EPA
530/SW
122c.2
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
PB-268 232
DESTROYING CHEMICAL WASTES IN COMMERCIAL SCALE
INCINERATORS,
U,S, ENVIRONMENTAL PROTECTION AGENCY
^ n»' »•** • •
\ JJJG i BM i
NOVEMBER 1976
'
•
EJBD
ARCHIVE
EPA
SW-
122C.2
Repository Material
Permanent Collection
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PB 268 232
DESTROYING CHEMICAL WASTES
IN COMMERCIAL-SCALE INCINERATORS
This final report(SW-122c. 2) dej&nbee work performed
for the Federal eolid--ttctffZemanaaement program
under contract no. 68-01-2966
and is reproduced as received from the contractor
oD
.o
0
U.S. ENVIRONMENTAL PROTECTION AGENCY
1977
REPRODUCED BY
NATIONAL TECHNICAL
INFORMATION SERVICE
U. S. DEPARTMENT OF COMMERCE
SPRINGFIELD. VA. 2U61
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA/530/SW-122C.2
3. Recipient's Accession No.
4. Ti:lc and Subt itle
Destroying Chemical Wastes in Commercial Scale Incinerators.
Facility Report No. 2 - Surface Combustion Division,
Midland-Ross Corporation
5. Report Date
November 1976
6.
Issue Date
7. Author(s) J
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This report as submitted by the grantee or contractor has been
technically reviewed by the U.S. Environmental Protection Agency
(EPA). Publication does not signify that the contents necessarily
reflect the views and policies of EPA, nor does mention of commercial
products constitute endorsement by the U.S. Government.
An environmental protection publication (SW-122c.2) In the solid
waste management series.
ii
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TABLE OF CONTENTS
Page
Table of Contents i
List of Tables ill
List of Figures vii
Foreword and Acknowledgements viii
1. SUMMARY 1
2. INTRODUCTION 5
3. PROCESS DESCRIPTION
3.1 Test Facility 7
3.2 Process Parameters 17
A. TEST DESCRIPTION
A.I Wastes Tested 19
A. 2 Operational Procedures 20
A.3 Sampling Methods 20
A.A Analysis Techniques 2A
A.5 Problems Encountered 25
5. TEST RESULTS
5.1 Introduction 26
5.2 Tests on API Waste 27
5.3 Tests on Stryene Waste 35
5.A Tests on Rubber Waste 42
5.5 Surface Combustion Background Test 49
6. WASTE INCINERATION COST
6.1 Capital Investment 50
6.2 Operating Costs 51
7. CONCLUSIONS
7.1 General Conclusions about the Pyrolysis Process 65
7.2 API Waste Tests 65
7.3 Styrene Waste Tests 66
7.A Rubber Waste Tests 67
iii
-------
TABLE OF CONTENTS
Page
APPENDIX
A Techniques of Sample Preparation and Analysis 70
B Sampling and Analytical Results 80
C Operating Data 117
D Assessment of Environmental Impact 146
E Metric to English Unit Conversion Table 150
iv
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LIST OF TABLES
Table Number Page
1-1 Summary of Operating Conditions and Test Results 2
3-1 Summary of Pyrolysis Test Conditions 18
5-1 Operating Conditions for Tests on API Wastes 28
5-2 Total Quantities of Pyrolyzer Effluents
from API Waste Tests 29
5-3 Organic Material in Pyrolyzer Effluents
from API Waste Tests 31
5-4 Normalized Distribution of Total Pyrolyzer
Effluent by Chemical Class of Major Components
for 2-API Test 32
5-5 Operating Conditions for Tests on Styrene Waste 36
5-6 Total Quantities of Pyrolyzer Effluents from
Styrene Waste Tests 37
5-7 Organic Material in Pyrolyzer Effluent
Fractions from Styrene Tests 3g
5-8 Normalized Distribution of Total Pyrolyzer
Effluent by Chemical Class of Major Components
for 6-STY Test 40
5-9 Operating Conditions for Tests on Rubber Waste 43
5-10 Total Quantities of Effluents from Rubber
Waste Tests 44
5-11 Organic Material in Pyrolyzer Effluent
Fractions from Rubber Tests 45
5-12 Normalized Distribution of Pyrolyzer Effluent by
Chemical Class of Major Components for 9-RUB Test 47
6-1 Capital Investment for Pyrolysis, Incineration and
Heat Recovery for 6000 Metric Tons/yr of Rubber
Waste 52
6-2 Operating Cost for Pyrolysis, Incineration and
Heat Recovery for 6000 Metric Tons/yr of Rubber
Waste 53
-------
LIST OF TABLES (continued)
Page
Table Number
6-3 Capital Investment for Pyrolysis, Incineration and
Heat Recovery for 2000 Metric Tons/Yr of Rubber
Waste 55
6-4 Operating Cost for Pyrolysis, Incineration and Heat
Recovery for 2000 Metric Tons/Yr of Rubber Waste 56
6-5 Capital Investment for Pyrolysis, Incineration and
Heat Recovery for 1000 Metric Tons/Yr of rubber
Waste 58
6-6 Operating Cost for Pyrolysis, Incineration and
Heat Recovery for 1000 Metric Tons/Yr of Rubber
Waste 59
6-7 Capital Investment for Pyrolysis, Incineration and
Heat Recovery of 300 Metric Tons/Yr of API Separator
Bottoms Waste 61
6-8 Operating Cost for Pyrolysis, Incineration
and Heat Recovery for 300 Metric Tons/Yr of
API Separator Bottoms Waste 6]
APPENDICES
B-l Data Obtained by EPA Method 5 Procedure 81
B-2 Volumes Sampled by Comprehensive Sampling Train 82
B-3 Results of Gravimetric Analyses on API Samples 83
B-4 Results of Gravimetric Analysis on Styrene Samples 84
B-5 Results of Gravimetric Analyses on Rubber Samples 85
B-6 Results of Gravimetric Analyses of Background
Samples and Controls 86
vi
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LIST OF TABLES (continued)
Table Number Page
B-7 Specific Compounds Identified in Feed and
Effluent Samples for 2-API Test 92
B-8 SSMS Data for API Feed and Effluent Samples 96
B-9 Specific Compounds Identified in Feed and
Effluent Samples for 6-STY Test 101
B-10 SSMS Data for Styrene Feed and Effluent 104
B-ll Compounds Identified in Feed and Effluent Samples
for 9-Rub Test 109
B-12 SSMS Data on Feed and Effluent Samples for
9-Rub Tests 112
B-13 Specific Compounds Identified in Effluent
Samples for 7-SCB Test 115
C-l Process Data for Run No. 1 - API Separator Bottom 117
C-2 " " " 118
C-3 " " " 119
C-4 " Run No. 2 - " 120
C-5 " " " 121
C-6 " " " 122
C-7 " Run No. 3 " 123
C-8 " " " 124
C-9 " " " 125
C-10 Process Data for Run No. 4 - Styrene Tar Waste 126
C-ll " " " 127
C-12 " " " 128
vii
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LIST OF TABLES (continued)
Table Number Page
C-13 Process Data for Run No. -5 - Styrene Tar 129
C-14 " " " 130
C-15 " " " 131
C-16 Run No. -6 - " 132
C-17 " " " 133
C-18 " " " 134
C-19 " Run No. -7 No Feed 135
C-20 " " " 136
C-21 " Run No. -8 - Rubber Waste 137
C-22 " " " 138
C-23 " " " 139
C-24 " Run No. -9 " 140
C-25 " " " 141
C-26 " " " 142
C-27 " Run No. -10 " 143
C-28 " " " 144
C-29 " " " 145
viii
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LIST OF FIGURES
Figure Number page
3-1 Schematic of Test Pyrolyzer/Incinerator System 8
3-2 Pyrolyzer with Safety Shield and Rubber Waste
Feed System 10
3-3 Pyrolyzer with Liquid Waste Feed System 11
3-4 Side View Rotary Hearth Pyrolyzer 12
3-5 Top View Rotary Hearth Pyrolyzer 13
3-6 Process Instrumentation for Pyrolyzer 14
3-7 Pyrolyzer Liquid Feed System 15
3-8 Rubber Waste Feed System 16
4-1 Comprehensive Sampling Train , 22
4-2 Photograph of Comprehensive Sampling Train 23
Appendices - Figures
A-l Sorbent Trap Extractor 71
A-2 Typical TGA Curve 75
A-3 Typical GPC Curve 77
B-l Gas Chromatographs for the ST-Pentane Extracts 87
B-2 Boiling Point Distribution Curves for Samples
from 2-API Test 95
B-3 Boiling Point Distribution Curves for
Samples from 6-STY Test 103
ix
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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
disposing 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 Surface Combustion
(Toledo, Ohio), which was the second facility of the series. A facility
report similar to this one has been published for the first test which
was conducted at the Marquardt liquid injection facility in Van Nuys,
California. The facility reports are primarily of an objective nature
presenting the equipment description, waste analysis, operational pro-
cedures, sampling techniques, analytical methods, emission data and cost
information. Facility 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
Arthur D. Little, Inc., is grateful to the Surface Combustion
personnel for their cooperation in conducting these facility tests.
Acknowledgement is also made of the extensive and fruitful interactions
between ADL and TRW personnel during the initial phases of this program.
The project is deeply indebted to Messrs. Alfred Lindsay and John Schaum,
of the Office of Solid Waste Management Programs, U. S. Environmental
Protection Agency, for their advice and technical direction.
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1. SUMMARY
Pyrolysis is a technique with potential for effecting recovery of
resources from chemical wastes of high organic content. Exploitation
of that potential is becoming increasingly attractive as shortages of
fossil fuels and chemical feedstocks increase. Furthermore, pyrolysis
is one of a fairly small number of techniques which can be applied to
tarry, semi-solid, or solid organic wastes. Consequently, pyrolysis
was chosen as one of seven different thermal destruction methods to be
investigated for their effectiveness in handling chemical wastes.
Tests were carried out at the pyrolysis unit located at the Toledo,
Ohio facilities of the Surface Combustion Division of the Midland-Ross
Corporation. The following chemical wastes were utilized.
• Petroleum refinery wastes (centrifuged API Separator Bottoms)
• Styrene production wasres
• Rubber manufacturing w.istes
These wastes were selected for pyrolysis because, based on information
obtained from the waste generators, it was anticipated that they would
be tarry solids or highly viscous liquids with fairly high gross heating
values (2800 - 5600 Kcal/Kg or 5000 - 10,000 Btu/lb) , and containing
only carbon, hydrogen and oxygen as substantial components. Of the
wastes actually received for testing, only the rubber waste conformed
to these expectations. The API separator bottoms had a high (70%)
water content and high (13%) ash content; the heating value was only
about 1400 Kcal/Kg (2500 Btu/lb). The styrene waste did have a high
heating value (8900 Kcal/Kg or 16,000 Btu/lb) but was a mobile liquid
suitable for combustion in a liquid injection incinerator or for use as
fuel in a steam generator. The styrene waste received also contained
almost 8% sulfur. The rubber waste was a solid with a water content
of about 30% and an estimated heating value of 5500 Kcal/Kg (9800 Btu/lb).
Only the rubber waste was truly representative of the type of waste for
which pyrolysis might be expected to be a leading method of treatment.
Table 1-1 presents a brief overview of the test results.
The products of pyrolysis are a vapor stream and a residual ash or
char. The effectiveness of a pyrolysis process is generally assessed in
terms of the vapor stream, since this is expected to contain the recoverable
resource(s) (energy content and/or organic chemicals of commercial value),
while the ash or char is usually destined for disposal. For the three
wastes tested at Surface Combustion, the average conversion of organic
material in the waste feed to organic material in the vapor stream was
70% for API waste, 60% for styrene waste, and 80% for rubber waste. In
each of these cases, the vapor stream was found to contain a wide variety
of organic compounds, ranging from gases, at normal temperature and pressure,
such as methane and acetylene, to high boiling (500°C) liquids and tars.
The heavier, condensable components of these streams are aromatic compounds,
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TABLE 1-1
SUMMARY OF OPERATING CONDITIONS AND TEST RESULTS
Operating Conditions
Temperature, °C
Waste Residence Time, min
Feed Rate, Kg/hr
Distribution of Products
Organic Vapors (% of Total Feed)
Ash (% of Total Feed)
Remainder
Percent of Organics in Feed
which were Found in Vapor
Percent of Organics in Feed
which were Found in Ash
Ratio of Light ( to Heavy
Organics in Pyrolyzer Effluents
API
Waste
760
12.5
14.7-25.3
9
20
Water
70
30
2.3
Styrene
Waste
650-760
12.5
5.3-10.0
57
<2
Soot
60
<0.01
0.4
Rubber
Waste
760
15
7.3-12.1
27
20
Water &
Soot
80
8
2.3
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including appreciable concentrations of polynuclear aromatic hydrocarbons.
In general, this chemical composition is similar to that of residual oils
or the products obtained from coking of coal. These compositions do not
appear to offer any possibilities for commercial recovery of specific
organic chemicals for recycle as feedstocks, so that the resource recovery
potential of pyrolysis of these wastes lies in the fuel value of the vapor
stream. It can therefore be concluded that the extent of resource recovery,
defined as conversion of organic material in the waste to a form suitable
for conventional heat recovery systems, is 70% for API and 80% for rubber.
For the styrene waste, no net benefit is achieved by pyrolysis since the
waste itself could be used directly in a heat recovery system.
The residual ash in all tests was found to contain mostly (>80%)
inorganic material. The average extents of conversion of organlcs in the
waste feed to ash were: 3% for API, <0.01% for styrene, and 4% for rubber
waste.
The results of these tests indicate that certain potential adverse
environmental impacts must be evaluated in any large-scale recovery of
the energy value of pyrolyzer effluents. Using the API and rubber wastes
for example, the occurrence of >125 mg/m of sulfur in the vapors could
lead to problems in meeting emissions standards for sulfur oxides from
combustion systems. Other potential problems are (1) the 350-500 mg/m'
of polynuclear aromatic hydrocarbons, a class which includes some species
recognized as carcinogens and (2) the occurrence of small but detectable
amounts of heavy metals such as the lead and zinc found in the API wastes.
While these factors will have to be considered carefully in the design of
an appropriate heat recovery system, they are by no means insurmountable
problems. These problems will be similar to those encountered in coke
making, gasification of coal, and the combustion of residual oils.
Capital and operating cost estimates prepared for three different
sizes of pyrolysis systems to treat rubber waste indicated that the over-
all operating costs will be highly dependent upon the capacity of the
system. Total estimated costs, including energy credits and capital
related items, vary from $117/metric ton for a unit capable of pyrolyzing
6000 metric tons/year of rubber waste to $526/metric ton for the pyrolysis
of 1,000 metric tons/year. Energy credits were $48.10/metric ton based
on energy costs of $7.93/million Kcal ($2.00/million Btu). Of the total
costs, direct operating labor, utilities, maintenance and residual ash
disposal account for approximately 60% while capital related items,
depreciation, interest and taxes and insurance account for the remainder.
The overall conclusions, based on tests of these three specific
wastes, are that pyrolysis is both technically and economically feasible
as a method of treating rubber wastes. For the API waste, pyrolysis is
technically feasible but probably not economically attractive compared
with the alternative of combustion in a fluidlzed bed incinerator. For
the styrene waste, pyrolysis has no advantages and some disadvantages
compared to destruction in other types of incinerators or as a fuel in a
steam generating boiler.
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These conclusions are strictly applicable only to the particular
wastes tested and might have been quite different, for example, if the
water content of the API waste bad been only 20%. Experience during
this program has made it clear that reliable information as to the
chemical and physical nature of the stream to be treated (and the range
of variation expected) is absolutely essential in developing strategies
for selection among thermal destruction processes.
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2. INTRODUCTION
The U.S. Environmental Protection Agency has sponsored a program*
to evaluate the effectiveness of a variety of types of commercial thermal
destruction facilities in destroying chemical wastes. Pyrolysis was
selected as one method for testing because it offers the potential for
recovery of resources from waste materials.
In a pyrolysis process, material is thermally decomposed in a non-
oxidizing environment. If the starting material is a hydrocarbon, such
as an alkane, the process is referred to as "cracking," since the products
are alkanes and alkenes of lower molecular weights than the original
hydrocarbon, plus some hydrogen. The usual objective is to convert a
relatively high molecular weight hydrocarbon (or mixture) to a more
convenient fuel form, especially one which burns more cleanly. In
contrast to conventional Incineration, which is intended to achievel
complete oxidation, pyrolysis ±, intended to produce a product stream
which contains a high energy content by virtue of its hydrocarbon
concentration. This feature of the pyrolysis process is increasingly
appealing with the advent of energy and raw materials shortages. In
addition, pyrolysis can be applied to tarry, semi-solid, and solid
organic chemical wastes that are not amenable to other treatment techniques.
The objective of this program was to evaluate the capabilities of
commercial scale facilities. However, a full scale pyrolysis facility ,
within the continental United States which would be available for this
test program could not be located. Because of the high priority assigned
to the resource recovery potential of pyrolysis, it was decided to conduct
a series of tests using the pilot plant pyrolysis unit operated by the
Surface Combustion Division of Midland-Ross Corporation in Toledo, Ohio.
This facility is a rotary hearth pyrolyzer which is coupled to a rich
fume incinerator for combustion of pyrolyzer effluent. This unit is
used on a regular basis by Surface Combustion in determining the design
conditions for the rotary hearth pyrolyzers which it manufactures. The
pyrolysis unit and incinerator are described in detail in Section 3 of
this report.
The chemical wastes selected for testing at this pyrolysis facility
were three which, based on the information supplied by the waste generators,
would be good candidates for resource recovery and/or would be difficult
to treat in other types of thermal destruction facilities. The criteria
for waste selection included:
• the waste should be a tarry, semi-solid or solid material
that was difficult to handle in conventional thermal
destruction facilities
• the waste should have a heating value high enough to make
recovery of fuel value attractive
"Contract No. 68-01-2966
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• the waste should be composed primarily of carbon, hydrogen
and/or oxygen, since the Surface Combustion facility was
not equipped with systems for removal of chlorides, sulfur
or nitrates from the incinerator effluent
• the waste should represent a high priority disposal problem
in terms of potential hazardousness and/or annual volume
generated.
The wastes selected for testing, and the descriptions of these wastes
originally provided by the waste generators, were:
• Centrifuged API Separator Bottoms. A sludge, with a heating
value of 2800-5600 Kcal/Kg (5,000-10,000 Btu/lb), containing
water, benzene soluble organics (30-50%) and ppm levels of
heavy metals.
• Tars from the Production of Styrene. A polymeric tarry
material with a heating value of 2800-5600 Kcal/Kg (5,000-
10,000 Btu/lb) containing styrene and ethyl benzene.
• Rubber Manufacturing Wastes. A solid material with a heating
value of 2800-5600 Kcal/Kg (5,000-10,000 Btu/lb) containing
SBR rubber, carbon black, plus salts, fatty acids, scrap,
etc., from the coagulation of latex.
The materials actually received for testing differed substantially
from expectations in the following ways:
• The API separator bottoms waste had a heating value of only
about 1400 Kcal/Kg (2500 Btu/lb), because it contained 70%
water and 13% ash.
• The styrene waste was a mobile liquid, not a tar, with a
sulfur content approaching 8% by weight.
• The rubber waste contained about 30% water but was otherwise
similar to expectations.
The difference between actual and predicted waste characteristics was
not unexpected because it Is well known that the composition of wastes
from production processes varies according to raw materials composition,
process operating conditions and product quality demands. Consequently,
it was necessary to recognize that a high degree of flexibility had to
be maintained in planning a program of this type and that the results,
while generally typical of a generic class of chemical wastes, may vary
widely depending upon the actual composition of the wastes being pyrolyzed.
The test program involved pyrolysis of each of the three wastes under
three different sets of conditions. On-line process instrumentation was
used to determine the pyrolyzer operating condition and provide quantitative
data on certain emissions. Samples were extracted from the pyrolyzer
effluent for comprehensive analysis. Stack samples from the rich fume
incinerator were collected to check on the environmental adequacy of the
test. Details are in Section 4 of this report.
Detailed information on process and analytical data are recorded in
Appendices A, B and C. The main body of the report presents data in a reduced
form for assessment of the effectiveness of the pyrolysis process (Section
5). Also included in the report are estimates of capital and operating
costs for pyrolysis of the API waste and rubber waste (Section 6).
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3.0 PROCESS DESCRIPTION
3.1 TEST FACILITY
The Surface Combustion pyrolysis/lncineratlon system as used for this
test program is shown schematically in Figure 3-1.
The test system included the following components:
• Pyrolyzer feed system
• Pyrolyzer
• Rich fume incinerator
• Induced draft fan and stack
• Inert gas generator
The pyrolyzer itself is the central piece of equipment in this system,
but because of the physical nature of many of the chemical wastes treated
by pyrolysls (e.g., semi-solid rubber waste), the feed system required also
becomes a very important operaticg consideration.
Waste was fed to the pyrolyzer where it was decomposed into pyrolysis
gas and a residual ash. This pyrolysis gas was sent to the rich fume
incinerator where it was burned using 200-400% excess air. The effluent
gas from the Incinerator was diluted with room air to lower the temperature
and discharged through the stack by an induced draft fan. An inert gas
generator was used during the test program to supply relatively large
quantities of inert gas to the pyrolyzer as a safety precaution during start-
up and operation. (In a commercial operation It is anticipated that this
inert gas would not be necessary.)
The schematic diagram of the pyrolysis system as shown in Figure 3-1
also indicates the location of the three sampling points.
3.1.1 Rotary Hearth Pyrolyzer
The rotary hearth is 76 cm (2.5 ft) in diameter and 2.5 cm (1 inch) deep.
A 15 cm (6 inches) diameter support pipe passes through the center of the
hearth. The hearth speed can be varied from 1/2 to 3 revolutions per hour.
The pyrolyzer is equipped with a 63,000 Kcal/hr (250,000 Btu/hr) burner.
Two insulating boards, vertically mounted at 135° to each other at 2.5 cm
(one inch) above the hearth, separate it into two zones. The burner is fired
into the larger zone (hot zone) and the smaller zone (cold zone) is used for
feeding waste and discharging residue. A plow mechanism is used to remove
residue from the hearth. Temperature and pressure in the pyrolyzer are
automatically controlled.
Pyrolysis of organic waste generates hydrocarbon vapors. Mixing of
these vapors with oxygen can create hazardous conditions as it is possible
to reach an explosive mixture of air and gases. The feed zone of the
pyrolyzer was continuously purged with an inert gas during the operation
to improve visibility and cool the feed zone as well as control the oxygen
concentration. Pyrolyzer pressure was maintained slightly above atmospheric
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00
INDUCED
DRAFT
FAN
ROOF
METHOD 5
SAMPLING
PORTS
EDOCTOR
AIR
AUXILIARY
BURNERS
VENTURI
EOUCTOR
AMBIENT
AIR
II
V
1
COMPREHENSIVE
SAMPLING TRAIN
PORT
ON-LINE
GAS
ANALYZERS
PORT
RESIDUE
SCRAPER
BLADE
FEED
BYPASS
COLLECTOR
FEED
STORAGE
TANK
WASTE
FEED
SAMPLE
I INERT GAS I
! GENERATOR !
L
(OFF,-SITE)
1
FIGURE 3-1 SCHEMATIC OF TEST PYROLYZER/INCINERATION SYSTEM
-------
pressure by automatically controlling the position of the damper in the
effluent gas duct. This positive pressure also reduced the chances of
infiltration of air into the pyrolyzer. The burner system was modified
so that burner flame-out would automatically cut off gas and air supply.
A safety shield was installed in front of the glass observation port to
protect personnel in case of rupture of the observation port. The
pyrolyzer and incinerator burners were equipped with u.v. flame detectors
and the temperature controllers had high limit contacts to shut the burner
off in case the temperature exceeded the limit. When the burner is shut off,
the air is turned off first (to exclude oxygen) and this, in sequence turns
off the gas at the air/gas ratio regulator.
Oxygen concentration in the pyrolyzer was monitored continuously
during the test program by an automatie-on line oxygen analyzer.
Figure 3-2 shows the pyrolyzer with shield over the glass window and
the rubber waste feeder on top of the pyrolyzer. Figure 3-3 shows the
pyrolyzer and the liquid feed tank.
A dimensional sketch for t ne rotary hearth pyrolyzer is shown in
Figures 3-4 and 3-5. Figure 3-6 shows the process instrumentation used
with the pyrolyzer.
3.1.2 Pyrolyzer Feed System
The liquid wastes, API separator bottoms and styrene tar, were fed by
Moyno®* pump. The feeding was done at room temperature. The piping arrange-
ment for the liquid feed system is shown in Figure 3-7. The feed tank was
equipped with a stirrer. The dimensions of the tank are 86 cm (34 inches)
diameter and 61 cm (24 inches) height. The modified feed nozzle had a slot
of size 0.32 cm x 20 cm (1/8" x 8") and a scraper attached to the nozzle
for even distribution of waste on the hearth.
The rubber waste was fed by a specially designed mechanism. A pneumatic
cylinder was used to operate a piston to push the waste through an orifice
and then through a spreader nozzle. Manual feeding of the waste from the
hopper into the feed cylinder was necessary in this test. (In the
commercial unit, a kneader-extruder type feed system would be used.) The
waste was distributed over the hearth by the 19 cm (7.5 inches) long feed
nozzle. Width of the nozzle was varied for each test to give different
layer thicknesses of waste on the hearth. A schematic of the rubber waste
feeding mechanism used for this test is shown in Figure 3-8.
Trademark of Robbins and Myers, Inc.
-------
Figure 3-2. Pyrolyzer with Viewport Safety Shield and
Rubber Waste Feed System
10
-------
Figure 3-3. Pyrolyzer with Liquid Waste Feed Tank
11
-------
BLOCK
BURNER
FIREBRICK
PYROLYSIS GAS
LIQUID
FEED
NOZZLE
-'''---''-''' ' ' -r -r * ' r r * r r f *
ASH
' DISCHARGE
/ CHUTE
DRIVE
UNIT
SOURCE: SURFACE COMBUSTION
WATER
SEAL
FIGURE 3-4 SIDE VIEW ROTARY HEARTH PYROLYZER
12
-------
125cm Diam.
SCRAPER BLADE
64cm(2'-1")
RESIDUE
COLLECTOR
76 cm (2'6") Diam.
15.2 cm (6") Diam
.1100°C(2000°F) BRICK
WINDOW
HOT ZONE
HEARTH
SOURCE SURFACE COMBUSTION
FIGURE 3-5 TOP VIEW ROTARY HEARTH PYROLYZER
-------
TO
INCINERATOR
GAS __-ii
SUPPLY *&**
GAS/AIR
RATIO REGULATOR
GLASS WINDOW
AND SHIELD
WATER SUPPLY
FOR SEALS
DRUM
INERT
GAS
GEN.
SOURCE: SURFACE COMBUSTION
FIGURE 3-6 PROCESS INSTRUMENTATION FOR PYROLYZER
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BURNER
V PYROLYZER
HEARTH
TANK _
MOYNO
PUMP
GV- GATE VALVE OR GLOBE VALVE
r'RV- PRESSURE RELIEF VALVE
SOURCE . SURFACE COMBUSTION
FIGURE 3-7 PYROLYZER LIQUID FEED SYSTEM
15
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PNEUMATIC
CYLINDER
PISTON
HOPPER
ORIFICE
FEED NOZZLE
HEARTH
SOURCE'- SURFACE COMBUSTION
FIGURE 3-8 RUBBER WASTE FEEDING SYSTEM
16
-------
3.1.3 Rich Fume Incinerator
The rich fume incinerator is equipped with two throat mix burners
of 126,000 Kcal/hr (500,000 Btu/hr) capacity each. Auxiliary fuel was
also used in the incinerator in this test series. The incinerator is
equipped with temperature controller and high limit safety shut-off
instrumentation. The burners are mounted at the top and gases flow
downward and are exhausted by an induced draft fan after dilution with
ambient air. The fan capacity is about 113 std. mVmin (4,000 scfm).
(In a commercial unit the rich fume incinerator would be followed by
a heat recovery boiler rather than the air dilution system used in the
test program.)
3.2 PROCESS PARAMETERS
Table 3-1 summarizes the test conditions for three runs of each
type of waste (API separator bottoms, styrene tar and rubber waste) and
one background burn (no waste f<~ed).
Gas and air flows into the system were monitored using orifice plates
(as shown in Figure 3-6) and water manometers. Due to the limited accuracy
with which it was possible to read the manometers (±10%), the accuracy of
the flow rates of gas and air were also about ±10%. Pyrolyzer gas flow
was, likewise, measured by orifice plate and manometer. Temperatures were
measured by thermocouples and were recorded by strip chart recorders.
Waste feed rate was measured by monitoring feed tank level for liquids
and timing the piston strokes for rubber waste. The overall average feed
rate was checked by weighing the waste between runs.
In the original test program, it was anticipated that several residence
times and pyrolyzer temperatures would be tested for each feed. When the
testing was actually conducted, however, It was necessary to use the
maximum pyrolyzer temperature 760°C (1400°F), and the maximum hearth
speed (3 revolutions per hour) in most cases in order to adequately destroy
the wastes. The maximum hearth speed was necessary in order to spread
the wastes thinly enough on the hearth to allow their complete pyrolysis.
With a pyrolyzer temperature of 760°C (1400°F) the temperature of the
pyrolysis gas ranged from 590-650°C (1000-1200eF). The variable changed
with each run was, therefore, the waste feed rate. The waste feed rate
was varied to find the maximum feed rate consistent with an acceptable
ash while operating at maximum temperature and.minimum residence time.
In the case of the rubber waste, it was also necessary to determine what
nozzle opening was needed to produce a thin enough layer of rubber waste on
the hearth to allow it to be adequately pyrolyzed.
17
-------
TABLE 3-1 SUMMARY OF PYROLYSIS TEST CONDITIONS
oo
Date ,
1-28/76
1-29/76
1-30-76
2-2-76
2-3-76
2-4-76
2-5-76
2-17-76
2-18-76
2-18-76
Run
No.
1
2
3
4
5
6
7
8
9
10
Waste
API Separator
Bottoms
it
ii
Styrene Tar
ti
it
No Feed
Rubber Waste
ii
ii
Fee
Kg/hr
16.7
L4.7
15.3
5.3
7.4
LO.O
-
.2.2
9.4
7.3
d Rate
Obs/hr!
(36.7)
(32.4)
(55.6)
(11.7)
(16.3)
(22.0)
-
(26.8)
(20.7)
(16.0)
Feeder
0.32cmxl5cm
Nozzle,
Movno Pumo
0.32cmx20cm
Nozzle,
Moyno Pump
ii
it
ii
ti
-
1.28cmxl9cm
Nozzle
0.96cmxl9cm
Nozzle
0.64cmxl9cm
Nozzle
Inei
FJ
m /hr
42.5
42.5
42.5
44.7
42.5
42.5
42.5
42.5
35.4
34.7
rt Gas
.ow
(SCFH)
(1500)
(1500)
(1500)
(1580)
(1500)
(1500)
(1500)
(1500)
(1250)
(1225)
Pyro
(°C)
760
760
760
760
650
760
760
760
760
760
. Temp
(°F)
1400
1400
1400
1400
1200
1400
1400
1400
1400
1400
Hearth
Speed
(rph)
3
3
3
3
3
3
3
2.5
2.5
2.5
Residence
in Hot
Zone
(mins)
12.5
12.5
12.5
12.5
12.5
12.5
12.5
15
15
15
Incii
Tempi
(°C)
830
830
830
830
830
880
825
825
820
820
lerator
irature
(°F)
1520
1520
1520
1520
1520
1610
1515
1515
1510
1510
%
Residue
19.4
19.7
37.5
1.4
2.9
0.5
-
29.9
(90-95Z
Lumps)
17.5
(60-70Z
Lumps
12.5
(5 to 10%
Lumps)
-------
4. TEST DESCRIPTION
4.1 WASTES TESTED
The three wastes selected for testing at Surface Combustion were API
Separator Bottoms, tars from the production of styrene, and rubber manufac-
turing wastes. Survey samples were received well in advance of the tests
and analyzed in order to determine appropriate sampling procedures. The
results of those survey analyses are summarized below.*
4.1.1 API Waste
The API waste was a grey-black, shiny goo which had a strong and
somewhat irritating odor. The waste was about 69% by weight water and had
an ash content of 11%. Elemental analyses showed the following composition
for the wet waste: C, 12.07%; H, 8.80%; N, 0.30%; and S, 1.44%. Examination
of the waste by X-ray fluorescence revealed Ca and Fe; smaller amounts of
Cu and Zn, plus traces of K, Cl, S, Ti, Sr, Pb, Ni and Si.
The organic portion of the waste was found by mass spectrometry to
consist of a complex mixture of hydrocarbons, with a substantial aliphatic
component.
The higher heating value of the waste was estimated at 1390 Kcal/kg
(2500 Btu/lb).
4.1.2 Styrene Waste
The styrene waste was a brown-black viscous liquid with some suspended
particulate. It had a pungent odor. The ash content was 0.9%. Elemental
analysis showed the following composition: C, 85.04%; H, 7.41%;
N, 0.03%; and S, 7.07%. Examination of the waste by X-ray fluorescence
revealed sulfur, but no trace metals.
The organic portion of the waste was found by mass spectrometry to
consist of a complex mixture of hydrocarbons, largely aromatic and of
fairly high molecular weight.
The higher heating value of the waste was found to be 8.9 x 10
Kcal/kg (16 x 10J Btu/lb).
4.1.3 Rubber Waste
The rubber waste was composed of slightly sticky black lumps of various
sizes. The waste had an ash content of 3.1%. Elemental analysis showed the
following composition: C, 73.9%; H, 9.40%; N, 0.09%; and S, 0.54%.
Examination of the waste by X-ray fluorescence revealed small amounts of
Ca, Cl and Fe, plus traces of Zn, K, S, Pb, Sr, and Ni.
The organic portion of the waste was found to consist largely of polymeric,
aromatic materials.
* Results of analyses of representative samples of the wastes actually tested
are presented in Chapter 5 and in Appendix B.
19
-------
The higher heating value of the waste was found to be 7.8 x 103 Real/kg
(14 x 103 Btu/lb).
4.2 OPERATIONAL PROCEDURES
Detailed operating procedures, including a test plan and safety plan,
were reviewed and approved prior to arrival of the sampling team on-slte.
A brief summary of the operating procedure follows:
Test Procedure
• Fill waste feed tank
• Ignite auxiliary fuel and allow system to reach thermal equi-
librium.
• Activate on-line instruments.
• Begin waste feed and allow system to reach equilibrium, as shown
by on-line instruments.
• Collect pyrolysis zone and stack samples.
• Discontinue waste feed.
• Maintain temperature with auxiliary fuel for about 30 min.
• Shut down system.
• Collect residue from pyrolyzer hearth.
4.3 SAMPLING METHODS
Sampling methods used in the tests at Surface Combustion are described
briefly below.
Five distinct samples were taken during each waste test:
• Composite sample of waste feed material.
• Sample of pyrolysis zone effluent fed to on-line Instruments
for continuous monitoring of test.
• Grab sample of pyrolysis zone effluent to evaluate process
effectiveness.
20
-------
• Grab sample of stack gases to verify that gaseous effluents
were vithin local emission regulations.
• Sample of solid residue from the pyrolysis zone.
The locations of sampling points are shown in Figure 3-1.
4.3.1 Waste Feed Sample
A. composite sample of the waste feed was obtained by collecting a
portion of the material in the waste feed drum during each test. The
three feed samples were blended to yield one representative sample (REP)
for each waste.
A.3.2 On-line Gas Monitoring
A portion of the pyrolyzer effluent was sampled through a 1.27 cm (0.5")
stainless steel probe and passed through an ice-cooled knock-out trap, then
through a heated Teflon** line to a gas conditioning system. The gas condi-
tioner was designed to delive.: a cool, dry, particulate-free sample to
the CO, C&2, 02, and NO analyzers. A fraction of the sample was also
supplied, untreated, to the hydrocarbon analyzer.
The Instruments used and their ranges were:
Hydrocarbons Beckman
Model 402 0.05 ppm- 10%
Carbon Monoxide Beckman
Model 865 2-220 ppm
Carbon Dioxide Beckman
Model 864 0.05 - 20%
Oxygen Taylor
OA 273 0.05 - 100%
Nitrogen Oxides Thermo Electron
Model 10A 0.05 ppm- 1%
4.3.3 Pyrolysis Zone Grab Sample
The train used for collecting this sample is shown schematically in
Figure 4-1 and in the photograph in Figure 4-2. The principal compo-
nents in this comprehensive sampling train were:
• a 1.27 cm (0.5") quartz sampling probe,
• a knock-out trap consisting of ice-cooled implngers to collect
readily condensable organlcs,
* Trademark of E. I. du Pont de Nemours and Company.
21
-------
PYROLYZER
EFFLUENT
PURGE
•o
,-J
HEATED AREA
ICE THERMOMETERS
BATH
ORIFICE
4 INCH
FILTER
HOLDER
SOLID
SORBENT TRAP
THERMOMETER
CHECK
VALVE
ICE
BATH
BVALVES IMPING ERS VACUUM
< (MAXIMUM SIX) GAUGE
r-hS-i
iXSn _ isj>i T jj
7
VACUUM LINE
MAIN
VALVE
\
DRY TEST METER AIR-TIGHT
PUMP
Figure 4-1. Modified Hot Zone Samoling Train
-------
Figure 4-2. Sampling Train for Grab Sample of
Pyrolysis Zone Effluent
23
-------
• a quartz fiber filter,
®*
• a sorbent trap filled with XAD-2 resin to collect organlcs
of moderate volatility,
• impingers containing aqueous sodium hydroxide to collect
acidic gases.
In addition, a portion of the pyrolyzer effluent was collected in
gas sampling bulbs from the bypass line of the hydrocarbon analyzer.
This allowed identification of effluent components too volatile for col-
lection in the comprehensive sampling train.
4.3.4 Stack Gas Grab Sample
The stack gas effluent was sampled isokinetically, according to the
EPA Method 5 procedure, along two perpendicular traverses at 8 points per
traverse. The train was a typical EPA Method 5 type, the RAC Staksamplr.«
The impingers contained aqueous NaOH to trap acidic sulfur gases. In
addition, length of stain tubes were used to provide real-time estimates
of sulfur dioxide concentration in the stack effluent.
4.3.5 Ash Sample
The solid residue from the hearth was composited after each run and
an aliquot taken for analysis.
4.4 ANALYSIS TECHNIQUES
4.4.1 Extractions and Sample Preparation
A detailed description of the specific solvents and techniques used
for the Surface Combustion Samples is given in Appendix A.
4.4.2 Analytical Methods
The techniques which were chosen for evaluation of the effective-
ness of thermal destruction of Industrial wastes were:
Low Resolution Mass Spectrometry (LRMS)
Infrared Spectrometry (IR)
Gas Chromatography/Mass Spectrometry (GC/MS)
Elemental Analysis
Inorganic Analyses were done by:
X-ray Fluorescence (XRF)
Spark Source Mass Spectrometry (SSMS)
Atomic Absorption Spectroscopy (AAS)
Specific Ion Electrode Methods (SIE)
* Trademark of Rohm and Haas Company, t Trademark of Research Appliance Corp.
24
-------
These techniques were applied to the Surface Combustion samples where
appropriate.
In addition, a number of analytical techniques were added because
of the special features of the pyrolysis process. Because the pyrolysis
process is intended to allow resource recovery through conversion of
waste to readily utilized fuels, several techniques were utilized to
reveal the distribution of boiling points and/or molecular weights of
feed and effluent samples. These techniques, which are described in
Appendix A, were:
• Thermogravimetric Analysis (TGA)
• Boiling point distribution curves
• Gel Permeation Chromatography (GPC)
4.5 PROBLEMS ENCOUNTERED
4.5.1 Facility-related
Surface Combustion had originally intended to run the waste tests
with the pyrolyzer at slightly negative pressure using cylinder nitrogen
to provide an Inert atmosphere in the pyrolysis zone. During one of the
check-out burns on styrene waste, however, it appeared that these opera-
ting conditions were inadequate. Air leaked into the pyrolyzer, causing
a minor explosion and rupture of the pyrolyzer viewing port.
As a result of this, conditions for the set of 10 tests were altered.
The pyrolyzer was operated at a slightly positive pressure, using flue gas
(DX-gas) as an inert medium. The DX-gas was created by combustion of
natural gas. In addition, Surface Combustion Installed an on-line oxygen
monitor. If the oxygen level in the pyrolysis zone exceeded 0.5%, the
pyrolysis unit was to be shut down.
4.5.2 Waste-related
The waste-related problems encountered were primarily associated with
the waste feed system. The API waste was found to contain occasional
lumps, which clogged the waste feed system. Also, appreciable difficulties
were encountered in devising a system which would feed the solid, but com-
pressible, rubber waste.
During the styrene waste tests, there was occasional plugging of the
pyrolysis zone sample lines due to condensation of effluent.
25
-------
5. TEST RESULTS
5.1 INTRODUCTION
Process and analytical data are presented in detail in the Appendices.
In this section, the data are presented in a reduced form, which facili-
tates assessment of the effectiveness of the pyrolysis process for treat-
ment of each waste tested. The techniques used for reduction of the data
are described briefly below. Throughout, gas volumes refer to standard
conditions of 21.1°C (70°F) and 760 mm of mercury (29.92" of mercury).
5.1.1 On-Line Hydrocarbon Analyzer Data
The hydrocarbon analyzer provided an on-line estimate of the concen-
tration of gaseous (MW <_ ^ 100) hydrocarbons as % by volume of CHi*. The
results of analyses of gas bulb samples provided estimates of the average
molecular weight and carbon number of the hydrocarbon material in the
volatile pyrolyzer effluent. These estimates were used to convert "ppm
by volume as CHi*" to "mg/ra3 of gaseous hydrocarbon." The "mg/m3" values
were combined with the pyrolyzer effluent flow rate (m3/hr) to calculate
the production of gaseous hydrocarbons in Kg/hr.
5.1.2 Grab Samples of Pyrolyzer Effluent
For these samples, gravimetric determinations were made in ADL labora-
tories. These were combined with ADL data on the volume of effluent sampled
plus Surface Combustion data on the total pyrolyzer effluent flow to give
reduced values in units of mg/m3 and Kg/hr.
In the discussion which follows, the syllable, "GOO," refers to material
collected in the Knockout trap and on the filter of the sampling train
(Figure 4-1). The syllable, "ST," refers to the sorbent trap in that train.
Together, GOO and ST include the readily condensable (MW >100) fractions of
pyrolyzer effluent.
The syllable, -P-, in a sample code always indicates a portion of the
pyrolysis zone effluent.
5.1.3 Grab Samples of Stack Effluent
In this section of the report, all stack effluent data are presented
in units of mg/m3, based on ADL measurements of volume sampled and quanti-
ties of material collected. The syllable, -S-, in a sample code always in-
dicates a portion of the stack effluent.
5.1.4 Selection of "Typical" Waste Tests
Preliminary analyses of all the effluent samples collected during the
tests showed that the samples obtained from the three tests on each waste
had similar composition. Consequently, a set of samples corresponding to
one test condition for each waste was selected for detailed chemical analysis.
Selection criteria are specified in Appendix B.
26
-------
5.2 TESTS ON API WASTE
5.2.1 Operating Conditions
Table 5-1 presents the operating parameters for the three tests on
API wastes.
It is clear that the major difference among tests is the waste feed
rate and the waste layer thickness. The temperature was maintained at
the accessible maximum of 760°C (1400°F). The residence time was main-
tained at 12.5 min. throughout the tests.
5.2.2 Distribution of Pyrolyzer Effluent
In Table 5-2 are presented the data showing how the total mass of
API waste feed was distributed among pyrolyzer effluent samples in the
three tests.
The data indicate, first, that the total quantity of feed accounted
for by the effluent samples (27 to 42%) was low. The loss is primarily
due to the water (70 ± 5% by weight) In the waste feed. The percent
accounted for in the 3-API test is higher than in the other two tests.
This is because the large quantity of ASH collected in the 3-API test
contained a considerable amount of water. Other factors which contribute
to the apparent loss of waste feed material are losses on the walls of the
pyrolyzer effluent duct and losses in handling of the collected samples.
The data also indicate that the particular pyrolysis system used in
these tests has an effective capacity of about 17 Kg/hr (37 Ibs/hr) for
the API waste. When the waste feed was increased to 25 Kg/hr (55 Ibs/hr),
the system appeared to be overloaded. This is evidenced by the fact that
the absolute yield of volatile pyrolysis products (GOO plus ST plus
gaseous hydrocarbons) decreased in the 3-API test while the yield of ASH
increased dramatically.
5.2.3 Fate of Organic Components of the Waste
5.2.3.1 Quantitative
The analyses showed that the API waste contained 13.0% by weight of
organic material (material extractable with methylene chloride). It is
the fate of this organic portion of the waste which is of primary
importance in assessing the effectiveness of the pyrolysis process.
27
-------
Table 5-1
OPERATING CONDITIONS FOR TESTS ON API WASTES
1-API 2-API 3-API
Pyrolyzer Temperature 760°C 760°C 760°C
(lAOO'F) (1400°F) (1400°F)
Residence Time In Pyrolysis Zone 12.5 mla 12.5 mln 12.5 mln
Layer Thickness 2.54 cm 1.27 cm 1.91 cm
(1 in) (0.5 in) (0.75 in)
Inert Gas Flow 0.0118 m3/sec 0.0118 m3/sec 0.0118 m3/sec
(1500 SCFH) (1500 SCFH) (1500 SCFH)
Feed Rate 16.7 Kg/hr 14.7 Kg/hr 25.3 Kg/hr
£ (36.7 Ibs/hr) (32.4 Ibs/hr) (55.6 Ibs/hr)
Pyrolyzer Effluent Flow .0303 m3/sec 0.0317 m3/sec 0.0342 m3/sec
(3850 SCFH) (4030 SCFH) (4360 SCFH)
Pyrolyzer Effluent Temperature 582°C 577°C 582°C
(1080°F) (1070°F) (1080°F)
Stack Gas Flow* 1.00 m3/sec 0.98 m3/sec 0.89 m3/sec
(1.27 * 10s SCFH) (1.25 x 105 SCFH) (1.13 x 10* SCFH)
Stack Gas Temperature 355°C 362°C 355°C
(671°F) (684°F) (671°F)
*ADL values—all other data by Surface Combustion.
-------
Table 5-2
ro
Feed Rate
-P-ASH
-P-GOO
-P-ST
-P-Gaseous
TOTAL
TOTAL QUANTITIES OF PYROLYZER EFFLUENTS FROM API WASTE TREATMENT*
1-API 2-API
Kg/hr 16.7 14.7
Kg/hr 3.24 2.90
% of Feed 19.4 19.7
mg/m3 2410 2726
Kg/hr 0.263 0.311
% of feed 1.6 1.9
mg/m3 1320 1294
Kg/hr 0.144 0.148
% of feed 0.9 1.0
Hydrocarbons mg/m3 7270 6885
Kg/hr 0.793 0.786
7. of feed 4.7 5.3
% of feed 26.6 27.9
3-API
25.3
9.48
37.5
2285
0.281
1.1
910
0.112
0.4
6532
0.804
3.2
42.2
* "P-ASH" is the solid residue remaining on the hearth after pyrolysis. Together, "P-GOO" (the
condensable organics in the pyrolyzer vapor stream effluent), "P-ST" (the organics trapped by
the solid sorbent) and "P-Gaseous Hydrocarbons" (the true volatiles) constitute the portion of
pyrolyzer effluent delivered to the heat recovery system.
-------
Table 5-3 shows how the organic material is distributed among the
various effluent fractions. For the 2-API test, which was selected
as typical, the total recovery of organics was 85%. This probably repre-
sents complete recovery within experimental error. Of the total organic
effluent, 27% was in the ASH, 14.9% in the GOO, 9.1% in the sorbent trap,
and 49% in the gaseous hydrocarbon fraction. The total amount of waste
organic material which was converted to a form suitable for introduction
to the rich fume incineration was thus 73%.
5.2.3.2 Qualitative
Table 5-4 summarizes the results of the LRMS analyses of the
various samples from the 2-API test. These data have been normalized
to reflect the total amount of organic effluent found in each fraction.
(Normalized values do not add to 100% because some components in each
sample were present at concentrations too low for compound identification.)
The organic material in the waste feed (REP-SOL fraction) consisted
largely of unsaturated aliphatic hydrocarbons (42.7%) and aromatic hydro-
carbons (39%) of up to three fused rings (anthracene and phenanthrene).
The higher molecular weight polynuclear aromatic hydrocarbons, such as
pyrene, were not found in the waste.
The total volatile effluent (GOO-SOL plus ST plus gaseous hydrocar-
bons) was found to have an aliphatic component very close to that of the
feed (43.1%). This consisted of roughly equal parts of methane (CH^) and
acetylene (C2H2) in the gaseous hydrocarbon fraction.
The volatile effluent is seen to contain relatively more unsubstltu-
ted aromatics than the waste. Furthermore, the volatile effluent contains
detectable levels of polynuclear aromatic hydrocarbons. Table 5-4 lists
individual concentrations for five species which were chosen as indicators
of polynuclear aromatics; these account for 2.9% of the organics in the volatile
effluent from the pyrolyzer.
A small quantity (0.2%) of high molecular weight oxygenated aromatic
material was found in the volatile effluent samples. These materials may
have been formed by partial oxidation of waste material in the direct-fired
pyrolyzer.
In contrast to the volatile effluent, the ASH was found to contain
very little purely aliphatic organic material. The ASH was highly enrich-
ed in alkyl substituted aromatics (e.g., methyl naphthalenes, phenyl al-
kanes), which account for the high degree of aliphatic character in the
IR spectrum of this material. The ASH also contained small amounts of
polynuclear aromatics.
30
-------
Table 5-3
ORGANIC MATERIAL IN PYROLYZER EFFLUENTS FROM API WASTE TESTS*
1-API 2-API 3-API
ASH-SOL
ST
Kg/hr 0.56 0.44 1.82
% of Organic Effluent 33 27 61
GOO-SOL
Kg/hr 0.204 0.243 0.25
% of Organic Effluent 12 14.9 8.4
Kg/hr 0.144 0.148 0.122
% of Organic Effluent 8.5 9.1 3.7
GASEOUS HYDROCARBONS
Kg/hr 0.79 0.80 0.81
% of Organic Effluent 47 49 27
TOTAL ORGANIC EFFLUENT
Kg/hr 1.70 1.63 2.99
ORGANIC FEED RATE **
Kg/hr 2.17 1.91 3.29
TOTAL RECOVERY 78% 85% 91%
OF ORGANICS
* "P-ASH" is the solid residue remaining on the hearth after pyrolysis.
Together, "P-GOO" (the condensable organics in the pyrolyzer vapor stream
effluent), "P-ST" (the organics trapped by the solid sorbent) and "P-
Gaseous Hydrocarbons" (the true volatiles) constitute the portion of
pyrolyzer effluent delivered to the heat recovery system.
** 13% by weight of total feed, based on amount extracted from REP sample
with methylene chloride.
31
-------
Table 5-4
N>
Class
1. Aliphatics
2. Unsubstituted Aromatics
of < 3 Fused Rings
3. Substituted Aromatics
of < 3 Fused Rings
4. Polynuclear Aromatics:
Pyrene
Benzpyrene
Chrysene/
Benzanthracene
Benzfluoranthene
5. Micellaneous Aromatics
6. Diphenyl Thiophene
7. Oxygenated Aromatics
TOTAL
NORMALIZED DISTRIBUTION OF
BY CHEMICAL
% REP
42.7
LCS 1.4
1 37.6
;:
0
0
0
0
:s 4.4
1.0
0
87.1
CLASS OF MAJOR
PERCENT
P-ASH-SOL
0
1.2
21.5
0
0
0
0.3
1.4
0.3
0
24.7
TOTAL PYROLYZER EFFLUENT*
COMPONENTS FOR 2-API
OF EFFLUENT
P-GOO-SOL
+ Gaseous
P-ST HC's
0 43.1
4.3 4.4
6.8 1.5
1.3
0.5
0.5
0.6
4.4
0.1
0.2
18.7
TEST
Total
Volatile
Effluent
43.1
8.7
8.3
1.3
0.5
0.5
0.6
4.4
0.1
0.2
67.7
Total
Effluent
43.1
9.9
29.8
1.3
0.5
0.5
0.9
5.8
0.4
0.2
92.4
*"P-ASH" is the solid residue remaining on the hearth after pyrolysis. Together, "P-GOO" (the condens-
able organics in the pyrolyzer vapor stream effluent), "P-ST" (the organics trapped by the solid sorbent)
and "P-Gaseous Hydrocarbons" (the true volatiles) constitute the portion of pyrolyzer effluent delivered
to the heat recovery system.
-------
5.2.3.3 Physical Properties of Pyrolyzer Effluent
The TGA and the boiling point distribution curves indicate that the
condensable portion of pyrolyzer effluent includes components which boil
in the range of 150 to 500°C (300 to 930°F). These, in comparison to
typical petroleum products, correspond to the boiling point ranges of
kerosene and diesel oil (150 to 300°C) and heavier oils.
The total volatile effluent from the pyrolyzer is about one-third
by weight of these high-boiling species and about two-thirds very low
boiling species (methane and acetylene).
5.2.4 Fate of Inorganic Components of the Waste
5.2.4.1 Sulfur
Elemental analysis of the REP sample indicated that the waste con-
tained 1.5% by weight of sulfur.
Most of the sulfur in the waste feed was found in the ASH portion
of the pyrolyzer zone. Analysis of the 2-API-P-I impinger solution in-
dicated a total sulfur concentration of 136 mg/m3 of volatile pyrolyzer
effluent. This is consistent with the results of the gas bulb analysis
which showed * 70 ppm by volume of volatile sulfur species.
The diphenyl thiophene found in the waste and effluent samples
accounts for less than 10% of the total sulfur.
5.2.4.2 Trace Elements
The SSMS analysis of the 0-API-REP sample showed that the waste con-
tained some 63 elements, including a number of rare earth elements at
very low concentrations. A number of elements that were found at sub-
stantial concentrations (> 100 ppm) a^-e recognized as potentially hazard-
ous. These include zinc (1000 ppm), chromium (420 ppm), flourine (240
ppm), and lead (210 ppm).
Analysis of the ASH fraction of the pyrolyzer effluent by SSMS re-
vealed that all of the trace elements were enriched in this sample. In
fact, the concentrations found in the ASH could account, within experi-
mental error, for all of the trace materials in the waste feed. How-
ever, analysis of stack gas samples Indicated that small quantities of
some elements were found in the pyrolyzer effluent gas.
5.2.5 Analysis of Stack Gases
The objective of this test program was the evaluation of the pyroly-
sis process, per se, not the rich fume Incinerator in which the pyrolyzer
effluent was burned. A small number of analyses were, however, performed
on the incinerator stack gases.
33
-------
5.2.5.1 Particulate Loading
The stack partlculate loading, determined according to the EPA Method
5, was 87.6 mg/m3 for the 2-API test and 23.0 mg/m3 for the 3-API test.
(The filter from the 1-API test disintegrated and could not be weighed.)
These particulate loadings are well within stationary source standards of
180 mg/m3 for incinerators larger than 50 tons/day capacity.
5.2.5.2 Sulfur Dioxide
The sulfur dioxide level of the stack gases was found to be 30 to 50
ppm by analysis with Gas tec®* tubes during the test. Analysis of the
2-API-S-I impinger samples for total sulfur indicated a stack gas loading
of 47 mg/m3, as S, or 33 ppm as S02«
5.2.5.3 Trace Elements
One-half of the 2-API-S-F filter sample was analyzed directly by
SSMS. After the background due to the filter material had been subtracted,
the elements identified were: lead at about 0.05 mg/m3 and zinc at 0.05
mg/m3 of stack gas. These concentrations represent less than 5% of the
amount present in the waste feed.
* Trademark of Bendix Environmental Science Division.
-------
5.3 TESTS ON STYRENE WASTE
5.3.1 Operating Conditions
Table 5-5 presents the operating parameters for the three tests on
styrene wastes. The major differences among tests are the waste feed
rate and the pyrolyzer temperature. The rate at which waste could be fed
was limited by the capacity of the rich fume incineration used as an
afterburner.
5.3.2 Distribution of Pyrolyzer Effluent
In Table 5-6 are presented the data which show how the total mass of
styrene waste feed was distributed among pyrolyzer effluent samples in
the three tests.
The total percentages of feed accounted for in the pyrolyzer effluent from
the styrene tests are considerably higher than those for the API tests. This
is because the styrene waste concained very little water. A major contribution
to the 20-35% net loss of material is deposition of the pyrolyzer effluent
(soot) on the walls of the system. Some losses are also due to sample handling.
A significant feature of the data in Table 5-6 is that very little
residue (ASH) is formed during pyrolysis of the styrene wastes.
5.3.3 Fate of Organic Components of the Waste
5.3.3.1 Quantitative
The analyses showed that the styrene waste contained 98% by weight
of organic material (material extractable with methylene chloride). It
is the fate of this organic portion of the waste which is of primary
importance in assessing the effectiveness of the pyrolysis process.
Table 5-7 shows how the organic material is distributed among the
various effluent fractions. The total recovery of organics was lower
than in the API waste tests. Evidence obtained in the "background" test
indicates that substantial quantities of material were deposited in the
ductwork of the pyrolysis system.
For the 6-STY test which was selected as typical, the total recovery
of organics was 59%. Of the total organic effluent, 1.7% was in the ASH,
52.4% in the GOO, 19.2% in the sorbent trap, and 26.7% in the gaseous
hydrocarbon fraction.
35
-------
Table 5-5
OPERATING CONDITIONS FOR TESTS ON STYRENE WASTES
4-STY
inperature 760°C
(1400°F)
5-STY
650°C
(1200°F)
6-STY
760°C
(1400°F)
Residence Time In
Pyrolysis Zone
Inert Gas Flow
Feed Rate
Pyrolyzer Effluent
Flow
Pyrolyzer Effluent
Temperature
Stack Gas Flow*
Stack Gas Temperature
12.5 tnin
0.0124 m3/sec
(1580 SCFH)
5.32 Kg/hr
(11.7 Ib/hr)
0.0303 m3/sec
(3850 SCFH)
12.5 min
0.0118 m3/sec
(1500 SCFH)
7.41 Kg/hr
(16.3 Ib/hr)
0.0275 m3/sec
(3500 SCFH)
12.5 mln
0.0118 o3/sec
(1500 SCFH)
10.0 Kg/hr
(220 Ib/hr)
0.0313 m3/sec
(3980 SCFH)
560°C
(1050°F)
0.96 m3/sec
(1.22 x 105
SCFH)
360°C
(690"F)
550° C
(1020°F)
0.96 m3/sec
(1.22 x 105
SCFH)
365°C
(685°F)
600°C
(1115°F)
0.89 m3/sec
(1.13 x 10s
SCFH)
410°C
(775°F)
*ADL values - all other data by Surface Combustion
36
-------
Table 5-6
TOTAL QUANTITIES OF PYROLYZER EFFLUENTS
FEED RATE
ASH
GOO
ST
GASEOUS
HYDROCARBONS
TOTAL
FROM STYRENE WASTE TESTS*
Kg/hr
Kg/hr
% of Feed
mg/m3
Kg/hr
% of Feed
mg/m3
Kg/hr
% of Feed
mg/m3
Kg/hr
% of Feed
% of Feed
4-STY 5-STY
5.32
0.075
1.4
15,980
1.74
32.7
7,048
0.769
14.5
14,330
1.56
29.4
78
7.41
0.215
2.9
33,014
3.27
44.1
(sample lost)
-
-
13,490
1.33
17.9
64.9
6-STY
10.0
0.050
0.5
33,093
3.73
37.3
9,721
1.09
10.9
13,595
1.53
15.3
64
* "P-ASH" is the solid residue remaining on the hearth after pyrolysis.
Together, "P-GOO" (the condensable organics in the pyrolyzer vapor stream
effluent), "P-ST" (the organics trapped by the solid sorbent and "P-Gaseous
Hydrocarbons" (the true volatiles) constitute the portion of pyrolyzer
effluent delivered to the heat recovery system.
37
-------
Table 5-7
ORGANIC MATERIAL IK PYHOLYZER EFFLUENT
FRACTIONS FROM STYRENB TESTS*
ASH-SOL
ST
Kg/hr
% of Organic Effluent
GOO-SOL
Kg/hr
% of Organic Effluent
Kg/hr
% of Organic Effluent
GASEOUS HYDROCARBONS
Kg/hr
% of Organic Effluent
TOTAL ORGANIC EFFLUENT
Kg/hr
ORGANIC FEED RATE**
Kg/hr
TOTAL RECOVERY
OF ORGANICS
4-STY
5-STY
0.035
0.9
1.59
40.2
0.769
19.4
1.56
39.4
3.95
5.22
76%
0.040
0.9
2.86
67.6
(lost)
1.33
31.4
4.23
7.26
562
6-STY
0.096
1.7
3.01
52.4
1.10
19.2
1.53
26.7
5.74
9.80
59%
* "P-ASH" is the solid residue remaining on the hearth after pyrolysis.
Together, "P-GOO" (the condensable organics in the pyrolyzer vapor stream
effluent), "P-ST" (the organics trapped by the solid sorbent and "P-Gaseous
Hydrocarbons" (the true volatiles) constitute the portion of i»yrolyzer
effluent delivered to the heat recovery system.
** 98% by weight of total feed, based on amount extracted from REP sample
with methylene chloride.
38
-------
5.3.3.2 Qualitative
Table 5-8 summarizes the results of the LRMS analyses
of the various samples from the 6-STY test. These data have been
normalized to reflect the total amount of organic effluent found in each
fraction. (Values do not add to 100% because not all of the waste
components fall into the seven selected classes.)
The waste feed consisted largely of unsubstituted (27.8%) and
substituted (59.9%) aromatic species of up to three fused rings. No
purely aliphatic species were identified, nor were any higher molecular
weight polynuclear aromatics found.
The total volatile effluent (GOO-SOL plus ST plus gaseous hydro-
carbons) was found to contain 18.4% aliphatic material. This was mainly
methane and acetylene in the gaseous hydrocarbon fraction. The fact that
the ratio of unsubstituted to substituted aromatics is dramatically
increased in the effluent suggests that the aliphatic material arose from
alkyl sidechains of components in the waste feed.
In addition to the low molecular weight aromatics, pyrene (four
fused rings) is found in the effluent at a concentration of 1.6%. It is
probable that other polynuclear aromatics are also present at low levels.
The data suggest that diphenyl thiophene is formed during pyrolysis,
since the quantity found in the effluent exceeds that in the waste feed.
In contrast to the API tests, the styrene tests yielded ASH with very
little organic material.
5.3.3.3 Physical Properties of Pyrolyzer Effluent
The TGA and the boiling point distribution curves for the 6-STY
samples indicate that the condensable portion of pyrolyzer effluent has
a boiling point range of 150 to 500°C (300 to 900°F). This spans the
range covered by diesel oil and kerosene (150 to 300°C) and heavier oils.
i
The total volatile effluent from the pyrolyzer is about 60% by
weight of these high boiling species and about 18% very low boiling species
(methane and xylene in the gaseous hydrocarbon fraction).
5.3.4 Fate of Inorganic Components of the Waste
5.3.4.1 Sulfur
Elemental analysis of the REP sample indicated that the waste
contained 7.68% by weight of sulfur. The diphenyl thiophene in the waste
accounts for less than 2% of the total sulfur content. Most of the sulfur
is present as the free element (83).
39
-------
Table 5-8
Class
1. Aliphatics
2. Unsubstituted
Arooatics of
< 3 Fused Rings
3. Substituted
Aromatics of
< 3 Fused Rings
4. Pyrene
Benzpyrene
Chrysene/
Benzanthracene
Benzfluoranthene
5. Hiscellaneous
Aromatics
6. Diphenyl
Thiophene
7. Oxygenated
Aronatics
TOTAL
NORMALIZED DISTRIBUTION OF TOTAL PYROLYZER
EFFLUENT BY
CHEMICAL CLASS OF MAJOR COMPONENTS FOR 6-STY TEST
PERCENT OF EFFLUENT
% REP
0
27.8
59.9
0
0
0
0
3.4
1.1
0
92.2
ASH-SOL
0
0.5
1.0
0
0
0
0
0.005
0.08
0
1.6
GOO-SOL
+
ST
0
24.0
28.2
1.6
0
0
0
2.5
5.1
0
61.4
Gaseous
HC's
18.4
17.4
3.5
0
0
0
0
0
0
0
39.3
Total
Volatile
Effluent
18.4
41.4
31.7
1.6
0
0
0
2.5
5.1
0
100.7
Total
Effluent
18.4
41.9
32.7
1.6
0
0
0
2.5
5.2
0
102.3
-------
In the pyrolyzer gaseous effluent fractions, most of the sulfur
appears as carbon disulfide (1330 ppm), carbonyl sulfide (400 ppm) and
sulfur dioxide (200 ppm). These components account for 68% of the sul-
fur in the waste feed. In addition, some sulfur is found in the ASH
sample.
Analysis of the 6-STY-P-I impinger solution indicated that
753 mg/m3 of sulfur, as S, was present as acidic volatile species in
the pyrolyzer effluent. This value agrees (within 10%) with the total
concentrations of S02 and COS (821 mg/m3 as S) estimated from the gas
bulb analyses.
5.3.A.2 Trace Elements
The SSMS analysis of the 0-STY-REP sample showed that the waste
contained only low levels of the metals generally recognized as hazardous.
These included zinc (1.7 ppm), chromium (0.19 ppm), and lead (0.11 ppm).
All of these were found to be concentrated in the 6-STY-P-ASH sample.
The levels of trace metals found in the ASH could account, within
experimental error, for the total quantities in the waste feed.
5.3.5 Analysis of Stack Gases
The objective of this test program was the evaluation of the
pyrolysis process, per se, not the rich fume incinerator in which the
pyrolyzer effluent was burned. A small number of analyses were, however,
performed on the incinerator stack gases.
5.3.5.1 Particulate Loading
The stack particulate loading, determined according to EPA
Method 5, was 27.5 mg/m3 for the 5-STY test and 43.2 mg/m3 for the
6-STY test. (The filter from the 4-STY test disintegrated and could not
be weighed.)
5.3.5.2 Sulfur Dioxide
The S02 level of the stack gases was found to be 100-200 ppm by
analysis with Gastec® tubes during the test. Analysis of the 6-STY-S-I
impinger samples for total sulfur indicated a stack gas loading of
126 mg/m3 as S or 88 ppm as S02.
5.3.5.3 Trace Elements
One-half of the 6-STY-S-F filter sample was analyzed by SSMS.
After the background due to the filter material had been subtracted, the
only element found at significant concentration was sulfur at about
2 mg/m3 of stack gas.
41
-------
5.4 TESTS ON RUBBER WASTES
5.4.1 Operating Conditions
Table 5-9 presents the operating parameters for the three tests on
rubber wastes. The major differences among tests are the waste feed rate
and the waste layer thickness.
5.4.2 Distribution of Pyrolyzer Effluent
In Table 5-10 are presented the data which show how the total mass
of rubber waste feed was distributed among pyrolyzer effluent samples in
the three tests.
The data show that the total quantity of feed accounted for by the
effluent samples averaged 44%. The lower recoveries are in large part
due to the fact that the waste contained 30 + 5% water. Other sources
of loss are deposition of material in the pyrolysis system and sample
manipulat ions.
5.4.3 Fate of Organic Components of the Waste
5.4.3.1 Quantitative
The rubber waste material was found to contain 33% by weight of
organic material extractable with methylene chloride, 36% residue on ex-
traction and 30% water. It is the organic portion of the waste which is
of primary importance in assessing the effectiveness of the pyrolysis
process.
Table 5-11 shows the distribution of organic material among the
various effluent fractions. The total recovery of organics was 79% for
9-RUB, which probably represents complete recovery within experimental
error. Of the total organic effluent, 12.1% was in the ASH, 12.7% in
the GOO, 6.8% in the sorbent trap, and 68.4% in the gaseous hydrocarbon
fraction.
42
-------
Table 5-9
OPERATING CONDITIONS FOR TESTS ON RUBBER WASTES
8-RUB
9-RUB
10-RUB
Pyrolyzer Temperature
Residence Time in
Pyrolysis Zone
Layer Thickness
Inert Gas Flow
Feed Rate
Pyrolyzer Effluent
Flow
Pyrolyzer Effluent
Temperature
Stack Gas Flow*
Stack Gas Temperature
760°C
(1400°F)
760°C
(UOOCF)
760°C
(1400°F)
15 min
1.73 cm
(^0.68 in)
(0.0118 m3/sec)
(1500 SCFH)
12.1 Kg/hr
(26.7 Ibs/hr)
0.0286 m3/sec
(3640 SCFH)
15 min
1.42 cm
(MJ.56 in)
(0.0098 m3/sec)
(1250 SCFH)
9.41 Kg/hr
(20.7 Ibs/hr)
0.0260 m3/sec
(3300 SCFH)
15 min
1.09 cm
13 in)
(0.0096 m3/sec)
(1225 SCFH)
7.27 Kg/hr
(16.0 Ibs/hr)
0.0261 m3/sec
(3320 SCFH)
640°C
(1180°F)
0.94 m3/sec
(1.19 x 105
SCFH)
342°C
(660°F)
620CC
(1150°C)
0.97 m3/sec
(1.23 x 105
SCFH)
337°C
(640°F)
640°C
(1180°F)
0.96 m3/sec
(1.22 x 105
SCFH)
323°C
(630°F)
* ADL values - all other data by Surface Combustion
43
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Table 5-10
TOTAL QUANTITIES OF EFFLUENTS FROM RUBBER WASTE TESTS*
Feed Rate Kg/hr
ASH Kg/hr
% of feed
GOO mg/m3
Kg/hr
% of feed
ST mg/m3
Kg/hr
% of feed
Gaseous Hydrocarbons
mg/m3
Kg/hr
% of feed
TOTAL % of Feed
8-RUB 9-RUB 10-RUB
12.1
3.62
29.9
4,840
0.498
4.1
1,070
0.110
0.9
18,040
1.86
15.4
50.3
9.41
1.64
17.4
4.825
0.452
4.8
1,820
0.170
1.8
18,190
1.70
18.1
42.1
7.27
0.908
12
6,020
0.566
7
1,220
0.115
1
14,300
1.34
18
40.3
.5
.8
.6
.4
* "P-ASH" is the solid residue remaining on the hearth after pyrolysis.
Together, "P-GOO" (the condensable organlcs in the pyrolyzer vapor stream
effluent), "P-ST" (the organics trapped by the solid sorbent and "P-Gaseous
Hydrocarbons" (the true volatiles) constitute the portion of pyrolyzer
effluent delivered to the heat recovery system.
44
-------
Table 5-11
ORGANIC MATERIAL IN PYROLYZER EFFLUENT
FRACTIONS FROM RUBBER TESTS*
Ash-Sol
Kg/hr
% of Organic Effluent
Goo-Sol
Kg/hr
% of Organic Effluent
ST
Kg/hr
% of Organic Effluent
Gaseous Hydrocarbons
Kg/hr
% of Organic Effluent
Total Organic Effluent
Kg/hr
Organic Feed Rate**
Kg/hr
Total Recovery of Organics
8-Rub
1.66
41.5
0.373
9.3
0.110
2.7
1.86
46.5
4.003
4.029
99%
9-Rub
0.315
12.7
0.170
6.8
2.487
10-rub
0.302 0.087
12.1 4.4
0.416
21.2
0.115
5.9
1.70- 1.34
68.4 68.4
1.958
3.136 2.421
79% 81%
* "P-ASH" is the solid residue remaining on the hearth after pyrolysis.
Together, "P-GOO" (the condensable organics in the pyrolyzer vapor
stream effluent), "P-ST" (the organics trapped by the solid sorbent)
and "P-Gaseous Hydrocarbons" (the true volatiles) constitute the portion
of pyrolyzer effluent delivered to the heat recovery system.
** 33.3% of total feed, based on amount extracted from REP sample with
methylene chloride.
45
-------
5.4.3.2 Qualitative
The organic extracts of the REP, ASH, GOO, and ST samples were
analyzed by gel permeation chromatography (GPC) to determine the molecular
weight distribution. The results, normalized to reflect the percent
of total organic effluent in each fraction, are:
% of material in molecular weight class
MW: 106 - 101*
35 27 37
EFFLUENT
9-REP-P-ASH-SOL 4.7 6.0 0.2
9-RUB-P-GOO-SOL A.I 8.6
9-RUB-P-ST 0.9
When the GPC data are combined with the result that 68.4% of the
total organic effluent was in the gaseous hydrocarbon fraction (MW <100),
the total molecular weight distribution of the pyrolyzer organic effluent
b ecomes:
Including ASH Excluding ASH
MW 106 - 101* 4.7% 0%
MW 'HO3 10.1% 5%
MW 101*) molecular weight fraction of the rubber waste feed was
also predominantly aliphatic, as shown by the lack of response to the UV
detector in the GPC analysis. Overall, therefore, the aliphatic material
in the pyrolyzer effluent is only about one-third of that in the waste
feed. It seems that a substantial amount of the high (>ltf*) molecular
weight material in the waste has been converted, during pyrolysis, to low
-------
Table 5-12
NORMALIZED DISTRIBUTION OF PYROLYZER EFFLUENT
BY CHEMICAL CLASS OF MAJOR COMPONENTS FOR 9-RUB TEST *
Class % REP-SOL
1.
2.
3.
4.
5.
6.
7.
Aliphatics
Unsubstituted Aroma tics
of <3 Fused Rings
Substituted Aromatics
of <3 Fused Rings
Pyrene
Benzpyrene
Chrysene/Benzanthracene
Benzfluoranthene
Miscellaneous Aromatics
Diphenyl Thiophene
Oxygenated Aromatics
TOTAL
18.0
0
1.5
0
0
0
0
2.1
0
9.6
31.2
P-ASH-SOL
0
0.4
0.8
0
0
0
0
0
0
0
1.2
P-GOO-SOL
pisT
0
5.5
3.6
1.1
0.3
0.5
0.3
2.4
0
0.1
13.7
PERCENT OF
Gaseous
HC's
20.2
48.2
0
0
0
0
0
0
0
0
68.4
EFFLUENT
Total
Volatile
Effluent
20.2
53.7
3.6
1.0
0.3
0.5
0.3
2.4
0
0.1
82.1
Total
Effluent
20.2
54.1
4.4
1.0
0.3
0.5
0.3
2.4
0
0.1
83.3
* "P-ASH" is the solid residue remaining on the hearth after pyrolysis. Together, "P-GOO" (the con-
densable organics in the pyrolyzer vapor stream effluent), "P-ST" (the organics trapped by the solid
sorbent) and "P-Gaseous Hydrocarbons" (the true volatiles) constitute the portion of pyrolyzer
effluent delivered to the heat recovery system.
-------
molecular weight unsubstltuted aromatics (up to 3 fused rings).
In addition to the 1000.
On the other hand, the rubber waste test resulted in a very
substantial portion of the feed being converted to very volatile species
(methane and benzene).
5.A.4 Fate of Inorganic Components of the Waste
A total of 61 elements were detected in the 0-RUB-REP sample by
SSMS. Among the elements found at significant concentrations which are
generally recognized as potentially hazardous were: chromium (130 ppm),
lead (62 ppm), zinc (53 ppm), and fluorine (20 ppm). In a separate
analysis, mercury was found at a level of 0.3 ppm.
Analysis of the ASH fraction of the pyrolyzer effluent by SSMS
revealed that all of the trace metals were enriched in this sample. In
fact, the concentrations found in the ASH can account, within experimental
error for all of the trace elements in the waste feed.
5. A. 5 Analysis of Stack Gases
The objective of this test program was the evaluation of the pyrolysis
process, per se, not the rich fume Incineration in which the pyrolyzer
effluent was burned. A small number of analyses were, however, performed
on the incineration stack gases.
5.4.5.1 Partlculate Loading
The stack particulate loading, determined according to EPA Method 5,
was 10.3 mg/m3 for the 8-RUB, 14.0 mg/m3 for the 9-RUB, and 9.1 mg/m3 for
the 10-RUB test.
5.A.5.2 Sulfur Dioxide
Analysis of the 9-RUB-S-I impinger sample for total sulfur indicated
a stack gas loading of 39 mg/m3 as S, or 25 ppm as S02.
5.4.5.3 Trace Elements
One-half of the 9-RUB-S-F filter sample was analyzed directly by
SSMS. After the background due to the filter material had been subtracted,
no trace elements were identified in the stack gas particulate sample.
48
-------
5.5 SURFACE COMBUSTION BACKGROUND (SCB) TEST
The "background" test at Surface Combustion was made after the
styrene test. In retrospect, this decision may have been unwise. All
of the analytical data indicate that the samples collected during the
"background" burn were, though lower in quantity, qualitatively similar
to those of the styrene waste tests immediately preceding. (Appendix B)
For this reason, a detailed analysis of the effluent from the SCB burn is
not presented here.
The difficulty encountered in attempting to obtain a background
sample reemphasizes the fact that the "pyrolysis gas" produced from all
three wastes in fact contains substantial amounts of rather non-volatile
materials. These components of the pyrolyzer effluent begin to condense
if the temperature of the "pyrolysis gas" drops much below 500°C. Be-
sides causing potential plugging problems, this accumulation of material
in the ductwork produces "memory" effects in the pyrolysis system.
-------
6. WASTE INCINERATION COST
Individual economic analyses were prepared for pyrolysis and incineration
(with heat recovery) facilities of severalidifferent capacities for the de-
struction of rubber waste. An economic analysis was also prepared for the
pyrolysis of an API separator bottoms waste. An economic analysis was not
prepared for the pyrolysis of styrene waste.because the physical form of this
waste (liquid) would make it amenable to direct combustion in heat recovery
equipment.
Each of these economic analyses was based on the "close coupling" of the
pyrolyzer to a pyrolysis gas incinerator to preclude loss of sensible heat
and condensation of high molecular weight organlcs in the duct between the
pyrolyzer and incinerator.
The quantity of each type of waste to be destroyed is based on the
following estimates of waste generation from single sources:
Refinery API
separator bottoms
Rubber Waste
(Small Plant)
(Large Plant)
(From several
Plants)
Size Productions Units
Crude oil capacity 50,000 bbl/day
Waste Generated
..(Metric tons/yr)
300
SBR Rubber
SBR Rubber
SBR Rubber
125,000 metric tons/yr 1000
250,000 " 2000
750,000 " 6000
The size of pyrolyzer required for these wastes (with the exception of the
6000 metric ton/yr pyrolyzer) is smaller than that normally built by
Surface Combustion so the equipment cost estimates supplied for the pyrolyzer
and rich fume incinerator were scaled down from the larger units.
As can be seen in the operating cost estimates, the smaller units are
much more expensive to operate than the larger units. Net operating costs
range from about $117 to $526 per ton of rubber waste (corresponding to
6000 and 1000 metric tons/yr of rubber waste treatment capacity) up to
$895 per metric ton of API separator bottoms waste at 300 metric tons/yr.
6.1 CAPITAL INVESTMENT
The equipment costs for the pyrolyzer and fume incinerator plus the
necessary (uninstalled) instrumentation were supplied by Surface Combustion.
50
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The cost of the other major pieces of equipment were estimated by ADL
using cost data reported in the literature * ** and updated using the
Marshall and Swift Equipment (M&S) Index to a base of 460 (March 1976).
Each estimate is based on a system that includes waste storage, a feed
system, the pyrolyzer, fume incinerator and heat recovery. However, no
costs were included for air pollution control should it be required for
particulates or sulfur oxides.
In the case of the API separator bottoms, the storage and feed system
is relatively simple i.e., storage tank for about seven days waste and a
progressing cavity or gear type feed pump.
The rubber waste, on the other hand, would require a much more
sophisticated feed system. For the estimates, an extrusion type feeder has
been assumed to discharge directly into the pyrolyzer. A belt conveyor
would carry the rubber waste from the storage hopper to the feeder and
pyrolyzer.
A certain portion of the piping and wiring of the system would be done
during the construction of the equipment, but additional piping and wiring
would be necessary at the construction site.
The estimate of capital Investment requirements for three different
capacities of rubber waste and one capacity of API separator bottoms waste
are given in Tables 6-1, 6-3, 6-5 and 6-7.
6.2 OPERATING COSTS
The operating costs for three different capacity pyrolysis/incineration/
heat recovery systems for handling rubber waste and a smaller system for
handling API bottoms are presented in Tables 6-2, 6-4, 6-6 and 6-8. The
operating costs for these four systems are summarized below:
Waste Treated Net Operating Cost
Waste (metric tons/yr) ($/metric ton)
Rubber Waste
From Several Plants Combined 6000 $117.17
From a Large Plant 2000 295.69
From a Small Plant 1000 525.89
API Bottoms Waste 300 894.51
* K. M. Guthrie, Process Plant Estimating Evaluation and Control.
Craftsman Book Co. of America, Solano Beach, California (1974)
** C. Dryden and R. Furlow, Chemical Engineering Costs, Ohio State
University, Columbus, Ohio 1966
51
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TABLE 6-1
CAPITAL INVESTMENT FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
FOR 6000 METRIC TONS/YR OF RUBBER WASTE
Basis: 750 Kg/hr, 24 hrs/day, 330 days/yr
Purchased Equipment Size Cost (March 1976$)
Forced Draft Blower 7,500 scfm at 2 psi 10,000
Rotary Hearth Pyrolyzer 10 ft diameter 230,000
Incinerator Burner 30 million Btu/hr 36,000
Instrumentation Package 11,000
Extruder/Feeder 1,500 Ibs/hr 75,000
Feed Storage 3,000 cuft (5 days) 7,000
Feed Conveyor (Belt) 100 ft 5,000
Heat Recovery Boiler 30 million Btu/hr 105,000
Purchased Equipment Cost $479,000
Installed Equipment Cost (IEC) 550,000
Piping (40% IEC) 220,000
Foundations (5% IEC) 28,000
Buildings and Structures (25% IEC) 138,000
Electrical (Including Instruments) 50.000
Total Physical Plant Cost (TPPC) $986,000
Engineering and Construction 30% TPPC 297,000
Contingency 20% TPPC 197^000
Total Capital Investment $1,480,000
Round to $1,500,000
52
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TABLE 6-2
OPERATING COST FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
FOR 6000 METRIC TONS/YR OF RUBBER WASTE
Basis: Fixed Capital Investment (FCI) $1,500,000
750 kg/hr Waste
Operation 24 hrs/day 330 days/yr
Rubber Waste Heat Value 5500 K Cal/kg (9800 Btu/lb) at 30% water
90% Conversion of Organics in Waste to Pyrolysis Gas
Units per 2000 $ per Metric Annual
Variable Costs $/Unit Metric Ton Waste
Operating Labor*
Utilities
oil nr rae 7 . 93/MillionKCal
or oas (2.00/MillJonBtu) 2.66
Electricity* 0.015/kwh 250
Maintenance (8% FCI)
Solid Waste
Disposal (12%
Input) 6.50/Metric Ton 0.12
TOTAL VARIABLE COSTS
Fixed Costs
Depreciation (15% FCI)
Cost of Capital (10% FCI)
Taxes and Ins. ( 2% FCI)
Total Fixed Cost
Total Operating Cost
Credit for Recovered Heat (at 80% boiler efficient
From Rubber
Waste 7.93/Million Real 3.96
Ton Waste
52.13
21.11
3.75
20.00
0.78
$97.77
37.50
25.00
5.00
$67.50
$165.27
cy)
31. 40
Cost ($)
312,800
126,700
22,500
120,000
4,700
$586,700
225,000
150,000
30,000
$405,000
$991,700
188,400
From Auxiliary
Fuel 7.93/Million Kcal 2.11 16.70 100.100
Total Credit $48.10 $288,500
Net Operating Cost $117.17 $703,000
* See footnotes to Table 6-2
-------
FOOTNOTES TO TABLE 6-2
Operating Labor
Annual Cost
Pyrolyzer Feed System Operator 1 x 24 x 365 x $7.00 = $ 61,300
Pyrolyzer/Inclnerator Operator 1 x 24 x 365 x 7.50 » 65,800
Helper 1 x 24 x 365 x 6.50 = 56.900
Supervision (15% Direct Labor)
Supplies (20% Direct Labor)
Payroll Related Expense (35% Direct Labor)
1 x 24 x 365 x 6.50 =
Direct Labor $184,000
27,600
36,800
64,400
Total Operating Labor $312,800
Electric Power
Forced Draft Blower 75KW
Extruder/Feeder 65KW
Rotary Hearth 40KW
Waste Conveyor 5KW
185 Kwh/hr x
1000
750
250 kwh/metric ton
Rubber Waste
-------
TABLE 6-3
CAPITAL INVESTMENT FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
FOR 2000 METRIC TONS/YR OF RUBBER WASTE
Basis: 250 Kg/hr, 24 hrs/day, 330 days/yr
Purchased Equipment Size Cost (March 1976$)
Forced Draft Blower 2,500 scfm at 2 psi 5,500
Rotary Hearth Pyrolyzer 6 ft diameter 150,000
Incinerator Burner 12 million Btu/hr 12,500
Instrumentation Package 11,000
Extruder/Feeder 600 Ibs/hr 40,000
Feed Storage 1,000 cuft (5 days) 4,000
Feed Conveyor (Belt) 100 ft 5,000
Heat Recovery (Boiler) 10 million Btu/hr 50.000
Purchased Equipment Cost (PEC) $278,000
Installed Equipment Cost (IEC) 320,000
Piping (40% IEC) 128,000
Foundations (5% IEC) 16,000
Buildings and Structures (30% IEC) 96,000
Electrical (Including Instruments) 50.000
Total Physical Plant Cost (TPPC) $610,000
Engineering and Construction 30% TFPC 183,000
Contingency 20% TPPC 122.000
Total Capital Investment $915,000
Round to $920,000
55
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TABLE 6-4
OPERATING COST FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
FOR 2000 METRIC TONS/YR OF RUBBER WASTE
Basis: Fixed Capital Investment (FCI) $920,000
250 Kg/hr Rubber Waste
Operation 24 hrs/day 330 days/yr
Rubber Waste Heat Value 5500 KCal/kg (9,800 Btu/lb) at 30% Water
90% Conversion of Organics in Waste to Pyrolysis Gas
Units per $ per
Metric Ton Metric Ton Annual
Variable Costs $/Unit Waste Waste Cost ($)
Operating Labor*
Utilities
Oil or Gas
Electricity*
Maintenance (8%
Solid Waste
Disposal
(12% input)
7.93/Million KCal 2.66
(2.00/Million Btu)
0.015/kwh 300
FCI)
6.50/metric ton 0.12
156.40
21.11
4.50
36.80
0.78
312,800
42,100
9,000
73,600
1,600
Total Variable Costs $219.59 $439,100
Fixed Costs
Depreciation (15% FCI) 69.00 138,000
Cost of Capital (10% FCI) 46.00 92,000
Taxes and Insurance (2% FCI) 9.20 18.400
Total Fixed Costs $124.20 $248,000
Total Operating Costs $343.79 $687,500
Credit for Recovered Heat (80% Boiler Efficiency)
From Rubber Waste 7.93/Million KCal 3.96 31.40 63,000
From Auxiliary Fuel 7.93/Million KCal 2.11 16.70 33.500
Total Credit $ 48.10 $ 96,500
Net Operating Cost $295.69 $591,000
* See footnotes to Table 6-4
56
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FOOTNOTES TO TABLE 6-4
Operating Labor
Pyrolyzer Feed System Operator 1 x 24 x 365 x 7.00 =
Pyrolyzer/Incinerator Operator 1 x 24 x 365 x 7.50 =
Helper 1 x 24 x 365 x 6.50 -
Direct Labor
Supervision (15% Direct Labor)
Supplies (20% Direct Labor)
Payroll Related Expense (35% Direct Labor)
Total Operating Labor
Electric Power
Forced Draft Blower 30 KW
Extruder/Feeder 28 KW 75 Kwh/hr x
Rotary Hearth 12 KW
Rubber Conveyor 5 KW
Annual Cost
$ 61,300
65,800
56,900
$184,000
27,600
36,800
64.400
$312,800
250
= 300 Kwh/metric ton
Rubber Waste
57
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TABLE 6-5
CAPITAL INVESTMENT FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
FOR 1000 METRIC TONS/YR OF RUBBER WASTE
Basis: 125 Kg/hr, 24 hrs/day, 330 days/yr
Purchased Equipment Size Cost (March 1976$)
Forced Draft Blower 1,500 scfm 4,000
Rotary Hearth Pyrolyzer 4 ft diameter 113,000
Incinerator Burner 6 million Btu/hr 10,000
Instrumentation Package - 11,000
Extruder/Feeder 300 Ibs/hr 26,000
Feed Storage 500 cuft 5 days 2,000
Feed Conveyor (Belt) 100 ft 5,000
Heat Recovery Boiler 5 million Btu/hr 27.000
Purchased Equipment Cost $198,000
Installed Equipment Cost (IEC) 228,000
Piping (40% IEC) 91,000
Foundations (5% IEC) 11,000
Buildings and Structures (30% IEC) 68,000
Electrical (Including Instruments) 50.000
Total Physical Plant Cost (TPPC) $448,000
Engineering and Construction 30% TPPC 134,000
Conttngercy 20% TPPC 90.000
Total Capital Investment $672,000
Round to $670,000
58
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TABLE 6-6
OPERATING COST FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
FOR 1000 METRIC TONS/YR OF RUBBER WASTE
Basis: Fixed Capital Investment (FCI) $670,000
125 Kg/hr Rubber Waste
Operation 24 hrs/day, 330 days/yr
Rubber Waste Heat Value 5500 KCal/Kg (9800 Btu/lb) at 30% Water
90% Conversion of Organics in Waste to Pyrolysis Gas
Units per $ per
Metric Ton Metric Ton Annual
Variable Costs
Operating Labor*
Utilities
Oil or Gas
Electricity*
Maintenance
(8% FCI)
Solid Waste
Fixed Costs
Depreciation
Cost of Capital
Taxes and Ins.
Credit for Recovered
From Rubber Waste
From Auxiliary
Fuel
Net Operating Cost
$/Unit Waste
7.93/Million KCal
(2. 00 /Million Btu) 2.66
.015 kwh 320
6.50/metric ton 0.12
Total Variable Costs
(15% FCI)
(10% FCI)
(2% FCI)
Total Fixed Costs
Total Operating Costs
Heat (at 80% Boiler eff.)
7.93 Million KCal 3.96
7.93 Million KCal 2.11
Total Credit
Waste
312.80
21.11
A. 80
53.60
0.78
$393.09
100.50
67.00
13.40
$180.90
$573.99
31.40
16.70
$48.10
$525.89
Cost ($)
312,800
21,100
4,800
53,600
800
$393,100
100,500
67,000
13,400
$180,900
$574,000
31,300
16,700
$48,000
$526,000
*See Footnote to Table 6-6
59
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FOOTNOTES TO TABLE 6-6
Operating Labor Annual Cost
Pyrolyzer Feed System Operator 1 x 24 x 365 x 7.00 = $ 61,300
Pyrolyzer/Incinerator Operator 1 x 24 x 365 x 7.50 = 65,800
Helper 1 x 24 x 365 x 6.50 - 56.900
Direct Labor $184,000
Supervision (15% Direct Labor) 27,600
Supplies (20% Direct Labor) 36,800
Payroll Related Expense (35% Direct Labor) 64,400
Total Operating Labor $312,800
Electric Power
Forced Draft Blower 15 KW
1000 320 Kwh/metric ton
Extruder/Feeder 15 KW
40Kwh/hr x
125 Rubber Waste
Rotary Hearth 5 KW
Rubber Conveyor 5 KW
60
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TABLE 6-7
CAPITAL INVESTMENT FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
300 METRIC TONS/YR OF API SEPARATOR BOTTOMS WASTE
Basis: 38 Kg/hr, 24 hrs/day, 330 days/yr
Purchased Equipment Size Cost (March 1976$)
Forced Draft Blower 400 scfm at 2 psi 2,000
Rotary Hearth Pyrolyzer 2.3 ft diameter 83,000
Incinerator Burner 10,000
Instrumentation Package 11,000
Feed Pump 2,000
Feed Storage Tank 1,500 gal 1,500
Heat Recovery Boiler 1.2 million Btu/hr 11.500
Purchased Equipment Cost (PEC) $121,000
Installed Equipment Cost (IEC) $140,000
Piping 40% IEC 56,000
Foundations 5% IEC 7,000
Building & Structures (30% IEC) 42,000
Electrical (Including Instruments) 50.000
Total Physical Plant Cost (TPPC) $295,000
Engineering and Construction 30% TPPC 88,000
Contingency 20% TPPC 59.000
TOTAL CAPITAL INVESTMENT $442,000
Round to $440,000
61
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TABLE 6-8
OPERATING COST FOR PYROLYSIS, INCINERATION AND HEAT RECOVERY
FOR 300 METRIC TONS/YR OF API SEPARATOR BOTTOMS WASTE
Basis: Fixed Capital Investment (FCI) $440,000
38 Kg/hr Waste
Operation 24 hrs/day, 330 days/yr
API Waste Heat Value 1400 KCal/Kg (2500 Btu/lb) at 70% Water
75% Conversion of Organics in Waste to Pyrolysis Gas
Units per $ per
Metric Ton Metric Ton Annual
Variable Costs
Operating Labor*
Utilities
Oil or Gas
Electricity*
Maintenance
(8% FCI/yr)
Solid Waste
Disposal
(@ 10% input)
Fixed Costs
Depreciation
Cost of Capital
Taxes and Ins.
Credit for Recovered
From API Waste
From Auxiliary
Fuel
Net Operating Costs
$/Unit Waste
7.93/Million KCal , ,,
(2.00/Million Btu) °*°°
0.015/kwh 340
6.50/metric ton 0.10
Total Variable Cost
(15% FCI/yr)
(10 FCI/yr)
(2% FCI/yr)
Total Operating Cost
Heat (80% Boiler Efficiency)
7.93/Million KCal 0.84
7.93/Million KCal 5.54
Total Credits
Waste
373.33
52.80
5.10
117.33
0.65
$549.21
220.00
146.67
29.33
945.21
6.70
44.00
$50.70
$894.51
Cost ($)
112,000
15,700
1,500
35,000
200
$164,400
66,000
44,000
8,800
283,200
2,000
13,200
$15,200
$268,000
* See Footnotes to Table 6-8
62
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FOOTNOTES TO TABLE 6-8
Operating Labor Annual Cost
Pyrolyzer System Operator 1 x 24 x 365 x 7.50 $ 65,800
Supervision (15% Direct Labor) 9,900
Supplies (20% Direct Labor) 13,200
Payroll Related Expense (35% Direct Labor) 23,100
Total Operating Labor $112,000
Electric Power
Forced Draft Blower 7 KW
Rotary Hearth 4 KW
-^^^^^ ^™™™^^™ ^ •*"» w *^w»tf —-
hr 38 ~ API Waste
Feed Pumps 2 KW "
13 kwh x 1000 340 Kwh/ Metric ton
63
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The labor requirements for the system would be the same for either
1000 or 6000 metric ton/yr of rubber waste (one full time operator for the
feed system, one helper full time, and one operator full time for the
pyrolyzer, incinerator and boiler). For the API bottoms waste, one operator
(full time) should be able to handle the whole system.
The estimated auxiliary fuel and power requirements for the pyrolyzer
were supplied by Surface Combustion. The additional power included in
these estimates would be required for supplying compressed air to the
pyrolyzer/incinerator and to drive the extruder/feeder or feed pump.
As indicated in each of these operating cost estimates, the credit
for recovered heat is based on 80% recovery of the total heat input to the
incinerator in a heat recovery boiler. The total heat input to the incin-
erator was taken as the total heat value of auxiliary fuel plus 90% of the
gross heat value of the feed material in the case of rubber waste, and 75%
of the gross heat value in the case of API waste. This assumed 90%
conversion of the feed material organics to pyrolysls gas for the rubber
waste and 75% conversion of the feed material organics to pyrolysis gas
for the API waste.
As shown in Tables 1-1 and 5-11 the pyrolysis system was operated with
the rubber waste to yield ash containing only 4-12% of the organics present
in the feed. Although the material balance based on the analysis of the
pyrolysis gas indicates that less than 90% of the organics in the rubber
waste feed were converted to pyrolysis gas, only 80% of the organics in the
feed were accounted for by the material balance for these test runs.
Since there was no appreciable carbon (soot) formation in these test runs
and since the organics in the ash (at 4-12%) could be more accurately
measured than the weight of organics in the pyrolysis gas stream estimated,
it is more likely that conversion ranged from 88-96% of organics to pyrolysis
gas. For the purposes of these estimated operating costs 90% conversion of
rubber waste organics to pyrolysis gas was assumed.
In the case of the API waste approximately 25% of the organics in the feed
appeared in the ash (Table 5-3), so 75% conversion to pyrolysis gas was
assumed.
-------
7. CONCLUSIONS
7.1 GENERAL CONCLUSIONS ABOUT THE PYROLYSIS PROCESS
7.1.1 Physical Characteristics of Suitable Wastes
The pyrolysis process is particuarly well suited for destruction of
solid or semi-solid wastes with high water or ash content.
7.1.2 Chemical Characteristics of Suitable Wastes
The results of the tests indicate that an ideal waste, from the point
of view of production of clean gaseous fuel for recovery, is highly aliphatic.
For each of the wastes tested, the quantity bf aliphatic component in the
pycolyzer effluent was correlated with the aliphatic content of the original
waste. (In the case of atyrene, the waste feed "aliphatic content" was in the
form of alkyl substltuents on aromatic compounds.) Aromatic waste feed
components yield primarily aromatic effluent components, including substantial
quantities of polynuclear aromatics. The aliphatic/aromatic content of the
pyrolyzer effluent is of concern because aliphatics burn more cleanly in
a subsequent heat recovery system.
7.1.3 Operational Characteristics
The pyrolysis gases contain varying amounts of substances which condense
at normal temperatures and pressures; consequently, these gases must be either
combusted in a close-coupled heat recovery system or cleaned before they
could be put into gas distribution systems. Because the chemical nature of
the pyrolysis gas is similar to that from coking or gasification of coal,
i.e., containing known carcinogens, the same occupational health and safety
precautions are required. The operational characteristics of pyrolysis
systems require the usual attention to controlling combustible and potentially
explosive mixtures; however, these appear to be no more difficult to handle
than similar problems in other processes.
7.1.4 Economics
The capital investments and operating costs for a rotary hearth pyrolyzer
are greater than a conventional incinerator of equivalent capacity. For this
reason, the pyrolysis process is economically feasible only where energy
recovery from waste materials cannot be effected in a less costly manner.
Where thermal destruction of wastes containing high salt or ash content is
required, or where difficult to control air pollution problems might result,
the pyrolysis process may be the most economical.
7.2 API WASTE TESTS
7.2.1 Resource Recovery
A total of about 70%-75% of the organic material in the waste was converted
to a form which was combustible in the rich fume incinerator. Because the
65
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original waste was largely aqueous, this corresponds to only 9% by weight of
the total waste feed.
The pyrolysis gas was about 70% volatiles (£ r ) and about 30% condensable
aromatics at normal conditions. °
7.2.2 Solid Residue
The ASH, or solid residue, amounted to about 20% by weight of the total
API waste feed, and was about 85% inorganic material.
7.2.3 Potentially Hazardous Emissions
The API waste contains substantially higher levels of trace metals than
typical high ash fuels such as coal. The major portions of these are found
in the solid residue from the pyrolyzer. Less than 5% of the lead and zinc
content of the waste is found in the pyrolyzer gas.
3
The sulfur content of the pyrolysis gas is 136 mg/m as sulfur.
The pyrolysis gas contains 3.2% of polynuclear aromatic hydrocarbons
in the condensable fraction. This is equivalent to a pyrolysis emission
rate of about 350 mg/rn-*. Much of this material would probably be destroyed
in a properly controlled heat recovery process.
7.2.4 Engineering Considerations and Alternative Treatment Techniques
The high viscosity and ash content would make this waste unsuitable
for a conventional liquid injection incinerator. This waste could be
handled in a fluid bed incinerator, or, as these tests have shown, in a
pyrolyzerc It would probably be more economical to dispose of this waste
in a fluid bed incinerator, however, especially in view of the high water
content and low heat xalue. In any case, the high viscosity of this waste
would require a Hoyno , gear or other type of positive displacement pump
for feeding the incinerator (or pyrolyzer).
7.2.5 Economic Feasibility
The estimates Indicate that construction of a pyrolysis facility to
treat 300 metric tons per year of API waste would require a capital Invest-
ment of $444,000. The operating costs are estimated to be $283,000 per year
or $945/ton of waste.
If allowance is made for recovered heat at $7.93/million RCal
($2.00/million Btu) operating cost is $895/metric ton of waste.
7.3 STYRENE WASTE TESTS
7.3.1 Resource Recovery
A total of about 57% of the organic material in the waste was converted
to a form which was combustible in the rich fume incinerator. The pyrolysis
gas was about 27% volatiles (< Cj and about 73% condensable aromatics at normal
conditions.
66
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7.3.2 Solid Residue
The ASH, or solid residue, amounted to about 0.5% by weight of the total
waste feed, and was about 96% Inorganic material.
7.3.3 Potentially Hazardous Emissions
The styrene waste contained only low levels of metals recognized as
hazardous. The analyses indicate that none of these were present in the
pyrolysis gas.
3
The sulfur content of the pyrolysis gas was 753 rag/m as sulfur. This
was primarily carbon disulfide, carbonyl sulfide and sulfur dioxide.
The pyrolysis gas was found to contain 1.6% of polynuclear aromatic
hydrocarbons, as pyrene in the condensable fraction. This is equivalent to
an emission rate of 400 mg/m . Much of this material would probably be
destroyed in an efficient heat recovery process.
7.3.4 Engineering Considerations and Alternative Treatment Techniques
Samples of this waste obtained before the test program indicated a
relatively high viscosity. The waste actually obtained for the test was of
much lower viscosity and could have been burned in a conventional liquid injec-
tion incinerator. Upon pyrolysis of the highly unsaturated chemical components
considerable quantities of carbon particulates were generated which deposited
in the off-gas duct work. This carbon particulate represents both a loss of
fuel value and a potential handling problem.
7.3.5 Economic Feasibility
The economics of pyrolysis of this waste was not determined since the
waste is not suitable for pyrolysis.
7.4 RUBBER WASTE TESTS
7.4.1 Resource Recovery
A total of about 80%-90% of1 the organic material in the waste was
converted to a form which was deliverable to the rich fume incinerator. This
corresponds to about 27% by weight of the original waste feed.
The pyrolysis gas was about 70% true volatiles (£ Cg) and about 30%
condensable1 aroma tics.
7.4.2 Solid Residue
The ASH, or solid residue, amounted to about 20% by weight of the total
waste feed, and was about 80% inorganic material.
67
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7.4.3 Potentially Hazardous Emissions
The rubber waste contained significant concentrations of several metals
recognized as potentially hazardous. The analyses indicated that these
species are not present in the pyrolysis gas, but are concentrated in the
ASH.
The sulfur content of the pyrolysis gas was 189 mg/m as sulfur.
The pyrolysis gas was found to contain 2.1% of polynuclear aromatic
hydrocarbons in the condensable fraction. This is equivalent to an emission
rate of 490 mg/m3. Much of this material would probably be destroyed in an
efficient heat recovery process.
7.A.4 Engineering Considerations and Alternative Treatment Techniques
This waste is in a physical form (semi-solid lumps) which would make
it very difficult to incinerate in virtually any other type of thermal
destruction equipment. Even the destruction of this waste by pyrolysis
requires that the waste be fed to the pyrolyzer in a thin enough layer
on the hearth to allow complete pyrolysis. This can be accomplished by
extruding the waste (in the proper thickness) directly onto the hearth.
An important factor in the thermal destruction of this waste by
pyrolysis is the 80%-90% efficiency of conversion of the organic components
in the waste to pyrolysis gas.
7.4.5 Economic Feasibility
The estimates indicate the following costs for pyrolysis facilities to
treat rubber waste:
Operating Cost
Without Credit With Credit
Capital for Heat for Heat
Capacity Investment Recovery Recovery
1000 M.T./yr $670,000 $574/M.T. $525/M.T.
2000 M.T./yr $920,000 $344/M.T. $296/M.T.
6000 M.T./yr $1,500,000 $165/M.T. $117/M.T.
68
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APPENDIX A
Techniques of Sample Preparation and Analysis
A. Extraction of Collected Samples
B. Analyses of Gaseous Effluents
C. Additional Analytical Techniques
D. Sample Identification Codes
E. Vendors for Outside Analyses
69
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APPENDIX A
TECHNIQUES OF SAMPLE PREPARATION AND ANALYSIS
A.I EXTRACTION OF COLLECTED SAMPLES
A.1.1 Waste Feed Sample
A weighed aliquot of composited waste feed material was Soxhlet ex-
tracted with methylene chloride for 24 hours. The weights of residual
and extractable material were determined by drying to constant weight
at ambient temperature.
A. 1.2 Pyrolysis Zone Sample Train Components
The contents of the knock-out impingers (Figure 4-1) and the
pyrolysis zone probe washings (pentane plus acetone) were combined in the
field. These samples were evaporated to dryness on a hot plate and the
mass determined gravimetrically. The glass wool from the fourth impinger
of the knock-out train was Soxhlet extracted for 24 hours with methylene
chloride, then for 24 hours with methanol. The two extracts were combined
and evaporated to dryness. The mass of extracted material was determined.
The pre-tared pyrolysis zone filter was dried to constant weight to
determine the mass of collected material.
The filter, glass wool extract and dried knock-out trap samples
were then combined in a Soxhlet thimble and extracted for 24 hours with
methylene chloride. The extract was evaporated to dryness at ambient
temperature and the total mass of extractable material determined. This
is the fraction identified as GOO-SOL.
The sorbent trap was fitted into the specially designed extraction
apparatus shown in Figure A-l and extracted for 24 hours with pentane,
then for 24 hours with methanol. The two extracts were individually
evaporated to dryness at ambient temperature and the mass of material in
each determined gravimetrically.
70
-------
Condenser
Tef Ion Seals f=i=M 28/12
Flexible Teflon Coupling
250 Ml Flask
Figure A-l. Sorbent Trap Extractor
71
-------
A.2 ANALYSES OF GASEOUS EFFLUENTS
A.2.1 On-Line Instruments
A continuous recording was made of the output of each of the five
on-line instruments. In reducing the data, readings were made from the
charts.at 10 minute intervals and the values averaged. The range of
values and the fluctuations in those values during the course of a run
were:
Hydrocarbons 1.33 to 3.11% +0.07 to 0.37%
Carbon Monoxide 1436 to 2244 ppm + 8 to 41 ppm
Carbon Dioxide 10.1 to 11.1% + 0.06 to 0.4%
Nitrous Oxide 64 to 100 ppm + 2 to 10 ppm
Oxygen 0.0% + 0.2%
The instruments were calibrated (zero and span) at least every two
hours using the following gases (supplied with analyses by Matheson Gas
P roduc t s Company).
Analyzer Zero Gas Span Gas
Hydrocarbons air 40 ppm C3H8 in N2
Carbon Monoxide air 138 ppm CO
Carbon Dioxide air 12.4% C02
Nitrogen Oxides air 432 ppm NO in N2
Oxygen CO, C02, C3H8 air
span gas
The error introduced by use of span gas concentrations, very different
from the measured sample gas concentrations (for hydrocarbons and carbon
monoxide), would be expected tc introduce an error of no more than 10%.
The NOX analyzer could not be operated in the NOX mode (which converts
N02 to NO) for these sample streams. This is because the converter oper-
ates at a temperature of 750°C and NO is destroyed in the presence of
large quantities of hydrocarbon and in the absence of oxygen.
A.2.2 Gas Detecting Tubes
Bendix Gastec®* tubes number 5 M, Sulfur Dioxide, Mid-Range
These were
combined in
one cylinder.
Trademark of Bendix Environmental Science Division
72
-------
(100-3600 ppm) and a Bendix hand sampling pump were used to monitor the
stack effluent during API and styrene tests.
A.2.3 Gas Grab Samples
A metal bellows pump was used to transfer a portion of the pyrolysis
zone gaseous effluent from the bypass line of the hydrocarbon analyzer to
a 12 liter Saran gas sampling bag. The pumping rate was adjusted so that
the sample was composited over a one hour period.
To eliminate losses due to diffusion, portions of the collected
sample were transfered to glass bulbs with Teflon stopcocks. The 125 ml
bulbs were evacuated and flushed with sample several times before
filling.
The gas bulb samples were sent to an outside laboratory for quali-
tative and quantitative analysis. Unfortunately, the results of those
analyses showed oxygen concentrations of 7% and higher, Indicating that
leakage occurred somewhere in the sampling procedure. The reported
results were corrected to a zero oxygen concentration, but are inevitably
less accurate than they should have been.
The results of these analyses were used primarily to determine an
average molecular weight and carbon number for the very volatile portion
of the pyrolyzer effluent. For this purpose it is only the relative
abundances and not the absolute concentrations, of waste components which
is important.
A.3 ADDITIONAL ANALYTICAL TECHNIQUES
A number of techniques were used for qualitative and quantitative
analysis of waste feed and collected samples. These include:
Inorganic Species Organic Species
X-Ray Fluorescence (XRF) Infrared Spectroscopy (IR)
Atomic Absorption Spectro- Mass Spectroscopy (LRMS)
scopy (AAS)
Specific Ion Electrodes (SIE) C.H.N.S Analysis
Gas-detecting tubes Gas Chromatography (GC)
Silica Gel Column Chromatography
These techniques were applied to the Surface Combustion samples
where appropriate.
73
-------
Analyses performed in ADL laboratories on the Surface Combustion
samples Included LRMS on a DuPont (CEC) 21-110B high resolution mass
spectrometer using a glass Inlet and solids probe for sample Introduction,
IR on a Perkln-Elmer 521 grating spectrophotometer, and gas chromatography
using the system described below under boiling point distribution. Other
analyses were performed by outside laboratories, listed in Section E of
this appendix.
Because of the special features of the pyrolysis process investigated
at Surface Combustion, some additional techniques were used to characterize
the feed and effluent samples.
In a pyrolysis process, hydrocarbons are "cracked" to give organic
species of lower molecular weight. In order to evaluate the Surface
Combustion process, therefore, a number of methods were utilized which give
an estimate of the molecular weight distribution in the analyzed sample.
These methods, which are described briefly below, were Thermogravimetric
Analysis (TGA), Boiling Point Distribution, and Gel Permeation Chromato-
graphy (GPC). It should be pointed out that these techniques do not
provide a qualitative or quantitative determination of individual waste
or effluent components; rather, they determine qualitative and quantitative
changes in the distribution of sample components with respect to volatility
and/or molecular weight. (Within a homologous series or organic compounds,
volatility decreases monotonically with increasing molecular weight.)
A.3.1 Thermogravimetric Analysis
In a thermogravimetric analysis, the weight loss of a small (typically
<50 mg) sample of material is recorded as the temperature of the sample is
increased at a controlled rate.
In interpreting the TGA curves of the Surface Combustion samples,
the criterion used was that a distinct change in the slope of the
sample weight vs. sample temperature curve indicates the onset of a new
"fraction" of the sample.
For the analyses a DuPont Model 950 system was used. The heating was
performed in an inert (N2) atmosphere to minimize deterioration of the
sample during analysis. The sample temperature was increased at a rate
of 10-15°C/min. A typical curve is shown in Figure A-2.
A.3.2 Boiling Point Distribution
The boiling point distribution curve is an ASTM method for charac-
terizing complex mixtures of hydrocarbons. In the procedure, a standard
mixture of hydrocarbons is used to define a calibration curve of retention
time vs. boiling point for a gas chromatographic analysis under carefully
controlled conditions (e.g., carrier gas flow, temperature program).
*Standard Method of Test for Boiling Range Distribution of Petroleum Frac-
tions by Gas Chromatography, ASTM Designation: D2887-73.
-------
PART MO. 950251
TGA (FURNACE C)
WEIGHT, «"8
SAMI
0-
SIZE
»LE:
STY— SOL— RE
77.3 ^
F>
K.TUvw
.
X-AXIS
TEMP. SCA
SHIFT
LE 50 °C
inch
0 «J,
^^
^^
x
>
\
>
Y-AXIS
SCA
(SCA
SUP
\
\
LE 2n ""O-
LESET
PRESS
\
^^>
inch
riNG X2)
ION 0
75 ->
n.y
xj^
i,
I'O^
1*--'!
- fc
•^-^
-J.O *"
I1*-'
RUN
NO. DATE 3I2T/7L
OPERATOR
LASIG
HEATING RATE in °C
ATM
TIME
W*
2tj'll
~^
ICONS
JT1) V
r- t.S"
- t A
V
mm.
Mi (dynai«<'f_ -^/O)
TANT Z MC
«. (oil
73.
3r
17.
'
i -Vtill
J-2-
=
^
X^
rt-5-j_fc
20. 1 7»
80
60
40
20
50
100
150
200
250
300
350
400
450
500
T, °C (CORRECTED FOR CHROMEL ALUMEL THERMOCOUPLES)
FIGURE A-2 TYPICAL TGA CURVE
-------
The "unknown" sample Is chromatographed under the same conditions and the
integrated detector response for defined retention time intervals is
determined. The retention time intervals are related to boiling point
interval by use of the standard curve, and the cumulative amount of
sample boiling at or below a given temperature is plotted against temper-
ature. These analyses were done in ADL laboratories on a Varian Model
2700 gas chromatograph with a flame ionization detector. The column was
32 Dexsil®* 400 on 100/120 mesh Supelcoport®*, and the temperature was
programmed from 60°C to 350°C at I0°/min. The detector response was
integrated automatically with an Autolab System I integrator, which was
specially modified to perform integrations over specific time intervals
(rather than in response to changes in slope of detector output).
A.3.3 Gel Permeation Chromatography (GPC)
This technique, in contrast to the previous two, relies on molecular
size, rather than volatility, as an index of molecular weight. (Within
a homologous series, molecular size varies monotonically with molecular
weight.) The analysis is basically a chromatographic one, in which 'the
stationary phase is a solid material with pores of defined size and the
mobile phase is liquid. Molecules which are small enough to fill the
pores of the stationary phase "see" a larger column volume than do those
molecules which are too large to fit the pores. The retention time of
smaller molecules in the column is therefore Increased relative to that
of large molecules. (This is the opposite of the situation in gas chromo-
graphic methods, where retention time is longer for larger, higher molecular
weight species.) To achieve adequate resolution, one customarily uses a
series of columns of increasing pore size for a GPC analysis. The 'procedure
is calibrated by use of polymers of known molecular weight.
In ADL laboratories,.a Waters Model 6000A solvent delivery
system, interfaced with a Model A40 Absorbance detector (256 nm) and Model R401
differential refractometer was use,d. The columns were Waters y-Styrogel®
of nominal pore size: 100 A, 500A, and 10**X. Sample introduction was
made with a Model U6K Universal Injector. The solvent was tetrahydrofuran
and flow rate was 2.0 ml min"1.
A typical GPC output curve is shown in Figure A-3.
A.4 SAMPLE IDENTIFICATION CODES
In the sections which follow, analytical results are reported for
samples identified by codes which identify the source of the sample.
A.4.1 Each sample code begins with an Arabic numeral which identifies
the run number (1-10).
*Trademark of Supelco, Inc.
^Trademark of Waters Assoicates
76
-------
CHART NO. WO
NSTRUMENTS I N'' f -P"- ' .*" a T» r; i -US' :N
0-RUB-REP-SOL
I
Approximate Molecular Weight
Based on Polystyrene Standard
FIGURE A-3 TYPICAL GPC CURVE
-------
A.A.2 The next syllable of the code identifies the waste tested: API -
API Separator Bottoms, STY = styrene tars, SCB = Surface
Combustion background, and RUB = rubber manufacturing wastes.
A. 4 .3 All effluent samples are coded with a -P- (pyrolysis zone sample)
or -S- (stack sample) Immediately following the waste designation.
A.4.4 The next syllable in the sample code indicates the specific
source:
-REP- composite of waste feed
-ASH- residue from pyrolysis zone
-GB- gas bulb
-PW- probe wash
-KO- knock-out trap
-GW- glass wool from knock-out train
-F- filter
-ST- sorbent trap
-I- impinger
-GOO- combined KO + PW + F sample
A.4.5 The suffix -SOL- indicates that only the fraction of sample extract-
able with an organic solvent is included.
A.4.6 The suffixes -Pentane- and -Methanol- are used for the sorvent
trap samples only, to identify the two organic extracts obtained
from each trap.
A. 5 VENDORS FOR OUTSIDE ANALYSES
A.5.1 Elemental analysis (C,H,N,S)
Galbraith Laboratories
P.O. Box 4187 - Lonsdale
2323 Sycamore Drive
Khoxville, Tennessee 37921
A.5.2 Spark Source Mass Spectrometry
Accu-Labs Research, Inc.
11485 W. 48th Avenue
Wheat Ridge, Colorado 80033
For these wastes only the REP samples were submitted for the
extra-sensitive "spectrometric" analysis; others were submitted for the
less exacting "geoscan" analysis.
A.5.3 Mass Spectrometry of Gas Bulb Samples
Gollub Analytical Service Corporation
47 Industrial Road
Berkeley Heights, New Jersey 07922
78
-------
APPENDIX B
Sampling and Analytical Results
B.I Sampling Data
B.2 Gravimetric Data
B.3 Selection of "Typical" Runs
B.4 Chemical Analyses of API Waste Samples
B.5 Chemical Analyses of Styrene Waste Samples
B.6 Chemical Analyses of Rubber Waste Samples
B.7 Chemical Analyses of Background Test Samples
79
-------
APPENDIX B
Sampling and Analysis Data
B.I SAMPLING DATA
Table B-l presents the data obtained by the EPA Method 5 procedure
sampling of the stack gases. Table B-2 Indicates the volumes of pyrolyzer
effluent sampled by the comprehensive sampling train.
B.2 GRAVIMETRIC DATA
In Tables B-3 - B-6 are presented the absolute values of sample weights
determined for all 10 tests at Surface Combustion. Examination of the
data for solvent, sorbent trap and Soxhlet thimble controls in Table B-6
indicates that the values in B-3 through B-6 are uncertain by + 0,02 g.
One striking feature of the data in Tables B-3 through B-5 is
that, for some samples, the sum of soluble fraction and residual fraction
is considerably less than the initial sample weight. This JLs particularly
true for 0-API-REP (74% lost), 1-API- P-ASH (16.9X lost), 3-API-P-ASH
(38.3% lost) and 0-RUB-REP (30.4% lost). This weight loss is primarily
due to water in the sample, although some low boiling organic material is
apparently also lost from the 0-API-REP sample.
The significance of the ways in which the sample mass is distributed
among the various effluent fractions is discussed elsewhere in this report.
B.3 SELECTION OF "TYPICAL" TESTS
Preliminary analyses of all of the waste effluent samples showed
that the samples obtained from the three tests on each waste have similar
composition. The degree of similarity can be Illustrated by the elemental
analysis of the three API-GOO samples:
%C %H %N IS
1-API-P-GOO-SOL 85.05 6.43 0.76 1.56
2-API-P-COO-SOL 86.64 6.74 0.97 1.40
3-API-P-GOO-SOL 86.21 6.28 0.90 1.33
Another indication is the virtual identity of the gas chromatograms and
IR spectra of corresponding samples for the three tests on a waste. For
example. Figure B-l shows the gas chromatograms for the ST-Pentane
extracts for the three styrene burns. The similarity of chemical compo-
sition is not surprising, since the operational range of the pilot scale
pyrolysis unit was found to be relatively restricted.
80
-------
Q)
4J
5
1/18
i/29
1/30
2/2
2/3
2/4
2/5
2/17
2/18
2/18
M
W
|
Z
1
1-AP1-S
2-API-S
3-API-S
4-STY-S
5-STY-S
6-STY-S
7-SCB-S
8-RUB-S
9-RDB-S
10-RUB-S
STACK PARAMETERS
u
I
355
362
355
360
364
396
339
342
337
323
.#
CO
85
a. a
744
743
738
744
746
753
753
745
730
730
•«
PI
o
15.6
15.6
16.6
16.0
17.0
16.4
16.6
16.4
16.4
16.0
M
s
1.0
1.0
1.6
2.0
2.0
2.0
1.0
1.0
1.6
2.0
o>
a frt
«
u b
x -H
M <
-243
243
332
283
388
319
322
303
312
283
*e
O
CM
1.8
2.4
2.6
2.7
2.8
2.3
2.3
2.8
3.6
2.9
o
10 U
id eg
:*
u *
« iH
u v
V) >
29.8
29.5
28.9
29.1
29.1
28.1
30.2
27.5
28.8
27.7
Volumetric
Gas Velocity
m3/sec
2.18
2.16
2.11
2.12
2.12
2.05
2.20
2.01
2.10
2.02
SAMPLING PARAMETERS
01
•H
N
N>>
OW
35 -H
(.' U
•O «l
BOH 10
Z^
30.1
29.7
28.7
29.2
29.8
28.5
30.0
28.8
28.7
28.2
en
E
>> •o
*!4
d. rH S
H 0 <0
cnxn
1.491
1.444
1.391
1.412
1.441
1.329
1.528
1.435
1.410
1.430
CO
B
|||
C.I&
H o a
M> in
1.519
1.480
1.429
1.452
1.482
1.360
1.564
1.477
1.462
1.473
Isokineti-
city %
101.0
100.8
99.2
100.2
102.5
101.6
99.5
104.6
99.8
102.0
PARTICULATE DATA
u
u
a
u
u
.0
o
£f
41.0
70.0
20.0
20.5
25.2
30.2
8.2
B.O
13.5
6.0
•5
w
3
»4
01
U
•H
£^
*
59.6
12.9
*
15.5
28.6
5.2
7.2
7.0
7.4
u
u
5
i-t
t)
s«>
E-> B
129.6
32.9
40.7
58.8
13.4
15.2
20.5
13.4
Normalized
Catch mg/v*
87.6
23.0
27.5
43.2
8.6
10.3
14.0
9.1
oo
* Sample Lost
TABLE B-l. Data Obtained by EPA Method 5 Procedure
-------
Total Sample Volumes from
Pyrolyzer at Surface Combustion
«W
O 01
iH
2|
« 9
Q CO
1/28
1/29
1/30
2/2
2/3
2/4
2/5
2/17
2/18
2/18
Sample
Identifi-
cation
1-API
2-API
3-API
4-STY
5-SIY
6- STY
7-SCB
8-RIJB
9-ROB
10-RUB
Measured Dry
Volume @ STP
m3
0.895
0.900
6.890
0.357
0.808
0.539
0.897
0.329
0.306
0.280
Calculated
Moisture Con-
tent, %
23.9
21.7
25.3
9.4
8.9
8.4
8.1
16.4
14.7
15.1
I
iH
O
«J CO
01
S
-------
TABLE B-3
RESULTS OF GRAVIMETRIC ANALYSES ON API SAMPLES
Weight in Grams
Sample Source* 0-API 1-API 2-API 3-API
-REP-
aliquot size
-SOL-
-RES-
net loss
-P-KO
-P-F
-P-GW-SOL**
Total GOO
-P-GOO-SOL
-P-GOO-RES
-D-ST-Pentame
-P-ST-Methanol
P-ASH
aliquot size
ASH-SOL
ASH-RES***
See SAMPLE IDENTIFICATION CODE, Appendix A.
**There was no tare weight on the glass wool, so residue weight is unknown.
***Residue was dried at 110°C for 1 hour.
75.6330
9.8184
9.8396
74%
2.1927
.5607
.0997
2.8531
2.2207
.8615
1.5227
.0299
34.9361
6.0018
23.0509
1.8148
.5341
.7838
3.1327
2.4519
.4851
1.4614
.0258
28.2394
4.3498
23.9021
1.7455
.4823
.4942
2.7220
2.4519
.5308
1.0571
.0259
28.8325
5.5473
12.2458
83
-------
TABLE B-4
RESULTS OF GRAVIMETRIC ANALYSIS ON STYRENE SAMPLES
Weight in Grams
3.5298
.5062
2.2621
19.3956
.3388
9.5498
13.0635
4.7876
1.6077
Sample Source* 0-STY 4-STY 5-STY 6-STY
-REP-
aliquot size 58.6941
-SOL- 57.5449
-RES- .3214
net loss 1.4%
-P-KO
-P-F
-P-GW-SOL**
Total GOO 6.2981 29.2842 19.5688
-P-GOO-SOL 5.7364 25.6970 15.7280
-P-GOO-RES .4487 3.5044 3.3529
-P-ST-Pentame 2.7158 *** 5.6780
-P-ST-Methanol .0610 .0383
-P-ASH
aliquot size 34.6688 31.2235 20.6560
ASH-SOL 10.4547 4.273 .7630
ASH-REB 28.8343 30.8137 22.9033
*See SAMPLE IDENTIFICATION CODE, APPENDIX A.
**There was no tare weight on the glass wool, so residue weight is unknown.
***The sorbent trap broke during overnight pentame extraction.
84
-------
TABLE B-5
RESULTS OF GRAVIMETRIC ANALYSES ON RUBBER SAMPLES
Weight in Grains
Sample Source*
-REP-
Aliquot size
-SOL-
-RES-
net loss
-P-KO
-P-F
-P-GW-SOL**
Total GOO
-P-GOO-SOL
-P-GOO-RES
-P-ST-Pentane
-P-ST-Methanol
-P-ASH-
Aliquot size
ASH-SOL
ASH-RES
0-RUB
36.0786
12.0133
13.0938
30.4%
8-RUB
15.3127
7.0555
9.5249
9-RUB
17.3026
3.1898
14.7255
10-RUB
1.2054
.5423
.1531
1.9008
1.4266
.3779
.3935
.0278
1.0062
.4431
.2830
1.7323
1.2103
.3159
.6288
.0231
1.5885
.3404
.0572
1.9861
1.4613
.4737
.3710
.0324
16.6701
1.5962
15.5166
*See SAMPLE IDENTIFICATION CODE, APPENDIX A.
**There was no tare weight on the glass wool, so residue weight is
unknown.
85
-------
TABLE B-6
RESULTS OF GRAVIMETRIC ANALYSES OF
BACKGROUND SAMPLES AND CONTROLS
Weight in Grains
Sample Source*
-P-KO
-P-F
-P-GW-SOL*
-P-GOO-SOL
-P-GOO-RES
-P-ST-Pentane
-P-ST-Methanol
-P-ASH-SOL
-P-ASH-RES
7-SCB
.1207
.0291
.0349
.1378
.1138
.1229
.0211
SOXHLET
THIMBLE
CONTROL
-0.0185
- .0204
SORBENT
TRAP
CONTROLS
.0145; .0052
.0087; .0198
SOLVENT
BLANK
- .0224
****•
+0.0544
+0.0136
*See SAMPLE IDENTIFICATION CODE, APPENDIX A.
**There was no tare weight on the glass wool, so residue weight is
unknown.
***There was no ash from the background burn.
86
-------
FIGURE B-l GAS CHROMATOGRAPHS OFPENTANE EXTRACTS OF SORBENT TRAPS
FOR 4-STY, 5-STY. AND 6-STY TESTS
-------
Consequently, a set of samples corresponding to one test condition
for each of the wastes was selected for detailed chemical analysis. The
selection criteria were:
• The "typical" run should not be the first test on that waste.
This eliminates memory effects in the pyrolysis unit and
sample lines.
• No sample should have been lost for that run.
• The typical run should not correspond to the extremes of
variations in feed rate, pyrolyzer temperature, etc.
The runs selected for most detailed analysis were: 2-API, 6-STY,
9-RUB and the background test, 7-SCB.
B.4 CHEMICAL ANALYSES OF API WASTE SAMPLES
B.A.I Data From On-Line Analyzers
Run
1-API
2-API
3-API
Hydrocarbons
% (as CH4)
1.33 ± 0.07
1.26 ± 0.13
1.2 ± 0.1
CO
1436 ± 13
1966 ± 32
2174 ± 35
C02
10.8 ± 0.3
11.1 ± 0.4
11.1 ± 0.4
02
0.0 ± 0.2
0.0 ± 0.2
0.0 ± 0.2
NO
100 ± 4
94 ± 2
95 ± 4
The error estimates are standard deviations of individual (10 minute
Interval) readings from the mean.
B.4.2 Gas Bulb Analyses
The results of analyses by Gollub Analytical Service Corp. corrected
to zero oxygen concentration (see Appendix A-2) are shown below. The
error in the tabulated values is estimated to be ± 100 ppm.
88
-------
Concentration, ppm by volume
1-API 2-API 3-API
Carbon Dioxide 6.2% 6.9% 7.7%
Carbon Disulflde <80 <80 4100
Carbonyl Sulfide <80 <80 380
Sulfur Dioxide <80 <80 1100
Hydrogen <30 <30 7900
Methane 2300 2400 4100
Ethane 360 390 380
C3-C5 Hydrocarbon 660 680 1100
Benzene 670 590 690
Toluene 310 240 290
Xylene <80 «80 <80
Acetylene 2800 2400 3500
From these data it was calculated that the average molecular weight of the
hydrocarbon material in the gaseous pyrolyzer effluent is 32 and the aver-
age carbon number is 2.3. These estimates imply a C:H weight ratio in the
volatile hydrocarbon fraction of 6.27.
B.4.3 Elemental Analysis of Major Constituents
The data obtained
0-API-REP-SOL
2-API-P-GOO-SOL
2-API-AP1-P-ASH
were:
% C
84.72
86.64
19.70
% H
11.87
6.74
2.42
% N
0.16
0.97
0.67
% S
1.24
1.40
3.38
These values have an estimated error of + 0.05.
These data show, first, that both GOO and ASH have a higher nitrogen
content than the waste feed. The ash is also enriched in sulfur relative
89
-------
to the feed. These observations suggest that the nitrogen and sulfur in
the waste feed were present as nitrate and sulfate ions.
The data can also be used to calculate C:H weight ratios. These
ratios are 7.14 for REP-SOL, 12.85 for GOO, and 8.14 for ASH. The values
indicate that the GOO sample is much higher in unsaturates than the feed,
while the organic content of the ASH is only slightly less saturated than
the feed.
B.4.4 IR Spectra
0-API-REP-SOL
The curve was dominated by peaks corresponding to aliphatic hydro-
carbons with a small percentage of aromatic bands.
Absorption Maximum
Frequency, cm"1 Assignment
3100-3000 (w) aromatic CH stretch
2960, 2930, 2880, 2860 (s) aliphatic CH stretch
1600, shoulder at 1500 (w) aromatic ring stretch
1460, 1380 (m) aliphatic CH band
879, 810, 750, 730, 700 (w) aromatic ring substitution
patterns
2-API-P-GOO
The IR spectrum for this sample was qualitatively different from that
of the REP. The aromatic bands at 3100-3000, 1600 and 1500, and in the
870-700 cm"1 range were all of moderate Intensity. In addition there were
new, weak bands at 1705 and in the 1250-1150 cm"1 range which correspond
to an oxygenated species. This may be an ester of an a,B-unsaturated acid
or, more probably, an aromatic ketone. There is also a very weak band at
2230 cm-1 which corresponds to the -CSX stretching region; this probably
arises from an alkyne component of the sample.
2-API-P-ASH-SOL
In contrast to the GOO, the soluble portion of the ASH sample has an
IR spectrum virtually identical to that of the REP.
2-API-P-ST-Pentane
The IR spectrum is similar to that of the GOO and indicates that this
sample is more highly aromatic than the REP. There is also evidence of the
presence of oxygenated material (weak bands at 1705 and 250-1150 cm"1).
90
-------
2-API-P-ST-Methanol
The IR spectrum of this sample showed a broad absorption in the OH
stretching region, Indicating incomplete removal of solvent. In addition,
the bands at 1705 and 1250-1150 cm~* were of much greater intensity (m)
than in any other sample.
In summary the IR data indicate that the gaseous effluent from the
pyrolyzer (GOO and ST samples) is more highly aromatic than the waste
feed. This effluent also is enriched in oxygenated species relative to
the feed. The organic content of the ASH, appears to be mostly unpyro-
lyzed feed material.
B.4.5 Results of LRMS Analyses
In Table B-7 are the data obtained from LRMS analyses of the API
representative waste sample and the effluent samples from Run 2 on this
waste. The lower limit of detection was about 0.1% of the sample Intro-
duced to the Instrument, but compounds present at or above this concen-
tration accounted for >87% of the total volatilizable sample.
0-API-REP
The data show that the representative waste feed sample was composed of
42.7% aliphatic hydrocarbons, of which 35% were unsaturated. The remain-
der of the major components of the REP sample were aromatlcs of up to 3
fused rings (benzene, napthalene, phenanthrene, and anthracene), alkyl
derivatives of these aromatics, and phenyl-substituted alkenes. None of
the species usually referred to as polynuclear aromatics.(pyrene, benz-
pyrene, etc.). were detected in the waste feed.
2-API-P-ASH-SOL
The saturated and unsaturated aliphatics which were found in the REP
sample are virtually absent from the ASH sample. This would seem to be
consistent with the IR data. In fact, however, the ASH does appear to be
substantially enriched in alkyl substituted aromatics. Three species,
methyl-, dimethyl- and propyl- napthalene, account for 31.7% of the ASH
sample.
The ASH sample aromatics are distributed over roughly the same
molecular weight range as are those of the REP.
A-API-P-GOO-SOL
Like the ASH, the GOO fraction of the effluent contains no purely
aliphatic species but does contain alkyl substituted aromatics. The
91
-------
TABLE B-7
SPECIFIC COMPOUNDS IDENTIFIED IN FEED AND EFFLUENT SAMPLES FOR 2-API TEST
HW
106
116
118
120
128
130
132
134
J42
152
154
156
166
168
170
178
180
182
184
190
192
194
196
198
202
204
206
208
210
212
216
218
220
222
224
226
228
230
232
234
236
238
240
242
244
252
254
256
258
266
276
326
COMPOUND
Aliphatics
Ethyl Benzene
Indene
Indane
Trlmethyl Benzene
Napthalene
Methyl Indene
Methyl Indane/Dloethyl Styrene
Tetramethyl Benzene
Methyl Napthalene
Blphenylene/Acenapthylene
Biphenyl/Acenapthene
Dimethyl Napthalene
Fluorene
Dlphenyl Methane
Chilli, Propylnapthalene
Anthracene/Phenanthrene
Stllbene/Methyl Fluorene
Dlphenyl Ethane
Butyl Napthalene
Methylene Phenanthcene
Methyl Phenanthrene
Dlphenyl Propene/Methyj
Diphenyl Propane
C5 Alkyl Napthalene
Pyrene
Phenyl Napthalene
Dimethyl Phenanthrene
Methyl Phenyllndane/Hei
Dlphenyl Butane
Methyl Pyrene
Trlmethyl Phenanthrene
Benz Fluoranthene
Chrysene/Napthacene
Terphenyl
C18HI6
Butyl Anthracene
Dlphenyl Thiophene
Decahydro Benzanthracene
Dodecahydro Bencanthrac
Methyl Chrysene/Methylt
Trlphenyl Methane
Benzpyrene
Blnapthyl
C2 Benzanthracene, etc.
Anthanthrene
TOTAL
Concentration, %
Styrene
me
>
!
ie
. Stllbene
:ahydropyrene
izanthracene
ie
ene/Cg Napthalene
rlphenylene
OfD
I\Lr •
42.7
1.3
2.0
1.7
2.3
1.4
4.0
1.4
1.8
4.2
2.7
1.6
2.9
2.3
3.0
1.3
2.0
2.2
2.1
1.0
1.2
1.0
1.0
87.1
ASH
2.5
4.5
13.2
14.0
4.5
3.7
5.8
7.0
3.7
2.5
4.9
3.3
2.1
3.3
2.1
2.9
2.1
1.6
1.6
1.6
1.2
1.2
1.2
1.2
91.7
GOO
1.5
1.2
5.4
2.8
1.2
1.2
1.4
4.9
1.9
1.0
1.1
10.9
2.3
4.2
1.8
5.2
2.1
2.6
1.0
4.7
4.0
3.8
1.5
1.7
1.0
2.0
2.0
1.8
4.2
1.9
1.5
1.1
1.3
1.2
1.9
89.3
ST-Pentane
A
6.5
2.6
3.2
24.6
4.7
2.3
2.6
11.2
7.6
2.5
7.4
4.3
2.3
3.0
4.5
2.0
1.3
1.2
1.5
95.5
Aliphatics
2n
2n
2n
2n
2n
2n
2n
2
4
6
8
10
7.7*
9.3
6.5
4.1
6.3
4.8
4.0
42.7
-------
molecular weights of GOO constituents are shifted to a range about 50 amu
units higher than that of the REP and ASH aromatics.
Of particular significance is the appearance in the GOO fraction of
the higher polynuclear aromatics including 10.9% pyrene, and 4.2% benz-
pyrene, among others.
Also of interest is the tentative identification of the mwt 326 peak
as hydroxy octoxybenzophenone in the GOO. This compound is possibly
responsible for the carbonyl peak observed in the IR spectrum of the GOO
sample.
2-API-P-ST-Pentane
Again, no aliphatics are found. The aromatic species identified are
all of molecular weight <200. This is a definite shift to lower molecular
weight compared to REP.
B.4.6 TGA Data
As noted in Appendix A, the TGA data are reported as the percentage
of original sample mass lost in temperature intervals defined by distinct
changes in slope of the sample weight versus sample temperature curve.
0-API-REP-SOL
2-API-P-GOO-SOL
2-API-P-ST-Pentane
2-API-P-ASH-SOL
25-100°C
100-355
355-450
25-100°C
100-580
580-750
25-250°C
Total
92.4
Total
73.7
Total
20-275°C
275-500
Total
97.2
It is difficult to Interpret these data to yield quantitative compari-
sons of the feed and effluent samples. Qualitatively, it is clear that
the GOO sample is less volatile than the REP, with 26% of the sample re-
maining after heating to 750°C. The sorbent trap sample, on the other
hand, is much more volatile than the REP. Finally, the ASH-SOL sample is
slightly more volatile than the waste feed.
93
-------
B.4.7 Boiling Point Distribution Curves
The boiling point distribution curves for the feed and effluent
samples for the 2-API test are shown in Figure B-2.
These data confirm the results of the TGA experiments. The sorbent
trap curve is shifted to lower boiling points than the REP-curve. The
ASH-SOL curve is slightly displaced and the GOO-SOL curve more markedly
displaced towards higher boiling points. (The apparent shifts in vola-
tility are less dramatic in the boiling point data than in the TGA data,
because the former are normalized In a way which excludes the totally
non-volatile portion of the sample.)
B.4.8 SSMS Analyses for Trace Constituents
A portion of the 0-API-REP sample was subjected to spectrometrlc SSMS
analysis. This procedure, which has a detection limit of 0.01 ppm and a
precision of ± 100%, identified a total of 63 elements in the waste. In
addition, mercury was found to be present at a concentration of 1.7 ppm.
In Table B-8 are the SSMS data for all elements found at concentrations
>5 ppm.
Also in Table B-8 are data obtained by a less sensitive SSMS
technique (detection limit 1 ppm and precision ± 500%) for two effluent
samples: 2-API-P-ASH and 2-API-S-F. These data indicate that most of
the trace elements in the feed are emitted from the pyrolyzer in the ASH.
Detectable levels of a few elements, however, appear in the stack filter
sample.
B.4.9 Gastec® Analysis
Analysis of the stack effluent with Gastec® tubes showed 30-50 ppm
of S02 for all three tests.
B.4.10 Analyses of Impinger Solutions
Aliquots of the 2-API-P-I and 2-API-S-I impinger samples were oxidized
with hydrogen peroxide, boiled to destroy excess oxidant, then analyzed
for sulfate by the barium chloranilate method. The results were:
Concentration Total Sulfur in .
Sample as S0i»=, ppm Implngers, as S, mg
2-API-P-I 910 156
2-API-S-I 495 71
The amount of sulfur detected in the pyrolysis zone Impinger sample
is 8.5% of the quantity which would have been expected if all sulfur in
the waste feed had been converted to gaseous acidic sulfur species
94
-------
550
550
500
D
D
500
450
400
O A
O A •
° A »
O A
D
Q
D
D
a
o
450
400
o
o
350
O A
A •
350
£
I
o
CD
300
250
O A
O
O
A
300
250
200
200
150
100
a
D
A 2-API-P-ASH-SOL
° 2-API-P-GOO-SOL
a 2-API-P-ST/Pentane
• 0-API-REP-SOL
150
100
I 1
10 20 30 40 50 60 70 80 90 100
Cumulative % Mass
FIGURE B-2 BOILING POINT DISTRIBUTION CURVES FOR
SAMPLES FROM 2-API TEST
95
-------
TABLE B-8. SSMS Data for API Feed and Effluent Samples
0-API-
REP
2-API-P
ASH
2-API-
S-F
Aluminum
Calcium
Silicon
Sulfur
Magnesium
Phosphorus
Iron
Sodium
Potassium
Zinc
Strontium
Banium
Titanium
Chromium
Copper
Fluorine
Lead
Manganese
Lanthanum
Vanadium
Neodymium
Nickel
Praesodymium
Cerium
Chlorine
Zirconium
Tin
Rubidium
Cobalt
Samarium
Yttrium
Lithium
Molybdenum
Bromine
> 1%
> 1%
> 1%
> 1%
0.5%
0.5%
t>4600ppm
•v.2500
^1000
^1000
810
740
540
420
410
240
210
170
96
92
84
58
44
43
31
22
18
14
9.3
9.1
8.6
7.4
6.7
6.2
> 1%
> 1%
> 1%
> 1%
> 1%
•v, 1%
> 1%
*> 0.5%
^ .3%
> 1%
'V'lOOOppm
•vlOOO
^3000
•^3000
•\. 0.5%
700ppm
^3000
300
•x.1000
700
700
300
100
300
•v-lOOO
100
100
70
100
30
30
10
10
30
93
99
Entire filter analyzed 7-SCB-SF used as blank
Of.
-------
(H2S, S(>2, etc.). This Is consistent with the SSMS data showing substan-
tial amounts of sulfur In the ash.
B.4.11 Water Content of API Waste
During the separation of the 0-API-RZP sample Into organic soluble
and residual fractions a 74% loss of the original sample mass was noted.
It was presumed that most of this loss was due to water, which evaporated
when the fractions were dried.
In an attempt to accurately determine the water content of the waste,
an aliquot was placed in an oven at 110'C, and the weight loss recorded
at intervals. Drying to constant weight required 3.5 hours and indicated
a water content of 70.4%. A TGA analysis of a separate aliquot Indicated
a water content of 65.3% (weight lost up to 225°C),
The discrepancies among the three estimates of water content (75%,
70.4%, 65.3%) appear to be due to the fact that the waste is an oil-water
emulsion which is difficult to break.
It is concluded that the water content is 70+ 5%.
B.5 CHEMICAL ANALYSIS OF STYRENE WASTE SAMPLES
B.5.1 Data from On-Line Analyzers
Run
4-STY
5-STY
6-STY*
Hydrocarbons
% (as CHb
2.53 ± 0,12
2.38 ± 0.37
2.4
CO
ppm
2240 ± 23
2095 ± 41
2150
C02
%
10.7 ± 0.16
11.0 ± 0.4
6.9
02
%
0.0 ± 0.2
0.0 ± 0.2
0.0
NO
PP"
64 ± 10
78 ± 10
75
The error estimates are standard deviations of individual (10 minute
interval) readings from the mean.
* During the 6-STY run the sampling line plugged frequently and a Saran
bag grab sample was taken. The sample was then fed from the bag to
each analyzer in turn.
97
-------
B.5.2 Gas Bulk Analyses
The results of analyses by Gollub Analytical Service Corp. corrected
to zero oxygen concentration (see Appendix A. 2) are shown below. The
error in the tabulated values is estimated to be ± 100 ppm.
Concentration, ppm by volume
except as noted
Carbon Dioxide
Carbon Disulfide
Carbonyl Sulfide
Sulfur Dioxide
Hydrogen
Methane
Ethane
C3~Cs Hydrocarbon
Benzene
Toluene
Xylene
Acetylene
From these data it is calculated that the average molecular weight of the
hydrocarbon material in the gaseous pyrolyzer effluent is 51 and the aver-
age carbon number is 4.0. These estimates imply a C:H ration in the vola-
tile hydrocarbon fraction of 16. If the hydrogen found in the analyses
is included, the C:H ratio in the gaseous effluent drops to 9.
It should also be noted that these samples show relatively high
levels of carbon disulfide and carbonyl sulfide.
B.5.3 Elemental Analysis of Major Constituents
The data obtained were:
% C % H % N % S
0-STY-REP-SOL 84.46 6.96 .02 7.86
6-STY-P-GOO 87.76 5.93 2.92
6-STY-P-ASH 90.59 2.37 4.65
These data imply C:H weight ratios of 12.1 in the REP, 14.8 in the
GOO and 38.2 in the ASH. The ASH sample is therefore highly unsaturated
with respect to the feed.
98
4-STY
6.6%
600
150
60
2850
680
210
<150
1650
900
<70
2100
5-STY
8.7%
1320
329
260
9630
1700
356
<150
2770
870
105
1715
6-STY
8.7%
1333
400
200
9600
2800
480
<130
4933
920
130
1866
-------
In contrast to the API results, these data do not show enrichment of
nulfur In the COO and ASH samples. This is not surprising, since the
sulfur In the styrene tar was identified as free sulfur (in the survey
analysis) which might be readily volatilized.
B.5.4 IR Spectra
0-STY-REP-SOL
The IR spectrum of this sample resembled that of styrene-butadiene
rubber with the addition of extra bands at 865-740 cm"1 substituted aro-
matics.
Adsorption Maximum
Frequency in cm"1
3100 - 3000 (m/s)
3000 - 2850 (m/s)
1600 (m)
1595 (m/s)
1455 (m/s)
1370
1300 - 1000 (multiple, w)
960, 980 (w)
865 (w), 815 (w), 740 (s)
760, 700 (s)
6-STY-P-GOO
Assignment
Aromatic CH Stretch
Aliphatic CH Stretch
Aromatic OC
Aliphatic OH Bend
Aromatic substitution
patterns
C=C Stretch
Atomatic substitution
other than mono-
Monosubstituted aromatic
The spectrum of this sample was almost the same as that of the REP,
with the exception that the intensity of aromatic bands was somewhat
Increased relative to the aliphatic.
5-STY-P-ASH-SOL
This sample, again, was similar to the REP but appeared to have a
higher aliphatic content. The polysubstituted aromatic bands at 865, 815
and 740 cnr1 were relatively weaker in the ASH-SOL sample. Two new,
weak bands at 88p and 1415 cm'1 are possibly due to C-H deformation vibra-
tions of alkenes.
99
-------
6-STY-P-ST-Pentane
The IR spectrum of this sample was very much like that of the GOO.
There were two peaks, at 1490 cm"1 (m), and 790 cm-1 (m) which were not
readily assignable. These peaks were not present in the REP, GOO or
ASH samples.
6-STY-P-ST-Methanol
The IR spectrum of the methanol sample indicated substantial
quantities of oxygenated material. Evidence includes a peak at 1705 cor*
(m), carbonyl, and a number of peaks in the C-0 stretching region (around
1200 cm"1). There was also indication of residual solvent.
In summary, the IR spectra of the gaseous pyrolyzer effluent fractions
were similar to those of the waste feed, although slightly enriched in
aromatics. The ASH-SOL fraction showed some enrichment in aliphatics
relative to the REP. Some oxygenated material was found in the methanol
extract of the sorbent trap.
B.5.5 Results of LRMS Analyses
Table B-9 presents the data obtained from the LRMS analyses of
the styrene representative waste sample and the effluent samplers from
Run 6 on this waste.
The data show a remarkable similarity among the feed and effluent
samples. None of the samples has any significant contribution from purely
aliphatic compounds. The GOO sample is shifted slightly to higher, and
the ST sample to lower, molecular weight ranges, but the differences are
not dramatic. Some of the higher polynuclear aromatics are found in the
GOO sample.
B.5.6 TGA Data
The TGA data are reported as the percentage of original sample mass
lost in temperature intervals defined by distinct changes in slope of the
sample weight versus sample temperature curve.
0-STY-REP-SOL
20 - 75°C
75 - 300
320 - 450
Total 97.5
6-STY-P-GOO-SOL
20 - 100
100 - 580
580 - 700
Total 89.9
100
-------
TABLE B-9
SPECIFIC COMPOUNDS IDENTIFIED IN FEED AND
MW
92
104
128
134
142
154
160
166
168
178
180
182
190
192
194
196
202
204
206
208
210
218
230
236
242
306
EFFLUENT SAMPLES FOR 6-STY TEST
Concentration, %
COMPOUND
Toluene
Styrene
Napthalene
Butyl Benzene
Methyl Napthalene
Blphenyl/Acenapthene
C12H16
Fluorene
Diphenyl Methane
Anthracene/Phenanthrene
Stilbene/Methyl Fluorene
Diphenyl Ethane
Methylene Phenanthrene
Methyl Phenanthrene
Diphenyl Propene/Methyl Stilbene
Diphenyl Propane
Pyrene
Phenyl Napthalene
Dimethyl Phenanthrene
Methylphenyl Indane/Hexahydro Pyrene
Diphenyl Butane
Terphenyl
C16H12S Diphenyl Thiophene
Methyl Chrysene/Methyltriphenylene
Quarterphenyl
REP
1.8
6.0
5.5
21.8
15.5
10.4
2.5
1.8
7.6
7.3
3.5
1.1
1.8
2.9
1.1
1.6
ASH
2.1
5.6
4.2
4.2
21.1
21.8
9.2
2.8
4.9
2.8
5.6
1.4
2.1
4.9
2.1
GOO
4.2
1.2
3.6
23.3
12.3
1.7
5.2
1.9
3.1
10.6
1.2
1.2
2.0
2.1
9.2
ST
1.4
5.6
2.3
1.4
15.5
1.9
2.3
10.3
23.5
17.8
3.3
2.8
5.2
1.4
TOTAL 92.2 94.8 82.8 94.7
101
-------
6-STY-P-ST-Pentane
25 - 218
Total
6-STY-P-ASH-SOL
25 - 295
295 - 530
530 - 970
Total 91.7
It is difficult to make quantitative comparisons on the basis of
these data. Qualitatively, however, it is clear that the sample volatility
decreases in the order: ST > REP > ASH ^ GOO.
B.5.7 Boiling Point Distribution
The boiling point distribution curves for the feed and effluent
samples for the 6-STY test are shown in Figure B-3.
These data are consistent with the results found by TGA. The sorbent
trap sample curve is shifted to lower boiling points and the ASH and GOO
curves to higher boiling points than the REP sample. The difference be-
tween ASH and GOO is more pronounced in the boiling point curves because
they are normalized in a way that excludes from consideration the ex-
tremely non-volatile material.
B.5.8 SSMS Analyses for Trace Constituents
A portion of the 0-STY-REP sample was subjected to spectrometrlc
SSMS analysis. This procedure, which has a detection limit of 0.01 ppm
and a precision of ± 100%, identified a total of 32 elements in the waste.
In a separate analysis, mercury was found to be present at 0.02 ppm. In
Table B-10 are the SSMS data for all elements found at concentrations
>1 ppm. It is interesting to note that SSMS shows a very low sulfur
concentration, while a combustion technique (above) Indicated >7% sulfur.
The sulfur is added to this waste as the free element and is apparently
lost in the SSMS ashing technique.
Also in Table B-10 are data obtained by a less sensitive SSMS
technique (detection limit 1 ppm and precision ± 500%) for two effluent
samples; 6-STY-P-ASH and 6-STY-S-F. These data indicate that most of
the trace elemts In the feed are emitted from the pyrolyzer in the ASH.
B.5.9 Gastec® Analyses
Analysis of the stack effluent with Gastec® tubes showed 100-200 ppm
of S02 for all three tests.
102
-------
o
0
i
m
™
cL
1
c
£
f
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CD
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500
450
400
350
300
250
200
150
100
0
0
0 A
e A
AO
A O •
o
A • o
A O •
D
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A • D
A 0 •
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A • 0
A 0 •
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0 «
- A
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o
OH A 6-STY-P-ASH-SOL
a * o 6-STY-P-GOO-SOL
o 6-STY-P-ST/Pentane
• 0-STY-REP-SOL
—
. -
1 1 1 1__ i i i i i i i
550
500
450
400
350
300
250
200
150
100
n
0 10 20 30
40 50 60
Cumulative % Mass
70 80 90 100
FIGURE B-3 BOILING POINT DISTRIBUTION CURVES FOR
SAMPLES FROM 6-STY TEST
103
-------
TABLE B-10
Element
SSMS DATA FOR STYRENE FEED AND EFFLUENT
Samples
0-STY-
REP
6-STY-P-
ASH
6-STY-
S-F
Silicon
Aluminum
Sodium
Iron
Phosphorus
Magnesium
Sulfur
Calcium
Zinc
Potassium
Copper
Chromium
Manganese
Barium
Strontium
Titanium
Lead
Fluorine
Nickel
Cobalt
35ppm
32
32
31
18
13
9
6.2
1.7
1.4
0.54
0.19
0.37
0.25
0.15
0.16
0.11
0.20
0.03
0.010
SOOOppm
1000
3000
> 1%
lOOOppm
700
•\,3000
VJOOO
> 0.5%
300
lOOOppm
300
300
100
100
100
70
30
30
2900
Entire filter analyzed. 7-SCB-S-F used as blank.
-------
B.5.10 Analyses of Impinger Solutions
Aliquots of the 6-STY-P-I and 6-STY-S-I Impinger samples were oxidized
with hydrogen peroxide, boiled to destroy excess oxygen, then analyzed for
sulfate by the barium chloranilate method. The results were:
Total Sulfur in
Concentration as Impingers
S0u=» ppm as S, mg
6-STY-P-I 2575 443
6-STY-S-I 1150 172
The amount of sulfur detected In the pyrolysis zone impingers is 11%
of the quantity which would have been expected if all sulfur in the waste
feed had been converted to acidic sulfur gases O^S, SOo, etc.)* This is
consistent with the SSMS data which Indicate that substantial amounts of
sulfur are found in the ASH.
B.6 CHEMICAL ANALYSES OF RUBBER WASTE SAMPLES
B.6.1 Data From On-Line Analyzers
Hydrocarbons CO CO2 02 NO
% (as CHu) ppm % % ppm
8-RUB 3.09 ± 0.21 20fi3 ± 10 10.1 ± 0.1 0.0 ±0.2 75 ± 4
9-RUB 3.11 ± 0.08 1947 ± 14 9.97 ± 0.06 0.0 ± 0.2 75 ± 3
10-RUB 2.45 ± 0.18 2125 ± 8 9.89 '± 0.06 0.0 ± 0.2 66 ± 3
The error estimates are standard deviations of individual (10 minute
interval) readings from the mean.
B.6.2 Gas Bulb Analyses
The gas bulb samples from the rubber samples showed oxygen concen-
trations of >20%. It was impossible to correct these samples back to zero
oxygen concentration. The concentrations reported by Gollub are
tabulated below.
105
-------
Concentration, % volume;volume
8-RUB 9-RUB 10-RUB
Nitrogen 77+ 77+ 77+
Oxygen 20.6 21.4 20.7
Argon 0.97 0.97 0.99
Carbon Dioxide 0.60 0.18 0.78
Hydrogen <0.002 <0.002 <0.002
Carbon Monoxide 0.21 0.064 0.35
Methane 0.014 0.0028 0.015
Benzene 0.017 0.0067 0.030
If using the reported relative concentrations of methane1 and
benzene, an average molecular weight of 55 and average carbon number
of 4.2 are estimated. These imply a C:H weight ratio of 11.0. If
the mass spectrometric analyses are corrected to correspond to the
on-line instrument total hydrocarbon concentration, and assume that
hydrogen is present at the detection limit, the values are mw - 41, C no
3.1, and C:H ratio = 9.
B.6.3 Elemental Analysis of Major Components
% S
0.48
0.84
1.12
As for the API waste, the sulfur in the feed appears to be enriched
in the GOO and ASH. The nitrogen also appears to be enriched in the GOO;
the corresponding analysis was not performed on the ash.
The calculated C:H ratios are: REP, 7.87; GOO, 13.90; ASH, 17.23.
The GOO and ASH are clearly less saturated than the waste feed.
B.6.4 IR Spectra
0-RUB-REP-SOL
Overall, the infrared curve resembles those of butadiene-styrene •
polymers, with some additional bands (marked with an asterisk in the
following list).
106
The data obtained
0-RUB-REP-SOL
9-RUB-P-GOO
9-RUB-P-ASH
were:
% C
79.53
89.09
79.93
% H
10.10
6.41
4.64
% N
0.08
0.57
__
-------
Absorption Maximum
Frequency in cm"1
3100 - 3000 (w)
300 - 2850 (s)
1705* (m)
1640 (w)
1600 (w), 1495 (w)
1450 (w), 1380 (w), 1365 (w)
1260 (w)*
965, 910 (s, m)
880, 820, 720 (w)
760, 700 (m, s)
Assignment
Aromatic C-H Stretch
Aliphatic C-H Stretch
Carbonyl of conjugated
ester or aromatic ketone
Unconjugated alkene
Aromatic C-C
Aliphatic C-H bend
C-0 stretch of conjugated
ester, or aromatic ketone
Terminal vinyl group CH bend
Trisubstituted Aromatic
Monosubstituted Aromatic
9-RUB-P-GOO-SOT.
The spectrum of this sample is remarkably like that of the REP
except that the aromatic band intensities are somewhat increased and that
the butadiene-like bands at 950 and 910 cm'1are absent. The carbonyl
peak is of greatly reduced intensity. There is a new band at 750 cm"1(s),
which represents a disubstituted aromatic.
9-RUB-P-ASH-SOL
The IR spectrum of this sample shows very weak butadiene and carbonyl
bands. The intensity of the aromatic C-H stretching bands is also greatly
reduced compared to the REP. The aliphatic C-H stretching intensity is
still high.
9-RUB-P-ST-Pentane
In this sample the carbonyl and butadiene bands were very weak. The
aromatic substitution pattern was very different from that of the GOO and
REP samples, with strong bands at 815, 760 and 740 cm"1.
9-RUB-P-ST-Methanol
The strong carbonyl peak and C-0 stretching bands observed in the REP
sample reappear in this spectrum. The aromatic stretching and bending
bands are all of moderate intensity but somewhat shifted from those in the
REP. The butadiene peaks are absent.
107
-------
In summary, the infrared spectra for the rubber waste samples indi-
cate that the gaseous pyrolyzer effluent is more highly aromatic and the
ASH more highly aliphatic than the representative waste. The terminal
vinyl functional group (-HC=CH ) observed in the waste feed does not seem
to be present In any of the effluent samples. The carbonyl compound(s)
in the feed are found only in the sorbent trap methanol extract.
B.6.5 Results of LRMS Analyses
The data obtained from LRMS analyses of rubber feed and effluent
samples are present in Table B-ll.
0-RUB-REP
The data show that, of the material which is volatile in the LRMS in-
let, 48.7% is primarily unsaturated aliphatic compounds. Only a small number
of Individual aromatic compounds were present in concentrations high
enough for identification. Nonyl phenol accounts for 6.2% of the sample
and 3 other, unidentified, oxygenated species of molecular weight >300
account for an additional 19.8%.
0-RUB-P-ASH-SOL
No aliphatic material was detected in this sample. The number of
aromatic compounds detected was much larger than in the REP sample, but
the molecular weight range was comparable.
0-RUB-P-GOO-SOL
Again, no aliphatics were detected. The GOO sample shows a shift to
slightly higher molecular weight in the distribution of aromatic species.
In particular, detectable concentrations of the higher polynuclear aro-
ma tics are found In this sample.
It is interesting that the material tentatively identified as
hydroxyoctoxy benzophenone appears in this sample as well as in the
2-API-P-GOO-SOL sample.
9-RUB-P-ST-Pentane
The sorbent trap sample again shows no purely aliphatic compounds,
but it does show a shift to lower molecular weight.
B.6.6 TGA Data
The data are reported as the percentage of original sample mass lost
in temperature intervals defined by distinct changes in slope of the
sample weight versus sample temperature curve.
108
-------
TABLh
MW
92
104
116
118
128
134
142
144
146
152
154
156
166
168
170
178
180
182
184
190
192
194
196
202
204
206
210
216
218
220
220
226
228
230
232
236
238
240
242
244
246
232
254
256
264
266
300
302
304
326
COMPOUND
Alipnacics
Toluene
Styrene
Indene
Metnyl Styrene/Indane
Napthalene
Butyl Benzene
Methyl Napthalene
C11H12
CllH,,.
Bipnenylene/Acenapthylene
Blpnenyl/Acenapthene
Dimethyl Napthalene
Fluorene
Dipnenyl Metnane
Propyl Napthalene
Aiithracene/Phenanthrene
Stllbene/Methyl Fluorene
Diphenyl Methane
Butyl .iapLhalene
Methylene Phenanthrene
Metnyl. Pnenantnrene
Dipnenyl Propene/Metnyl Scilbene
'Jipheiv> 1 Propane
Pyrene
Phcr.yl it'apcnalene
Dimethyl Phenantnrene
Dipnenyl Butane
Methyl Pyrene
Nonyl Phenol
Trimetnyl Pnenantnrene
Benzfluoranthene
Cnrysene/.^aptnacene/Benzanthracene
Terphenyl
Dipnenyl Thlopnene
Decanydro Benzanthracene
Dodecanydro benzanthracene/Cg Napthalene
Methyl Chrysene/Hethyl Triphenylene
Triprvenyl .-(ethane
Octadecanyorochrysene
Benzpyrene
Binapthyl
C2 Benzar.tnracene, etc.
czla26uj
TOTAL
FEED AND EFFLUENT SAMPLES FOE
Concentration, Z
REP
4B.7
1.9
2.3
1.0
6.:
1.2
1.2
2.3
9.4
5.7
4.7
84.6
ASH
2.9
4.7
4.7
7.6
4.7
5.3
4.1
14.6
10.5
6.4
1.7
4.7
3.5
3.5
3.5
4.1
2.9
2.9
1.8
1.8
1.8
97.7
COO
2.6
1.3
3.0
1.2
9.8
3.2
1.8
6.2
11.1
4.9
3.0
3.8
3.5
1.4
2.9
6.1
3.9
1.5
1.9
3.2
1.4
3.3
2.0
1.2
1.0
1.4
86.6
ST
2.4
9.4
1.8
33.0
10.0
1.0
9.4
5.9
3.0
4.8
2.2
4.9
2.4
2.5
92.7
Aliphatics
2n
2n
2n
2n
2n
2n
2n
•t- 2
- 2
- 4
- 6
- 8
- 10
5.51
6.7
6.7
7.8
8.6
8.1
5.3
48. 71
-------
0-RUB-REP-SOL
30 - 250°C
250 - 350
350 - 450
Total 63.8
P-RUB-P-GOO-SOL
20 - 100°C
100 - 500
500 - 850
Total 78.3
P-RUB-P-ST-Pentane
20 - 250°C
Total
9-RUB-P-ASH-SOL
25 - 438°C
438 - 515
515 - 670
Total 97.2
For the rubber waste* in contrast to API and styrene wastes, .all of
the pyrolyzer effluent samples were more volatile than the REP waste feed
sample. As observed previously, the sorbent trap sample is the most
volatile of the effluent samples. For the rubber waste, the ASH contains
appreciably more volatile components than does the GOO.
B.6.7 Gel Permeation Chromatography (GPC)
The rubber samples were not suitable for gas chromatographic analysis
because they contained very non-volatile components. For these samples,
(GPC) provided a measure of molecular weight distribution. The data
obtained are given below, with molecular weights assigned based on poly-
styrene standards. These molecular weights may not be absolutely correct,
but do give an accurate indication of changes in the molecular weight
distribution.
MW % of Total
0-RUB-REP-SOL 106 - 5 x 101* 34
VL03 27
•\,102 38
110
-------
MW % of Total
9-RUB-P-GOO-SOL 5 x 103 - 103 11
103 - 102 21
5 ppm.
Also in Table B-12 are data obtained by a less sensitive SSMS
technique (detection limit 1 ppm and precision ± 500%) for two effluent
samples: 9-RUB-O-ASH and 9-RUB-S-F. These data indicate that most of
the trace elements in the feed are emitted from the pyrolyzer in the ASH.
B.6.9 Analyses of Impinger Solutions
Aliquots of the 9-RUB-P-I and 9-RUB-S-I Impinger solutions were
oxidized with hydrogen peroxide, boiled to destroy excess oxidant, and
analyzed for sulfate by the barium chloranilate method. The results were:
Concentration Total Sulfur
as SOi/5. ppm as S. mg
9-RUB-P-I 380 68
9-RUB-S-I 405 58
The amount of sulfur detected in the pyrolysis zone impinger is 39%
of the total which would be expected if all of the sulfur in the waste
feed were converted to acidic sulfur gases (HaS, S(>2» etc.). This is con-
sistent with the SSMS data, showing substantial sulfur in the ASH.
Ill
-------
TABLE B-12
SSMS DATA ON
Element
Calcium
Sulfur
Silicon
Iron
Aluminum
Sodium
Phosphorus
Potassium
Magnesium
Chlorine
Nickel
Chromium
Titanium
Lead
Zinc
Barium
Strontium
Fluorine
Manganese
Bismuth
Bromine
Molybdenum
Copper
FEED AND EFFLUENT
0-RUB-
REP
>1%
>1%
>0.5%
«\,2800ppm
1500
760
750
710
440
430
160
130
66
62
53
42
41
20
16
15
12
12
11
SAMPLES FOR 9 -RUB TESTS
9-RUB-P-
ASH
>1%
>1%
>1%
>1%
•x. SOOOppm
•v, 3000
•v, 1000
* 1000
* 3000
^ 3000
* 300
^ 700
•v-300
300
300
100
100
100
30
10
10
30
100
9-RUB-S-
F*
Cobalt
5.3
30
Entire filter analyzed. 7-SCB-S-F used as blank.
112
-------
B.7 CHEMICAL ANALYSES OF BACKGROUND TEST SAMPLES
B.7.1 Data From On-Line Analyzers;
Hydrocarbons, CO C02 02 NO
% (as CHu) ppm % £ ppm
7-SCB 0.06 ± 0.01 1766 ± 10 11.5 ± 01 0.0 ± 0.2 38 ± 2
The error estimates are standard deviations of individual (10 minute
interval) readings from the mean.
B.7.2 Gas Bulb Analysis
The results of analyses by Gollub Analytical Service Corp., cor-
rected to zero oxygen concentration, are:
Carbon dioxide 5.89 Ethane 0.016
Carbon disulfide <.009 C3-C5 Hydrocarbon <0.019
Carbonyl sulfide <.009 Benzene 0.020
Sulfur dioxide <.009 Toluene <0.009
Hydrogen <.004 Xylene <0.009
Methane 0.006 Acetylene <0.009
B.7.3 Elemental Analyses for Major Constituents
Sample % C % H % S
7-SCB-P-GOO-SOL 85.04 7.46 2.99
These are very similar to the results for the 6-STY-P-GOO-SOL sample.
B.7.4 IR Spectra
7-SCB-P-GOO-SOL
The IR spectrum of this sample is qualitatively very similar to that
of the 6-STY-P-GOO-SOL sample. The background sample has a higher ratio
of aliphatic to aromatic stretching intensities. The spectrum of the
background sample also has a carbonyl peak [1735 cm'1, (w)] which is
missing in the corresponding styrene sample.
7-SCB-P-ST-Pentane
This sample has an IR spectrum which matches, peak for peak, the
spectrum of the 6-STY-P-ST-Pentane sample.
In summary, the IR data imply that the material found in the gaseous
pyrolyzer effluent from the background test was primarily due to residues
from the preceding styrene test.
113
-------
B.7.5 Results of LRMS Analyses
Since all of the other evidence indicated that these samples resembled
those for the styrene tests, a detailed LRMS analysis on the background
sample was not performed. Major components identified in the LRMS spectra
of the background GOO and effluent samples are listed in Table B-13.
B.7.6 Analyses of Impinger Solutions
Aliquots of the 7-SCB-P-I and 7-SCB-S-I Impinger samples were oxi-
dized with hydrogen peroxide, boiled to destroy excess oxidant, then
analyzed for sulfate by the barium chloronilate method. The results were:
Concentration, Total Sulfur
as S0u=t ppm as S, mg
7-SCB-P-I 310 54
7-SCB-S-I 550 86
These values are unexpectedly high, since the unit was operating with
natural gas. It seems probable that the sulfur is due to carry-over from
the styrene burn Immediately preceding.
B.7.7 Other
Because all of the preliminary analyses Indicated that the collected
7-SCB effluent samples represented carry-over from the 6-STY test Immedi-
ately preceding, no further analyses of the 7-SCB samples was done. [The
7-SCB-S-F (stack filter) was analyzed by SSMS and the results used to
make corrections for the elements present in the filter medium.]
114
-------
TABLE B-13
SPECIFIC COMPOUNDS IDENTIFIED IN EFFLUENT SAMPLES FOR 7-SCB TEST
Concentration %
7-SCB-P-GOO-SOL 7-SCB-P-S"
Pentene
92 Toluene
104 Styrene
128 Napthalene
134 Butyl Benzene tr.
142 Hethyl Napthalene > 1%
152 Biphenylene/Acenapthylene > 1%
154 Biphenyl/Acenapthene
160 C12H16
166 Fluorene
168 Diphenyl Methane
178 Anthracene/Phenanthrene >10Z
180 Stilbene/Methyl Fluorene > 1%
182 Diphenyl Ethane
190 Methylene Phenanthrene
192 Methyl Phenanthrene > 1% tr.
194 Diphenyl Propene/Methyl Stilbene > 1%
196 Diphenyl Propane
202 Pyrene >10%
204 Phenyl Napthalene tr. > 1%
206 Dimethyl Phenanthrene tr.
208 Methyl Phenyl Indene/Hexahydro tr.
Pyrene
210 Diphenyl Butane > 1%
218 > 1% tr.
230 Terphenyl >10% tr.
236 Diphenyl Thiophene >10% > 1%
242 Methyl Chrysene/Methyl Triphenylene tr.
306 Quaterphenyl tr.
115
-------
APPENDIX C
OPERATING DATA
116
-------
TABLE C-l
PROCESS DATA FOR RUN NO. -1
WASTE - API SEPARATOR BOTTOM
DATE - 1.28.76
Time
10:43
11:15
11:30
11:46
12:00
1:30
1:45
2:00
2:15
2:30
3:00
3:30
Pyro . Burner
Air
AP*
2.35
2.8
2.6
2.6
2.5
2.6
2.7
2.7
2.6
2.4
2.4
2.3
SCFH*^
1750
1940
1840
1840
1800
1840
1850
1850
1840
1750
1750
1730
Pyro . Burner
Gas
AP
8.5
8.5
8.5
8.5
8.5
8.6
8.5
8.6
8.5
8.5
8.5
8.6
SCFH
182
182
182
182
182
185
182
185
182
182
182
185
Inert Gas
AP
0.9
0.9
0.9
0.9
0.9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
SCFH
1430
1430
1430
1430
1430
1500
1500
1500
1500
1500
1500
1500
.Effluent Gas
AP
0.54
0.83
0.76
0.77
0.77
0.82
0.80
.0.81
0.79
0.78
0.82
0.78
SCFH
3250
3950
3760
3800
3800
3900
3875
3880
3850
3825
3900
3815
Pyro.
Press
AP
.04
.06
.05
.05
.06
.05
.04
.06
.04
.04
.05
.03
Pyro.
Temp
°F
1400
1400
1400
1400
1400
1400
1400
1400
1400
1400
1400
1400
Effluent
Gas
Temp
°F
960
1080
1090
1090
1090
1105
1100
1105
1100
1090
1090
1080
*°2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.2
0.2
0.2
NOTE: Feed Started at 11:00 a.m. and stopped at 3:43 p.m.
* Pressure Differential - inches of water
** Flow rate - standard cubic feet per hour.
-------
TABLE C-2
PROCESS DATA FOR RUN NO. -1
WASTE - API SEPARATOR BOTTOM
DATE - 1.28.76
Time
10:43
11:15
11:30
11:46
12:00
1:30
1:45
2:00
2:15
2:30
3:00
3:30
Incinerator Burner Gas
Burner //I Burner //2
AP*
.8
.7
.7
.7
.7
.6
.6
.6
.6
.6
.6
.6
SCFH*'
290
270
270
270
270
255
255
255
255
255
255
255
AP
.8
.7
.7
.7
.7
.6
.6
.6
.6
.6
.6
.6
SCFH
290
270
270
270
270
255
255
255
255
255
255
255
Incinerator
Air
AP
19.5
23.5
23.5
24.5
24.0
25.5
25.5
24.5
25.5
25.5
25.5
25.0
SCFH
34,000
37,500
37,500
38,500
38,000
39", 000
39,000
38,500
39,000
39,000
$9,000
J8.750
Incinerator Auxiliary Gas
Burner //I Burner //2
AP
2.75
2.5
2.5
2.5
2.5
2.1
2.3
2.2
2.1
2.1
2.2
'2.3
SCFH
445
425
425
425
425
390
410
400
390
390
400
410
AP
2.75
2.5
2.5
2.5
2.5
2.1
2.3
2.2
2.1
2.1
2.2
2.3
SCFH
445
425
425
425
425
390
410
400
390
390
400
410
Incin.
Temp.
°F
1520
1520
1510
1520
1520
1520
1520
1520
1520
1520
1515
1520
Vapor
Inlet
°F
860
920
950
960
1000
1020
1015
1035
1000
1000
1020
960
Stack
Temp.
°F
650
680
670
670
675
670
670
665
670
670
680
670
* Pressure Differential - inches of water
** Flow rate - standard cubic feet per hour.
-------
TABLE C-3
PROCESS DATA FOR RUN NO. -1
WASTE - API SEPARATOR BOTTOM
DATE - 1.28.76
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
3 PER HOUR
12.5 MINS
36.7 LBS/HR
136.5 LBS
26.5 LBS
1 INCH
1/8" x 6" NOZZLE, MOYNO PUMP
COMMENTS - FEED NOZZLE CLOSER TO HOT ZONE, NO SCRAPER
-------
TABLE C-4
PROCESS DATA FOR RUN NO. -2
WASTE - API SEPARATOR BOTTOM
DATE - 1.29.76
Time
12:45
1:03
1:15
1:30
1:45
2:15
2:45
3:15
Pyro. Burner
Air
AP*
1.9
2.1
2.4
2.4
2.4
2.5
2.5
2.6
SCFH**
1575
1650
1760
1760
1760
1820
1800
1840
Pyro . Burner
Gas
AP
7.0
7.2
8.5
8.5
8.5
8.5
8.5
8.5
SCFH
167
170
183
183
183
183
183
183
Inert Gas
AP
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
SCFH
1500
1500
1500
1500
1500
1500
1500
1500
Effluent Gas
AP
.57
.74
.86
.8
.83
.86
.92
.93
SCFH
3350
3800
4020
3900
3950
4000
4150
4170
Pyro.
Press
AP
.06
.08
.07
.06
.07
.07
.07
.07
Pyro.
Temp
°F
1400
1400
1400
1400
1400
1400
1400
1400
Effluent
Gas
Temp
°F
1010
1050
1070
1080
1085
1090
1090
1090
%o2
0.0
0.0
0.0
0.0
0.0
0.0
0.3
0.0
NOTES: Feed Started at 1:00 p.m. and stopped at 3:30 p.m.
* Pressure Differential - inches of water
** Flow rate - standard cubic feet per hour.
-------
TABLE C-5
PROCESS DATA FOR RUN NO. -2
WASTE - SEPARATOR BOTTOM
DATE - 1.29.76
Time
12:45
1:03
1:15
1:30
1:45
2:15
2:45
3:15
Incinerator Burner Gas
Burner #1 Burner #2
AP *
.7
.7
.7
.65
.6
.65
.6
.65
SCFH**
270
270
270
265
255
265
255
265
AP
.7
.7
.7
.65
.6
.65
.6
.65
SCFH
270
270
270
265
255
265
255
265
Incinerator
Air
AP
21.0
25.0
25.0
25.0
24.5
25.3
25.5
26.0
SCFH
35,500
38,750
38,750
38,750
38,500
38,600
39,000
39,500
Incinerator Auxiliary Gas
Burner #1 Burner //2
AP
2.8
2.3
2.3
2.6
2.5
2.5
2.5
2.2
SCFH
450
412
412
435
425
425
425
400
AP
2.8
2.3
2.3
2.6
2.5
2.5
2.5
2.2
SCFH
450
412
412
435
425
425
425
400
Incin.
Temp.
°F
1520
1520
1520
1520
1520
1515
1520
1515
Vapor
Inlet
°F
890
980
1000
995
1000
1000
980
1010
Stack
Temp.
°F
650
680
680
680
710
685
700
680
* Pressure Differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-6
PROCESS DATA FOR RUN NO. -2
WASTE - API SEPARATOR BOTTOM
DATE - 1.29.76
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
3 PER HOUR
12.5 MINS
32.4 LBS/HR
81.0 LBS
16.0 LBS
1/2 INCH
1/8" x 8" NOZZLE, MOYNO PUMP
COMMENTS - FEED NOZZLE LOCATED AWAY FROM HOT ZONE AND A SCRAPER
ATTACHED TO FEED NOZZLE
122
-------
TABLE C-7
PROCESS DATA FOR RUN NO. -3
WASTE - API SEPARATOR BOTTOM
DATE - 1.30.76
Time
9.57
10:25
10:45
11:15
11:34
11:45
12:00
12:30
1:00
1:30
OTES : Feec
Pyro . Burner
Air
AP *
3.2
2.3
2.8
2.8
2.8
2.8
2.8
2.8
2.9
2.8
1 Started
SCFH**
2040
1720
1900
1900
1900
1900
1900
1900
1940
1900
I at 10:3
Pyro . Burner
Gas
AP
8.6
8.4
8.5
8.6
8.5
8.5
8.5
8.5
8.5
8.5
0 a.m. a
SCFH
185
182
183
185
183
183
183
183
183
183
nd stopp
Inert Gas
AP
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
ed at 1:
SCFH
1500
1500
1500
1500
1500
1500
1500
1500
1500
1500
40 p.m.
Effluent Gas
AP
.81
.65
1.1
.98
.99
.99
.99
1.1
1.0
1.0
SCFH
4150
3600
4550
4300
4320
4320
4320
4550
4340
4340
Pyro.
Press
AP
.05
.06
.06
.05
.05
.05
.05
.06
.05
.05
Pyro.
Temp.
°F
1400
1400
1400
1400
1400
1400
1400
1400
1400
1400
Effluent
Gas Temp
°F
900
1010
1075
1110
1110
1110
1110
1105
1120
1120
%o2
0.2
0.2
0.2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-8
PROCESS DATA FOR RUN NO. -3
WASTE - API SEPARATOR BOTTOM
DATE - 1.30.76
Time
9:57
10:25
10:45
11:15
11:34
11:45
12:00
12:30
1:00
1:30
Incinerator Burner Gas
Burner 01 Burner #2
*
AP
.7
.7
.75
.7
.7
.7
.7
.7
.65
.7
**
SCFH
270
270
280
270
270
270
270
270
260
270
AP
.7
.7
.75
.7
.7
.7
.7
.7
.65
.7
SCFH
270
270
280
270
270
270
270
270
260
270
Incinerator
Air
AP
17.5
20.5
23.5
23.5
24.5
25.5
25.5
25.5
25.5
25.5
SCFH
32,400
35,000
37,500
37,500
38,400
)9,000
J9.000
J9.000
39,000
19,000
Incinerator Auxiliary Gas
Burner #1 Burner #2
AP
2.7
2.8
2.55
2.5
2.4
2.4
2.3
2.3
2.3
2.25
SCFH
440
450
430
425
415
415
410
410
410
405
AP
2.7
2.8
2.55
2.5
2.4
2.4
2.3
2.3
2.3
2.25
SCFH
440
450
430
425
415
415
410
410
410
405
Incin.
Temp.
°F
1520
1520
1515
1515
1520
1520
1520
1520
1520
1520
Vapor
Inlet
°F
750
860
920
975
990
990
1000
1000
1010
1010
Stack
Temp.
°F
600
630
700
690
715
695
680
680
680
680
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-9
PROCESS DATA FOR RUN NO. -3
WASTE - API SEPARATOR BOTTOM
DATE - 1.30.76
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
3 PER HOUR
12.5 MINS
55.6 LBS/HR
176.0 LBS
66.0 LBS
3/4 INCH
1/8"x 8" NOZZLE, MOYNO PUMP
COMMENTS - FEED NOZZLE AWAY FROM HOT ZONE AND A SCRAPER
ATTACHED TO IT.
125
-------
TABLE C-10
PROCESS DATA FOR RUN NO. -
WASTE - STYRENE TAR WASTE
DATE - 2.2.76
Time
11:15
11:45
12:00
12:30
1:00
1:30
2:00
2:30
Pyro . Burner
Air
AP*
2.4
2.4
2.3
2.1
1.85
1.8
1.6
1.7
SCFH**
1750
1750
1725
1650
1550
1530
1440
1480
Pyro . Burner
Gas
AP
8.5
8.4
8.4
6.9
6.7
6.6
5.7
6.2
SCFH
183
181
181
165
162
161
150
157
Inert Gas
AP
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
SCFH
1580
1580
1580
1580
1580
1580
1580
1580
Effluent Gas
AP
.78
.87
.84
.79
.76
.75
.72
.78
SCFH
3900
4100
4020
3900
3850
3800
3700
3820
Pyro.
Press
AP
.05
.06
.06
.06
.06
.06
.06
.05
Pyro.
Temp.
°F
1400
1400
1400
1400
1400
1400
1400
1400
Effluent
Gas Temp
°F
1010
1040
1040
1030
1060
1070
1070
1070
%o2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
NOTES: Feeded Started at 11:30 a.m. and stopped at 2:30 p.m.
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-ll
PROCESS DATA FOR RUN NO.-
WASTE - STYRENE TAR WASTE
DATE - 2.2.76
Time
11:15
11:45
12:00
12:30
1:00
1:30
2:00
2:30
Incinerator Burner Gas
Burner //I Burner //2
AP*
.85
.7
.7
.7
.7
.7
.7
.7
SCFH **
300
270
270
270
270
270
270
270
AP
.85
.7
.7
.7
.7
.7
.7
.7
SCFH
300
270
270
270
270
270
270
270
Incinerator
Air
AP
19.0
25.5
25.0
26.0
26.0
26.0
26.5
26.5
SCFH
33,800
39,000
38,600
39,500
39,500
39,500
40,000
40,000
Incinerator Auxiliary Gas
Burner //I Burner if 2
AP
2.8
2.4
2.4
2.4
2.4
2.4
2.4
2.3
SCFH
450
41j
415
415
415
415
415
410
AP
2.8
2.4
2.4
2.4
2.4
2.4
2.4
2.3
SCFH
450
415
415
415
415
415
415
410
Incin.
Temp.
°F
1500
1510
1510
1520
1520
1515
1520
15-15
Vapor
Inlet
°F
800
1080
1110
1120
1100
1110
1160
1100
Stack
Temp.
°F
620
700
730
700
700
690
700
680
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-12
PROCESS DATA FOR RUN HO. -4
WASTE - STYRENE TAR
DATE - 2.2.76
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
3 PER HOUR
12.5 MINS
11.67 LBS/HR
35.0 LBS
0.5 LBS
1/8" x 8" NOZZLE, MOYNO PUMP
COMMENTS - THE SCREEN AT THE BOTTOM OF THE TANK PLUGGED UP PARTIALLY
AND FEED RATE HAD DECREASED FROM INITIAL FEEDING RATE.
SCREEN REPLACED BY LARGER SIZE SCREEN FOR THE REMAINING
TEST RUNS.
1.3.0
-------
TABLE C-13
PROCESS DATA FOR RUN NO. -5
WASTE - STYRENE TAR
DATE - 2.3.76
Time
10:15
10:45
11:00
11:30
12:00
12:30
Pyro. Burner
Air
AP *
1.9
1.85
1.75
1.5
1.0
0.9
SCFH*'
1570
1550
1500
1400
1140
1080
Pyro . Burner
Gas
AP
7.0
7.0
6.0
5.6
2.7
2.9
SCFH
166
166
154
148
104
107
Inert Gas
AP
1.0
1.0
1.0
1.0
1.0
1.0
SCFH
1500
1500
1500
1500
1500
1500
Effluent Gas
AP
.71
.75
.7
-
-
.56
SCFH
3900
3850
3700
-
-
3300
Pyro.
Press
AP
.03
.04
.04
.05
.03
.06
Pyro.
Temp.
°F
1200
1200
1200
1200
1200
1200
Effluent
Gas Temp
°F
920
1000
1020
1050
1020
1010
%o2
0.1
0.1
0.1
0.1
0.1
0.1
NOTE: Feed Started at 10:30 a.m. and stopped at 12:45 p.m.
* Pressure differential - inches of water
** Flow rate - standard rtihir feet ner hour
-------
TABLE C-14
PROCESS DATA FOR RUN NO.-5
WASTE - STYRENE TAR
DATE - 2.3.76
Time
10:15
10:45
11:00
11:30
12:00
12:30
Incinerator Burner Gas
Burner //I Burner //2
AP*
.8
.7
.7
.6
.65
.65
SCFH **
290
270
270
250
250
250
AP
.8
.7
.7
.6
.65
.65
SCFH
290
270
270
250
250
250
Incinerator
Air
AP
18.5
24.5
25.0
27.0
26.0
27.0
SCFH
33,300
38,300
38,800
40,200
39,500
40,200
Incinerator Auxiliary Gas
Burner //I Burner //2
AP
2.8
2.6
2.4
1.6
2.2
2.3
SCFH
450
435
415
330
400
407
AP
2.8
2.6
2.4
1.6
2.2
2.3
SCFH
450
435
415
330
400
407
Incln.
Temp.
°F
1510
1515
1510
1510
1520
1520
Vapor
Inlet
°F
790
1030
1160
1190
1220
1280
Stack
Temp.
°F
610
700
690
720
690
700
* Pressure differential - Inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-15
PROCESS DATA FOR RUN NO. -5
WASTE - STYRENE TAR
DATE - 2.3.76
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
3 PER HOUR
12.5 MINS
16.3 LBS/HR
35 LBS
1 LB
1/8" x 8" NOZZLE, MOYNO PUMP
COMMENTS - PROBLEMS WITH MEASUREMENT OF EFFLUENT GAS FLOW AS
THE PRESSURE TAPS FOR MANOMETER WERE PLUGGING UP DUE
TO SOOT IN THE EFFLUENT GAS
-------
TABLE C-16
PROCESS DATA FOR RUN NO. -6
WASTE - STYRENE TAR
DATE -2.4.76
Time
10:00
10:15
10:30
10:50
11:25
12:00
12:30
1:00
Pyro. Burner
Air
AP*
2.3
1.85
2.3
2.0
1.6
1.55
1.9
2.0
SCFH**
1730
1550
1730
1610
1440
1420
1570
1610
Pyro. Burner
Gas
AP
8.4
6.6
8.4
7.5
5.5
5.3
6.6
7.3
SCFH
182
162
182
172
147
145
163
170
Inert Gas
AP
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
SCFH
1500
1500
1500
1500
1500
1500
1500
1500
Effluent Gas
AP
.85
.75
1.0
.84
.84
.88
1.2
1.4
SCFH
4100
3800
-
3950
3950
4050
-
Pyro.
Press
AP
.08
.05
.08
.09
.07
.09
.15
.19
Pyro.
Temp.
°F
1400
1400
1400
1400
1400
1400
1400
1400
Effluent
Gas Temp
°F
1020
1060
1100
1100
1100
1105
1160
1180
»o2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
NOTE: Feed Started'at 10:25 a.m. and stopped at 1:25 p.m.
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-17
PROCESS DATA FOR RUN NO.-6
WASTE - STYRENE TAR
DATE - 2.4.76
Time
10:00
10:15
10:30
10:50
11:25
12:00
12:30
1:00
* Pr<
** Flc
Incinerator Burner Gas
Burner //I Burner //2
AP*
.8
.8
.65
.7
.7
.7
.65
.6
issure di
>w rate -
SCFH**
290
290
260
270
270
270
260
250
.fferenti
standai
AP
.8
.8
.65
.7
• /
.7
.65
.6
al - inc
d cubic
SCFH
290
290
260
270
270
270
260
250
hes of v
feet per
Incinerator
Air
AP
16.5
17.5
25.0
26.0
26.5
26.0
27.0
28.0
ater
hour
SCFH
31,500
32,400
38,800
39,500
39,800
39,500
40,200
41,000
Incinerator Auxiliary Gas
Burner //I Burner //2
AP
2.8
2.8
2.2
2.1
2.1
2.3
1.8
1.7
SCFH
450
4.0
400
390
390
410
360
350
AP
2.8
2.8
2.2
2.1
2.1
2.3
1.8
1.7
SCFH
450
450
400
390
390
410
360
350
Inc in.
Temp.
°F
1610
1610
1610
1610
1610
1610
1610
1610
Vapor
Inlet
°F
850
895
1225
1160
1280
1220
1300
1330
Stack
Temp.
°F
625
625
790
770
770
750
780
780
-------
TABLE C-18
PROCESS DATA FOR RUN NO. -6
WASTE - STYRENE TAR
DATE - 2.4.76
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
3 PER HOUR
12.5 MINS
22 LBS/HR
66 LBS
0.31 LBS
1/8" x 8" NOZZLE, MOYNO PUMP
COMMENTS - PROBLEMS WITH PLUGGING OF PRESSURE TAPS FOR ORIFICE METER
IN THE EFFLUENT GAS DUCT FROM PYROLYZER
134
-------
TABLE C-19
PROCESS DATA FOR RUN NO. -7
WASTE - NO FEED (BACKGROUND DATA)
DATE - 2.5.76
Time
10:00
10:30
11:00
11:30
12:00
12:30
1:00
Pyro . Burner
Air
AP**
2.35
1.70
1.50
1.50
1.60
1.30
1.40
SCFH**
1750
1500
1400
1400
1440
1300
1350
Pyro. Burner
Gas
AP
8.25
6.0
5.4
5.3
5.2
4.6
4.7
SCFH
180
154
145
144
142
135
137
Inert Gas
AP
1.0
1.0
1.0
1.0
1.0
1.0
1.0
SCFH
1500
1500
1500
1500
1500
1500
1500
Effluent Gas
AP*
1.3
1.1
1.0
1.0
0.99
0.93
0.96
SCFH
4800
4400
4200
4200
4150
4040
4100
Pyro.
Press
AP*
0.15
0.13
0.12
0.13
0.11
0.12
0.11
Pyro.
Temp.
8F
1400
1400
1400
1400
1400
1400
1400
Effluent
3as Temp
°F
1160
1190
1210
1210
1220
1200
1200
zo2
0.1
0.1
0.1
0.1
0.1
0.1
0.1
u>
* Higher AP readings are due to the plug-up of pressure taps from carbon soot formed in
prior runs with styrene tar waste
** Pressure differential - inches of water
***Flow rate - standard cubic feet per hour
-------
TABLE C-20
PROCESS DATA FOR RUN NO. -7
WASTE - NO FEED (BACKGROUND DATA)
DATE - 2.5.76
Time
10:00
10:30
11:00
11:30
12:00
12:30
1:00
Incinerator Burner Gas
Burner #1 Burner //2
AP*
0.7
0.7
0.7
0.7
0.6
0.7
0.7
SCFH**
270
270
270
270
252
270
270
AP
0.7
0.7
0.7
0.7
0.6
0.7
0.7
SCFH
270
270
270
270
252
270
270
Incinerator
Air
AP
24.5
22.5
23.5
24.0
24.0
24.0
24.0
SCFH
38,400
36,600
37,500
38,000
38,000
38,000
38,000
Incinerator Auxiliary Gas
Burner //I Burner //2
AP
2.8
2.8
2.8
2.8
2.7
2.8
2.7
SCFH
450
450
450
450
442
450
442
AP
2.8
2.8
2.8
2.8
2.7
2.8
2.7
SCFH
450
450
450
450
442
450
442
Incin.
Temp.
°F
1520
1510
1510
1510
1515
1515
1510
Vapor
Inlet
°F
1000
1025
1040
1040
1060
1040
1030
Stack
Temp.
°F
650
650
650
650
650
660
660
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-21
PROCESS DATA FOR RUN NO. -8
WASTE - RUBBER WASTE
DATE - 2.17.76
Time
10:00
10:30
10:45
11:00
11:30
12:10
Pyro. Burner
Air
AP*'
2.5
2.2
2.2
2.2
2.3
2.2
SCFH**
1800
1675
1675
1675
1725
1675
Pyro . Burner
Gas
AP
8.5
8.5
8.5
8.5
8.5
8.5
SCFH
183
183
183
183
183
183
Inert Gas
AP
1.0
1.0
1.0
1.0
1.0
1.0
SCFH
1500
1500
1500
1500
1500
1500
Effluent Gas
AP
.61
.61
.6
.63
.73
.89
SCFH
3350
3350
3300
3450
3700
4100
Pyro.
Press
AP
.06
.06
.06
.06
.09
1.
Pyro.
Temp.
°F
1400
1400
1400
1400
1400
1400
Effluent
Sas Temp
°F
1120
1160
1170
1180
1190
1190
%o2
0.1
0.1
0.2
0.2
0.2
0.2
u>
NOTE: Feed started at 10:15 a.m. and stopped at 12:15 p.m.
* Pressure differential - inches of water
**Flow rate - standard cubic feet per hour
-------
TABLE C-22
PROCESS DATA FOR RUN NO. -8
WASTE - RUBBER WASTE
DATE - 2.17.76
Time
10:00
10:30
10:45
11:00
11:30
12:10
Incinerator Burner Gas
Burner tfl Burner #2
AP*
.75
.7
.7
.6
.65
.55
SCFH**
280
270
270
250
260
240
AP
.75
.7
.7
.6
.65
.55
SCFH
280
270
270
250
260
260
Incinerator
Air
AP
20.0
23.5
23.5
24.0
25.0
25.0
SCFH
34,750
37,500
37,500
38,000
38,800
38,800
Incinerator Auxiliary Gas
Burner //I Burner 02
AP
2.85
2.4
2.4
2.2
2.0
2.0
SCFH
455
415
415
400
380
390
AP
2.85
2.4
2.4
2.2
2.0
2.0
SCFH
455
415
415
400
380
380
Incin.
Temp.
°F
1510
1510
1510
1520
1515
1515
Vapor
Inlet
°F
940
1070
1105
1105
1130
1150
Stack
Temp.
°F
620
660
660
670
665
665
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-23
PROCESS DATA FOR RUN NO. -8
WASTE - RUBBER WASTE
DATE - 2.17.76
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
2.5 PER HOUR
15 MINS
26.75 LBS/HR
53.5 LBS
16 LBS
5/8" to 3/4"
1/2" x 7-1/2" NOZZLE, PISTON
COMMENTS - 90 TO 95% OF THE RESIDUE WAS IN THE LUMP FORM. THESE LUMPS
WERE CHARRED ON THE OUTSIDE, BUT THE CORE WAS NOT PYROLYZED.
THE SPEED OF THE PISTON TRAVEL WAS FAST AND IT WAS IN THE
MAGNITUDE OF 2 TO 3 SECONDS. THE NUMBER OF STROKES WERE
3 PER MINUTE.
139
-------
TABLE C-24
PROCESS DATA FOR RUN NO. -9
WASTE - RUBBER WASTE
DATE - 2.18.76
Time
8:15
8:30
8:45
9:00
9:35
10:00
NOTE: Fe
*
Pyro . Burner
Air
AP *
2.8
1.6
2.0
2.0
1.7
2.0
ed start
SCFH**
1900
1440
1610
1610
1480
1610
ed at 8:
J4 C C___.
Pyro . Burner
Gas
AP
7.0
6.0
7.4
7.5
6.4
7.5
30 a.m. i
_•. j _i _ j
SCFH
166
154
170
172
160
172
md stopj
__i. ~_ _ i
Inert Gas
AP
0.7
0.7
0.7
0.7
0.7
0.7
>ed at 10
SCFH
1250
1250
1250
1250
1250
1250
:20 a.m.
Effluent Gas
AP
.63
.44
.6
-
-
SCFH
3400
2600
3300
-
-
Pyro.
Press
AP
.04
.03
.06
.07
.07
.08
Pyro.
Temp.
°F
1400
1400
1400
1400
1400
1400
Effluent
,>as Temp
°F
1120
1140
1140
-
1160
1170
%o2
0.4
0.4
0.3
0.2
0.2
0.2
** Flow rate - standard cubic feet per hour
-------
TABLE C-25
PROCESS DATA FOR RUN NO.-9
WASTE - RUBBER WASTE
DATE - 2.18.76
Time
8:15
8:30
8:45
9:00
9:35
10:00
Incinerator Burner Gas
Burner //I Burner #2
AP*
.75
.75
.75
.6
.65
.6
SCFH **
280
280
280
250
260
250
AP
.75
.75
.75
.6
.65
.6
SCFH
280
280
280
250
260
250
Incinerator
Air
AP
17.5
20.0
23.0
22.5
22.0
23.0
SCFH
32,400
34,750
37,000
36,800
36,250
J7.000
Incinerator Auxiliary Gas
Burner //I Burner //2
AP
2.8
2.8
2.3
2.2
2.4
2.0
SCFH
450
450
410
400
415
380
AP
2.8
2.8
2.3
2.2
2.4
2.0
SCFH
450
450
410
400
415
380
Incin.
Temp.
°F
1500
1510
1510
1515
1510
1510
Vapor
Inlet
°F
950
965
1040
1100
1000
1160
Stack
Temp.
°F
590
600
650
650
620
660
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-26
PROCESS DATA FOR RUN NO. -9
WASTE - RUBBER WASTE
DATE - 2.18.76 (A.M.)
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
2.5 PER HOUR
15 MIN
20.7 LBS/HR
34.5 LBS
6 LBS
1/2" to 5/8"
3/8" x 7-1/2" NOZZLE, PISTON
COMMENTS - 60 to 70% OF THE RESIDUE WAS IN THE FORM OF LUMPS WHICH
WERE PYROLYZED ONLY FROM THE OUTSIDE. THE REMAINING RESIDUE
WAS IN THE FORM OF SMALL PARTICLES AND WAS COMPLETELY
PYROLYZED. THE PISTON TRAVEL SPEED WAS FAST ( 2 to 3 SECONDS)
AND NUMBER OF STROKES WERE 2/MIN.
-------
TABLE C-27
PROCESS DATA FOR RUN NO. -10
WASTE - RUBBER WASTE
DATE - 2.18.76
Time
12:55
1:15
1:45
2:00
2:35
Pyro. Burner
Air
AP*
1.5
1.45
1.85
1.6
1.9
SCFH**
1400
1375
1535
1440
1575
Pyro . Burner
Gas
AP
5.2
5.2
6.8
5.6
7.1
SCFH
145
145
165
148
168
Inert Gas
AP
.65
.65
.65
.65
.65
SCFH
1225
1225
1225
1225
1225
Effluent Gas
AP
.47
.52
.64
.58
SCFH
2900
3050
3400
3250
Pyro.
Press
AP
.05
.07
.07
.07
.06
Pyro.
Temp.
°F
1390
1395
1400
1400
1400
Effluent
,as Temp
°F
1140
1170
1170
1180
1190
%o2
0.35
0.4
0.3
0.3
0.3 •
NOTE: Feed started at 1:15 p.m. and stopped at 3:00 p.m.
* Pressure differential - inches of water •
** Flow rate - standard cubic feer npr hour
-------
TABLE C-28
PROCESS DATA FOR RUN NO. -10
WASTE - RUBBER WASTE
DATE - 2.18.76
Time
12:15
1:15
1:45
2:00
2:35
Incinerator Burner Gas
Burner #1 Burner //2
*
AP
.6
.55
.55
.55
.5
**i
SCFH
250
240
240
240
230
AP
.6
.55
.55
.55
.5
SCFH
250
240
240
240
230
Incinerator
Air
AP
22.0
23.5
24.0
25.5
23.5
SCFH
36,250
37,500
38,000
39,000
37,500
Incinerator Auxiliary Gas
Burner #1 Burner 92
AP
2.3
1.7
1.65
1.9
1.5
SCFH
410
350
345
370
330
AP
2.3
1.7
1.65
1.9
1.5
SCFH
410
350
345
370
330
Incin .
Temp.
°F
1510
1520
1510
1510
1410
Vapor
Inlet
°F
1000
1100
1240
1110
1225
Stack
Temp.
°F
600
620
630
630
630
* Pressure differential - inches of water
** Flow rate - standard cubic feet per hour
-------
TABLE C-29
PROCESS DATA FOR RUN NO. -10
WASTE - RUBBER WASTE
DATE - 2.18.76 (P.M.)
HEARTH CYCLE TIME
RESIDENCE TIME
IN HOT ZONE
FEEDING RATE
TOTAL AMOUNT FED
RESIDUE COLLECTED
LAYER THICKNESS
FEEDER
2.5 PER HOUR
15 MINS
16 LBS/HR
28 LBS
3.5 LBS
3/8" to 1/2"
1/4" x 7-1/2" NOZZLE, PISTON
COMMENTS - RESIDUE CONTAINED ONLY ABOUT 5-10% LUMPS AND REST OF IT WAS
IN THE PARTICLE FORM WHICH WAS ALMOST COMPLETELY PYROLYZED.
145
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APPENDIX D
ASSESSMENT OF ENVIRONMENTAL IMPACT
OF DESTROYING CHEMICAL WASTES
at
SURFACE COMBUSTION DIVISION
MIDLAND-ROSS CORPORATION
2375 DORR STREET
TOLEDO, OHIO 43691
The rotary hearth pyrolyzer will be evaluated for its capability of
destroying the following chemical wastes:
Styrene Tars
Rubber Wastes
API Separator Bottoms (petroleum wastes)
The pilot size pyrolyzer is estimated to have a maximum capacity of
45 kilograms per hour. It is equipped with a rich fume incinerator for
combustion of the off-gases from the pyrolyzer. The incinerator exhausts
to the atmosphere through a short stack (approximately 8 meters high) at
a temperature of approximately 870°C. There is no water used in the
pyrolyzers; consequently, the emissions to the environment will be stack
gases and solid wastes such as the waste shipping containers and char
from the pyrolyzer.
The pyrolyzer is located in a building within the extensive manufac-
turing complex of Surface Combustion. It is estimated to be approximately
0.1 kilometers from the edge of their property. The surrounding area is
industrial/residential. On one side of the Surface Combustion property,
furthest from the location of the pyrolyzer, is a high concentration of
homes and apartment buildings. Other residences are scattered among the
various industrial properties and the closest of these is approximately
0.2 kilometers away. A cemetary and a vacant food storage warehouse are
the closest properties to the location of the pyrolyzer. In addition,
an asphalt blending plant is located adjacent to the Surface Combustion
properties and other manufacturing or research development facilities are
located in the immediate vicinity. The University of Toledo Campus is
within one kilometer of the site. The vegetation in the immediate vicinity
of the plant is urban in nature, i.e., trees and lawns. The only apparent
wildlife in the Immediate vicinity is the usual birdlife found in such •
urban developments and, probably, the normal rodent population. A major
motor vehicle artery lies on one side of the property and there is heavy
traffic within less than 0.2 kilometers of the pyrolyzer. The traffic
density has been so heavy in the past as to effect the carbon monoxide
readings on sensitive instruments being used to monitor combustion
-------
processes. Operation of the rich fume incinerator la moderately noisy
(estimated to be between 85 and 90 db at the unit) which should not
present any impact on the neighborhood noise level above that of the
vehicular traffic.
The most severe potential environmental impacts are expected to be
from (1) storage and handling of the wastes prior to testing, (2) the
emissions that occur during the test and (3) the disposal of the shipping
containers, undegraded wastes and the residue remaining from pyrolysls.
Before discussing the unique aspects of each area of concern, it is well
to recognize that the components Identified in the wastes are not excep-
tionally toxic. Information taken from the Toxics Substances List of
1974, list the following pertinent information for the identified con-
stituents.
Styrene - Range of lowest level of reported toxicity
to man is from 376 - 600 ppm: inhalation
effects are principally irritation and
nervous system. OSHA standards for time
weighted average exposure in air is 100 ppm
with ceiling of 200 ppm and peak exposures
of 600 ppm.
Butadiene - OSHA standard is time weighted average
exposure in air of 1000 ppm.
Nonylphenol - (mixed isomers) reported LD50 in rats is
1620 mg/kg.
Methylnaphthalene - Oral LD50 in rates is 4360 mg/kg.
Dimethyl Naphthalene - Not reported in Toxic Substances List
Sulfur - Not included in Toxic Substances List.
Consequently, the most significant problem expected from these
wastes is hazardous in nature such as the possibilities of explosive mix-
tures occurring in tightly enclosed spaces, fire, etc., since they are
not apparently very toxic to human or animal life.
Storage and Handling
Upon receipt, the waste shipments will be inspected by the Receiving
Dock personnel at the Surface Combustion and the Senior Research and
Development Engineer in charge of the program. Storage of the 12 drums
of each waste will be either on an outdoor concrete pad adjacent to the
pyrolyzer building or in an appropriate storage building. Since none
of the wastes are highly fluid, diking around the storage area is not
considered necessary. Any leakage or spillage will be absorbed with
sawdust and put into containers for subsequent treatment or disposal.
There will be a characteristic hydrocarbon odor in the immediate vicinity
when drums are opened prior to sampling and feeding into the pyrolyzer.
147
-------
Odor detection beyond the boundaries of the property should not be ap-
parent especially because of the high density of vehicular traffic In the
area.
Test Runs
The greatest potential environmental Impact foreseen during the test
would occur if the rich fume incinerator failed and the hot gases from
the pyrolyzer vented to the stack. Because the stack refractory will be
hot, there is an excellent possibility that ignition of these gases would
occur. However, the conditions for combustion will be less than optimum
and it is expected that a smoke plume would occur. The design of the
system is such as to make this an unlikely occurrence and furthermore,
If such a failure did occur, it is not likely to be of long duration. -A
less obvious environmental impact would occur if all of the sulfur con-
tained In the styrene tar wastes reported to the off-gases and was burned
to sulfur oxides In the rich fume incinerator. Dispersion calculations
based on the assumption that all of the sulfur was emitted as oxides
from the stack during peak feed rates indicated that ground-level condi-
tions might reach a value of 117 micrograms per cubic meter at a distance
of 0.3 kilometers from the stack when the wind velocity is under 3 meters/
second and 153 micrograms per cubic meter at a distance of 0.17 kilometers
from the stack and a wind velocity of 7 meters per second. These concen-
trations are above the annual arithmetic standards for primary ambient
air quality of 80 micrograms per cubic meter but below the maximum 24
hour concentration of 365 micrograms per cubic meter permitted once per
year.
This information will be reviewed with the Toledo Pollution Control
Agency, 26 Main Street, Toledo, Ohio 43605, by Surface Combustion for
purposes of ascertaining if such conditions are permitted under the appli-
cable codes. Because of the proximity of the asphalt blending plant, it
is doubtful that if the worst conditions prognosticated above occurred,
there will be any significant additional environmental impact. Because
the maximum concentration level estimated above is approximately 1/8 of
the threshold odor of concentration (0.47 ppm) for S02 it is highly
unlikely that the ground-level 862 concentrations will be detectable
except by ambient air monitoring equipment. To prevent these conditions
from occurring, it is proposed to periodically monitor these sulfur
dioxide emissions from the stack and establish a maximum level at which
operations would be curtailed.
Disposal of Containers and Residues
The anticipated method for disposal of emptied shipping containers
char residue from the tests, and any excess wastes not used in the test
program will be via Glass City Disposal Company Into a landfill at Bryan,
Ohio, which is operated by H&H Industry. This landfill is reportedly
approved by the State of Ohio for drummed chemical wastes including those
with high heating values. In the eventuality that approval for landfill
148
-------
of any excess wastes Is not forthcoming, It is expected that the excess
wastes will be pyrolyzed and only the empty drums and excess char would
go to landfill. No material will be sent to landfill until the results
of analyses on wastes and residues have been obtained and examined to
insure that they are compatible with landfilling regulations.
149
-------
APPENDIX E
METRIC TO ENGLISH UNIT CONVERSION
Equivalent
Metric Units English Units
1 KCal 3.966 Btu
1 m3 35.3 CuFt
uo].467a
SH-122c.2
150
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