process. The venturi/packed column and baghouse APCS units will be operated at
their normal, design settings. The scrubber system will be operated at as close to total
recirculation (zero to minimum blowdown) as possible.
93 SAMPLING AND ANALYSIS PROCEDURES
The RKS sampling locations and the scope of the sampling effort are shown in Figure 8.
For all tests, the planned sampling matrix will entail:
• Obtaining three grab samples of the soil feed to the kiln
• Obtaining three grab samples of the treated soil discharge
• Obtaining a composite sample of the scrubber system liquor
• Obtaining a composite sample of the baghouse flyash
• Continuously measuring O2, CO, and total unburned hydrocarbon (TUHC)
concentrations in the kiln exit flue gas; O2, CO2, and NOX concentrations in the
afterburner exit flue gas; O2, CO2, and NOX in the baghouse exit flue gas; and O2
and CO concentrations in the stack gas
In addition, for nine of the tests the RKS combustion gas will be sampled for:
• SVOCs and pesticides at the afterburner exit and baghouse exit using
Method 0010
93
-------
IB-/KQS3
2 1
L U. J
£|jj
t
||
j >
•••^•i
BAQHOUSE
i ,
FLUE GAS
REHEAT
l
PACKED
COLUMN
SCRUBBER
—> a
— r-
— — «o
-i
f -.
VENTURI
SCRUBBER
-1
t
W W
LL ^
(^
AFTER-
BURNER
' '
i
t-
— — 0
-— eg
Continuous monitors Flue gas
Method 0010, EPA multiple Method 0050,
SoU Treated Scrubber Baghouse Heated SVOCs and Method 0030, Method 23, metals train, test particnlate
Sampling point feed soil liquor ash 02 CO CO2 NOX TUHC pesticides VOCs PCDD/PCDF trace metals and HC1
1. Soil feed X
2. Treated soil discharge X
3. Kiln exit flue gas XXX X
4. Afterburner exit flue gas XXX XXX
5. Scrubber liquor X
6. Baghouse hopper X
7. Baghouse exit flue gas XXX X X X X
8. Stack gas XX X
Figure 8. Test sampling locations.
94
-------
• VOCs at the afterburner exit using Method 0030, the volatile organic sampling
train (VOST) j . . ..*
• PCDDs/PCDFs at the afterburner exit and baghouse exit using Method 23
9 Trace metals and mercury at the baghouse exit using the EPA multiple metals
sampling train
• Particulate and HC1 at the kiln exit, the baghouse exit, and the stack using EPA
Method 0050 ;
The three soil feed samples will be collected at equally spaced time intervals over each
test's duration. The first soil feed sample for a test will be taken after a time interval equal to
two kiln solids residence times has elapsed since the initiation of soil feed to the kiln for the
tests. Each successive soil feed sample will be taken at equally spaced time intervals, expected
to be 1 hour. Three treated soil discharge samples will also be collected, one to correspond to
each of the three feed samples collected. These samples will be collected after one kiln solids
residence time has passed since the soil feed collection event.
As noted above, for all tests runs, the RKS scrubber system will be operated at as close
to total recirculation (zero blowdown) as possible. After each test run, the scrubber system will
be drained to a collection tank. A composite scrubber liquor sample will be collected from a tap
in the recirculation loop just prior to the system's draining. The scrubber liquor filtrate and
suspended solids are planned to be separately analyzed because, in a typical field application of
DFTD treatment of contaminated soil, the scrubber system scrubber liquor discharge would most
likely be filtered to give two separate discharge streams for treatment and disposal, a solids filter
cake and a scrubber liquor filtrate discharge. Accordingly, after collection, the scrubber liquor
sample will be filtered to remove the suspended scrubber liquor solids.
Test program samples will be analyzed for matrix-specific combinations of SVOCs and
pesticides, VOCs, PCDDs/PCDFs, trace metals and mercury, total organic halides, soluble
inorganic halides, moisture and ash content, and oil and grease as follows: ;
« The three soil feed and three treated soil discharge samples for each test will be
analyzed for SVOCs and pesticides, and VOCs
• A test composite soil feed, a test composite treated soil, the scrubber liquor
filtrate, scrubber liquor solids, and baghouse ash for each test will be 'analyzed for
all test program analytes noted above ;
• TCLP leachates of the test composite soil feed, test composite treated soil, and
baghouse ash for each test will be analyzed for trace metals and mercury
• The flue gas sampling trains taken for flue gas sampling tests will be analyzed for
the sampled analyte set
95
-------
9.4
CURRENT STATUS
The draft QAPP for the test program was in preparation and all soil feed material had
been received at the IRF at the close of FY94. RKS modifications will be initiated in late
October, after the completion of the testing phase of the SITE demonstration of the Sonotech
pulse combustion system discussed in Section 5. Testing is scheduled to be completed during the
first half of FY95.
96
-------
SECTION 10
EXTERNAL COMMUNICATIONS
During FY94, five research reports were prepared or finalized and five technical papers
were presented or published. These are listed in Table 41. This level of external communication
and technology transfer testifies to the high level of research being supported at the IRF.
Table 42 lists some of the visitors to the IRF during FY94. The length of the list attests
to the visibility of the work being performed at the IRF to the incineration research community.
Of particular interest are the two international delegations, one from the Ukrainian Republic
and the other from the Russian Federation, that visited the facility in December 1993 and
January 1994. These visits, co-hosted by DNA, were specifically to witness the liquid missile
propellant incineration tests.
97
-------
TABLE 41. IRF PROGRAM REPORTS AND PRESENTATIONS IN FY94
Reports
• Waterland, L. R., "Operations and Research at the U.S. EPA Incineration Research
Facility, Annual Report for FY93," Draft, November 1993, Revised, February 1994,
published as EPA/600/R-94/091, June 1994.
• Venkatesh, S., L. R. Waterland, and C. G. Goldman, 'Test Incineration of Ballistic
Missile Propellant: Phase I Testing," Draft, April 1994, Revised, October 1994.
• Lee, J. W., W. W. Vestal, S. Venkatesh, and C. G. Goldman, "Pilot-Scale Incineration
Tests of Fluff Waste and Contaminated Soil from the M. W. Manufacturing
Superfund Site," Draft, May 1994.
• Venkatesh, S., and S. King, "Treatability Testing of the M. W. Manufacturing
Superfund Site Contaminated Soil in a Thermal Treatability Unit (TTU)," Draft,
September 1994.
• Lee, J. W., D. J. Fournier, Jr., C. King, S. Venkatesh, and C. G. Goldman, "Evaluation
of Rotary Kiln Operation at Low to Moderate Temperature Conditions," Draft,
September 1994. .
Papers and Presentations
• Carroll, G. J., and S. Venkatesh, "The Effectiveness of Sorbents for Solid-Bed Metal
Capture in an Incinerator: Screening Tests at the Incineration Research Facility,"
presented at the Twentieth Annual RREL Research Symposium, Cincinnati, Ohio,
March 1994.
• Manning, J. A., and R. C. Thurnau, "Evaluation of Rotary Kiln Incineration as a
Thermal Desorber," presented at the Twentieth Annual RREL Research Symposium,
Cincinnati, Ohio, March 1994.
• Waterland, L. R., and S. Venkatesh, "Dioxin Emission Measurements from a Rotary
Kiln Incinerator," presented at the 1994 Incineration Conference, Houston, Texas,
May 1994.
• Venkatesh, S., L. R. Waterland, and J. W. Lee, "Trace Metals Partitioning in a Rotary
Kiln Incinerator," presented at the 1994 Incineration Conference, Houston, Texas,
May 1994.
• Waterland, L. R., and S. Venkatesh, "Measured Dioxin Emissions from a Pilot-Scale
Rotary Kiln Incinerator," paper 94-WA85.04, presented at the 87th Annual Meeting of
the Air and Waste Management Association, Cincinnati, Ohio, June 1994.
98
-------
TABLE 42. VISITORS TO THE IRF
Person
D. Casteel
M. Richards
B. Khona
M. Gowdy
P. Farber
R. Odom
A. George
S. Duff
T. Backhaus
D. Oberacker
G.Carroll
F. Culclague
G. Golden
D. Oberacker
R. Schultz
C. Klyne
J. Anthony
R. Rozsak
U.Kryhko
S. Fushnitskaya
C. Sokol
M. Ovhurenko
Y. Bogushevsky
A. Modano
A. Walsh
D. Oberacker
S. Schulberg
B. Blackburn
D. Oberacker
W. Absher
R. Schultz
C. Klyne
N. Shumkov
M. Stepanov
A. Golovatsky
L. Shalnova
V. Potrokhov
U. Gorlov
A. Kusov
V. Mayev
R. Oliver
A. Walsh
J. Anthony
L. Tipton
Affiliation
Pine Bluff Arsenal
EPA/RREL
EPA Region HI
ANL
ANL
Marsten-Bentley
Marsten-Bentley
Olin
Olin
EPA/RREL
EPA/RREL
Pine Bluff Arsenal Fire Department
EPA/RREL
DNA
Office of Secretary of Defense
SAIC/CVR
DNA
Committee of the Defense Industry,
Republic of Ukraine
On Site Inspection Agency
On Site Inspection Agency
SAIC
EPA/RREL
S-Cubed
S-Cubed
EPA/RREL
DNA
DNA
Office of the Secretary of Defense
Committee of the Defense Industry
IDA
SAIC
SAIC/CVR
On Site Inspection Agency
Date
10/1/93
10/25-29/93
11/2-4/93
11/4/93
11/30/93
11/30/93
11/30-12/2/93
12/9/93
12/14-17/93
12/17/93
1/27-29/94
1/31-2/1/94
Purpose of visit
Analytical consulting
Witness M. W. Manufacturing
site material tests
Facility tour, discuss RMA test
possibilities
Discuss use of metal
suspensions in TTU tests
UDMH safety training
Propellant incineration test
plan review
Project review
Facility familiarization tour
Review final propellant test
plans, witness initial UDMH
incineration
Witness UDMH incineration
Propellant test QA review
Witness, UDMH incineration
(continued)
99
-------
TABLE 42. (continued)
Person
D. Oberacker
S. Schulberg
G. Carroll
H. Wilson
J. Hopkins
D. Johnson
J. Patch
B. Mitchell
J. Shumate
J. Shunk
D. Rcstal
R. Thurnau
J. Wallace
M. Shekhter
B. Curlin
J. Schneider
M. Gowdy
C. Swanstrom
J. DuWaldt
K. Smith
M. Richards
J.Martin
Z. Plavnik
M. Shekhtcr
K. Partymiller
K. Enwright
D. Cordary
D.Frank
G. Connors
H. Schaeffer
V. Wolfe
M. Mueller
J. Robertson
R. Trosper
R. Chapman
J. Walsh
D. Twachtmann
M. Schneckenberger
C. Swanstrom
Affiliation
EPA/RREL
S-Cubed
EPA/RREL
EPA/SHEMD
EPA/SHEMD
Booz-Allen
Booz-AUen
Arthur D. Little
ADPC&E
ADPC&E
ADPC&E
EPA/RREL
S-Cubed
Sonotech
ANL
ANL
ANL
ANL
ANL
ANL
EPA/RREL
EPA/RREL
Sonotech
Sonotech
PRC
PRC
PRC
PRC
Atlanta Gas Light
Atlanta Gas Light
Atlanta Gas Light
Blue Circle Cement
Blue Circle Cement
F. S. Sperry
Firebridge
Georgia Tech
Law Environmental
Ecology & Environment
ANL
Date
2/23-24/94
3/1-2/94
3/2/94
3/8/94
4/20/94
5/2/94
5/11/94
5/31/94
6/7-9/94
6/9/94
6/10/94
6/18/94
Purpose of visit
Propellant incineration test QA
review
Environmental audit
RCRA Compliance Evaluation
Inspection
Propellant incineration test QA
review
Pulse combustion system
installation
RMA test health and safety
review
RMA test planning
RMA test health and safety
review
Sonotech SITE test visitors day
Inspect the Sonotech pulse
combustion system
Southern Shipbuilding test
planning
RMA test planning
(continued)
100
-------
TABLE 42. (continued)
Person
M. Richards
A. Leitzinger
K. Partymffler
S. Schulberg
B. Blackburn
C. Swanstrom
O. Cooper
G. Carroll
M. Gowdy
C. Swanstrom
M. Richards
K. Partymffler
Z. Plavnik
R. Thurnau
J. Bacon
G. Thomasson
C. Partridge
R. Thurnau
Z. Plavnik
D. Oberacker
K. Partymiller
M. Gowdy
C Swanstrom
Affiliation
EPA/RREL
EPA/RREL
PRC
S-Cubed
S-Cubed
ANL
ANL
EPA/RREL
ANL
ANL
EPA/RREL
PRC
Sonotech
EPA/RREL
Pine Bluff Arsenal
Pine Bluff Arsenal
NCTR
EPA/RREL
Sonotech
EPA/RREL
PRC
ANL
ANL
Date
6/28/94
8/4-5/94
;>
8/9-11/94
8/31-9/1/94
9/7/94
9/12/94
9/20/94
9/21-22/94
9/27/94
9/29/94
Purpose of visit
Sonotech SITE test QA review
RMA test planning
Project review
RMA test planning
Witness Sonotech test
Witness Sonotech test
Discuss possible joint test
programs
Witness Sonotech testing
Witness Sonotech testing
RMA test planning
101
-------
SECTION 11
PLANNED EFFORTS FOR FY95
Near-term project efforts in FY95 will focus on completing test program efforts initiated
or underway during FY94 through test report preparation and submittal. Specifically:
• The test report summarizing the results of the TTU tests to evaluate the
effectiveness of sorbents as additives for metal capture, discussed in Section 6, will
be completed
• The SITE demonstration tests of the Sonotech pulse combustion system, discussed
in Section 5, will be completed, and test program efforts carried through sample
analysis, data evaluation, and test reporting
• The bench-scale treatability tests with contaminated materials from the Southern
Shipbuilding Superfund site, discussed in Section 8, will be completed, and test
program efforts carried through sample analysis, data evaluation, and test
reporting
The first major test program to be initiated during FY95 will be the DFTD treatability
tests of contaminated soils from RMA, the third-party test program for ANL discussed in
Section 9. Current plans are to complete needed modifications to the RKS in October and
November. The entire quantity of soil of each type received for testing will then be mixed to
uniform composition and testing to establish that the test soils can be fed to the RKS using the
screwfeeder chosen will be performed. The actual treatability test program is scheduled to begin
in January 1995.
Two other major test program are planned to be initiated during FY95. In the first new
program, with support from the Agency's Environmental Technology Initiative (ETI), several
developing concepts for continuously monitoring flue gas emissions of trace metals and trace
organic constituents from waste combustion processes will be evaluated in tests to be performed
in the RKS. The possibility of coordinating this planned test program with a similar one being
initiated with Department of Energy (DOE) support by the DOE's Savannah River Laboratory
will be aggressively pursued.
The second new test program to be planned and initiated in FY95 will investigate the
effects of incineration system design and operation on emissions of dioxins and furans. Initial
test planning efforts suggests that testing to develop more definitive data on the relationships
between post-combustion particulate collection temperature and residence time, and dioxin/furan
emission levels, and on the role of particulate trace metal content will be performed.
102
-------
Further TTU testing to extend the data base developed during FY94 on the performance
of potential sorbent additives for trace metal capture in thermal treatment processes is also
planned for FY95.
103
-------
SECTION 12
REFERENCES
1. "Guidance on Setting Permit Conditions and Reporting Trial Burn Results, Volume n
of the Hazardous Waste Incineration Guidance Series," EPA/625/6-89-019, January
1989.
2. 40 CFR Part 266, Subpart H.
3. Fournier, Jr., D. J., W. E. Whitworth, Jr., J. W. Lee, and L. R. Waterland, "The Fate of
Trace Metals in a Rotary Kiln Incinerator with a Venturi/Packed Column Scrubber,"
EPA/600/2-90/043, February 1991.
4. Fournier, Jr., D. J., and L. R. Waterland, "The Fate of Trace Metals in a Rotary Kiln
Incinerator with a Single-Stage Ionizing Wet Scrubber," EPA/600/2-91/032, September
1991.
104
*U.S. GOVERNMENT PRINTING OFFICE: 1995-650-006/22035
------- |