EPA
530/SW
122C.3
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB-265 540
DESTROYING CHEMICAL WASTES IN COMMERCIAL
SCALE INCINERATORS FACILITY REPORT NO. 3 -
SYSTEMS TECHNOLOGY
TRW Defense and Space Systems Group
Redondo Beach, California
P re pared fo r
Environmental Protection Agency, Washington, D. C.
1977
EJBD
ARCHIVE
EPA
SW-
122C.3
Enviro-
Protect
JUI
UEW.PV Repository Material
Permanent Collection
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
PB 265 540
4. 1'itlr imil Suhtnlr
DESTROYING CHEMICAL WASTES IN COMMERCIAL SCALE INCINERATORS
Facility Report No. 3 - Systems Technology
5. Report Date
April 1977
6.
7. Author(s)
D. G. Ackerman, J. F. Clausen, R. J. Johnson, C. A. Zee
8. Performing Organization Kept.
No*
9. Performing Organization Name and Address
TRW Defense and Space Systems Group
One Space Park, Redondo Beach, California 90278
10. Project/Task/Wotk Unit No.
11. Contract/Grant No.
68-01-2966
12. Sponsoring Organization Name and Address
U.S. Environmental Protection Agency
Office of Solid Waste
Washington, D. C. 20460
13. Type of Report & Period
Covered
Facility test report
u.
15. Supplementary Notes
16. Abstracts
Incineration tests of selected chemical wastes were conducted at the fluidized bed
incinerator facility operated by Black Clawson Fibreclaim, Inc., in Franklin, Ohio.
These tests were performed under contract with Systems Technology Corporation to deter-
mine the effectiveness of thermal destruction of two different industrial liquid wastes
1) an aqueous phenol sludge, and 2) an aqueous solution of methyl methacrylate monomer.
Each waste was burned at two different conditions to determine the effects of normal
operating and equipment variables. Analysis of combustion gas samples indicated
destruction efficiencies of over 99.999 percent for each waste consitituent. Standard
EPA Method 5 tests were performed on stack emissions to determine particulate loading
and composition. No organics were detected in the scrubber water or ash. Test re-
sults indicated that either waste can be effectively destructed in a fluidized bed
reactor. Estimated cost of destroying 13.2 million liters/year of aqueous methyl
mpt.harrylate was $6 million capital investment and an operating cost of $255/metric ton
17. Key Words and Document Analysis. 17o. Descriptors
Waste Disposal
Industrial Wastes
Phenols
Incinerators
Field Tests
Gas Sampling
Chemical Analysis
Cost Analysis
!7b. Jdennfiers/Open-Ended Terms
Systems Technology Corporation
Black Clawson Fibreclaim
Fluidized Bed Incineration
Methyl Methacrylate
Cost of incinerating 23.8 million liters/year of
aqueous phenol waste was estimated to be $6
million capital investment and $124/metric ton
operating cost.
REPRODUCED BV
NATIONAL TECHNICAL
INFORMATION SBtVlCE
U. S. DEPARTMENT OF COMMERCE
SPR1NGFIILD. VA. 2T161
17c. COSATI Field/Group 07-01, 14-02, 14-01
IB. Availability Statement
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No ' s
22. Price ftc AO $
/»PAOl
FORM NTis-sa 1REV. 10-731 ENDORSED BY ANSI AND UNESCO.
THIS FORM MAY BE REPRODUCED
U9COMM-DC 8Z65-P74
-------
DESTROYING CHEMICAL WASTES IN
COIiMERCIAL-SCALE INCINERATORS
Facility Report No. 3
This final report (SW-122c) describes work performed
for the Federal solid waste management program
under contract no. 68-01-2966
and is reproduced as received from the contractor
5
00
e
00
U.S. ENVIRONMENTAL PROTECTION AGEMCY
1977
-------
This report has been reviewed by the U.S. Environmental Protection
Agency and approved for publication. Publication does not signify
that the contents necessarily reflect the views and policies of the
Environmental Protection Agency, nor does mention of commercial
products constitute endorsement or recommendation by the U.S. Government.
An environmental protection publication (SW-122c) in the solid waste
management series.
n
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FOREWORD
The tests described in this report are part of a program designed to
evaluate the environmental, technical, and economic feasibility of dis-
posing of industrial wastes via incineration. This objective is being
pursued through a series of test burns conducted at commercial incinerators
and with real-world industrial wastes. Approximately eight incineration
facilities and seventeen different industrial wastes will be tested under
this program. The incineration facilities were selected to represent the
various design categories which appear most promising for industrial waste
disposal. The wastes were selected on the basis of their suitability for
disposal by incineration and their environmental priority.
This report describes the test conducted at Systems Technology
(Franklin, Ohio), which was the third facility of the series. Facility
reports similar to this one have been published for the first two tests
which were conducted at the Marquardt liquid injection facility in Van Nuys,
California, and the Surface Combustion pyrolysis facility in Toledo, Ohio.
The facility reports are primarily of an objective nature presenting the
equipment description, waste analysis, operational procedures, sampling
techniques, analytical methods, emission data and cost information. Facil-
ity reports are published as soon as possible after the testing has been
completed at a facility so that the raw data and basic results will be
available to the public quickly.
In addition to the facility reports, a final report will also be
prepared after all testing has been completed. In contrast to the facility
reports which are primarily objective, the final report will provide a
detailed subjective analysis on each test and the overall program.
ACKNOWLEDGEMENTS
TRW wishes to express its sincere appreciation to Systems Technology
Corporation and Black Clawson Fibred aim, Inc., for their cooperation in
conducting these facility tests. The assistance of Messrs. John Miller
and Robert Griffin of Systech, and Earl Blakely and John Neal of Black
Clawson, is gratefully acknowledged. The project is deeply indebted to
Messrs. Alfred Lindsey and John Schaum of the Office of Solid Waste
Management Programs, U. S. Environmental Protection Agency, for their
advice and technical direction.
111
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CONTENTS
Page
1. Summary 1
2. Introduction 4
3. Process Description 6
3.1 Facility Process 6
3.1.1 Fluidized Bed Reactor 6
3.1.2 Air Supply System 6
3.1.3 Waste Feed System 6
3.1.4 Auxiliary Fuel Feed System 8
3.2 Instrumentation 8
3.3 Emission Controls 10
4. Test Description 11
4.1 Wastes Tested 11
4.1.1 Phenol Waste 12
4.1.2 Methyl Methacrylate Waste 15
4.2 Operational Procedures 17
4.2.1 Test Procedures 17
4.2.2 Safety Procedures 19
4.2.3 Test Commentary 20
4.2.4 Disposal of Waste Residues 21
4.3 Sampling Methods 21
4.3.1 On-Line Gas Monitoring 22
4.3.2 Sampling of Combustion Products 22
4.3.3 Sampling Emissions and Waste .Products 28
4.4 Analysis Techniques 29
4.4.1 Extractions and Sample Preparation 30
4.4.2 Analytical Methods 33
IV
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CONTENTS (CONTINUED)
Page
4.5 Problems Encountered 36
4.5.1 Vortex Flow in Exhaust Stack 36
4.5.2 Combustion Zone Sample Probe Plugging 36
4.5.3 Variation in Concentration of Methyl Methacrylate 37
Waste
4.5.4 Saturation of Gastec Tubes with Condensed Water 37
4.5.5 Exhaust Plume Fallout 38
5. Test Results 39
5.1 Operational and Field Data Summary 39
5.2 Analytical Data Summary 39
5.2.1 Combustion Products 41
5.2.2 Final Emissions 49
6. Waste Incineration Cost 62
6.1 Capital Investment 6?
6.2 Annual Operating Costs 64
7. References 69
Appendices
Appendix A - Assessment of Environmental Impact of Destructing 70
Chemical Wastes at Systech Waste Treatment Center
Appendix B - Sample Train Operation and Sample Volume Data 73
Appendix C - Calculation of Waste Destruction Performance 77
Appendix D - Analytical Chemistry Details 80
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FIGURES
Page
3-1 Facility Process Flow Schematic Diagram 7
3-2 Overall View of Facility 8
3-3 Facility Instrumentation Schematic Diagram 9
3-4 Main Facility Instrumentation and Control Panel 10
4-1 Location of Trailer and Sampling Trains at Systech 23
4-2 Closer View of Sampling Train Locations 23
4-3 Sampling System for On-Line Instruments 24
4-4 - Instrument Racks 26
4-5 Combustion Zone Sampling Train Schematic 27
4-6 Water Cooled Probe Design 28
4-7 Sorbent Trap Extractor 31
5-1 Filters from Combustion Zone Gas Sampling Train 49
5-2 Filters from Stack Gas Sampling Train 51
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TABLES
Page
1-1 Results Summary 2
4-1 Organic Composition of Phenol Waste Representative Sample 13
4-2 Trace Metals in the Phenol Waste 14
4-3 Organic Composition of Methyl Methacrylate Waste Represert- 16
tative Sample
4-4 Trace Metals in the MMA Waste 18
4-5 Description of On-Line Instruments 25
4-6 Summary of Analytical Methods 34
5-1 Incinerator System Parameters Data Summary 40
5-2 Gas Composition Data Summary 41
5-3 Results of Gas Chromatographic Analyses of Combustion 43
Gas Samples
F-4 Results of Gas Chromatographic Analyses of Sorbent Trap 44
Extraction Controls
5-5 Summary of Survey Analysis on the Combined Probe Wash and 45
Parti oil ate Filter Extracts
5-6 Summary of Survey Analysis on Sorbent Trap Extracts 47
5-7 Approximate Hydrocarbon Content in Grab Gas Samples by LRMS 48
5-8 Trace Metals on Particulate Filters by AAS 50
5-9 Particulate Loading in the Effluent Gas 52
5-10 Survey for Trace Metals in the Stack Filter Digests by ICPOES 53
5-11 Limits of Detection for Elements Undetected by ICPOES 54
5-12 Survey for Trace Metals in Stack First Liquid Impinger 55
Samples by ICPOES
5-13 Results of Scrubber Water Extract Analyses by GC 57
5-14 Summary of Survey Analysis of Scrubber Water Extracts 58
5-15 Trace Elements in Scrubber Waters by AAS 60
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TABLES (CONTINUED)
Page
5-16 Results of Sand Extract Analysis by GC 61
5-17 Summary of Survey Analysis of Sand Extracts 61
6-1 Capital Investment - 13.2 Million Liter/Year Methyl 63
Methacrylate Waste Incineration Plant
6-2 Capital Investment - 23.8 Million Liter/Year Phenol 65
Waste Water Incineration Plant
6-3 Annual Operating Cost - 13.2 Million Liter/Year Methyl 67
Methacrylate Waste Incineration Plant
6-4 Annual Operating Cost - 23.8 Million Liter/Year Phenol 68
Waste Water Incineration Plant
B-l Sampling System Data Summary 74
B-2 Systech Sample Gas Volumes at Standard Conditions 75
B-3 Collected Water Volume Data 76
D-l IR Data For Probe Wash and Filter Extract Survey Residues 81
D-2 IR Assignments for Sorbent Trap Extract Survey Residues 82
D-3 LRMS Assignments for Sorbent Trap Extract Survey Residues 83
D-4 IR Assignments for Scrubber Water Extract Survey Residues 84
D-5 LRMS Assignments for Scrubber Water Extract Residues 85
D-6 IR Assignments for Sand Bed Extract Survey Residues 85
D-7 LRMS Assignments of Representative Phenol Waste 87
D-8 LRMS Assignments for Representative Methyl Methacrylate Waste 88
viii
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1. SUMMARY
Incineration tests of selected chemical wastes were conducted at the
fluidized bed incinerator facility operated by Black Clawson Fibred aim,
Inc., in Franklin, Ohio. These tests were performed under contract with
Systems Technology Corporation to determine the effectiveness of thermal
destruction of two different industrial liquid wastes: 1) an aqueous
phenol sludge, and 2) an aqueous solution of methyl methacrylate monomer.
Each waste was burned at two different conditions to determine the effects
of normal operating and equipment variables.
The phenol sludge contained 86 percent water and 5.5 percent ash with
the remaining organic portion consisting mainly of phenol and cresols.
The wastes elemental composition was approximately 6 percent carbon and
10.5 percent hydrogen. Nitrogen, sulfur, and halogen (as chlorine) levels
were relatively low at 0.1, 0.5, and 0.07 percent, respectively, the
major inorganic components of the ash were S, Na, Fe, Ca, Si, AT, K, Mg,
and P. Heat content of the phenol sludge could not be determined due to
the high water content, but is probably less than 1500 kcal/kg.
The methyl methacrylate waste also had a high water content, 38 per-
cent water, and contained approximately 2 percent ash. The aqueous phase
and the organic phase, which 1s almost entirely the monomer, tend to
separate on standing and vigorous mixing 1s required to keep the waste
homogeneous. The waste was composed of about 33 percent carbon, 9.5 per-
cent hydrogen, and 0.7 percent halogens (as chlorine) with only tracer of
nitrogen and sulfur at 600 ppm and 800 ppm, respectively. The major
inorganic components of the ash were Na, S, Ti, Al, Ca, Pb, Si, Mgs and P.
Heat content could not be measured on this Waste either and is similarly
believed to be less than 1500 kcal/kg.
The fluidized bed incinerator utilized for testing is of commercial
design and capacity. The reactor is 7.6 meters in diameter by 10 meters
high, and has an input feed rate of over 1000 liters per hour. Auxiliary
fuel can be injected simultaneously with low heat content wastes to support
combustion when required. Reactor bed operating temperature range is 650
to 1050°C. The incinerator is equipped with a Venturi scrubber and mist
separator which remove up to 98 percent of the particulate and reduce the
stack exhaust gas temperature to 82°C.
Test burn operating conditions for each waste are summarized in
Table 1-1, beginning with the range of test conditions for each waste,
including bed and freeboard temperatures, residence time, waste feed rate,
and waste/auxiliary fuel ratio. The ratio of waste feed rate to auxiliary
fuel feed rate was utilized as the test variable for each waste. A base-
line test with auxiliary fuel only was performed to obtain background
emissions data. Auxiliary fuel (Number 2 oil) was required to destruct
these wastes because of the water content: 86 percent water in the phenol
waste and 38 percent water in the methyl methacrylate waste.
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Table 1-1. Results Summary
Bed Temperature, Average (°C)
Freeboard Temperature (°C)
Residence Time (sec)
Waste Feed Rate (1/min)
Waste/Auxiliary Fuel* (1/1)
Quality of Stack Emissions
Parti cul ate (mg/m )
Trace Metals (mr/m )
Quality of Combustion Gas:
Total Organics (mg/m )
Waste Content (mg/m )
Trace Metals (mg/m )
Quality of Scrubber Water:
Total Organics (mg/1)
Trace Metals (mg/1)
Quality of Ash (Fluidizing Sand):
Waste Content (mg/kg ash)
Destruction Efficiency:
Total Organics (percent)
Waste Constituents (percent)
Capital Cost ($)
Operating Costs* ($/metric ton)
Plant Size (1/yr)
Phenol Waste
740-757
813-899
12-14
34-50
2.3-3.0
1280-1430
0.44-0.87 Pb
7.0-7.6
Not Detected
(<0.03)
1.0-1.2 Pb
Not Detected
0.50-2,7 Pb
Not Detected
99.97-99.98
>99.999
6,075,200
125
22.7 million
Methyl Methacrylate
774-788
824-843
12
30-36
2.0-2.6
560-630
0.55-2.2 Pb
7.5
Not Detected
0.85-4.7 Pb
Not Detected
0.45-1.8 Pb
Not Detected
99.99
^99.999
5,984,200
255
13.2 million
No. 2 oil utilized as auxiliary fuel for all tests
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Participate loadings up to 1430-mg/m were measured In the stack gases.
Most of the particulate consisted of fine sand particles disintegrated from
the fluidizing bed by direct injection of these high water content wastes.
Since both of the wastes tested contained lead, trace metal analyses in-
dicated the presence of lead in the combustion gases, stack emissions, and
scrubber water. Scrubber water analysis did not indicate the presence of
any organic material above the detection limits noted in Table 1-1. No
waste-constituents were found in the fluidlzing sand samples, above the
detection limits of the analysis.
Incineration of each waste was accomplished with high efficiencies in
the fluidized bed reactor, as indicated in Table 1-1. Waste destruction
efficiencies were over 99.999 percent for each test. The total organic
destruction efficiencies were 99.97 to 99.99 percent. Destruction effi-
ciency for total organics compares the input rate of combined waste and
auxiliary fuel to emitted rate of all organic material found in the com-
bustion zone samples. Waste destruction efficiency compares only waste
input rate to concentration of organic waste constituents in the combustion
gas. All samples were taken at the combustion zone exit prior to the
scrubber system. A sample destruction efficiency calculation is presented
in Appendix C. In addition to the fact that the waste constituents could
not be detected in the combustion gas (less than 01. mg/m3), no significant
evidence of any toxic by-products of the waste destruction, such as poly-
nuclear organic material (POM) was found.
Capital and operating cost estimates were prepared for fluidized bed
reactor-venturi scrubber systems to destruct each of the two wastes.
Capital investment, not including land costs, for a facility to incinerate
13.2 million liters/yr of aqueous methyl methacrylate is approximately
six million dollars, with an operating cost equivalent to $255/metric ton
of waste destructed. A facility to incinerate 23.8 million liters/yr of
aqueous phenol waste would also require a capital investment of six
million dollars, less land costs, and an operating cost of $124/metric
ton.
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2. INTRODUCTION
The objective of this facility test program is to evaluate the effec-
tiveness of thermally destructing specific industrial chemical wastes in an
existing commercial scale processing facility. These facility tests are
part of an overall U.S. Environmental Protection Agency sponsored pro-
gram involved with selective testing of sixteen different wastes at seven
generic types of thermal destructing facilities. The purpose of the test
program is to acquire useful disposal technology as well as economic infor-
mation. This report describes test operations and results of incinerating
two different liquid wastes, phenol and methyl methacrylate, in a 7.6-meter
diameter, commercial, fluidized bed incinerator at Franklin, Ohio, under
contract with Systems Technology Corporation (Systech).
The Systech Waste Treatment Center is adjacent to the Franklin Solid
Waste and Fiber Recovery Plant, operated by Black Clawson. Systech has an
exclusive contract with Black Clawson for the destruction of liquid wastes
in the fluidized bed reactor. This plant was designed and constructed under
a Demonstration Grant from the Office of Solid Waste Management Programs,
U.S. Environmental Protection Agency. In continuous operation since 1971,
the plant has met the complete waste disposal requirements of the city of
Franklin.
This fluidized bed reactor was selected for the program as a modern,
well-instrumented incinerator of commercial capacity and design. Manufac-
tured by Dorr-Oliver, the unit has an input feed rate of up to 1,360 liters
per hour of high heat content liquids (over 5,560 kcal/kg) and up to
7,570 liters per hour of liquids with a heat content of 1,670 kcal/kg.
Municipal wastes are burned at a maximum rate of 135 metric tons in 24 hours
Heat release capability is 15 million kcal/hr. The fluidized bed system is
equipped with a venturi scrubber to control particulate emissions.
The two wastes tested at the Systems Technology facility, an aqueous
methyl methacrylate monomer waste and an aqueous phenolic waste, were
selected on the basis of their suitability for the fluidized bed reactor.
The methyl methacrylate waste is a flammable, green-black liquid. Its
vapor is heavier than air and may travel a considerable distance to a source
of ignition and flash back. Also, at elevated temperatures, such as in fire
conditions, polymerization may take place. For these reasons, the fluidized
bed incinerator, with its nearly isothermal conditions and lower operating
temperature, is ideal for the destruction of the methyl methacrylate waste.
The aqueous phenol waste is a black, thick liquid with a large volume of
suspended solids and contains over 85 percent water. The fluidized bed
incinerator was selected for the destruction of the aqueous phenol waste
because of (1) its ability to handle suspended solids, and (2) its lower
operating temperature resulting in lower thermal energy requirement for
converting the water contained in the waste to steam at the incineration
temperature. An additional consideration was that both the aqueous methyl
methacrylate waste and the aqueous phenol waste were readily available at
the Systems Technology facility.
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The methyl methacrylate waste is generated from the manufacture of
acrylic plastic material, such as Lucite and Plexiglas. Methyl methacrylate
wastes are also generated from the manufacture of surface-coating resins,
such as latex paints, lacquer resins, and enamel resins. The phenol waste
is generated from the scrubbing of gasoline with caustic to remove hydrogen
sulfide and phenol, and is a major waste stream from petroleum refineries.
Because of the size of the acrylic plastic and the petroleum refining in-
dustries, both the methyl methacrylate waste and the phenol waste are
generated in large quantities. It is estimated that the methyl methacrylate
waste is generated at the rate of 1 to 10 million kg per year, whereas the
phenol waste is generated at the rate of over 50 million kg per year.
Two months after completion of these tests, Systech stopped inciner-
ating liquid industrial wastes in the fluidized bed reactor, at Black
Clawson's request. This request was made because some of Systech's wastes
caused operating problems which included:
0 Disintegration of the sand bed, apparently due to the thermal
effect of injecting liquid directly into the bed.
0 Abnormal buildup of multilayered, multicolored crust on the
wall of the reactor in the vicinity of the freeboard/bed
interface.
0 Buildup of ash of an abnormal physical character in the duct
work leading from the reactor to the scrubber.
0 Oefluidization of the bed due to agglomeration and to con-
tamination by chunks of the deposits described above.
Systech believes that defluidization of the bed or abnormal crust or ash
buildup would not develop during the incineration of the wastes tested
during this program. Some depletion of the bed sand was observed during
these tests, however, during which high water content wastes were in-
jected directly into the bed.
The following report sections describe in detail the incinerator
process equipment (Section 3), and the waste destroyed and test and
sampling procedures followed (Section 4). Test results are presented and
discussed (Section 5), including effectiveness of destruction of the wastes.
An estimate of the capital investment and operating costs of disposing of
wastes using this type of incinerator equipment is also included in the
report (Section 6).
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3. PROCESS DESCRIPTION
3.1 FACILITY PROCESS
The fluidlzed bed reactor facility process is shown schematically in
Figure 3-1. Basic system components include:
• Fluidized bed reactor
• Fluidizing air blower
• Waste feed system
• Auxiliary fuel feed system
• Instrumentation
• Emission control system
Following is a description of the incinerator and feed systems. Facil-
ity instrumentation and emission controls are discussed in subsequent Sec-
tions 3.2 and 3.3, respectively.
3.1.1 Fluidized Bed Reactor
The top of the fluidized bed reactor is shown in Figure 3-2. Manu-
factured by Dorr-Oliver, the reactor has an inside diameter of 7.6 meters
and an elevation of 10 meters. The silica bed is 1 meter deep at rest,
extending up to 1.8 meters in height when fluidizing air is passed through
the bed. Waste and auxiliary fuel are injected radially into the bed and
reacted at temperatures from 600° to 810°C. Further reaction occurs in the
reactor freeboard volume above the bed at temperatures up to 980°C. Con-
struction is of carbon steel with refractory lining.
Maximum heat release of the reactor is 15 million kcal/hr. Input feed
rate is up to 1,360 liters per hour of liquids over 5,560 kcal/kg heat con-
tent, and up to 7,570 liters per hour of liquids with a heat content of
1,670 kcal/kg. Municipal wastes are combusted at a maximum rate of
135 metric tons in 24 hours.
3.1.2 Air Supply System
A fluidizing air blower (Figure 3-1) powered by a 225 kilowatt
(300 horsepower) electric motor provides a maximum of 440 m^/min of air to
fluidize the bed. Additional combustion air of up to 115 m^/min is supplied
to overbed air nozzles by the same blower. The reactor preheat burners have
a separate air supply blower, as shown in Figure 3-1.
3.1.3 Haste Feed System
Liquid wastes were pumped directly from a tank truck into the reactor
by a recirculating pump system supplied by Systech, and not part of the
system shown in Figure 3-1. Wastes were injected radially into the reactor
bed through a single 9.5 mm diameter nozzle. Flow rates were determined
'. ' recording waste liquid level changes in the calibrated tanker as a func-
tion of time.
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.~™v:r—rpr£
T****"^ JT
CMAJM u
t. ******r *m i,i <, *m**j+.* t**g • • -^—.
~
Figure 3-1. Facility Process Flow Schematic Diagram
-------
VENTURI I
SCRUBBER^-4
FUIIDIZED' B|
BED REACTOR "
Figure 3-2. Overall View of Facility
3.1.4 Auxiliary Fuel Feed System
Auxiliary fuel (No. 2 fuel oil) was fed radially into the bed through
10 bed nozzles manifolded around the reactor circumference. A maximum of
18 bed guns are shown in Figure 3-1, but this number is not normally used.
Fuel oil flow was measured by a flow totalizer (total volume meter) in the
feed line, and verified by recording oil tank liquid level versus time.
3.2 INSTRUMENTATION
Instrumentation capability provided at this facility for the test pro-
gram is shown in Figure 3-3. Instruments were calibrated by Black Clawson
personnel prior to initiation of testing. Measurements were made of all
process parameters, including pressures, temperatures, and flow rates. On
line measurement of oxygen content in the exhaust stack was also conducted.
Additional on line gas analysis instruments were monitored in the TRW sam-
pling trailer. The main facility instrumentation and control panel are
shown in Figure 3-4.
8
-------
o
o
o
CD
Figure 3-3. Facility Instrumentation Schematic Diagram
-------
Figure 3-4. Main Facility Instrumentation and Control Panel
3.3 EMISSION CONTROLS
Atmospheric emissions from the combustion of liquid wastes during the
Systech incineration tests were controlled by a venturi scrubber, shown in
Figure 3-1. The top of the scrubber can also be seen in Figure 3-2. Recir-
culating water is injected into the venturi to scrub particulate matter
from the combustion gas stream and quench the gas temperature from ^820°
to'v80°C prior to emission into the atmosphere through the stack. Spent
scrubber liquid is sent to the Miami Conservancy District Wastewater Treat-
ment Plant (adjacent to the incinerator) for processing.
10
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4. TEST DESCRIPTION
This section presents the manner In which the tests were carried out.
It 1s divided Into the following subsections, listed in order of
discussion:
• Physical and chemical description of the wastes that were
tested
• Operational procedures used and a test-by-test commentary
• Sampling methods
• Analysis techniques
• Description of the problems encountered related to the facility
and sampling.
4.1 WASTES TESTED
The two wastes selected for testing at Systech were from processes
using phenol and methyl methacrylate (MMA). Survey samples were obtained
as early as possible before the tests and representative samples were
taken at Systech from the waste-containing tank trucks at the start of
each test day. The character of both of these wastes changed noticeably
from the survey to the representative samples. The survey sample of the
phenol waste contained so much solIds KI3 percent) that it poured in
lumps. However, the representative sample had a smooth consistency and
much lower solids content. The survey sample of the MMA waste was a high
heat content material of almost pure monomer (^98 percent), whereas the
representative sample was a highly watered waste stream. Thus, most of
the analyses performed on the survey samples had to be repeated and the
results reported in this section, except as noted, are from the repre-
sentative waste samples. The analyses used to characterize the wastes
and to determine the expected compounds of interest in the test burn
samples were:
• Thermal content
• Viscosity
• Specific gravity
0 Loss on ignition (LOI)
• Percent water
• C,H,N,S, and halogens
• Infrared spectroscopy (IR)
• Low resolution mass spectroscopy (LRMS)
11
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• Combined gas chromatography/mass spectroscopy (GC/MS)
• Spark source mass spectroscopy (SSMS)
The results from these analyses are discussed 1n the following sections.
4.1.1 Phenol Waste
The phenol waste was a greenish-black opaque liquid with a large
amount of suspended solids. It had a strong phenol odor with an accom-
panying odor resembling that of crude oil. Neither heat content or vis-
cosity could be measured on this waste. The waste would not Ignite in
the calorimeter due to its high water content and fts high solids load-
ing interfered with viscosity measurements. The waste had a specific
gravity at 15°C of 1.0623, an LOI of 94.5 percent, and was determined to
be 86 percent water.
Elemental analyses performed showed the composition of the waste to
be:
carbon — 5.9 percent
hydrogen — 10.5 percent
nitrogen — 0.10 percent
sulfur — 0.5 percent
halogens as chlorine — 0.07 percent
4.1.1.1 Organic Composition
The organic portion, that part of the representative waste which was
not water or solids (as determined by LOI), consisted of about half phenol
with cresols and substituted benzenes making up most of the remaining
organics. The concentration of the organic constituents in the waste,
as determined by GC/MS using the total ion monitor for normalized quanti-
tation is shown in Table 4-1. The composition of the representative
sample is essentially the same as the survey sample (Reference 1), except
that the ethanol, acetone, 2-butanone, butanol, and 2-ethoxyethanol were
not present in the survey sample.
A survey analysis by IR and LRMS was performed on the representative
sample of the phenol waste to look for organic species not necessarily
detected in the other analyses. An aliquot of the representative phenol
waste sample was evaporated in air at approximately 50°C to remove the
water and some of the volatile compounds already quantified by GC. The
resulting spectra were clearly Indicative of phenol as the major constit-
uent. Most of the peaks can be assigned to phenol. Certain broad areas
of absorption, 1400 to 1500 cm'1, are attributed primarily to p-cresol
also being present in the sample. There were no indications of any other
species being present. The IR normally does not indicate a compound's
presence at levels below 5 percent weight composition In the sample. The
LRMS spectral patterns obtained from the samples at sample probe tempera-
tures from 50° to 400°C indicated the presence of the constituents phenol,
12
-------
Table 4-1. Organic Composition of Phenol Waste
Representative Sample
Compound
Ethanol
Acetone
2-Butanone (MEK)
Butanol
2-Ethoxyethanol
Toluene
Xylene (two isomers)
Isopropyl benzene
Phenol
o-Cresol
m-Cresol
Estimated Level in
the Waste Sample
(Percent w/w)a
0.06
0.07
0.05
<0.01
0.07
0.3
0.6
0.8
3.7
0.9
1.9
aSample contained 86 percent water and approximately
5.5 percent nonignitable solids.
cresols, and aliphatic and unsaturated hydrocarbon oils. Spectral assign-
ments can be found in Table D-7 in the appendix.
There was also strange evidence of either one or perhaps both of two
classes of compounds: (1) methyl esters of various different carboxylic
acids, and (2) sulfur containing hydrocarbons such as sulfides, dlthianes
and trithianes. These materials were not seen in the GC/MS analysis of
these samples (Table 4-1) and are believed to be of low enough volatility
so as to not elute from the chromatographlc columns- The sulfur contain-
ing hydrocarbons could account for some of the 0.5 percent sulfur found
in the elemental analysis.
4.1.1.2 Trace Elements
Trace elemental analysis was performed by SSMS. This analysis showed
the major species to be sulfur, sodium, and Iron. The concentrations of
the other elements detected down to 0.1 ppm as well as all toxic elements
are presented in Table 4-2. The corresponding concentrations of these
elements in the resulting combustion gas have been calculated based on
average fuel and air feed conditions at Systech and are also Included in
this table. The SSMS data are typically accurate within 500 percent and
should thus be regarded only as estimates. For this reason, and also
because its volatility makes 1t extremely difficult to detect by SSMS,
13
-------
Table 4-2. Trace Metals In the Phenol Waste
Element
Ca
Si
Al
K
Mg
P
Pt
Ti
Sn
Zn
V*
Cr*
Cu
Mo
Zr
Mn
Pb*
B
Ba*
Ce
Nb
Ni
La
Cd*
Sr
Li
Nd
Ag
Hg*a
Rb
Y
Sb*
Se*
As*
Be*
Co*
Approximate
Concentration
in Waste (ppm)
310
240
86
75
40
33
16
15
6
6
5
4
4
4
4
3
3
1
1
1
1
1
0.6
0.5
0.5
0.3
0.2
0.1
0.1
0.1
0.1
0.08
0.06
0.03
0.01
0.01
Calculated Theoretical .
Concentration in Combustion
Gas (mg/m3)
26
20
7.3
6.4
3.4
2.8
1.4
1.3
0.5
0.5
0.4
0.3
0.3
0.3
0.3
0.3
0.3
0.1
0.1
0.1
0.1
0.1
0.05
0.04
0.04
0.03
0.02
0.01
0.01
0.01
0.01
0.007
0.005
0.003
0.001
0.001
Potentially toxic metals - AC6IH TLV of <1 mg/m3 for an 8-hour exposure
(Reference 3).
aDetermined by atomic fluorescence.
14
-------
the element mercury was determined by a highly quantitative atomic fluo-
rescence technique in order to be sure of an accurate measurement.
4.1.2 Methyl Methacrylate (MMA) Waste
The MMA waste was a medium brown liquid with a gritty sediment that
tended to settle out of solution. The waste also had two liquid phases
which at least partially separate on standing. It had a strong pungent
odor characteristic of acrylic acid compounds. Heat content on this waste
could not be determined due to its high water content. Its other phys-
ical characteristics were:
• Viscosity of 1.42 centistokes at 37°C
• Specific gravity of 1.0158 at 15°C
• LOI of 98.3 percent
• Water content of 38 percent
Elemental analyses performed showed the composition of the waste to be:
carbon - 38.2 percent
hydrogen —9.5 percent
nitrogen -0.06 percent
sulfur - 0.08 percent
halogens as chlorine -0.73 percent
4.1.2,1 Organic Composition
The composition of the organic constituents of the aqueous methyl
methacrylate waste burned at Systech is presented in Table 4-3. The
identification and quantisation was performed by GC/MS using normalized
total ion monitor response for the quantitative estimates. This method
of quantification is not as accurate as calibrating instrument response
for each individual waste constituent but it provides a good indicator
of the relative amounts of each waste constituent present and is suffi-
cient to meet the objective of the analysis.
The composition of the representative waste sample is considerably
different than that of the survey sample from which the analytical plan
was formulated (Reference 1). The basic difference is the large amount
of water, 38 percent, in the representative waste. There was also a
larger number of organic constituents in the representative waste. Nota-
ble among these additional constituents were a considerable amount of
phenol and cresols. Their presence 1s Intriguing but most likely due
to cross contamination from the phenol waste tests. Since the run tank
containing the methyl methacrylate waste had just previously been used
for the phenol waste run tank, it is possible that some residual, phenol
rich, sludge may have remained in the tank.
15
-------
Table 4-3. Organic Composition of Methyl Methacrylate
Waste Representative Sample
Compound
Methanol
Acetone
Methylene chloride
2-Butanone
Methyl propanoate
Methyl methacrylate
2-Ethoxy ethanol
Toluene
Xylene
2-Ethoxy ethyl acetate
Phenol
Cresols
Estimated Levels
(percent w/w)a
4.9
0.7
0.7
1.1
0.4
33.9
0.4
1.1
0.9
0.4
12.6
3.4
Sample contains 38 percent water and approximately 1.7 percent
nonignitable solids.
The presence of dimers, trimers and possibly higher polymers from
methyl methacrylate has been suggested in manufacturers literature as
possibly being present in the waste. Polymerization, which can occur in
reagent grades of these compounds without the addition of an inhibitor,
is not believed to have any impact on the performance of the incinerator/
reactor since the polymer is also readily combustible under the conditions
used at Systech.
A survey analysis of the MMA representative sample of the actual
waste burned at Systech was analyzed by IR and LRMS to look for species
not necessarily detected in the other analyses. An IR spectrum of the
MMA representative waste sample was obtained from an aliquot of the sample
from which the water had been removed by evaporation at approximately
50°C. The IR indicated an aliphatic ester. Comparison of the standard
IR spectra for methyl methacrylate monomer and polymers with the waste
sample spectrum indicated that some polymerization had taken place. The
MMA monomer had evaporated off, but its presence had already been estab-
lished by GC/MS. A strong peak at 2920 cm-1 indicated that higher molec-
ular weight hydrocarbons, perhaps as oils, are likely present in the waste.
There were no other features in the spectra which indicated any other
classes of compounds.
16
-------
The LRMS data on the same residue used In the IR show that hydrocarbon
oils are the major constituents of the residue after removal of water and
volatiles. (The volatile? were quantified by GC and are discussed earlier.)
Ad1pates and/or sebecates as well as some phthaiate esters are present in
minor amounts. The levels which these materials are present in the waste
is estimated at much less than 1 percent. There is no mass spectral evi-
dence of polymerized methyl methacrylate. The LRMS spectrum interpreta-
tion can be found in Table D-8 in the appendix.
4.1.2.2 Trace Elements
Trace elemental analysis was performed by SSMS. This analysis showed
the major elements to be sodium, sulfur, and titanium. The concentrations
of other elements detected down to 0.1 ppm as well as all toxic elements
are presented in Table 4-4. The corresponding concentrations of these
elements in the resulting combustion gas have been calculated based on
average fuel and air feed conditions at Systech and are also included in
the table. The SSMS data are typically accurate within 500 percent and
should thus be regarded only as estimates. For this reason, and also
because its volatility makes it extremely difficult to detect by SSMS, the
element mercury was determined by a highly quantitative atomic fluores-
cence technique in order to be sure of an accurate measurement.
4.2 OPERATIONAL PROCEDURES
Detailed operating procedures, including both a test plan and a
safety plan, were reviewed and approved prior to arrival of the TRW
sampling team on site. Procedures and operating conditions were also
recorded during the field tests. Following are brief summaries of both
plans, a test-by-test commentary on events that took place in the field,
and information on the disposal of the waste residues.
4.2.1 Test Procedures
Fluidized bed reactor tests were run with two wastes, phenol and
methyl methacrylate, as previously described in Section 4.1. The basic
procedure for each waste test was:
• Connect waste tanker and operate recirculation system
• Obtain waste sample and fresh scrubber water sample
• Verify instrumentation and sampling systems ready
• Ignite on auxiliary fuel (No. 2 oil) and stabilize temperatures
t Activate on-line analyzer system
• Initiate waste fuel combustion and observe effluent
• Stabilize flow rates and temperatures
• Extended bum duration
Process data acquisition
Combustion gas composition data acquisition
17
-------
Table 4-4. Trace Metals in the MMA Waste
Element
Al
Ca
Pb*
Si
Mg
P
Cr*
Fe
Ba*
Zn
Cd*
Cu
Mn
Pt
Sn
Bi
K
Mo
Ni
Sb*
Sr
Ag
Co*
Zr
B
Rb
V*
Nb
W
As*
Hg*a
Be*
Se*
Approximate
Concentration
in Waste (ppm)
160-315
160-315
160-315
no
75
57
38
38
35
26
21
19
10
4
4
2
2
2
2
2
2
0.4
0.4
0.4
0.2
0.2
0.2
0.1
0.1
0.04
0.03
0.006
0.004
Calculated Theoretical
Concentration in Combustion
Gas (mg/m3)
9-18
9-18
9-18
6.4
4.4
3.3
2.2
2.2
2.0
1.5
1.2
1.1
0.6
0.2
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.02
0.02
0.02
0.01
0.01
0.01
0.006
0.006
0.002
0.002
0.0003
0.0002
*Potentially toxic metals -AC6IH TLV of <1 mg/m3 for an 8-hour exposure
(Reference 3).
aDetermined by atomic fluorescence.
18
-------
Combustion zone and stack gas sampling
Spent scrubber liquid sampling
a Transfer to auxiliary fuel combustion
• Shutdown and secure
• Acquire sand sample from reactor bed
The test series for each waste consisted of two bum periods during
which a 3-hour combustion gas sample was acquired at steady state oper-
ating conditions. A 3-hour sampling run with No. 2 oil only was also
required to obtain background data.
Target test conditions for each waste were:
• Fluidizing air flow rate - 425 m3/min
• Auxiliary fuel flow rate — 15 liters/min
• Waste flow rate - 30 to 50 liters/min
• Average bed temperature — 760° to 815°C
Waste flow rates were selected for each test to evaluate the effects
on destruction efficiency, if any, of varying the waste/auxiliary fuel
volumetric flow rate ratios between 2:1 and 3:1. Air and auxiliary fuel
flow rates were held essentially constant to maintain a fluidized bed
temperature between 760° and 815°C.
4.2.2 Safety Procedures
Safety requirements for handling and incinerating these specific
wastes were established and adhered to, including the following:
• Only authorized personnel with prior approval were permitted
in the test area during operations.
• Waste hookup and unloading were performed only by personnel
wearing suitable protective clothing and trained in handling
such materials.
• Water hose with a pistol-grip nozzle was available in the
immediate area for washdown of personnel or spills.
• Visual observation of the test system was maintained at all
times during operation.
• Canister gas masks and emergency oxygen resuscitation units
were available in immediate area.
• Emergency agencies' telephone numbers were posted near the
test area.
19
-------
4.2.3 Test Commentary
Two test conditions were evaluated with both the phenol and methyl
methacrylate wastes. Since auxiliary fuel was required for the combustion
of each waste, a baseline test was conducted with No. 2 oil only to obtain
background data. For convenience in facility scheduling, the first phenol
test was performed before the background data test.
Test I - First Phenol Test
After stabilization of bed temperature at an average of 760°C with
No. 2 oil, waste phenol flow was initiated. Waste flow was gradually
increased until bed temperatures began to decrease below 760°C, then flow
was held constant until system temperatures stabilized. Waste and fuel
oil rates were checked, and the waste/auxiliary fuel volumetric flow
ratio was 3.0:1. Combustion zone and stack gas sampling were then con-
ducted at steady-state reactor operating conditions. Average temperatures
were 740°C in the bed and 899°C in the freeboard volume above the bed.
Combustion zone sampling was performed for 2-1/4 hours before the probe
gradually became plugged with the fines from the sand bed and sample flow
decreased to zero. Although a 3-hour hot zone sample was intended, the
actual sample acquired was of sufficient quantity for analysis, and the
test was terminated. The probe plugging instance is discussed further
in Section 4.5. Calculated combustion zone residence time was 14 seconds.
Test II - Background Test
A baseline test was performed with No. 2 oil to obtain background
data on combustion zone and stack gases with auxiliary fuel only. No
nozzle plugging occurred, and a 3-hour combustion zone sample was obtained
at steady-state operating conditions of 777°C bed and 793°C freeboard
average temperatures. A 1-hour stack gas sample was also acquired during
the same period. Residence time for this test and all subsequent tests was
12 seconds.
Test III -Second Phenol Test
The second test condition with waste phenols was performed at a lower
waste flow rate than the first test, reducing the waste/auxiliary fuel
volume flow ratio to 2.3:1. Average steady-state operating temperatures
were 757°C in the bed and 813°C in the freeboard. After 1 hour of com-
bustion zone sampling, the probe again began plugging and sample flow
decreased. An air back purge through the probe did not remove the obstruc-
tion, but a water back purge cleared the probe, and the 3 hours of sam-
pling at the hot zone was completed. Some participate in the sample probe
was lost by back purging during the run, as described in Section 4.5.
Test IV - First Methyl Methacrylate Test
Each of the methacrylate tests was performed with a watery waste,
rather than the concentrated waste originally expected (see Section 4.1
for detailed explanation). The first test was conducted at a waste/
auxiliary fuel volume flow ratio of 2.0:1. Average steady-state oper-
ating temperatures were 774°C in the bed and 824°C In the freeboard. A
20
-------
3-hour combustion zone gas sample and a 1-hour stack sample were obtained
without incident.
Test V - Second Methyl Methacrylate Test
The waste/auxiliary fuel flow ratio was increased to 2.6:1 for the
second methacrylate test. Stack and combustion zone gas samples were
acquired at average temperatures of 788°C in the bed and 843°C in the
freeboard. The test was terminated after 2 hours and 43 minutes of hot
zone sampling when bed temperatures began to increase at steady flow con-
ditions. Since the waste tank was nearing depletion, the temperature
increase was most likely due to a stratification in the waste. A
recirculation system was used to mix the wastes in the tanker trailer,
but mixing was apparently inefficient. As a layer of more highly con-
centrated waste was reached, bed temperatures increased. The auxiliary
fuel oil feed rate was gradually reduced to maintain constant tempera-
tures. It was finally turned off completely, but the bed temperatures
continued to increase. Since an adequate gas sample had already been
acquired, the test was terminated rather than reduce waste flow rate
to compensate for the bed temperature rise.
4.2.4 Disposal of Waste Residues
The phenol waste consigned by Systech for these tests was consumed
in the tests. The tank trailer was returned to the Systech facility
where it was washed out with water. The washings were introduced into
Systech's waste treatment plant. There was residual methyl methacrylate
in the tank trailer after the testing was completed. This excess was
returned to the Systech facility where it was introduced into their nor-
mal recovery and treatment process for this waste.
The scrubber waters were pumped to the municipal water treatment
plant adjacent to the Systech and Black Clawson facilities. There was
no disposal of the sand contained in the reactor. Additional sand was
added to the existing bed to compensate for sand losses prior to and
during the tests.
4.3 SAMPLING METHODS
Sampling methods used in the tests at Systech were chosen to cover
three basic areas:
(1) Continuous, on-line monitoring of gas composition to deter-
mine and follow steady state conditions
(2) Collection and concentration of hot zone combustion prod-
ucts to identify and quantify the trace organic and
inorganic species formed
(3) Collection of final emission and waste products to evalu-
ate the environmental safety of the tests
21
-------
Following is a brief summary of the methods for each of these areas.
More detailed discussions can be found in the Systems Technology Analyt-
ical Plan (Reference 1). The locations of the trailer and sampling trains
at the site are shown in Figures 4-1 and 4-2.
4.3.1 On-line Gas Monitoring
Gases were drawn continuously from the hot zone through a ceramic
probe and then through a heated Teflon sample line to the trailer. The
gas then entered the system shown in Figure 4-3. The gas conditioner
supplied a cool, dry, participate free sample to all of the analyzers
with the exception of the hydrocarbon (HC) monitor which used an untreated
sample. A heated Teflon line carried the HC gas sample from a tee in the
unconditioned sample line to the HC analyzer.
The monitoring instruments used are listed with their operating
ranges in Table 4-5. Data was recorded on Hewlett-Packard 680M strip
chart recorders. Figure 4-4 shows the instrument racks mounted in the
sampling trailer. The analyzers, recorders, and manifold valves were
all located in racks to provide ease of operation and accessibility.
4.3.2 Sampling of Combustion Products
The sampling train used to collect hot zone gases, vapors, and partic-
ipate is shown schematically in Figure 4-5. It consisted of a standard
EPA Method 5 train with the following Important modifications presented in
order according to flow direction through the train.
• There was a stainless steel jacketed, water-cooled probe
(shown schematically in Figure 4-6) with a quartz liner.
The liner provided an inert surface for the sample gas and
the cooled, stainless steel jacket cools this gas in order
to quench any further reactions of the sample constituents.
and to yield a gas temperature compatible with train mate-
rials. Further cooling of the gas can be achieved by aspi-
rating an air/water mixture into the space between the steel
jacket and quartz liner.
0 Special fittings were fabricated to allow a back purge of the
probe with purified compressed air while the sampling train
was not in operation. This eliminated the possibility of
contamination from the relatively high amounts of organic,
partial combustion products produced during start-up and
shutdown of the incinerator. The back purge connection
was made at the point where the dogleg from the probe liner
mates with the filter housing.
0 A chromel/alumel thermocouple was potted Into the dogleg
going from the quartz probe liner to the filter housing to
check the temperature of the gas stream at that point.
22
-------
COMBUSTION
ZONE TRAIN
Figure 4-1. Location of Trailer and Sampling Trains at Systech
DUCT TO
SCRUBBEK
PROTECTIVE TARP
FOR COMBUST ION
ZONE TRAIN
PROTECTIVE
TARP FOR
STACK TRAIN
TOP OF
FLUSDIZED
BED REACTOR
Figure 4-2. Closer View of Sampling Train Locations
23
-------
ro
2B
l-3
HCF
l-2
COMPRESSED
AIP SOURCE
»VENT
IN
CO
our
2 WAY BALL VALVE
WHITEYJS-4234
3 WAY BALL VALVE
WHITEY SS-43X54
55-45X38
5 WAY BALL VALVE
WHITEY 55-432
FLOWMETER WITH INTEGRAL
CONTROL/SHUTOFF VALVE
HYDROCARBON REMOVAL
FILTER
PRESSURE REGULATOR WITH
GAGE (2 STAGE)
DRYER/FILTER
CONDENSATE TRAP
- 1/4- TUBE
• 1/5- TUBE
Figure 4-3. Sampling System For On-Line Instruments
-------
Table 4-5. Description of On-Line Instruments
Species Analyzed
Manufacturer
and Model
Range1*
Total hydrocarbons (HC)
Carbon monoxide (CO)
Carbon dioxide (C02)
Oxygen (02)
Oxides of nitrogen (NO )
A
Beckman
model 402
Beckman
model 865
Beckman
model 864
Taylor
OA 273
Thermo
Electron
model 10-A
0.05 ppm - 10% with
eight ranges
2-200 ppm
10-100 ppm
0.05 - 5%
0.02 - 20%
0.05 - 5%
0.25 - 25%
1 - 100%
0.05 - 10,000 ppm
with eight ranges
All of these manufacturers report an accuracy of ±1 percent of full
scale for their instruments.
• An ultrahigh-purity glass fiber filter was used, Gelman
Spectroquality Type A. The filters were muffled to remove
organics and have extremely low background levels of inor-
ganics. They were tared by desiccating and weighing on con-
secutive days to a constant weight (±0.1 mg), and were then
stored and handled throughout the tests and analyses in
glass petri dishes.
• A solid sorbent trap, designed to adsorb the organic con-
stituents in the sample gas stream,» is located downstream
of the heated filter and upstream of the first impinger.
The sorbent trap, with overall dimensions of 170 x 45 mm,
contained ^40 g of XAD-2, an AmbeHite resin of the type
commonly used as a chromatographic 'support.
• A Teflon valve was added to the glass connector between the
sorbent trap and the first impinger through which glass
bulbs or Tedlar bags were filled with the sample gas to be
analyzed for volatile or gaseous components not collected
by the sorbent traps.
This hot zone train was operated at a flow rate of approximately
30 liters/min for 3 hours during each test, thereby sampling an average
of 4 to 5 cubic meters. Gas volumes were measured to 0.03 liter, with
25
-------
MANIFOLD
HALVES AND
FLOWMETERS
Figure 4-4. Instrument Racks
26
-------
ro
INCINERATOR
WALL
WATER
COOLED
PROBE |V»
HEATED AREA
QUARTZ
LINER
THERMOMETERS
ORIFICE
4 INCH
FILTER
HOLDER
SOLID
SORBENT
TRAP
GAS
SAMPLE
VALVE
THERMOMETER
CHECK
VALVE
BVALv!S IMPINGERS VACUUM
\ (MAXIMUM SIX) GAUGE
C/
LINE
DRY TEST METER
AIR-TIGHT
PUMP
Figure 4-5. Combustion Zone Sampling Train Schematic
-------
COOLING
WATER
INLFT
PROBE
LINER
AIR/WATER COOLANT
FOR SAMPLE GAS
INLET
COOLING
MATER
OUTLET
Figure 4-6. Water Cooled Probe Design
a leak rate of less than 0.6 I1ter/m1n. Operating parameters for the
train and sample volume data are tabulated in Appendix B.
The following hot zone samples were obtained from each test:
• Solvent probe wash
0 10 cm diameter participate filter
0 Solid sorbent trap
• Grab gas
0 Combined impinger solutions
0 Acidified split of combined liquid impingers
0 Spent silica gel
The location of the hot zone sampling train at the test site 1s shown in
Figures 4-1 and 4-2.
4.3.3 Sampling Emissions and Waste Products
Samples of the stack effluent, spent scrubber water, and solid com-
L stor residue (bed sand), were taken during and after each test to
28
-------
evaluate the environmental safety of the final emissions. An EPA Method 5
test was performed at the stack for participate mass loading and composi-
tion determinations. Location of the sampling train at the test site Is
shown in Figure 4-2. Only one point in the 3-meter diameter stack was
sampled. Selection of the sample point is discussed in Section 4.5. Sam-
pling was carried out for 1 hour at approximately 20 liters/min. Gas vol-
umes were measured to 0.03 liter, with a leak rate of less than 0.6 liter/
min. Operating parameters for the train and sample volume data are tabu-
lated in Appendix B.
Oxidizing agents (H202 and (NH^SgOeJ were added to tne impingers to
aid scrubbing of trace metals. The following samples were obtained for
each test from the stack sampling train:
• Aqueous probe wash
• 10-cm diameter particulate filter
• Impinger solutions
0 Acidified split of impinger solutions
• Spent silica gel
Scrubber water samples were taken from a tap in the scrubber recircu-
lation line. Prior to each test the scrubber system was filled with city
water, cycled through the scrubber system and then drained. The system
was then filled and circulated again before the fresh scrubber water (FSW)
sample was taken. The spent scrubber water (SSW) was sampled Immediately
after the test was concluded. The sample was taken from the same tap with
the recirculation pump still operating in order to maintain mixing and pre-
vent sedimentation. The scrubber water samples were placed in one gallon
glass jugs and were refrigerated prior to shipment to TRW.
The fluidizing sand sample was taken approximately one half hour after
each test was concluded. The effect of the fluidizing air was considered
adequate to have thoroughly mixed the sand during the test. A 0.7 kg
representative sample was placed in an amber glass jar for storage and
shipment.
4.4 ANALYSIS TECHNIQUES
Samples taken as described in Section 4.3, were analyzed for both
organic and inorganic constituents. When necessary, extractions were per-
formed first to concentrate the sample in a suitable form for analysis.
Techniques used for these extractions and analyses will be briefly summa-
rized here. For more detailed discussions, see the Systems Technology
Analytical Plan (Reference 1).
29
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4.4.1 Extractions and Sample Preparation
Both solvents and acids were used to extract organics and inorganics
respectively, from the appropriate samples. These procedures and the basic
sample preparation steps are listed by sample type:
• Probe Washes
Combustion Zone
The quartz liner had been rinsed first with pentane to remove
organic matter. A water rinse was added to the procedure in
order to remove the fine particulate upon which the pentane
had little effect. The aqueous probe rinsings, particulate
included, were extracted with pentane, first by adding the
pentane probe rinsings, then with additional portions of
clean pentane. This pentane extract was combined with the
pentane solution from the filter extractions. The particulate
was recovered, dried and weighed. The weight value was then
added to the filter weight.
Stack
The aqueous probe rinse was evaporated to dryness and the
residue weighed. This weight was added to the weight of the
particulate on the filter for total mass loading calculations
in accordance with EPA Method 5 procedures.
• Filters
Combustion Zone
The tared sample filters plus two controls were desiccated
and weighed on consecutive days to a constant weight ±0.1 mg,
and then extracted in a Soxhlet apparatus for 24 hours with
pentane. Solvent extracts were evaporated to 10 ml for analy-
sis. The filters were then plasma ashed and extracted with
constant boiling aqua regia for two hours. This acid extract
was reduced to 50 ml for analysis.
Stack
The tared sample filters were weighted as for the combustion
zone filters, low temperature plasma ashed, and extracted
with constant boiling aqua regia for two hours. The acid
extracts were reduced to 50 ml for analysis.
• Solid Sorbent Traps
Combustion Zone
The XAD-2 resin was extracted in the Soxhlet-type apparatus
shown in Figure 4-7 with pentane and methanol for 24 hours
30
-------
-CONDENSER
TEFLON
SEAT
-24/40 JOINTS
28/12
TEFLON
SLEEVE
GLASS J4
WOOL
XAD2
FRIT
28/12
-FLEXIBLE TEFLON
COUPLING
24/40 JOINTS
250ml FLASK
Figure 4-7. Sorbent Trap Extractor
31
-------
with each solvent. These extracts were evaporated to 10 ml
for analysis. Two unused traps were also extracted for back-
ground values and a blank on the solvent was also run.
Stack
No solid sorbent traps were used in the stack sampling train.
t Grab Gas
Combustion Zone
No special preparation was required.
Stack
No gas samples were taken at the stack.
• Impingers
Combustion Zone and Stack
The volume of liquid 1n the impingers was measured and the
spent silica gel was weighed in the field after each test
burn to determine the amount of water collected. The liquid
impingers from the combustion zone were also combined and
150 to 300 ml aliquots acidified in the field to stabilize
the metals for analysis. The stack impinger samples were
also acidified. No extractions or other special preparation
steps were performed on any of the impinger samples.
• Scrubber Waters
300 to 1000 milliliter aliquots of the scrubber water samples
were extracted for organics according to the procedure for the
separatory funnel extraction for oil and grease from water
recommended by the EPA Handbook on Methods for Chemical Analy-
ses of Mater and Wastes with the substitution of pentane for
Freon (National Environmental Research Center, Cincinnati,
Ohio, 45268, EPA-626-/6-74-003). However, instead of evapo-
rating the material to the dried residue, the extracts were
concentrated to a 10 milliliter sample by use of a Kuderna-
Danish concentrating evaporator. Aliquots of this 10-milliliter
sample were then used for the survey analysis (IR and LRMS)
and for gravimetric determination of residual material after
evaporation at ambient conditions and immediate weighing.
• Solid Combustion Residues
Approximately 150 g portions of the sand sample from the flu-
idized bad were extracted in a Soxhlet apparatus for 24 hours
with pentane. The solvent extracts were then evaporated to
10 ml for analysis.
32
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4.4.2 Analytical Methods
After extraction of the samples for organic material and other prep-
aration for Inorganic material, the concentrated extracts* and aqueous
solutions were analyzed by several methods which are summarized In Table 4-6.
A general treatment of the sample preparation and analytical procedures is
discussed below.
4.4.2.1 Organic Analyses
The concentrated solvent extracts of the filters, sorbent traps.
scrubber waters, and sand bed samples were analyzed by gravimetry, IR, LRMS
and GC techniques. An aliquot of each extract was evaporated at ambient
conditions to remove the solvent. The residue was weighed and analyzed
by IR and LRMS.
The IR and LRMS analyses yield qualitative information about the
classes or types of compounds (e.g., hydrocarbons, phenols, ROMs, etc.)
present as well as an idea of the complexity of the concentrated sample.
Knowledge of the classes of compounds present provides a measure of the
toxicity, if any, of the residue. The detection limits for these analyt-
ical techniques vary somewhat with the type of compound (see Table 4-6).
The grab gas samples contained in the Tedlar®f1lm bags were ana-
lyzed on the mass spectrometer. The bags were placed in a covered box and
heated to about 70°C to ensure vaporization of any condensete. A portion
of the gas sample was vacuum transferred into the inlet system of constant
volume and measurable pressure. Test samples were introduced to the mass
spectrometer with interspersed control samples of standard ppm butane as
well as background control samples to ensure that the instrument was not
slowly accumulating a "memory" in the m/e peaks of interest.
Separation and quantisation of organic compounds known to be present
in the wastes and therefore possibly present in the concentrated extracts,
were performed by gas chromatography with flame ionization detection
(GC/FID) using the following parameters:
• Van'an 1860, dual differential FIDs
• Columns: dual, 183 x 0.32 cm o.d. stainless steel, 3% SE-30
on 100/120 mesh Chromosorb WHP
• Temperatures: column, 35° to 250°C at 6°C/min, 8 minute hold
at 2500C; injector, 250°C; detector, 300°C
• Flow rates: helium carrier, 30 ml/min; air, 300 ml/min;
hydrogen, 30 ml/min
a Attenuation: 1 x 10~10 a/mv full scale
The SE-30 columns were substituted for the Chromosorb 102 columns mentioned
in the Analytical Plan for Systech (Reference 1). when it was determined
that they would provide a general improvement in performance.
33
-------
Table 4-6. Summary of Analytical Methods
Method
Instrument Manufacturer
and Model
Detectability for a Compound or
Element Being Searched For
u>
Organic Analyses
Gravlmetry
Infrared
Spectrophotometry
(IR)
Low Resolution Mass
Spectrometry
(LRMS)
Gas
Chromatography
(GC)
Combined Gas
Chromatography/Mass
Spectrometry
(GC/MS)
Inorganic Analyses
Inductively Coupled
Plasma Optical Emission
Spectrophotometry
Mettler, mlcrobalance
Perkin Elmer, 521
Hitachi-Perkin Elmer,
RMU-6 Mass
Spectrometer
Van an, 1860 dual
FID
Varian, 1860 GC and
Hitachi-Perkin Elmer,
RMU-6 MS
or
Finnigan, 9500 GC and
Finnigan, 3100D Quadrapole
Mass Spectrometer
Applied Research
Laboratories, QA-137
1 ug •
^3-5% of the sample
being examined
MO pg
of a 1 mg sample)
M yg per ul of sample
MOO ng per yl of sample
M). 5-2000 ppb
-------
Table 4-6. Summary of Analytical Methods (Continued)
Method
Atomic Absorption
Spectrophotometry
(AAS)
Spark Source
Mass Spectrophotography
(SSMS)
Instrument Manufacturer
and Model
Jarrell Ash, 810
AEI Scientific
Apparatus Ltd.-, MS 702R
Detectablllty for a Compound or
Element Being Searched For
-0.001 ppm
%50-100 ppb
Ct>
01
-------
4.4.2.2 Inorganic Analyses
Inorganic analyses were performed using atomic absorption spectro-
photometry (AAS), and inductively coupled plasma optical emission spectro-
photometry (ICPOES). Selected samples of the acid extractions of the
stack particulate filters and the acidified splits of the impingers were
surveyed for trace metals by ICPOES. The ICPOES analysis determines
32 elements, including most of the toxic elements of interest to the
program, down to ppb levels with an accuracy of 100 to 200 percent. The
purpose of this survey is primarily to check that the metals in these
test samples are in approximately the same amounts relative to each other
as they were in the waste material. Those elements which from the results
either of the ICPOES survey or of the analysis of the waste material seem
to be present at potentially toxic levels, were determined quantitatively
by AAS. The sensitivity of this method varies from approximately 1.0 to
0.001 ppm for the elements which were determined, with an accuracy between
10 to 50 percent.
In addition to the AAS and ICPOES analyses performed on the test
samples, spark source mass spectrophotography (SSMS) was used to analyze
the waste materials for trace elements.
4.5 PROBLEMS ENCOUNTERED
Problems which occurred during the Systech test program are described
in the following paragraphs. In spite of detailed planning and prepara-
tion for these field tests, a few incidents occurred that had not been
anticipated. Corrective actions were immediately taken in each case, and
testing was completed as scheduled. All required samples were obtained,
and no problems were encountered in the laboratory analyses.
4.5.1 Vortex Flow in Exhaust Stack
Velocity traverses made in the exhaust stack indicated a steep gradi-
ent in velocity, with flow in the center of the stack even reversing in
direction. This flow condition results from the, tangential flow of gases
from the scrubber duct into the vertical stack without any straightening
vanes to redirect the flow. This anomaly was also observed by previous
sampling teams (Reference 2) at this facility. Since standard EPA
Method 5 (Reference 3) stack sampling techniques were not suitable for
this turbulent flow, the decision was made to sample at the average veloc-
ity point. All stack samples were taken at this point, located 0.6 meter
inward from the wall of the exhaust stack, which was 3 meters in diameter
at the sampling location.
4.5.2 Combustion Zone Sample Probe Plugging
Plugging of the quartz liner of the hot zone sampling probe occurred
during both of the waste phenol destruction tests. The first phenol test
(Test I) was terminated after a sufficient sample had been acquired, but
at less than the 3 hours intended (2-1/4 hours), because of plugging.
Combustion zone sampling during the second phenol test (Test III] was
36
-------
performed for the full 3 hours by back purging the probe liner with water
when plugging occurred. A small amount of participate was flushed from
the probe liner during this purge, affecting the total material weighed at
the conclusion of the test, and must be estimated as part of the particulate
loading. The probe was most likely plugged by fine sand particles from the
reactor bed. The Black Clawson operators indicated that burning of watery
wastes, such as the phenols, usually causes fracturing and depletion of the
reactor bed sand.
4.5.3 Variation in Concentration of Methyl Hethacrylate Waste
The methyl methacrylate waste received for the test program had a high
percentage of water compared to the waste sample received earlier. Arrange-
ments for supplying the waste in each case was made by Systech. When the
waste to be destructed was found to be different than the original sample,
the waste supplier was contacted by Systech. Systech was then informed that
the watery waste was more typical of the plant waste stream. For this rea-
son, the watery waste methacrylate was destructed during this test series
using No. 2 oil as auxiliary fuel to support combustion. Samples of the
waste feed were taken to undergo the same analysis procedures performed
with the initial waste samples.
4.5.4 Saturation of Gastec® Tubes with Condensed Water
During the testing at Systech, it was planned to use the Gastec®
tubes at the wet scrubber outlet in the same manner as they were used at
the first facility. Both the Marguardt and the Systech effluent gases were
saturated with water vapor but the considerably cooler ambient temperatures
at Systech made condensation in the Gastec® tubes a significant problem.
The indicating solids were completely saturated with condensed water and
no readings could be obtained.
Pieces of copper tubing a few meters long and a glass, water-knock
out trap were used at Systech in an attempt to correct the problem. How-
ever, this approach was unsuccessful and the solid contents of the tubes
still became saturated. In addition the use of a condensing apparatus
raises the question of whether the sought for species is being removed
from the gas as a result of the condensation, thereby resulting in an
erroneously low reading.
Bendix Corporation, the manufacturers of the Gastec tubes, was con-
tacted and they also felt that the tubes will not operate reliably, if
at all, when water condenses in the indicating portion of the tubes. They
also agreed that removing the water by means of condensing or passing the
gas stream through a drying agent will likely result in low values due to
either gas solubility in the condensed water or gas absorption/reaction
on the drying agent.
In future field tests, Gastec tube measurements will have to be made
where the gases are dry. The best place for this is the sample by-pass
output 0* the gas conditioner. Values measured at the by-pass outlet
would indicate composition before the scrubber, and not the final effluent
concentration. However, species found to be at safe levels before the
scrubber can be assumed to be at safe levels in the final effluent gases.
37
-------
4.5.5 Exhaust Plume Fallout
During the first phenol waste test* a lingering blue-gray haze was
observed trailing the normal steam plume from the exhaust stack. This
test was performed at a phenol feed rate of 50 liters/min and at a waste/
auxiliary fuel ratio of 3:1. For the subsequent tests, waste feed flow
rate was reduced, and plume fallout was no longer observed. Analytical
results later indicated that a waste destruction efficiency of over 99.999%
was achieved during the first phenol waste test even at the 50 liters/min
feed rate.
38
-------
5. TEST RESULTS
The test burns at Systech consisted of a background test on the auxil-
iary fuel (No. 2 oil), two tests of phenol waste, and two tests of methyl-
methacrylate (MMA) waste. The results of these tests described in the fol-
lowing sections include:
• Data taken in the field during the tests
t Data from analysis of the test samples in the laboratory
5.1 OPERATIONAL AND FIELD DATA SUMMARY
The data presented in this section were collected from the operation
of:
• Systech fluidized bed incinerator facility
• TRW on-line gas composition monitors
All recorded data for the incinerator operating conditions were provided by
Systech and are summarized in Table 5-1. Temperatures and pressures in the
reactor stayed fairly consistent through each test and from one test to
another. Conditions at the sampling port for the combustion zone train
were closest to those reported for the reactor freeboard.
Readings from the on-line gas monitors were continuously recorded on
strip charts. Resulting scans were averaged, over the 2-3 hour long test
runs and concentration values obtained are shown in Table 5-2. Percent
excess air was calculated according to the equation in EPA Method 3 (Ref-
erence 3).
An attempt was also made to use the Gastec® tubes to detect SOX and
hydrocarbon species at the stack. However, because of the high moisture
content of the stack gases and low ambient temperatures, the detection
tubes became saturated with condensed water and 'thus accurate readings
could not be obtained. The condensation problem was discussed further in
Section 4.5.
5.2 ANALYTICAL DATA SUMMARY
The data obtained from analysis of all samples taken during the five
test burns at Systech will be presented in this section in the following
order with the organic composition discussed before the inorganic
composition:
Combustion Zone
• Combustion gas
39
-------
Table 5-1. Incinerator System Parameters Data Summary
Test No.
Waste Tested
Waste/Auxiliary Fuel Ratio
Flow Rates
Waste ( liter s/m1n)
Aux. fuel (Hters/m1n)
Fluidizing Air (m^/mln)
Overbed Air (m3/min)
Scrubber Quench Water
(liters/min)
Scrubber Seal Water
(liters/min)
Temperatures
Reactor Bed TE-1 (°C)
Reactor Bed TE-2 (°C)
Reactor Bed TE-3 (°C)
Reactor Bed Controller (°C)
Reactor Freeboard (°C)
Reactor Duct North End (°F)
Scrubber Inlet (°C)
Scrubber Outlet (°C)
Pressures
Waste Feed Pump
(kilopa seals)
Windbox (cm H20)
Bed Differential (cm HgO)
Freeboard (cm H20)
Exhaust Oxygen (percent)
Calculated Residence Time (sec)
I
Phenols
3.0:l<2>
49.9
16.4
350
72
2.3
1.6
743
757
721
735
899
888
85
92
270
152
81
8.9
9.60)
14
II
/ • \
_(1)
-
-
12.1
435
105
2.3
1.6
782
779
766
779
793
768
76
82
_
157
79
10.7
14.8
12
III
Phenols
2.3:1
33.6
14.8
425
105
2.3
1.6
760
763
749
754
813
796
80
85
T90
168
86
17.8
17.7
12
IV
Methyl
Metha-
crylate
2.0:1
29.5
15.0
425
105
2.3
1.6
774
777
771
771
824
796
80
85
140
168
81
15.7
14.5
12
V
Methyl
Metha-
crylate
2.6:1
36.4
14.0
425
105
2.3
1.6
791
791
782
788
843
841
82
91
190
163
81
14.7
14.1
12
(1)
(2)
(3)
Background test with auxiliary fuel (No. 2 oil) only
Volumetric flow ratio - liters per minute waste/liters per minute auxiliary fuel
Oxygen content of exhaust gases in stack as measured by Black Clawson personnel
40
-------
Table 5-2. Gas Composition Data Summary
Test
No.
I
II
III
IV
V
°2
(percent)
10.7
15.4
12.6
13.4
11.6
co2
(percent)
9.4
5.9
7.6
7.4
8.0
CO
(ppm)
6-7
5
8-26
8-10
10-20
N0x
(ppm)
56
10
41-51
-c
-c
(percent)
79.9
78.7
79.8
79.2
80.4
HC
(ppm)
5-20
10-50
0-33
0-40
0-10
EAb
(percent)
103
286
149
178
121
As methane
Excess air
cInstrument was down due to a broken power supply
Final Emissions
t Stack gas
• Scrubber water
• Solid Residue (bed sand)
Methods and techniques for the preparation and analysis of the test
samples can be found in Section 4.4.
5.2.1 Combustion Products
Samples of the combustion products were taken from the head space
above the fluidized bed reactor with the sampling train described in Sec-
tion 4.3.2. These samples were then separated into their organic and inor-
ganic constituents and analyzed by appropriate techniques. Analysis of the
combustion products is aimed mainly at identifying and quantifying any
unburned waste material or hazardous partial combustion products. The pro-
duction of potentially toxic levels of trace metals from burning these
wastes is also examined. Where quantified species are calculated back to
mg/m3 in the sample gas stream, the gas volume data used is summarized in
Appendix B.
41
-------
5.2.1.1 Organic Composition
The organic analyses were divided into: (1) quantitative determina-
tion of uncombusted known constituents from the waste material or other
specific compounds that could be expected to be present, and (2) qualita-
tive surveys to identify unexpected compounds.
Quantisation for Specific Compounds
Specific compounds such as phenol, cresols, and methyl methacrylate
monomer were analyzed by gas chromatography with flame ionization detection
(GC/FID). Samples which yielded quantities at or above the level of inter-
est were also analyzed by combined gas chromatography/mass spectrometry
(GC/MS) to identify the compounds present. The level of interest for this
program is defined as 0.1 mg/m3 of sample gas, the threshold level of nearly
all the most toxic species as defined by OSHA and other health and safety
organizations. Detection limits for many of the quantitative techniques
used extend down to gg/m3 levels. However, specific analyses to identify
compounds below the level of interest were not routinely performed.
Results of Gas Chromatographic Analyses
This section presents the results of the analysis for the specific con-
stituents of the wastes which were identified as being present in the survey
and representative waste samples. Gas chromatography with flame ioniza-
tion detectors (FID) were employed. The details of this analytical proce-
dure can be found in Section 4.4. The instrument parameters were estab-
lished so that all the compounds listed in Tables 4-1 and 4-3 would be well
separated and could be detected if present at or below the criterion level
of 0.1 ug/m • The instrument was calibrated, i.e., instrument response was
measured, with known amounts of pure phenol and'methyl methacrylate monomer
(MMA) which are the principal organic constituents of the wastes.
At the instrument sensitivity settings used for all the samples, the
minimum detectable quantities were:
• phenol: 0.003 microgram per microliter of concentrated
extract (yg/yl)
0 MMA: 0.02 microgram per microliter of concentracted
extract (yg/yl)
These minimum detectable quantities when related to the average combustion
zone sample gas volume of about 4.5 m3 are 0.007 and 0.04 mg/m3 for phenol
and MMA, respectively. These values change somewhat depending on sample
volume size (Table B-2).
The results of the GC analysis for the specific organic waste constitu-
ents plus possible unexpected compounds are given in Table 5-3. The table
shows that none of the compounds found in the waste were detected above the
limits set for phenol and MMA which are described earlier. Table 5-3 thus
nas been completed with "ND" (not detected) and the appropriate minimum
42
-------
Table 5-3. Results of Gas Chromatographic Analyses
of Combustion Gas Samples
Sample
SY-I-CG-PF & PW
SY-II-CG-PF & PW
SY-III-CG-PF & PW
SY-IV-CG-PF & PW
SY-V-CG-PF & PW
SY-I-CG-ST-P
SY-I-CG-ST-M
SY-II-CG-ST-P
SY-II-CG-ST-M
SY-III-CG-ST-P
SY-III-CG-ST-M
SY-IV-CG-ST-P
SY-IV-CG-ST-M
SY-V-CG-ST-P
SY-V-CG-ST-M
MMA Waste,. ,
Constituents, (a)
mg/m3 as MMA
__
ND (<0.04)
—
ND (<0.04)
ND (<0.05)
-_
~
ND (<0.08)
ND (<0.08)
—
—
ND (<0.07)
ND (<0.07)
(Lost)
ND (<0.09)
Phenol /Waste
Constituents, (a)
mg/m3 as Phenol
ND (<0.01)
ND (<0.01)
ND (<0.01)
—
—
ND (<0.01)
ND (<0.01)
ND (<0.01)
ND (<0.01)
ND (<0.01)
ND (<0.01)
—
—
(Lost)
—
ND: Not detected
PF & PW: Combined organic extracts from the particulate filter
and probe washings
ST-P: Sorbent Trap; pentane extract
ST-M: Sorbent Trap; methanol extract
ee Tables 4-1 and 4-3 for list of waste constituents
43
-------
detectable quantity. The minimum detectable quantities vary somewhat
depending on the size of the original gas sample (Table B-2). The units
for all the hot zone samples are milligrams of species per cubic meter of
sampled gas, water vapor included.
Analytical Efficiency
Table 5-4 reports the results of the analyses of several control sam-
ples used to determine recoveries or analysis efficiencies. An unused
sorbent trap was doped with phenol and designated SY-CG-ST-C3. Similarly,
a MMA doped trap was designated SY-CG-ST-C4. They were extracted, concen-
trated, and analyzed using the same procedures for the sample traps. In
addition, city water was doped with known amounts of phenol and MMA,
extracted, concentrated, and analyzed just as the scrubber water samples.
From the sorbent trap, the recovery of phenol is excellent, and the recov-
ery of MMA is adequate. The table shows that the first extraction with
pentane recovered the bulk of the dopants. From the tap water, the recov-
ery of phenol is poor, and the recovery of MMA is excellent. It should be
noted that the extraction and analysis procedures used for the Systech
samples have been standardized for all test samples from all facilities in
this program. Thus these procedures cannot be expected to be optimum for
each species of interest. The recovery factors given in Table 5-4 have
been applied to the appropriate Systech samples shown in Table 5-3, espe-
cially as they relate to the minimum detectable levels of phenol and MMA
in the various sample forms studied. It was.noted that in all cases the
minimum detectable levels are below 0.1 mg/m an agreed upon level below
which analyses are curtailed.
Table 5-4. Results of Gas Chromatographic Analyses
of Sorbent Trap Extraction Controls
Sample Name
Phenol Doped Trap;
Pentane Extract
Phenol Doped Trap;
Methanol Extract
MMA Doped Trap;
Pentane Extract
MMA Doped Trap and
Methanol Extract
mg Taken
MMA
-
-
V
t
13.1
Phenol
V
J
\ 6.2
.
-
mg Found
MMA
-
-
6.5
<0.2
Phenol
6.1
<0.03
_
-
Percent
Recovery
MMA
-
-
50
<1.5
Phenol
98
<0.5
_
-
44
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Qualitative Surveys
Samples were surveyed by gravimetric, infrared spectrometry (IR), and
low resolution mass spectrometry (LRMS) techniques. Since the qualitative
results correlate more to sample type than to waste burn, the data are dis-
cussed in the following order:
• Combined particulate filter and probe wash extracts
• Sorbent trap extracts
• Grab gas samples.
Combined Probe Wash and Particulate Filter Extracts
The types of organic material found in this survey are typical of those
compounds found in most of the other organic residues obtained in the survey
analyses from these tests. Hydrocarbon oils, phthalic acid esters, silicons
oils (or greases), and an antioxidant were found. The amounts at which
these materials were found are presented in Table 5-5. The values have
been corrected for those obtained from blanks and controls which were con-
siderably lower.
Further separation and identification of these compounds were not car-
ried out because of the relative nontoxic nature of the classes of com-
pounds represented. Additional details of the survey analyses on these
samples can be found in Appendix D.
Table 5-5. Summary of Survey Analysis on the Combined
Probe Wash and Particulate Filter Extracts
Test No.
I
II
HI
IV
V
Volume of
Sampled Gas3
(n>3)
1 atm and 21<>C
3.29
5.13
4.45
5.57
4.22
Amount of
Material Found
as Residue0
(mg)
7.76
6.20
1.11
7.85
5.32
Concentration
in Sample
Gas
(mg/m3)
2.4
1.2
0.2
1.4
1.3
aIncludes water vapor
Corrected for blank extraction thimbles and solvent
45
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Sorbent Traps
The amounts of material extracted from the sorbent traps and found as
a residue after mild evaporation are presented in Table 5-6. The amounts
have been corrected for the unused, control sorbent trap extracts. On the
average, the sample trap extracts had four times the residue as the control
trap extracts. The types of material found in the trap extracts by IR and
LRMS analyses were essentially the same for all samples.
The compounds found in the extracts from the sorbent traps consisted
primarily of hydrocarbons and phthalic acid esters. Fatty acids and a
squalene type compound(s) were also present at lesser levels. Traces of
silicones were present in some of the samples. Details of the IR and LRMS
spectra interpretation are described in Appendix D.
The fact that the residues from the sample traps average four times
greater than the residues from the control traps tends to indicate that the
traps did indeed collect these materials while in the hot zone train. How-
ever, the general makeup of the residues is essentially the same in both
sample and control trap extracts and this raises some doubt as to the main
source(s) of these compounds. No work was performed to examine this situa-
tion in greater detail because of the general, nontoxic nature of the resi-
dues found.
Grab Gas Samples
The contents of the Tedlar®gas sampling bags were analyzed by intro-
ducing a portion of the gas into the mass spectrometer and measuring its
pressure at constant volume. Spectral evidence of the common, expected
components of both air and the combustion gases, such as N2, 02, H20, C02,
H2, CO, and AR, were seen. In addition, evidence of ppm levels of hydro-
carbons were also seen as evidenced by peaks at 41, 43, 55, and 57 AMU.
No evidence of any other organics was detected and this includes the waste
constituents (e.g., phenol and MMA).
A 14 ppm butane in nitrogen standard was used to determine instrument
response to hydrocarbons at the same pressures and volumes used for the
samples. Using the height of the 43 AMU peak for calibration, the hydro-
carbon levels in the grab gas samples were measured. The results, corrected
for instrument background, are listed in Table 5-7. The results show 2 to
4 ppm as butane, C^IQ. When these values are multiplied by four to obtain
a hydrocarbon value as methane, CH4, the resulting range of 8 to 16 ppm is
in fair agreement with the on-line hydrocarbon analyzer data (Table 5-2).
46
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Table 5-6. Summary of Survey Analysis on Sorbent Trap Extracts
Test
No.
I
II
III
IV
V
Material
Extracted by
Pentane
(nig) a
8.0
8.5
5.4
7.7
Sample Lost
Material
Extracted by
Methanol
(mg)a
9.3
26.0
25.0
26.5
4.1
Total
Extractables
(ng)a
17.3
34.5
30.4
34.2
Not
Available
Volume of
Sample Gas
(m3)
3.29
5.13
4.45
5.57
4.22
Concentration
of Extractables
in Sample Gas
(mg/m3)
5.2
6.7
6.8
6.1
Not
Available
Corrected for control sorbent trap extract weights.
-------
Table 5-7. Approximate Hydrocarbon
Content In Grab Gas
Samples by LRNS
Test No.
I
II
II*
III
IV
V
Hydrocarbon Level
(ppm as butane)
2
3
4
2
3
3
*Redundant sample was taken at the
hydrocarbon analyzer bypass outlet.
5.2.1.2 Inorganic Characterization
Inorganic elemental concentrations were determined by analysis of the
participate filters and aqueous impinger samples. Figure 5-1 shows a photo-
graph of the particulate filters obtained from sampling the combustion gases
from Tests I through V, in order going from left to right and top to bottom.
Trace metals on the particulate filters were put into solution by acid diges-
tion of the filters. Quantitative analysis for selected elements were then
performed by atomic absorption spectrometry (AAS). The elements to be ana-
lyzed were selected by the following criteria:
(1) Potentially toxic (e.g., Pb, Cd, Sb, and Hg)
(2) Present at significant levels as determined by the:
(a) survey analysis of the wastes (Section 4.1),
and/or survey analysis of the stack filter acid
digests (Section 5.2.2.1).
Using these criteria, seven elements were selected for quantitative
analysis by atomic absorption spectrometry (AA'S). Four potentially toxic
elements (Ba, Cd, Cr, and Pb) were found at relatively high levels by the
ICPOES survey of the stack filter digests. The other three elements (Sb,
V, and Zn) analyzed were chosen on the basis of the waste analysis data.
Both the filter digests and the impingers from the combustion zone sampling
train were analyzed. Data from the filters are presented in Table 5-8,
along with the stack filter data for comparison. None of the seven elements
48
-------
Figure 5-1. Filters from Combustion Zone
Gas Sampling Train
analyzed were detected in the impinger samples. The calculated detectable
limits in the combustion gas stream for these elements were:
Sb - 0.02 mg/m3
V - 0.03 mg/m3
Zn - 0.0007 mg/m3
Cd - 0.001 mg/m3
Cr - 0.003 mg/m3
Pb - 0.007 mg/m3
Ba - 0.03 mg/m3
5.2.2 Final Emissions
Emissions from the Systech fluidized bed process were sampled and ana-
lyzed to evaluate the environmental safety of the waste burns. All of the
final process effluents were sampled; these were stack gas, scrubber water,
and solid residue (bed sand).
49
-------
Table 5-8. Trace Metals on Participate Filters by MS
Test No.
I
II
III
IV
y
Sampling Train
Combustion Zone
Stack
Combustion Zone
Stack
Combustion Zone
Stack
Combustion Zone
Stack
Combustion Zone
Stack
Element Concentration in Gas Stream (mg/m3)
Bal
<0.142
<0.07
<0.27
<0.26
<0.04
<0.93
<0.08
<0.55
<0.60
<0.40
Cd
0.029
0.062
0.009
0.007
0.039
0.026
0.035
0.029
0.67
0.16
Cr
0.068
0.065
0.10
0.042
0.12
0.093
0.13
0.082
0.26
0.18
Pb
1.16
0.87
0.13
0.086
1.03
0.44
0.85
0.55
4.74
2.21
Sb
0.029
0.022
<0.001
<0.021
0.021
<0.024
0.031
<0.014
0.058
<0.012
V
<0.0033
<0.004
<0.002
<0.007
<0.002
<0.008
<0.002
<0.005
<0.002
<0.004
Zn
0.36
0.24
0.24
<0.23
0.25
0.17
0.32
0.12
0.66
0.072
in
o
Barium had very high and erratic background levels in the filter material.
o
"<", a less than or equal to sign indicates those elements which were detected but not significantly
above background levels.
"<", a less than sign indicates the detection limit for elements which were not detected.
-------
5.2.2.1 Stack Gas
Stack effluents were sampled during the tests with a standard EPA
Method 5 train. The samples obtained were analyzed to determine particu-
late loading in the effluent gas and elemental composition of the particu-
late. Figure 5-2 shows the particulate filters obtained from sampling the
stack gas from Tests '. throughV, in order going from left to right and top
to bottom. The Test I filter stuck to the filter housing gasket and sub-
sequently was torn while being removed.
Particulate loading was determined by adding the weight gain on the
filters to the weight of residue in the probe washes. This total was then
divided by the dry sample gas volume and the loading values obtained are
listed in Table 5-9.
After weighing, the filters were acid digested and selected samples
were surveyed for trace metals by inductively coupled argon plasma optical
emission spectroscopy (ICPOES). The results of this survey are shown in
Table 5-10. Of the 32 elements that are determined by the ICPOES analysis,
eleven were not detected in the filter digest samples. These eleven ele-
ments with their lower detection limits are listed in Table 5-11, along with
a calculation of the average detectable limit for each of these elements in
the flue gas.
Figure 5-2.
Filters from Stack
Gas Sampling Train
51
-------
Table 5-9. Particulate Loading in the Effluent Gas
Test
I - Phenol
II - Background
III - Phenol
IV -MMA
V -MMA
Weight on
Filter
(mg)
2,184
691
1,084
822
909
Weight in
Probe Wash
(mg)
47
5
14
16
19
Total
Weight
(mg)
2,231
696
1,098
838
928
Sample Gas
Volume, Dry
(m3)
1.56
0.98
0.86
1.34
1.65
Particulate Loading
mg/m^
1,430
710
1,280
630
560
Grains/scf
0.62
0.31
0.56
0.27
0.25
in
ro
-------
Table 5-10. Survey for Trace Metals in the Stack
Filter Digests by ICPOES
Element
Al
Ba
B
Ca
Cd
Cr
Cu
Fe
Pb
Mg
Mn
Ni
P
K
Si
Ag
Na
Sr
Ti
V
Zn
Concentration in Stack Gas (mg/m )
Test II
(Background)
<0.55a
<0.44-
<0.83
0.55
0.007
0.036
0.035
0.15
0.082
<0.36
0.004
0.004
0.075
ND (<0.012)
<0.28
0.004
2.7
<0.015
0.082
0.0005
<0.15
Test III
(Phenol)
<0.72
<0.90
<1.5
1.01
0.016
0.061
0.47
4.5
0.40
<0.31
0.015
0.012
0.31
3.1
<0.09
0.001
89.
<0.017
0.048
0.0015
<0.28
Test V
(MMA)
<0.83
<0.44
<0.38
1.6
0.15
0.13
0.38
0.56
2.3
<0.53
0.013
ND (< 0.0002)
0.68
2.4
<0.07
0.013
23.
<0.018
0.088
0.0008
<0.22
a
a less than or equal to sign indicates those elements which
were detected but not significantly abqve background levels.
53
-------
Table 5-11.
Limits of Detection for Elements
Undetected by ICPOES
Element
Au
As
Be
Co
Eu
Mo
Se
Te
Sn
W
U
ICPOES
Detection
Limit
(ppb)
5
40
1
16
15
11
60
65
50
90
80
Average
Detectable Limit
in Flue Gas
(mg/m3)
0.0001
0.001
0.00003
0.0004
0.0004
0.0003
0.002
0.002
0.001
0.002
0.002
aBased on an average wet sample gas volume of
2.0 m3
The results of this survey indicate four elements (i.e., cadmium, chro-
mium, lead, and barium) are present at potentially toxic levels. To be sure
of an accurate measurement of the levels of these and certain other toxic
metals which the waste analysis indicated might be present at levels of
interest, a quantitative determination by AAS was performed on seven ele-
ments. Data obtained from the AAS analyses on the stack filter digests is
summarized along with data from the combustion zone filter digests in
Table 5-8. The AAS data confirms the ICPOES survey in that there were rel-
atively high levels of certain elements in the effluent gas.
Trace metals in the form of very fine particulate or vapor can pass
through the filter. Thus to be sure of a quantitative measurement of total
metal emissions, both ICPOES and AAS analyses were also performed on the
impinger samples from the stack sampling train. 'The first liquid impinger
samples from selected tests were surveyed for inorganics by ICPOES and the
results are shown in Table 5-12. Only eleven elements were detected in the
samples, thus most of the data in this table are detection limits for the
undetected elements. The AAS analysis was performed on both the first
and the combined second and third impinger samples from all five
54
-------
Table 5-12. Survey for Trace Metals in Stack First
Liquid Impinger Samples by ICPOES
Element
Al
As
Ba
Be
B
Ca
Cd
Cr
Co
Cu
Eu
Fe
Au
Pb
Mg
Mn
Mo
Ni
P
K
Se
Si
Ag
Na
Sr
Te
Sn
•y
Concentration in Stack Gas (mg/nr)
i
Test II
(Background)
^.OOB1
<0.01
<0.08
< 0.0002
0.22
0.027
<0.003
<0.002
<0.004
0.001
<0.004
0.002
<0.001
<0,02
<0.0001
< 0.0002
<0.003
<0.003
<0.12
8.7
<0.015
1.2
0.005
<0.15
<0.0002
<0.02
<0.012
Test III
(Phenol)
-------
Table 5-12.
Survey for Trace Metals in Stack First Liquid
Impinger Samples by ICPOES (Continued)
Element
Ti
W
U
V
Zn
Concentration in Stack Gas (mg/m )
Test II
(Background)
0.004
<0.02
<0.02
0.001
< 0.0005
Test III
(Phenol)
0.004
<0.02
<0.02
0.001
0.005
Test V
(MMA)
0.003
<0.01
<0.01
<0.0001
< 0.0003
tests. Although oxidizing reagents had been added to the impingers to
enhance inorganic recoveries, none of the seven elements analyzed by AAS
were detected above the reagent solution backgrounds. The calculated
detection limits in mg/m3 of flue gas for these elements were:
Sb
V
Zn
Cd
0.04
0.06
0.001
0.003
Cr - 0.006
Pb - 0.01
Ba - 0.06
The results from the impinger analysis indicate that the emitted inorganics
were in a sufficiently large particulate form to be collected on the par-
ti cu late filter.
5.2.2.2 Scrubber Water
The recirculated scrubber water was sampled, before and after each test
to obtain fresh scrubber water (FSW) and spent scrubber water (SSU) samples,
respectively. Aliquots of these samples were both solvent extracted for
analysis of organics and acidified to stabilize inorganics for analysis.
Comparison of the analytical results for the FSW and SSW samples yields an
estimate of how much, if any, hazardous species were added to the scrubber
water during each test.
The FSW samples obtained contained visible suspended solids, which
raised the possibility of cross-contamination between tests. It was also
observed during the tests that the scrubber could not be flushed out and
cleaned reliably. Thus, the analyses of FSW samples have been treated and
reported as separate data and have not been subtracted from SSW results.
56
-------
Organic Composition
As with other samples for analysis of organics, the scrubber water
extracts were quantitatively analyzed for specific compounds and qualita-
tively surveyed for overall composition.
Quantitative Results
The results of the analysis of scrubber water extracts for specific
waste constituents are presented in Table 5-13. None of the compounds
found in the wastes, and listed in Tables 4-1 and 4-3, was found in any of
the fresh or spent scrubber water extracts. The lower limits of detection
are shown as the numbers accompanying the "ND" (not detected) designation.
The levels are reported as phenol and MMA since these compounds were used
to calibrate and measure instrument response. However it is stressed that
analysis parameters were designed to separate and detect all the waste con-
stituents as a minimum.
Table 5-13. Results of Scrubber Water
Extract Analyses by GC
Test and
Sample
Identification
MMA Waste
Constituents,
mg/liter as MMA
Phenol Waste
Constituents,
mg/liter as Phenol
I -
II -
III -
IV -
V -
FSW
SSW
FSW
SSW
FSW
SSW
FSW
SSW
FSW
SSW
ND (<0.6)
b
ND
ND (<0.2)
ND (<0.6)
ND (<0.2)
ND (<5)
ND (<0.4)
ND (<1)
b
ND (<1)
ND (<0.4)
a
ND = not detected
3SY-II Scrubber water sample was accidentally destroyed by sample
bottle breakage at the Systech facility
57
-------
Qualitative Survey Data
Allquots of the solvent extracts were evaporated at ambient conditions.
The residue obtained from this step was then weighed and analyzed by 1R and
LRMS techniques. The concentration of extractable species in the scrubber
waters, as calculated from the extract residue weights is presented in
Table 5-14. The data from the IR and LRMS analyses indicate that hydro-
carbon based oils and phthalic acid esters are the major components of the
residue. These materials are commonly used as lubricants and also as plas-
ticisers in polymeric materials. A compound believed to be azeleic acid
(nonane dioic acid) 1s also present at lesser levels. It is not surprising
that these materials are present in scrubber liquids since the several pumps
and valves that the water flows through in the facility must be lubricated.
The IR and LRMS spectra were also searched for any evidence of the
constituents found in the representative wastes. No evidence of any of
these species was found. Further details on the data interpretation can
be found in Appendix D.
Table 5-14. Summary of Survey Analysis of
Scrubber Water Extracts
Test and
Sample
Identification
I -FSW
SSW
II -FSW
SSW
III -FSW
SSW
IV - FSW
SSW
V - FSW
SSW
Control Sampleb
Volume of Water
Extracted
(liters)
0.065
0.903
0.345
-a
0.337
0.905
0.351
0.905
0.348
0.902
0.922
Weight of Residue
in Extract
(mg)
1.1
0.9
1.8
—
6.6
1.8
2.7
0.4
1.6
1.3
2.4
Concentration
in Scrubber
Sampl e
(mg/ liter)
17
1
5
—
2
2
8
< 1
5
1
3
aSample was lost
bWater with known amounts of phenol and methyl methacrylate monomer added
58
-------
Inorganic Characterization
The acidified allquots of the scrubber water samples were analyzed by
AAS for seven elements Including the four (I.e., Ba, Cd, Cr, and Pb) found
to predominate in the filter digest samples. The results of this analysis
are summarized in Table 5-15. No values are reported for the SSW sample
from run I because an acidified split was not made in the field and thus a
reliable sample was not available.
The data show no significant changes in trace metal concentrations and
no clear trends. For Tests II and III, the FSW values are higher overall
than the SSW and for Tests IV and V, the opposite is true. No conclusions
can be made from this result since the flow of these trace metals through
the scrubber is a dynamic process. Whfle operating, some water in the
scrubber is bled off to compensate for condensation of water in the combus-
tion gases. Thus trace metals found in the fresh scrubber water could increase
or decrease depending on water input/output rates.
5.2.2.3 Solid Residue IBed Sand)
The bed sand is not, strictly speaking, an effluent of the Systech
process. The sand charge remains in the fluidized bed with fresh make-up
sand being added periodically. The objective of analyzing the sand samples
that were taken at the end of each test, was to determine whether any
residual hazardous materials were present which would effect disposal
methods for the sand if it had to be disposed of. However, there i-s little
likelihood that disposal of the sand would actually occur in practice.
Organic Composition
Portions of the sand samples were extracted in a Soxhlet apparatus
with pentane. The resulting extracts were then analyzed by the quantitative
and qualitative methods described previously in Section 5.2.1.1.
Quantitative Data
The results of the GC analysis for the compounds identified in the
wastes and searched for in the sand residue extracts are presented in
Table 5-16. The results are reported in milligrams per kilogram of sand,
which is the same as ppm on a weight to weight basis. None of the com-
pounds known to be in the phenol or MMA wastes were found in any of the
sand residues above the detection limits shown in the table. Phenol and
MMA monomer standards were used to determine instrument response.
Qualitative Survey Data
Evaporated aliquots of the solvent extracts were weighed and the
gravimetric results are shown in Table 5-17. Milligram quantities of
residues were found in the extracts. The control samples for the sand
extractions did not yield enough of a residue to be weighable. Thus, no
background corrections were needed. The IR data indicated only hydrocarbon
oils or greases and lesser amounts of ester compounds. The LRMS data con-
firmed the IR results but in addition found traces of di-tert-butyl-methyl
59
-------
Table 5-15. Trace Elements in Scrubber Waters by AAS (ppm)
Test
No.
I
II
III
IV
V
Ba
FSW
--
1.0
0.55
0.52
0.55
SSW
0.38
0.57
0.28
0.56
0.81
Cd
FSW
—
0.07
0.06
0.01
0.03
SSW
0.04
0.02
0.02
0.03
0.33
Cr
FSW
—
0.24
0.29
0.03
0.06
SSW
0.23
0.24
0.03
0.17
0.08
Pb
FSW
—
1.4
1.1
0.25
0.55
SSW
2.7
0.25
0.50
0.45
1.8
Sb
FSW
—
ND
ND
ND
ND
SSW
ND1
ND
ND
ND
ND
V
FSW
--
ND
ND
ND
ND
SSW
ND*
ND
ND
ND
ND
Zn
FSW
—
3.8
3.4
0.45
1.2
SSW
0.69
0.54
0.19
0.79
0.35
*ND - not detected, detection limits for Sb and V are 0.5 and 0.2 ppm, respectively.
FSW — fresh scrubber water
SSW - spent scrubber water
-------
Table 5-16. Results of Sand Extract
Analysis by GC
Test No.
I
II
III
IV
V
MMA Waste Constituents,
mg/kg as MMA
— _
ND (<1)
—
ND (<1)
ND (<1)
Phenol Waste Constituents,
mg/kg as Phenol
ND (<0.2)
ND (<0.2)
ND (<0.2)
—
—
a
ND: not detected
Table 5-17.
Summary of Survey Analysis
of Sand Extracts
Test No.
I
II
III
IV
V
Amount of Sand
Extracted
(kg)
0.158
0.154
0.154
0.161
0.161
Amount of Residue
in Extracts
(mg)
8.0
7.2
5.4
3.3
8.3
Concentration- of
Extrac tables
(mg/kg)
51
47
35
20
52
phenol (an antioxidant also known as BHT) and methyl abietate. Also seen
in the SY-I and SY-IV samples was a trace of an incompletely identified
chlorinated aromatic with a molecular weight believed to be 228. Its source
is not known. Constituents of the waste materials were specifically searched
for and were not detected in any of the samples. Further details of this
survey work can be found in Appendix D.
Inorganic Characterization
The bed sand samples were not analyzed for their inorganic constituents
for several reasons. First, since the bed sand is not recharged between runs
and municipal waste was burned between TRW's tests,-any residues associated
with the sand could not be related to contributions from the phenol or methyl
methacrylate wastes. Second, it is impossible'to analyze for inorganics on
the sand without analyzing to some degree the sand itself, which again would
have no relationship to contributions from the wastes burned.
61
-------
6. WASTE INCINERATION COST
Individual economic analyses were performed to determine the costs of
incinerating, on an industrial basis, the two high water content waste mate-
rials tested at the Systems Technology Corporation Incinerator at Franklin,
Ohio. The economic analyses were divided into capital investment and annual
operating costs. For each disposal facility, equipment prices, fuel con-
sumption, and manpower requirements estimates for the Dorr-Oliver fluidized
bed reactor-Venturi scrubber system were based on data obtained from Sys-
tems Technology Corporation. The costs of other portions of the disposal
facilities and associated labor were estimated using the method of Happel
("Chemical Process Economics," second edition, John Happel and Donald G.
Jordan, 1974), data from Guthrie ("Capital Cost Estimating," Chemical Engi-
neering, March 24, 1969), and standard engineering reference methods.
Equipment costs were adjusted to January 1976 prices using the Marshall &
Swift Index. Land prices are not included in the two disposal plant cost
estimates. Transportation costs were included for the methyl methacrylate
waste disposal economic analysis, which is premised upon a central facility
at Franklin, Ohio incinerating waste materials from the methyl methacrylate
plants within 240 kilometer rail shipping distance. Transportation costs
were not included for the phenol waste water disposal economic analysis,
since the incinerator was assumed to be located at the refinery generating
the waste to be disposed.
6.1 CAPITAL INVESTMENT
The capital investment for the facility to incinerate 13.2 million li-
ters per year of aqueous methyl methacrylate manufacturing wastes shown in
Table 6-1 is based upon a design concept which employs a 7.6 meter freeboard
diameter Dorr-Oliver fluidized bed reactor, equipped with Venturi scrubber
and auxiliary equipment. The facility costs include a methyl methacrylate
waste storage tank (60-hour capacity), fixed rate waste feed pump, fuel oil
storage tank (5-day capacity), auxiliary air compressor (for fuel gun inser-
tion and removal), ash-water slurry bleed pump, and ash-water slurry settling
tank (5-hour retention capacity). A sludge pump for solids removal from the
settling tank, an emergency overflow sump (18925 liter capacity) for the
scrubber, and twin emergency sump pumps complete the purchased equipment
list. It was assumed that a waste to fuel ratio of 2.3 represented average
fuel consumption for proper operation of the incinerator.
The size of the facility was based upon three-shift, 5-day per week,
52 weeks per year operation, to dispose of the 13.2 million liters of waste
estimated available from plants 1n the Franklin, Ohio shipping area. The
methyl methacrylate waste incineration plant has a nominal thermal capacity
of 15 million kcal per hour; the actual thermal load, based on fuel values
for the 2200 LPH of waste and 924 LPH of No. 2 fuel oil, is 70 percent of
nominal thermal capacity.
The total capital investment for the methyl methacrylate waste incin-
eration facility is estimated at $5,984,200. It should be noted that the
facility would incinerate annually 11,250 metric tons of water only 1,250
62
-------
Table 6-1. Capital Investment
13.2 Million Liter/Year* Methyl Methacrylate Waste Incineration Plant
Equipment
Size
Estimated Costs
Equipment** Labor
01
OJ
1-Dorr-Oliver reactor, Venturi scrubber, and
auxiliary equipment
1-Waste storage tank
1-Waste pump
1-Ash-water slurry bleed pump
1-Ash-water slurry settling tank
1-Sludge pump
1-No. 2 fuel oil storage tank
1-Air compressor
1-Emergency overflow sump
2-Sump pumps
Instruments (10% of equipment)
(Key Accounts)
Insulation (10% of key accounts)
Piping (45% of key accounts)
Foundations 4% of key accounts)
Buildings 4% of key accounts
Structures (4% of key accounts)
Fire Protection (0.75% of key accounts)
Electrical (4.5% of key accounts)
Painting & Cleanup (0.75% of key accounts)
7.6
m free board diam. $1,250,000
13,250 liters 15,700
2250 lph@ 400 kilopascals
100 1pm
38,000 liters
200 1pm
100,000 liters
2.8 scmm @ 345 kilopascals
18,925 liters
1000 1pm
800
900
400
000
100
300
500
3,000
7
1
9,
5,
$1,293,700
129.400
$1,423,100
142,300
640,400
56,900
56,900
56,900
10,700
64,000
10.700
$2,461,900
$129,000
19.400
$148,400
213.500
640,400
85,400
39,800
11,400
69,600
96,000
69,600
$1,374,100
Equipment & Labor
Overheads (30% of Equipment & Labor)
Total Erected Cost
Engineering Fee (10% of Erected Cost)
Contingency Fee (10% of Erected Cost)
Total Capital Investment
*90% (W/W) Water; 10% (W/W) Organic Liquids
**F.O.B. Cost
$3,836,000
1,150.800
$4,986,800
498.700
498,700
$5,984.200
-------
metric tons of liquid organic materials (almost completely insoluble in
water). If the organic liquids phase of the methyl methacrylate waste were
separated by centrifugation at the source plants, the capital investment
for incineration of the resultant 1,420,000 liters of organic materials
(equivalent to 28 days of full scale incinerator operation) could be pro-
rated downwards, on a basis proportional to the fraction of overall operating
time. This would require that the subject fluidized bed incinerator be
employed for the majority of the year on wastes other than the methyl meth-
acrylate organic liquid phase material. An additional capital outlay would
be required at the waste source plants, for the facility to separate the
phases by centrifugation and to remove residual organic materials from the
centrifugate water phase (by techniques such as a combination of activated
carbon adsorption and ozonization) to produce an acceptable industrial
outfall. The total capital outlay for this alternative treatment and
incineration technology would probably be slightly over $1,000,000.
The capital investment shown in Table 6-2 for the facility required to
incinerate 23.8 million liters (26,300 metric tons) per year of phenol waste
water is based on the fluidized bed Incinerator system required at a re-
finery site to burn a 1:2.3 fuel oil: waste (volume) ratio, for a waste feed
rate of 72,000 liters per day. The fluidized bed reactor required is 7.6
meter freeboard diameter - the size used at Franklin, Ohio. The facility
design concept includes the Venturi scrubber and auxiliary equipment, a
phenol waste water agitated storage tank (approximately one week storage
capacity), fixed rate waste feed pump, fuel oil storage tank (1 day storage
capacity), auxiliary air compressor (for fuel gun insertion and removal),
ash-water slurry bleed pump, and ash-water slurry settling tank with 5-hour
retention capacity. The design differs only slightly from that of the
facility for incinerating methyl methacrylate waste. The remainder of the
phenol waste water facility includes a sludge pump for solids removal from
the settling tank, an emergency overflow sump (18,925 liter capacity) for
the scrubber and twin emergency sump pumps.
The estimated capital investment for the phenol waste water incinera-
tion plant is $6,075,200, not including land cost.
6.2 ANNUAL OPERATING COSTS
The annual operating costs consist of labor, fuel, other utility, solid
waste disposal and freight costs (where applicable) plus cost of capital,
equipment depreciation, maintenance, taxes and Insurance. The labor costs
have been calculated on the number of personnel assigned to operate the sys-
tem at the rates given by Systems Technology Corporation for Franklin, Ohio.
Costs for supervision, supplies and payroll-related expense have been
included, at rates prevalent in the chemical Industry.
The utility costs include those for electricity and water consumption
Annual electricity usage was calculated based on the motor horsepower
requirements for the equipment sizes and capacities shown in Tables 6-1 and
6-2. Water consumption data was taken from the sdata given on the Dorr-Oliver
process control diagram for the fluidized incinerator system. The amount of
No. 2 fuel oil consumed was based on actual test data for the two wastes at
the Franklin, Ohio site.
64
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Table 6-2. Capital Investment
23.8 Million Liter/Year Phenol Waste Water Incineration Plant
Ol
in
Equipment
1 -Dorr-Oliver reactor, Venturi scrubber, and
auxiliary equipment
1 -Waste storage tank, agitated, carbon steel
1- Waste pump
1-Ash-water slurry bleed pump
1 -Ash-water slurry settling tank
1 -Sludge pump
1-No. 2 fuel oil storage tank
1-Air Compressor
1- Emergency overflow sump
2-Sump pumps
Instruments (10% of equipment)
(Key Accounts)
Insulation (10% of key accounts)
Piping (45% of key accounts)
Foundations (4% of key accounts
Buildings (4% of key accounts
Structures (4% of key accounts
Fire Protection (0.75% of key accounts)
Electrical (4.5% of key accounts)
Painting & Cleanup (0.75% of key accounts)
Equipment & Labor
Overheads (30% of Equipment & Labor)
Total Erected Cost
Engineering Fee (10% of Erected Cost)
Contingency (10% of Erected Cost)
Total Capital Investment
*F.O.B. Cost
Estimated
Size Equipment*
7.6 m free board dram. $1,
568,000 liters
3200 Iph @ 400 kilopascals
100 1pm
38,000 liters
200 1pm
32,000 liters
2.8 scum @ 345 kilopascals
18,925 liters
1000 1pm
$1,
$1,
250,000
38,000
800
900
7,400
1,000
6,700
5,300
500
3,000
313,600
131,400
445,000
144,500
650,300
57,800
57,800
57,800
10,800
65,000
10,800
$3,894,300 JF.499 ,800
1,168,300
$5,062.600
506,300
506,300
$6,075,200
Costs
Labor
•«•—••—•—•"•—
$131,000
19.700
' 150.700
216,800
650,300
86,700
nn CAA
40,500
11,600
70,200
97,500
^n inn
70, ZOO
$1,394,500
-------
The annual operating costs for the incineration of 13.2 million liters
of methyl methacrylate waste at a central facility are sumnarlzed in Table
6-3. The estimated annual operating expense for the plant based on 15 shift
per week operating is $3,193,400, or $255.08 per metric ton. If the alter-
native treatment and incineration technology cited 1n Section 6.1 is employed,
the reduction in plant investment-associated annual costs (depreciation, cost
of capital, maintenance and taxes and insurance) would be over $1,700,000
with an additional reduction of over $800,000 based on zero fuel oil consump-
tion and reduced freight cost. Order of magnitude cost-per-ton estimate for
the alternative technology is $50.00.
The annual operating costs for the plant to incinerate 23.8 million li-
ters of phenol containing waste water are summarized in Table 6-4. The esti-
mated annual expense based on 330 day per year, three shift per day operation
is $3,268,600 or $124.24 per metric ton.
The cost of capital shown is based on the assumption that private debt
financing is used for each facility.
66
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Ot
-si
Table 6-3. Annual Operating Cost
13.2 Million Liter/Year Methyl Methacrylate Waste Incineration Plant
Item Cost - $/Year
Depreciation (15% of plant Investment)
Cost of Capital (10% of plant Investment)
Maintenance (8% of plant investment)
Utilities
Electric power [400 KW (24) (260) + 20 KW (24) (105)1 $0.15 =
Water 568 1pm (260) (1440) @ $0.066/1000 liter
Fuel Oil, No. 2 36,230 bbl @ $13.00/bbl
Solid Waste Disposal @ $6.50/ton for 9,350 metric tons
Freight 150 mi. 9 $1.42/cwt 12,500 metric tons@ $31.30/metric ton
Labor
Chief Operator 1 x 24 x 260 x $6.60 i
Operator Helper 1 x 24 x 260 x' $5.00 '
Supervision (15% of Operating Labor) =
Supplies (20% of Operating Labor) =
Payroll Related Expense (35% of Operating Labor) =
$38,200
14,000
471 ,000
72,400
10,900
14,500
25,300
$ 897,600
598,400
478,700
523,200
60,800
391 ,900
123,100
Taxes & Insurance (2% of plant Investment) 119,700
Total $3,193,400
Cost per metric ton of methyl methacrylate waste @ 12,500 metric tons/year $255.08
-------
Table 6-4. Annual Operating Cost
23.8 Million Liter/Year Phenol Waste Water Incineration Plant
Item
Cost - $/Year.
oo
Depreciation (15% of plant investment)
Cost of Capital (10% of plant investment)
Maintenance (8% of plant Investment)
Utilities
Electric power (400 KW (24)(330) + 20 KM (24)(35)1 $.015
Water 568 1pm (330)(1440) @ $0.066/1000 liter
Fuel Oil, No. 2 64,850 bbl 0 $13.00/bbl.
Solid Waste Disposal 0 $6.50/metr1c ton for 11,900 metric tons
Labor
Chief Operator 1 x 24 x 330 x $6.60 \
Operator Helper 1 x 24 x 330 x $5.00 r
Supervision (15% of Operating Labor
Supplies (20% of Operating Labor)
= $47,800
= 17,800
= 843,100*
= 91,900
= 13,800
= 18,400
$ 911,300
607,500
486,000
908,700*
77,300
156,300
Payroll Related Expense (35% of Operating Labor)
Taxes & Insurance
(2% of plant investment)
= 32,200
Total
121.500
$3,268,600*
Cost per metric ton of phenol waste water @ 26,300 metric tons/year
$ 124.24
*In the event that other refinery wastes can be used as fuel, utility
and total cost per year will decrease to $65,600 and $2,425,500
respectively; cost per metric ton of phenol waste water would then be $92.18.
-------
7. REFERENCES
1. TRW Document #27003-6002-RU-00, "Analytical Plan for Facility No. 3.
Tests to be Conducted at Systems Technology", by J. F. Clausen and
D. R. Moore.
2. "Fluidized Bed and Scrubber Emissions, City of Franklin Solid Waste
and Fiber Recovery Plant, Franklin, Ohio", Air Pollution Control
Division, Environmental Sciences, Inc., Feb. 28, 1972.
3. American Conference of Governmental Industrial Hygienists, Threshold
Limit Values, "National Safety News", October 1974.
4. Environmental Protection Agency, Standards of Performance for New
Stationary Sources., Federal Register, Vol. 36, No. 247, Dec. 1971
69
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APPENDIX A
ASSESSMENT OF ENVIRONMENTAL IMPACT OF DESTRUCTING CHEMICAL WASTES
AT
SYSTECH WASTE TREATMENT CENTER
BAXTER ROAD AT ROUTE 73
FRANKLIN. OHIO 45005
The Systech Waste Treatment Center In Franklin, Ohio, is adjacent to
the Franklin Solid Waste and Fiber Recovery Plant operated by Black Clawson.
Systems Technology Corporation has an exclusive contract with Black Clawson
for the destruction of liquid wastes in the fluidized bed incinerator.
Destruction of the following wastes will be evaluated using this incinerator:
(1) Waste phenols - 16,000 gallons (90% water)
(2) Methyl methacrylate - 3,500 gallons (concentrated)
The South-West Air Pollution Control Office, Cincinnati, Ohio, has been
notified of the schedule for destruction testing of these specific wastes.
The operating permit issued to the Franklin Solid Waste Recycling Plant by
the State of Ohio EPA Includes permission for Systech to incinerate liquid
industrial wastes at this facility.
Manufactured by Dorr-Oliver, this incinerator has a capacity of up to
360 gallons per hour of high heat content liquids (over 10,000 Btu/lb) and
up to 2,000 gallons per hour of liquids with a heat content of 3,000 Btu/lb.
The fluidized bed system is equipped with a high energy venturi scrubber.
Scrubber water is sent to the Miami Conservancy District Wastewater Treat-
ment Plant (adjacent to the incinerator) for processing. After scrubbing
exhaust gases are emitted into the atmosphere through a stack approximately
60 feet above ground level at a temperature of 180° to 190°F. Solid resi-
due (ash) is disposed of on-site in an approved landfill.
The incinerator facility is located in the Franklin Environmental Com-
plex, which also includes the Systech Waste Treatment Center and the Miami
Conservancy District Waste Water Treatment Plant. The surrounding area
includes industrial, commerical, agricultural, and residential developments.
Adjacent industries include Logan Long Paper Products, a producer of roofing
felt. A gasoline service station is also located nearby. The nearest resi-
dences are located approximately 250 yards east of the facility across Holes
Creek (a small tributary of the Miami River) and are dispersed among small
farms. Prevailing winds are from the southwest at usual velocities up to
10 miles per hour. Local vegetation includes trees, brush, weeds, and farm
crops. Birds and rabbits are the most apparent wildlife in the area.
i
Vehicular traffic includes about 30 trucks per day hauling municipal
waste to the Solid Waste and Fiber Recovery Plant (the fluidized bed incin-
erator also processes an average of 35 tons per day of municipal waste).
Delivery of the liquid wastes for this test program has a negligible effect
on overall traffic at the facility. Operation of the incinerator is only
slightly noisy even within the building, and only a white steam plume can
he seen from surrounding areas. The incineration facility normally operates
8 hours per day for a 4 day week, and employs eight persons.
70
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The prevention of any detrimental environmental impacts from the fol-
lowing aspects of the operation are expected to result from proper control
and testing: (1) storage and handling of wastes prior to destruction,
(2) emissions occurring during tests, and (3) disposal of liquid and solid
residue remaining after combustion. The most significant potential hazard
would result from contact with waste liquid and/or fumes during a spill.
The "Fire Protection Guide on Hazardous Materials," published by the National
Fire Protection Association describes these wastes as follows:
Phenol Toxic, causes severe burns, lethal amounts
(pure crystals) may be absorbed through skin or inhaled.
Methyl Slight irritant to eyes, skin, and respira-
methacrylate tory tract.
Storage and Handling
Liquid wastes will be received by tank truck and transferred to stor-
age tanks by Systech personnel trained in handling these materials. Avail-
ability and operation of safety equipment will be verified prior to any
waste transfer operation. Safety equipment includes: protective clothing,
fire extinguisher, oxygen mask, stretcher, and washroom facilities. Leaks
and any spills will be washed down with water. All rinse or wash down
liquids will be incinerated in the same manner as test wastes.
Incineration Tests
Operation temperature and residence time of the fluidized bed incin-
erator should provide essentially complete combustion of the wastes, result-
ing in harmless exhaust emissions. On-line monitoring of gases from the
combustion zone will be utilized as an indication of combustion efficiency.
The venturi scrubber is expected to remove trace amounts of HC1 gen-
erated by the combustion process. Emissions of SOX should be limited since
sulfur was found to be a minor waste constituent. In addition, the Black
Clawson scrubber should be effective in removing particulate from the
exnaust stream. Analysis of the two wastes incncatea tne presence of some
trace metals. Of the two wastes, phenol manufacturing waste presents the
worst case condition anticipated during the test burn program. Calcula-
tions for the predicted emissions levels (before scrubbing) were made to
assess potential environmental problems. The results of these calculations
are as follows:
Phenol Waste
S02 141 ppm
HC1 9 ppm
Zn 0.03 ppm
Cr 3 ppm
*
Waste phenols will contain 90% water.
71
-------
These levels are expected to be reduced via effective scrubbing; there-
fore, no serious environmental problem Is anticipated. As a precaution,
however, stack emissions (downstream of the scrubber) will be checked for
hazardous gaseous species using Gastec® analyzers for specific gases and
vapors. Particulate matter will be collected using a standard EPA Method 5
sampling train.
Disposal of Residues
Residue material from the incineration process will consist of scrubber
water and ash. Liquid residue from the scrubber will be analyzed by both
Black Clawson and the Miami Conservancy District Uastewater Treatment Plant
personnel before discharge to the on-site water treatment plant. Solid
residues (ash) will also be tested by the Miami Conservancy District per-
sonnel prior to on-site landfill. Wastes remaining in the storage/run tanks
and wash down liquids from any spills will be incinerated at the conclusion
of the test program.
72
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APPENDIX B
SAMPLE TRAIN OPERATION AND SAMPLE VOLUME DATA
For each test burn, data were collected on the operation of the
two sampling trains. This information is presented in Table B-l. The
gas velocity and stack pressure at the combustion zone (reactor freeboard)
were both theoretically calculated since no pi tot tubes could be used to
take a direct measurement at that point. The percent of isokinetic at
which the gas samples were drawn from both the stack and combustion zone
sampling sites was calculated from the following equation given in
EPA Method 5:
I =
(0-™ Dn2)
V 144 /
The terms of this equation are defined and values measured for each test
burn are summarized in Table B-l. It was assumed for the purpose of
these calculations that the 0.5-inch diameter combustion zone probe would
behave roughly the same as a 0.5-inch nozzle.
Tables B-2 and B-3 summarize the sample gas and collected water
volume data, respectively. The gas volumes are corrected to standard
conditions and are given for both the wet and the dry gas streams. The
wet gas volumes include water vapor. Dry gas volumes were used only to
calculate grain loadings for EPA Method 5. All other calculations of
species concentrations in the sampled gas were performed with the wet (or
true) gas volumes.
73
-------
Table B-l. Sampling System Data Summary
Run/Train
Run 1
Stack
Combustion Zone
Run II
Stack
Combustion Zone
Run III
Stack
Combustion Zone
Run IV
Stack
Combustion Zone
Run V
Stack
Combustion Zone
Sampling
Time
e(min)
100
135
60
180
60
173
60
180
60
163
Gas Volume
vm (ft3)
56.1
106.9
35.5
181.1
30.1
138.4
46.0
181.4
60.1
139.8
Liquid
Volume
Vwlml)
896
265
321
186
283
285
398
504
648
341
Stack
Temp.
ism
155
1650
150
1460
130
1414
140
1515
160
1550
Dry Gas
Meter Temp .
V°F>
82
89
82
95
74
84
86
102
90
100
Nozzle
Diameter
Dn (in.)
0.5
*
0.5
*
0.5
*
0.5
*
0.5
*
Gas
Velocity
Vs( ft/sec)
14.5
34.8
12.6
40.7
11.5
40.7
16.0
41.1
28.9
41.8
Barometric
Pressure
PBar(1n. Hg)
30.08
30.08
29.84
29.84
30.49
30.49
30.20
30.20
30.02
30.02
Stack
Pressure
Ps
(in. Hg)
30.10
30.34
29.86
30.15
30.51
31.01
30.22
30.66
30.04
30.45
Pressure
Drop
AH
(in. H20)
0.9
1.5
1.4
3.5
1.0
2.0
2.2
3.5
4.1
2.5
Percent
I sold net ic
95
120
93
110
85
90
92
120
74
100
*No nozzle was used for the combustion zone sampling train.
-------
Table B-2. Systech Sample Gas Volumes at Standard Conditions
Test
No.
I
II
III
IV
V
Stack
Dry
ft3
55.15
34.66
30.44
47.32
58.11
m3
1.56
0.98
0.86
1.34
1.65
Wet
ft3
97.62
49.88
43.85
75.64
88.80
m3
2.76
1.41
1.24
2.14
2.51
Hot Zone
Dry
ft3
103.75
172.48
137.41
172.67
132.75
m3
2.94
4.88
3.89
4.89
3.76
Wet
ft3
116.31
181.28
157.05
196.54
148.89
m3
3.29
5.13
4.45
5.57
4.22
75
-------
Table B-3. Collected Mater Volume Data
Test
I Hot Zone
Stack
II Hot Zone
Stack
III Hot Zone
Stack
IV Hot Zone
Stack
V Hot Zone
Stack
Water Volumes in Impingers
1st Imp. (ml)
Initial
100
100
100
100
100
100
100
100
100
100
Final
295
380
200
350
325
305
295
267
363
345
2nd Imp. (ml)
Initial
TOO
100
100
100
100
100
100
100
100
100
Final
135
355
135
160
227
160
297
283
143
362
3rd Imp. (ml)
Initial
-
-
-
-
-
Final
10
325
10
2
15
10
60
35
3
115
4th Imp. (g)
Initial
-
_
_
—
-
Final
25.2
35.6
40.6
9.3
47.3
7.9
51.6
12.5
31.5
25.5
Total Liquid
Sample (ml)
440
1060
345
512
567
475
652
585
509
822
o»
-------
APPENDIX C
CALCULATION OF WASTE DESTRUCTION PERFORMANCE
The waste destruction performance data presented in Table C-l were
calculated for the four runs where waste was actually burned, that 1s,
there is no data for the fuel oil background run, SY-II. Input into
these calculations was taken from several other sources in this report
and the locations of the sources are indicated in the example below.
The waste destruction efficiency (DEWaste) *s based upon com-
paring a waste input rate to a waste emitted rate.
nc - waste input - waste emitted Y 1nftq, /r ,»
utwaste " waste input * I0°* *c'1'
Equation (C-l), restated in another form, is
DE = Iwaste " EjFRqaS E"aSteJ X 100% (C-2)
waste
where:
I t = input rate of organic portion of aqueous
waste feed, milligrams per second.
VFR = volumetric flow rate of combustion gases from
9 the reactor, cubic meters per second. It is the
sum of the fluidizing air, the overbed air and
the water vapor from the aqueous waste
(from Table 5-1).
Eu,ae*o fmn/m3} = concentration of organic waste constituents in
waste tmg/m ; combustion gas as determined by GC (the sum of
the resultant concentrations for the three
samples from eacn run (Table 5-3).
Similarly the destruction efficiency for tbtal organics (DEtotal organics)
compares the input rate of combined waste and auxiliary fuel to the emitted
rate of all organic material found in the combustion zone samples.
nc - !fuel - CVFRgas Etotal organics]
DEtotal organic 1 X 10°*
-------
where :
I. = Input rate of organic portion of waste plus fuel oil (when
Tuel used). Calculated from the data in Table 5-1. Units are
milligrams per second.
E,. . , . = sum of the concentrations of all organics found
total orgamcs -n tnfi Combust1on 20ne samples. (Tables 5-5,
5-6, 5-7) Units are milligrams per cubic meter.
The calculation for test number SY-I is presented below as an
example. Initially Iwaste 1s calculated, then VFRgas, and finally
Ewaste 1s added to E062 x 1t)6 m9/l x °'082 = 72f00°
where:
49.9 min = aqueous waste feed rate (Table 5-1)
= minutes to seconds conversion
1.062 • specific gravity of aqueous waste at 15°C (dimensionless)
0.082 = weight fraction of waste constituents in waste
(dimensionless)
VFR = fluidizing air + overbed air + water vapor
gas
= [340 ]J^-+ 72 m3/min + 49.9 x ^^ x 1.062 x
vn PS ?H2ix m°1e H2° x 0.024 m3] jnin_
X0.86 g x i8 g H90 x mole J 60 sec
348 m3 „ 72 m° „ 61 mj| min
72 m3 61 m3]
min min J
min x min x min J 60 sec
3
m
where:
340 andI|J!L = air feed rates (Table 5-1)
78
-------
49.1 4^-= waste feed rate (Table 5-1)
1.062 = specific gravity of waste at 150°C (Page 4-2)
0.86 —|- = water content of waste (Page 4-2)
3
^TfioltT" = approximate molar volume of water vapor at
atmospheric pressure and 21 C.
Calculation of DEwaste
72,000mg -
DE . = 5§c \_sec m^/x 100% = gg.9997« (C-3)
waste 72j(JOO m|
The destruction efficiencies for total organics, DEtotal Oroanic are
calculated in a similar manner using equation C-3 and inputing the com-
bined waste and auxiliary fuel feed and the concentration of total organics
found (Tables 5-5, 5-6 and 5-7).
79
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APPENDIX D
ANALYTICAL CHEMISTRY DETAILS
This appendix consists of additional discussion of the organic
analysis test results presented In Section 5. The discussion deals with
the details of the IR and LRMS data Interpretation related to the various
survey analysis residues from the sample extracts. The preparation of
these residues Is discussed In Section 4. The results of these Inter-
pretations are presented In Section 5. Sections D.I through D.5 discuss
the survey results of the following sample forms In respective order:
• Combined probe wash and filter extracts, D.I
• Sorbent trap extracts, D.2
• Scrubber water extracts, D.3
• Fluidized sand bed extracts, D.4
• Representative samples of the phenol and methyl methacrylate
wastes, D.5
D.I Combined Probe Wash and Filter Extracts (PF and PW).
The following paragraphs describe the results of the survey analyses
performed on the residues of the subject concentrated extracts. The
amounts of organic residue obtained from careful evaporation of a 2 cc
aliquot of organic concentrate are presented In Table 5-5. The amounts
shown have been corrected for control samples involving extraction of
precleaned thimbles and evaporation of the unused solvent. The amounts
recovered In the blanks represent from 2 to 17 percent of the total
weight obtained.
The Infrared spectra of these samples Indicated by the relative
intensities of key peaks that the major constituents were aliphatic
hydrocarbons. The presence of an ester at moderate levels or higher is
also indicated. The presence of silicone oil or grease in varying
amounts is shown by the spectra. The spectra for these samples were all
exceedingly similar, thus indicating that the major constituents of
these residues were the same. Band assignments for typical spectra is
shown in Table D-l.
Low resolution mass spectra (LRMS) were obtained on three of these
residues:
(1) SY-I-CG-PF+PW (phenol waste test)
(2) SY-II-CG-PF+PW (fuel oil background)
(3) SY-IV-CG-PF+PW (methylmethacrylate waste test).
80
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Table D-l. IR Data for Probe Wash and Filter
Extract Survey Residues
Maximum Absorbance
(Frequency in CM-1)
2970, 2950, 2850
1740
1470
1380
1265
1120 to 1020
800
Assignment
6~CHn, 6-CHp
-C=0, ester
-CH2-scissor and asym bending -CH3
sym. bending -CH*
asym. C-O-C stretch
Si-O-Si stretch and sym. C-O-C stretch
Si-CH3 rocking
The interpreted mass spectra are summarized as follows:
0 The SY-I-CG-PF+PW sample contained hydrocarbon oils and phthlate
esters as major constituents of the residue. A trace of silicones
was also seen.
• The SY-II-CG-PF+PU sample contained hydrocarbon and phthaiate
esters. Di-tert-butylmethylphenol (BHT), silicones, and di-tert-
octylresorcinol were found at minor levels in the extract.
• The SY-IV-CG-PF+PW sample contained hydrocarbons and silicones as
major components, phlhalates at moderate levels and di-tert-
butylmethyl phenol at a minor level.
These residues contain the same major constituents whose source is
believed to background artifacts.
D.2 Sorbent Trap Extracts (ST)
This section provides some of the details of the survey analysis
performed on the sorbent trap extracts in pentane and methanol. Analyses
performed include residue weight, IR, and LRMS. The amounts of low
volatile residue in the extracts are presented in Table 5-6. The details
of the other analyses are presented below.
The IR spectra of the pentane extracts were essentially the same
with the exception of changes in relative intensity of some peaks. The
spectra indicate hydrocarbons, some esters and silicones whose source
could have been lubricants or processing aids in the resin. The reason
for this belief is that these materials are present in all samples
including the control (unused) traps but are absent in the pentane and
methanol solvent blanks. The amounts of these materials are larger in
81
-------
the residues from the actual sample traps (Table 5-6) suggesting that
the test traps did Indeed pick up some of these materials during the
sampling or because of their use, release more of this material. There
was no evidence of either phenol or methyl methacrylate monomer or waste
constituents in the respective test samples nor in the extract residues
from the two "doped" sorbent traps with known added amounts of these
materials. This is not surprising since these relatively volatile
materials added in milligram quantities to the traps, and already found
in the extracts by GC were likely to be lost in the evaporation. (These
survey procedures are not the prime methods for specific, expected waste
constituents. The added phenol and MMA were found in the gas chromato-
graphic analysis of the same extracts discussed earlier.
The IR spectra of the concentrated methanol extract residues indi-
cated that similar materials were extracted from all the traps. The
quality of the spectra from the methanol extracts is poorer since traces of
the methanol solvent are in the residue and interfere. Evidence of
hydrocarbons and esters are present. There was no evidence of phenol or
methyl methacrylate in the respective IR spectra, nor were there any
traces of these compounds in the "doped" sorbent traps. Again, this is
not surprising due to their volatilities. Band assignments made for
these data are given in Table D-2.
TABLE D-2. IR Assignments for Sorbent Trap
Extract Survey Residues
Absorbance Maxijnum
(Frequency, cm"1)
Assignment
2970, 2950, 2870
1740
1670
1460
1380
1260
1050
1020
800
Aliphatic Hydrocarbons
ester, C=0
Assym. bending of -CH3 or -CHg scissor
methyl
Asym. C-O-C stretch
Sym. C-O-C stretch
Si -CH- rocking
Inspection of the low resolution mass spectra of the residues obtained
from mild evaporation of sorbent trap extract residues provided data
which confirm the observations made on the IR. The types of compounds in
the residues included major amounts of hydrocarbons, and phthaiate esters.
Fatty acids or long chains hydrocarbons with several carboxylic acid
groups were also present. The LRMS data were searched for evidence of
the components of the waste feed but no such evidence was found. In
82
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addition the data were searched for possible partial decomposition,
pyrolysls products or secondary combustion products such as POM but,
again, nothing was detected.
Some general observations on the behavior of the traps was also
obtained from these analyses.
• There does not appear to be any preferential extraction of any
one type of these materials by either pentane or methanol.
However, methanol is shown to be more effective in extracting
larger amounts of these compounds.
• These compounds still appear to be found in the resins in spite
of the intensive extraction and clean up procedures used as
described in Section 4. Based on our experience with the traps
from the tests at the Marquardt Company (Facility One), methylene
chloride was added to the solvents used in sequential extraction
of the resin prior to use. Its use has not solved this mild
contamination problem which to the analyst is annoying, but does
not present any serious detrimental impact on the analysis of
samples.
The mass spectral pattern discussed below is typical of the LRMS data
taken from all the sorbent trap extract residues in pentane and methanol.
It is stressed that this is low resolution mass spectrometer analysis of
a mixture and several compounds present may contribute to a specific
spectral pattern. Therefore, specific compounds present may not be
determined with any real confidence. However the classes of compounds do
become quite apparent as shown in Table D-3.
TABLE D-3. LRMS Assignments for Sorbent Trap
Extract Survey Residues
Peak Pattern
27, 29, 41, 43, 44, 55, 57,
etc. increasing by 14 AMU
beyond 300 AMU
66, 73, 147
70, 81, 95, 109, 121, 123, 137
149*
205, 223, 236, 278
Assignments
Alkanes and olefins, either
as compounds or as substitutes
of compounds
Sili cones*
Believed to be squalene,
C30H50
Phthalate esters
Butyl phthalate ester
*Not found in all samples
83
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D.3 Survey Analysis of Scrubber Water Extracts
Samples of the wet scrubber's recirculating water were taken before
each test when the scrubber system had been previously drained and filled
twice with city water. At the completion of each test a sample of the
used scrubber water was taken. These samples were designated FSW (fresh
scrubber water) and SSW (spent scrubber water), respectively. These
samples were extracted and analyzed per the procedures described In
Section 4.4.
The results of the gravimetric portion of the survey analysis of
these samples is summarized in Table 5-14. The IR spectra of these
samples were essentially identical and indicate hydrocarbon oils and
esters of phthalic acid. These materials are commonly used as lubricants
and also as plasticisers In polymeric materials. It is not surprising
that these materials are present in a scrubber since the several pumps
and valves in the facility must be lubricated. These spectra were also
searched for any evidence of the constituents found in the representative
wastes. No evidence of any of these species was found. The Table D-4
presents the IR spectral band assignments for the residue of the scrubber
water extracts.
Table D-4. IR Assignments for Scrubber Water
Extract Survey Residues
IR Absorption Maximum
(frequency in cm-1)
Assignment
2980, 2940, 2870
1730
1460, 1380
1260
1120
1080
C-H stretch, aliphatic hydrocarbons
C=0 stretch
Asymetric and symetric -CH3 bending
=C-0-C symetric stretching (ester)
=C-0-C symetric stretching (ester)
Orthosubstuted phenyl
The low resolution mass spectral (LRMS) data confirm the conclusions
made from the IR data. Selected sample residues were analyzed and the
data indicate the presence of phthalates and hydrocarbon oils. Azelaic
acid (nonanedioc acid) or its esters are also believed to be present as a
minor constituent(s). The spectral pattern of Table D-5 is typical of
the very similar pattern which these samples exhibited.
The phenol, methlmethacrylate, benzenes, toluenes and cresols
originally detected in the two wastes were specifically searched for in
the LRMS of the residues. They were not detected in the LRMS data nor
was there any evidence of toxic by-products.
84
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Table 0-5. LRMS Assignments for Scrubber Water
Extract Residues
Spectral Pattern
(Atomic Mass Units. AMU)
Assignment
27,29,41,43,55,57,69,71,83,
85,97,99
70,112,171 plus portions of
the picket! pattern above.
149,167,185 plus portions
of the pickett pattern
above
Typical pickett pattern from
normal and branched aliphatic
and olefinic hydrocarbons
Believed to be azelaic add
and/or its esters
phthaiic acid and/or its esters
0.4 Fluidized Sand Bed Extracts
The samples of the sand bed, which were taken after each test, were
extracted with pentane and given the standard survey analyses. The
results of the gravimetric analyses are presented in Table 5-17. Parts
per million quantities of a residue were found in the extracts. The
control samples for this procedure did not yield enough of a residue to
be weighed, thus there are no background contributions. The IR spectra
for these residues are essentially all the same and Indicate hydrocarbon
oils/greases as the primary constituent of these small residues with the
distinct possibility of an ester and si 11 cones being present. The IR
band assignments for a typical spectra are presented in Table D-6.
Table D-6. IR Assignments for Sand Bed
Extract Survey Residues
Maximum Absorbance
(frequency in cm0'
2970, 2940, 2870
1740
1460
1380
1260
1100
1020
800
Assignment
6 C-H
C=0 stretch
6 C-H
-CH3
asym. C-O-C stretch
Si-0-51
sym. C-O-C stretch and S1-0-S1
Si -CH3 rocking
85
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Two survey samples were selected using IR, as being typical of all
the sand extracts. These two samples were subjected to LRMS analysis to
confirm the IR data.
The sand residue extract from SY-I (from a phenol waste test) con-
tained hydrocarbon oils as the major constituent of the evaporated
extract residue. Di octyl phthaiate was present at a moderate level.
Minor amounts of di-tert-butyl methyl phenol (also known as BHT, an
antioxidant), and methyl abietate, a wood resin derivative possibly
coming from the extraction thimbles, were also seen. An incompletely
identified chlorinated, substituted aromatic (apparent molecular weight
228) was also seen at minor levels. Its source is unknown.
The other sand extract that was examined by LRMS was from SY-IV.
This sand sample was from a test with methyl methacrylate waste. Com-
pounds found in the residue included hydrocarbon oils (major), phthalates
and fatty acids (moderate) and di-tert-butyl methyl phenol (minor). The
unknown chlorinated aromatic (MW228) was also present at minor levels.
There was no evidence in the spectra of the silicones seen in their
spectra.
These materials are believed to be more examples of the low level
contamination of samples by these ubiquitous organics which can occur dur-
ing even the most carefully controlled sampling and analysis procedures.
It is not believed that these materials come from the sand bed itself,
which when taken from the fluidized bed incinerater, is hot to a cherry
red color and which has been standing for as much as one half hour after
all fuel flow has stopped. Trace contamination during sample acquisition,
storage, preparation and analysis is believed responsible. No further
work was done to identify the source(s) of these materials other than
to stress awareness of the problem of contamination as it applies to all
procedures and operations.
D.5 LRMS Survey of Representative Phenol and MMA Wastes
The LRMS data on the representative sample of the phenol waste were
obtained by using the direct solids probe technique on the same residue
from evaporation of the waste used in the IR. The interpreted spectra is
summarized in Table D-7. At the lower probe temperature of 150°C the
major constituents were phenol, cresol isomers, and aliphatic hydrocarbon
oils. Phthalates were present at minor to moderate levels. There was
also a very strong peak at m/e 74. This peak frequently occurs in the
fragment pattern of methyl esters of various different carboxylic acids
with a wide range of molecular weights. The other class of compounds
suggested by this intense peak are sulfur containing hydrocarbons such as
sulfides, dithianes, and trithianes. The spectrum from the same sample
at a probe temperature of 250°C had increased peal* intensities at the
higher molecular weight end of the spectrum. The same m/e 74 peak is
easily the most intense peak. Other strong peaks are apparent as indicated
in Table D-7. The point is stressed that in this survey type analysis,
several compounds may contribute to a particular peak pattern in the
Foectrum. The resulting interpretation and assignments in Table D-7
86
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Table D-7. LRMS Assignments of Representative
Phenol Waste (Water Removed)
Mass Spectral Pattern
(AMU)
Assignment
27,29,41,43,55,57,
increasing by 14 AMU
74
39,50,51,53,65,66,94
27,51,53,77,79,107,108
149,167,223
77,107,108,121,122
208
65,66,139
245,246,247
74,228
185
256
274,275
287,288
302,303
Hydrocarbons either as oils or
substituents on other molecules,
major Methyl esters, sulfurhydro-
carbons, major
Phenol, major
Cresols, major
Phthalates, minor
Ethyl phenol or dimethyl phenol, minor
Possible anthraquinone, or
methoxyphenanthrene, minor
Nitro phenol, minor
Possible di-phenylphenol or 2 Biphenyl-
phenyl ether., minor
Possible methyl-n-tridecanoate, minor
Possible sebacic acid compounds, minor
Relatively low intensity possibly a
methyl substituted benzantracene or
Benzo phenanthrene.
Not assigned, minor
Not assigned, minor
Not assigned, minor
cannot always be confirmed. The available literature on standard mass
spectra of the sulfur compounds mentioned above is some what limited.
However, without literature confirmation, it is believed that some of the
unidentified minor constituents in the table may be part of this class of
sulfur containing compounds whose presence is indicated by the very intense
74 AMU peak. It should be pointed out that these unidentified higher
molecular weight compounds are minor constituents in the phenol waste.
LRMS at 400°C did not reveal any additional spectral features not found
at 250°C.
The LRMS analysis of the MMA representative waste, after water and
MMA removal by evaporation, indicated primarily hydrocarbon oils with
minor or trace levels of esters, fatty acids, etc., (Table D-8). Peaks
at 252,253 AMU suggest the presence of a POM but no confirmation exists.
87
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Table 0-8. LRMS Assignments for Representative
Methyl Methacrylate Waste (Water Removed)
Mass Spectral Pattern
(AMU)
Assignment
41,43,55,57, etc., Increasing
by 14 AMU (0*2) extending above
400 AMU
149,167
185
211,225
252,253
309,323
Hydrocarbon oils with molecular
weights greater than 400, major
Phthaiate esters, minor
Adi pates, sebecates, minor
Possible p-tertbutylphenyl
phenyl ether, trace
Possible a benzpyrene, or a
benzo fluoranthene, trace
Unassigned, trace
uo!467b
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