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

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 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

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                          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

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                         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

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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

-------
    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

-------
                                      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

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                           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

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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

-------
                             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

-------
     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

-------
                                  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

-------
                                  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.

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                                 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

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                      Condenser
  Tef Ion Seals  f=i=M 28/12
                                  Flexible Teflon Coupling
                       250 Ml Flask
Figure A-l.   Sorbent Trap Extractor
               71

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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

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 (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

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      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.

-------
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                                        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

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                  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

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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

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                 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

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                                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

-------


















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450






400





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250




200



150
100
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e A
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A O •
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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.

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                                                 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

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                                                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

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                          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

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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

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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

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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

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                  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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