&EPA
          u States
         Environmental
         Age-
           .stnal Environmental R
            itorv
             Triangle Park NC 2771 1
EPA-600/2-78-190
August 1978

Comparative Cost
Analysis and
Environmental
Assessment for
Disposal of
Organochlorine
Wastes

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                 RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and  application of en-
vironmental technology.  Elimination  of  traditional grouping  was consciously
planned to foster technology transfer  and a maximum interface in related fields.
The nine series are:

    1. Environmental Health Effects Research

    2. Environmental Protection Technology

    3. Ecological Research

    4. Environmental Monitoring

    5. Socioeconomic Environmental  Studies

    6. Scientific and Technical Assessment Reports (STAR)

    7. Interagency Energy-Environment Research and Development

    8. "Special" Reports

    9. Miscellaneous Reports

This report has been assigned to the  ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment,  and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the  control and treatment
of pollution sources to meet environmental quality standards.
                        EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.

This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                 EPA-600/2-78-190
                                      August 1978
   Comparative Cost Analysis
and  Environmental Assessment
for Disposal of Organochlorine
                  Wastes
                      by
                C.C. Shih, J.E. Cotter, D. Dean,
              S.F. Paige, E.P. Pulaski, and C.F.Thorne

                     TRW, Inc.
                   One Space Park
               Redondo Beach, California 90278
                 Contract No. 68-02-2613
                    Task No. 12
                Program Element No. IAB606
              EPA Project Officer: Ronald A. Venezia

            Industrial Environmental Research Laboratory
              Office of Energy, Minerals, and Industry
               Research Triangle Park, NC 27711
                    Prepared for

            U.S. ENVIRONMENTAL PROTECTION AGENCY
              Office of Research and Development
                 Washington, DC 20460

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                                  ABSTRACT

     This report compares the costs and environmental  Impacts  associated  with
the disposal of liquid organochlorlne wastes  by land-based  Incineration,  at-
sea Incineration, and chlorolysls at a Houston, Texas  location.   All  three
methods are viable options for the disposal of these wastes.   At  typical  unit
disposal costs of $80 to $91  per metric ton,  at-sea  Incineration  Is the least
costly option.  Comparable costs are $181  to  $212 per  metric ton  at a central-
ized land-based Incinerator,  and $134 to $158 per metric  ton by the Hoechst-
Uhde chlorolysls process If suitable feedstocks are  available. Environmentally,
maximum ground level concentrations of Inorganic chlorine and  organochlorlne
species and partlculates emitted from land-based Incinerators  and chlorolysls
are all several orders of magnitude lower than their respective Threshold
Limit Values (TLVs) or are within air quality standards.  The  only wastewater
problem Identified for both disposal processes Is discharges with high total
dissolved solids.  For at-sea Incineration, the maximum sea level  concentra-
tion of hydrogen chloride 1s  4.4 mg/cu m and  below its TLV  of  7 mg/cu m.  The
maximum sea level concentration of unburned wastes 1s  several  orders  of
magnitude lower than the TLV  of most organochlorlne  compounds. Water quality
1s not measurably Impacted by at-sea Incineration.
                                     11

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                                  CONTENTS
Abstract	   11
Figures	   iv
Tables  	    v

   1.   Introduction and Summary	    1
        1.1  Introduction  	    1
        1.2  Summary	    5
   2.   Land-Based Incineration 	   10
        2.1  General Description	   10
            2.1.1  The Rollins Incineration facility 	   10
        2.2  Cost Analysis	   12
            2.2.1  Capital Investment	   13
            2.2.2  Annual operating costs	   15
            2.2.3  Unit disposal cost	   18
        2.3  Environmental Assessment	   24
   3.   At-Sea Incineration	   31
        3.1  General Description	   31
            3.1.1  The M/T Vulcanus	   31
        3.2  Cost Analysis	   34
            3.2.1  Capital Investment	   34
            3.2.2  Annual operating costs	   35
            3.2.3  Unit disposal cost	   35
        3.3  Environmental Assessment 	   38
   4.   Chlorolysls	   48
        4.1  General Description	   48
        4.2  Cost Analysis	   51
            4.2.1  Capital Investment	 .   52
            4.2.2  Annual operating costs	 .   52
            4.2.3  Unit disposal cost	   55
        4.3  Environmental Assessment 	   62
            4.3.1  Emissions characterization for chlorolysis	   62
            4.3.2  Environmental Impact analysis 	   79
   5.   Comparative Cost Analysis and Environmental  Assessment	   84
        5.1  Cost Analysis Comparison 	   84
        5.2  Comparison of Environmental Impacts	   89
        5.3  Integration of Analysis Results	   92

References	   94

Appendices

   A.  Calculation of Unit Cost of Disposal of Organochlorlne Wastes . .   97
   B.  A1r Quality Simulation Methodology	103

                                    111

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                                   FIGURES

Number                                                .                   Page
   1      Schematic of Rollins Environmental  Services  Incinerator.  ...   11
   2      Effect of carbon tetrachlorlde selling  price and  discounted
            cash flow rate of return (DCFRR)  on unit disposal  cost  of
            organochlorlne wastes  by chlorolysls  	   60
   3      Flow diagram for the Hoechst-Uhde chlorolysls process	63
   4      Pretreatment section 	   65
   5      Reaction and distillation section	68
   6      Incineration section 	   72
   7      Absorption section 	   74
  B-l      Ground level  concentration as  a function  of  downwind distance
            at three effective stack heights, h.  Emission  rate  Is
            6.05 kg/hr	114
  B-2     Ground level  concentration as  a function  of  downwind distance
            at three wind speeds,  u.  Emission rate 1s 6.05 kg/hr.  .  .  .  115
                                     1v

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                                   TABLES

Number                                                                   Page
   1      Production of Chlorine,  Chlorinated  Organics  and
            Organochlorine Residues 1n the United  States	     1
   2      Comparison of Disposal Methods  for Organochlorine Wastes.  .  .     6
   3      Elemental  Composition and Heating Value  of Organochlorine
            Wastes	    14
   4      Capital Investment for a Central Land-based Incineration
            Facility	    16
   5      Annual Operating Cost for Disposal of 23,420 Metric Tons/Year
            of a Representative Organochlorine Waste at a Central
            Land-based Incineration Facility	    17
   6      Calculation of Discounted Cash  Flow  for  the Disposal  of the
            CMW Waste by Land-based Incineration at 15% Discounted
            Cash Flow Rate of Return	    19
   7      Unit Disposal Cost for Organochlorine Wastes at a Central
            Land-based Incineration Facility	    21
   8      Effect of Discounted Cash Flow  Rate  of Return (DCFRR) on Unit
            Disposal Cost of Organochlorine Wastes by Land-based
            Incineration	    23
   9      Stack Emissions Used for Land-based  A1r  Quality Simulation.  .    25
  10      Summary of Air and Water Quality Effects Associated with
            Land-based Incineration 	    26
  11      Potential  Operational Malfunctions at a  Land-based
            Incineration Facility  	    30
  12      M/T Vulcanus, General Information 	    33
  13      Unit Disposal Cost for Organochlorine Wastes by At-sea
            Incineration	    37
  14      Analysis of Organochlorine Waste Burned  At-sea (The CMW
            Waste)	    40
  15      Elemental  Analysis of CMW Waste 	    41
  16      Emission Rates Used for  At-sea  Air Quality Simulation:
            HC1 and Unburned Wastes	    41
  17      Emission Rates Used for  At-sea  Air Quality Simulation:
            Inorganics	    42

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                             TABLES (Continued)
Number                                                                   Page
  18      Summary of Major Air and Water Quality Effects  Association
            with At-sea Incineration	    42
  19      Potential  Operational  Malfunctions During an At-sea
            Incineration Operation	    46
  20      Operating  Characteristics of Chlorolysis  Processes	    49
  21      Annual Operating Cost for Processing 25,000 Metric Tons/Year
            of a Mixed Vinyl  Chloride Monomer and Solvent Waste at a
            Chlorolysis Plant 	    53
  22      Annual Operating Cost for Processing 25,000 Metric Tons/Year
            of Vinyl Chloride Monomer Waste at a Chlorolysis Plant. .  .    54
  23      Calculation of Discounted Cash Flow for Chlorolysis  of Mixed
            Vinyl Chloride Monomer and Solvent Waste at 15% Discounted
            Cash Flow Rate of Return	    56
  24      Calculation of Discounted Cash Flow for Chlorolysis  of Vinyl
            Chloride Monomer Waste at 15% Discounted Cash Flow Rate
            of Return	    57
  25      Unit Disposal Cost for Organochlorine Wastes at a
            Chlorolysis Plant 	    59
  26      Analyses of Vinyl Chloride Monomer and Chlorinated Solvents
            Waste Fractions	    64
  27      Emissions  from the HC1 Column Chlorolysis Process, Based
            Upon 25,000 Metric Tons/Year	    69
  28      Emissions  from the NaOH Absorber Chlorolysis Process, Based
            Upon 25,000 Metric Tons/Year	    70
  29      Wastewater Discharges from Incineration Pit 	    75
  30      Maximum Emissions from the Absorption Unit for Chlorolysis
            Process, Based Upon 25,000 Metric Tons/Year 	    76
  31      Wastewater Discharges from Absorption Pit 	    76
  32      Wastewater Discharges from Absorption Pit 1n Emergency
            Situations	    76
  33      Total Air Emissions from the Chlorolysis  Process	    77
  34      Total Wastewater Discharges from the Chlorolysis Process
            Under Normal Flow Conditions	    77
  35      Potential  Operational Malfunctions at a Chlorolysis  Plant .  .    78
  36      Summary of Chlorolysis Process Units and  Emission
            Constituents	    79
  37      Summary of Air Quality Simulation Results for a Chlorolysis
            Plant	    81
                                     vl

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                             TABLES  (Continued)
Number
  38      Threshold Limit Value and  Tox1c1ty Data  for  Selected
            Compounds Emitted from the Hoechst-Uhde Chlorolysls
            Process	    82
  39      Cost Comparison for Disposal of Organochlorlne  Wastes  ....    85
  40      Comparison of Discounted Cash Flow Rates of  Return  for the
            Disposal of Organochlorlne Wastes ....  	    88
  41      Comparable Ground Level/Sea Level  Concentrations  of
            Emissions from Land-based Incineration, At-sea
            Incineration and Chlorolysls	    90
  42      Comparison of Wastewater Emissions from Land-based
            Incineration, At-sea Incineration and Chlorolysls 	    91
 A-l      Calculation of Discounted  Cash Flow	101
 A-2      Value of Constants Utilized 1n the Calculation  of Unit
            Disposal Cost by the DCF Method	102
 B-l      Emission Rates Used for A1r Quality Simulation  for At-sea
 (a)        and Land-based Incineration 	   108
 B-l      Emission Rates Used for A1r Quality Simulation  for the
 (b)        Chlorolysls Process  	   109
 B-2      Annual Percent Frequency of Pasquill Stability Categories
            for All Wind Directions and Speeds	110
 B-3      Average Wind Speeds  (Meters/Second) and Prevailing Wind
            Direction for Three  Coastal Areas 	   Ill
 B-4      Average Wind Speed and Direction at Houston, Texas	112
 B-5      Results of Air Quality Simulation  for Land-based Incineration:
            HC1, Trace Metals, Unburned Waste and Particulates	118
 B-6      Results of Air Quality Simulation  for At-sea Incineration:
            HC1, Unburned Wastes and  Inorganics  	   119
 B-7      Results of Air Quality Simulation  for At-sea Incineration:
            Selected Trace Elements  	   120
 B-8      Results of A1r Quality Simulation  for Chlorolysls  Process:
            Emissions from NaOH  Absorber	122
 B-9      Results of A1r Quality Simulation  for Chlorolysls  Process:
            Emissions from Incineration Unit	123
 B-10      Results of Air Quality Simulation  for Chlorolysis  Process:
            Emissions from Absorption Unit	124
 B-ll      Results of Air Quality Simulation  for Chlorolysls  Process:
            Emissions from Absorption Tank	125
                                     vii

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TABLES (Continued)
Number
B-12
B-13

Results of A1r Quality Simulation for Chlorolysls Process:
Emissions from HC1 Column 	
Ground Level Concentrations of Emissions from a Chlorolysis
Plant 	
Pase
126
127

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                        1.   INTRODUCTION AND  SUMMARY
1.1   INTRODUCTION
     Liquid organochlorlne residues  are  generated  by a variety of Industrial
processes for the production of materials  such  as  vinyl chloride monomer,
chlorinated solvents, and pesticides.  Estimated chlorinated organics produc-
tion and the resulting organochlorlne  residues  generated  in the United States
are presented in Table 1.
                 TABLE 1.  PRODUCTION OF CHLORINE,  CHLORINATED
                           ORGANICS AND ORGANOCHLORINE RESIDUES
                           IN THE UNITED STATES
Item
Chlorine
Chlorinated Organics
Organochlorlne Residues
Percent Residues
Average % Chlorine
In Residues
Quantity
1965
5,912
6,622
247
3.73%
Produced
1967
6,967
7,575
272
3.60%
58.1 % 58.7 %
, Thousands
1970
8,854
8,709
298
3.41*
60.1 %
of Metric
1975
10,487
11,793
389
3.30*
60.6 %
Tons
1978
12,700
14,290
472
3.30*
60.6 *
  Source:  The 1965, 1967, 1970 and 1975 figures were obtained from Reference
           1.  The 1978 figures were extrapolated from the 1975 figures by
           using the projected 1978 chlorine production and assuming that the
           chlorinated organics/chlorine production ratio will be the same as
           that 1n 1975.

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     Liquid organochlorine residues requiring disposal  are generally non-
aqueous, contain 50 to 70 percent by weight of chlorine,  and have heating
values in the 9,300 to 14,000 kJ/kg (4,000 to 6,000 Btu/lb) range.   These
wastes can also be mixed with each other without chemical  reactions  or heat
effects.

     Various methods of disposal for these organochlorine wastes  include
land burial, deep well injection, chemical destruction, land-based  incinera-
tion followed by neutralization, land-based incineration  with hydrogen
chloride recovery, at-sea incineration, and recovery processes such  as
chlorolysls.  Three of the common methods for the disposal  of liquid organo-
chlorine wastes are considered in the present study:  conventional land-based
incineration followed by scrubbing and neutralization of  the hydrogen
chloride formed, at-sea incineration utilizing shipboard  incinerators, and
chlorolysls, a process for converting organochlorine wastes to carbon
tetrachloride as a saleable product.  Objectives of this  study are to
compare the costs and the environmental  Impacts associated with these three
disposal  methods.

     In cost analysis, the overall approach utilized  consists of  the following
elements:  (1) determine the capital investment cost and  annual operating
costs for a representative disposal facility; (2) calculate the unit costs,
in terms of $ per metric ton, for the disposal of a number of representative
organochlorine wastes by using the discounted cash flow technique;  (3) Iden-
tify the cost sensitive parameters and assess the effects of these  parameters
on the unit disposal cost; and (4) compare the calculated unit disposal costs
with the actual costs charged by waste disposal operators, wherever  possible.
Steps involved in environmental assessment Include:  (1)   identify the
air emissions and liquid and solid discharges from the  disposal process;
(2) generally characterize the transport and fate of the pollutant materials
within air, water, and land environments; and  (3) identify and predict the
general environmental impacts that may result from the  effects of these
pollutants on air and water quality.  Results of cost analysis and environ-
ment assessment for the three disposal processes are compared, Integrated,
and summarized 1n this report.

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     The primary data base for the analysis  performed  1n  this  study  is
comprised of two EPA sponsored studies  (References  2 and  3), plus additional
information provided by operators of land-based and shipboard  incinerators.
Results from the first EPA sponsored study,  "Environmental  Assessment -
At-Sea and Land-Based Incineration of Organochlorine Wastes",  form the basis
of discussion of environmental impacts  of land-based and  at-sea  incineration
in this report.  The second EPA sponsored study, "Chlorolysis  Applied to  the
Conversion of Chlorocarbon Residues Possibly Containing Oxygenated Analogs",
provides material balance and cost information needed  to  characterize the
emissions from chlorolysis and to calculate  the unit disposal  costs  for
chlorolysis.

     In the comparative cost analysis and environmental assessment,  the
facility operated by Rollins Environmental  Services,  Inc.,  located at
Houston, Texas was selected as the model representative of  land-based incine-
ration.  This is a centralized incineration facility extensively used for the
contract disposal of organochlorine wastes, and has the capacity for disposal
of 23,420 metric tons of liquid organochlorine wastes  per year.   Cost analysis
and environmental assessment for at-sea Incineration were based on the M/T
Vulcanus, which has the capacity for incinerating 69,000 metric tons per  year
of liquid organochlorine wastes, at an average incineration rate of 23 metric
tons per hour and assuming 3000 hours of incinerator operation per year.   For
chlorolysis, the Hoechst-Uhde plant design for processing 25,000 metric  tons
per year of liquid organochlorine wastes was the basis for  analysis.  The
comparative analysis performed was for these plant capacities  representative
of commercial scale operations, and no attempt was made to  address disposal
costs and environmental Impacts on a common capacity basis.

     It has been estimated that approximately 80 percent of the U.S. organo-
chlorine wastes are generated along the Gulf Coast.  To eliminate the cost of
waste transportation from consideration, a Houston, Texas location was selected
for analyzing all three waste disposal options.

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     Theoretically, most pumpable liquid organochlorine wastes  could  be
disposed of by land-based or shipboard incineration.   The major requirements
are that the waste should not be corrosive,  and/or  contain more than  1 percent
solid particulates and trace element levels  that could have  adverse effects
on the environment.  For chlorolysis, acceptable feedstocks  should be free of
particulates and should not contain nitrogen or phosphorus.   Additional  res-
trictions for chlorolysis feedstocks are that the sulfur content should  not
exceed 25 ppm because of material corrosion  problems,  and the aromatic
hydrocarbon content should not exceed 5 weight percent because  of material
temperature limitations.  Chlorolysis 1s, therefore, more suited for  the
disposal of aliphatic chlorinated hydrocarbons, and for wastes  as produced  in
the manufacture of vinyl chloride monomer (VCM) and chlorinated solvents.

     Although a wide variety of liquid organochlorine  wastes could be disposed
of by either of the three alternative methods, five typical  wastes were  selected
for the comparative economic analysis.  The five wastes  included a perchloro-
ethylene waste, a hexachlorocyclopentadiene waste, a mixed  VCM  and chlorinated
solvent waste, a VCM waste, and a waste produced during  the manufacture  of
ally! chloride, eplchlorohydrin, dichloroethane, and vinyl  chloride  (hereafter
referred to as the combined manufacturing waste, or CMW).   The  mixed  VCM and
chlorinated solvent waste and the VCM waste were selected  because both wastes
are suitable feedstocks for chlorolysis and have been  analyzed  in the Hoechst-
Uhde report (Reference 3).  The CMW waste was selected because  the waste
composition and physical properties are representative of the average of
organochlorine wastes, and because the waste has been  successfully burned on
board the M/T Vulcanus.  The perchloroethylene and hexachlorocyclopentadiene
wastes were selected to examine the effects of chlorine content and  heating
value on the cost of disposal.  Strictly speaking, the CMW waste, the perchlo-
roethylene waste, and the hexachlorocyclopentadiene waste are not suitable
feedstocks for chlorolysis.  The sulfur contents for the CMW waste and the
hexachlorocyclopentadiene waste are 90 ppm and 200 ppm,  respectively, both
exceeding the 25 ppm sulfur limit.  The perchloroethylene waste contains 9.2
percent by weight of chlorinated benzene, exceeding the 5  percent by  weight

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limit for aromatlcs.   However, all  three wastes  can  be  blended with VCM wastes
to meet the chlorolysls feedstock acceptability  criteria.

     In environmental  impact analysis,  the  CMW waste was considered for both
land-based and shipboard incineration.   Again, this  was because  the  CMW
waste is representative of the average  of organochlorine wastes, and measured
emissions data are available from tests conducted on board  the M/T Vulcanus.
The mixed VCM and chlorinated solvent waste was  considered  in the environmental
impact analysis for chlorolysls, because it is the most probable feedstock and
the base case analyzed by Hoechst-Uhde.  Comparative environment assessment
was not performed for five typical  organochlorine wastes, as was in the case
of cost analysis, due to the paucity of measured emissions  data.

     This report consists of five sections, the  first of which 1s the  introduc-
tion and summary of all significant findings.  Section  2 provides a general
description and results of cost analysis and environmental  assessment  for
land-based Incineration.  Sections 3 and 4  are organized 1n the  same  fashion
as Section 2, and discuss at-sea incineration and chlorolysls, respectively.
In Section 5, costs and environmental impacts associated with  the disposal  of
organochlorine wastes by the three alternative methods  are  compared.   Appendix
A presents the cost model utilized In the calculation of unit  disposal  costs.
The model used for air quality simulation 1s described  in Appendix  B.
1.2  SUMMARY
     The present study has demonstrated that land-based Incineration, at-sea
Incineration, and chlorolysls are all viable options for the disposal of
liquid organochlorine wastes.  The attractiveness of each disposal method
depends on the physical and chemical characteristics of the waste requiring
disposal, the market demand for saleable products generated, and the waste
volume of concern.  The major findings of the analysis performed are
summarized 1n Table 2 and discussed as follows.

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                                     TABLE 2.  COMPARISON OF DISPOSAL METHODS FOR ORGANOCHLORINE  WASTES
Disposal
Method
Land- based
Incineration
At-sea
Incineration
Process Applicability Unit Disposal Cost ,
$/Metr1c Ton
Suited for the disposal of 181-212
other types of liquid wastes
as well as sludges, solids,
semi-solids and contaminated
containers.
Applicable to the disposal of 80-91
other types of liquid wastes;
however, liquid wastes requiring
disposal should not contain
more than 1 percent solid
participates.
Environmental Impacts
Maximum ground level HC1 con-
centration Is three orders of
magnitude lower than Threshold
Limit Value (TLV). Unburned
wastes were not detected.
Scrubber wastewater contains
high total dissolved solids (TDS).
Maximum sea level HC1 concentra-
tion Is below TLV. Maximum sea
level concentration of unburned
waste Is 2.8 ug/m3. Water
quality 1s not measurably
Impacted.
Potential Malfunctions
Incinerator flameout,
spills and leaks due
to seal deterioration,
mechanical failure, or
manual errors , tank
overfill.
Incinerator flameout,
spills during loading,
spills and leaks due to
seal and pump failures.
Chlorolysls         Suited for the disposal  of
                    liquid aliphatic chlorinated
                    hydrocarbons only.   Acceptable
                    feedstocks should be free of
                    participates, and contain less
                    than 25 ppm sulfur and less
                    than 5 weight percent aromatic
                    hydrocarbons.
136-196
Maximum ground level concentra-
tions Of HC1, C12, COC12, CC14
and S02 are several orders of
magnitude lower than their
respective TLVs.  Scrubber
wastewater contains high TDS,
but the water quality Impacts
are less than would be expected
from land-based Incineration.
Credit should be given for
resource recovery.
                                                        Tank  overfill,  Inciner-
                                                        ation flameout,  spills
                                                        and leaks  due to seal
                                                        and pump failures.
   Unit disposal  costs for land-based Incineration  and chlorolysis were  calculated at 15X discounted cash flow rate of return.
   Unit disposal  costs for at-sea Incineration were based on  prices  charged  by Ocean Combustion Services, B.V.

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•  The capital  Investment cost of a  land-based  Incineration  facility
   located 1n the Houston, Texas area,  with  a heat  release rate of
   100 GJ per hour (95 million Btu per  hour) and  average  liquid feed
   rate of 2.27 cubic meters per hour (600 gallons  per  hour),  Is
   $4,600,000.

•  At 15% discounted cash flow rate of return  (DCFRR),  the unit cost of
   disposal of liquid organochlorlne wastes  at  a  centralized land-based
   Incineration facility ranges from $181  to $212 per metric ton,
   depending on the chlorine and heat content of  the waste.  The unit
   disposal costs calculated at 15% DCFRR  are  1n  good agreement with
   actual costs charged by contract waste  disposal  companies.

0  Reliable capital Investment and operating costs  for  at-sea  Incinera-
   tion are not available at the present time.  However,  preliminary
   estimates by Global Marine Development  Inc.  have Indicated  that  the
   capital Investment cost of modifying a  World War II  T2 tanker to an
   at-sea Incineration vessel would be $10,400,000.  Such a  vessel  would
   have a load capacity of 12,000 metric tons and an Incineration  rate
   of 95 metric tons per hour.

•  Based on prices charged by Ocean Combustion Services,  B.V., the  unit
   cost of disposal of liquid organochlorlne wastes by  at-sea  Incinera-
   tion ranges from $80 to  $91  per metric ton, depending on the  heat
   content of the waste.  Unit disposal costs by at-sea Incineration
   were not calculated using the discounted cash  flow technique because
   of the absence of reliable financial data.

•  The capital Investment cost for a chlorolysls  plant  processing  25,000
   metric tons of organochlorlne waste per year 1s $27,210,000, based
   on the Hoechst-Uhde design and a Gulf Coast location such as Houston,
   Texas.

•  At a carbon tetrachloride selling price of $300 per metric ton  and
   assuming 15% DCFRR, the unit cost for the disposal of organochlorlne
   wastes by chlorolysls ranges from $134 to $196 per metric ton,
   depending on the chemical composition of the waste.

0  Disposal by chlorolysls is favored for organochlorlne wastes with
   higher carbon content and lower hydrogen and oxygen content, such
   as the perchloroethylene wastes, the mixed VCM and solvent waste,
   and the VCM waste.  At a carbon tetrachloride selling price of $300
   per metric ton and  15% DCFRR, chlorolysls has a cost advantage of
   $45 to  $76 per metric ton over land-based Incineration for the
   disposal of these organochlorlne wastes.

0  In terms of unit disposal costs, land-based Incineration 1s con-
   siderably more expensive than at-sea Incineration, mainly due to the
   cost of hydrated lime needed for the neutralization of hydrochloric
   acid, and the higher unit costs for capital related charges and
   operating labor.

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t  The unit disposal  cost of organochlorine wastes  by chlorolysls  is
   very sensitive to  the carbon tetrachlorlde selling price.  At a
   carbon tetrachlorlde selling price of around  $285  per metric ton
   and 15% DCFRR, chlorolysls becomes less  attractive than  land-based
   incineration for the disposal  of the mixed vinyl chloride monomer
   and chlorinated solvent waste  and the vinyl chloride  monomer waste.
   At a carbon tetrachloride selling price  of around  $315 per metric
   ton and 15% DCFRR, chlorolysis becomes Increasingly cost competitive
   with at-sea incineration for the disposal  of  these two organo-
   chlorine wastes.

•  Land-based Incineration cannot be cost competitive with  at-sea
   incineration, because the net  operating  cost  for land-based Incinera-
   tion, without taking into account any return  on  Investment, is
   higher than the unit disposal  costs charged for  at-sea incineration.

•  For chlorolysls, the charges for the disposal  of organochlorine
   wastes only represent a fraction of the  total  annual  revenue.   By
   lowering the DCFRR to the 10.8 to 13.4%  range, chlorolysls can  be
   made to be cost competitive with at-sea  incineration  for the
   disposal of organochlorine wastes, at a  carbon tetrachlorlde selling
   price of $300 per  metric ton.

•  The maximum ground level concentrations  of hydrogen chloride  and
   unburnedowastes emitted from land-based  Incineration  are 540  and
   180 ng/m  . respectively.  These levels are several orders  of
   magnitude lower than their respective Threshold  Limit Values
   {TLV's).  Water quality Impacts of the scrubber  water will  be
   reflected in the need for additional downstream  treatment  and  in
   possible adverse effects of high total dissolved solids  (TDS).

•  The maximum sea level concentration of hydrogen  chloride from  at-
   aea Incineration is below its Threshold Limit Value (TLV)  of
   7 mg/m3.  The predicted maximum sea level concentration  of un-
   burned waste, based on the lowest observed destruction efficiency
   of 99.96 percent, 1s 2.75 ug/m  •  Water  quality  is not measurably
   impacted.

•  The predicted ground level concentrations of  hydrogen chloride,
   chlorine, carbonyl chloride, carbon tetrachlorlde, and sulfur  dioxide
   at distances downwind from a chlorolysis plant are several  orders  of
   magnitude lower than their respective TLV's.   Wastewater from  the
   chlorolysls process has high TDS.  However, water  quality  impacts
   resulting from chlorolysls, 1n terms of TDS,  are much less  than would
   be expected from land-based Incineration.

•  In all three cases compared, trace element emissions  are dependent
   upon their concentrations in the feedstock.
                                 8

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t  Chlorolysls has an apparent ecological  advantage  over the
   other two disposal options 1n that chemical  wastes  are recycled
   to yield saleable products.  Thus, an environmental  credit
   should be given equal  to the emissions  that  would have resulted
   from the manufacture of equivalent quantities  of  carbon
   tetrachlorlde.

•  The largest spill possibility at a land-based  Incineration
   facility exists 1n the storage tank and transfer  area.  All  of
   this area should be paved, diked, and drained  to  a  catch basin
   with pumped return to storage tanks.  The other major failure
   cause could come from Incineration malfunctions,  such as burner
   flameout.  Well-designed combustion controls,  however, should
   provide a large amount of protection against these  potential
   problems.

•  The greatest possibility of spills related to  at-sea Incinera-
   tion occurs during loading.  To prevent flameout, a positive
   and rapid waste feed shutoff system must be  available.

•  The Hoechst-Uhde chlorolysls design 1s  considerably more complex,
   from an equipment standpoint, than land-based  or  at-sea Inciner-
   ation.  Increased complexity generally leads to Increased
   reliability problems, but the use of redundant equipment and
   maintenance surveillance associated with general  chemical  plant
   practice will minimize equipment failure problems.

•  Chlorolysls should be considered as a desirable disposal method
   for liquid organochlorlne wastes If the selling price for  carbon
   tetrachlorlde remains stable, mainly because 1t conserves
   resources and causes minimum environmental damage.   However,
   only approximately 10 percent of the organochlorlne wastes
   generated 1n the U.S. are available and considered  as suitable
   feedstocks for chlorolysls.

•  At-sea Incineration Is most cost-effective for the  disposal  of
   large quantities of liquid organochlorlne wastes.  There are
   some major uncertainties and data gaps 1n analyzing Us environ-
   mental Impact, Including the size distribution and  composition
   of particulates produced, ultimate fate of plume and plume
   constituents during the typical "coning aloft" pattern of  plume
   behavior, and the extent to which HC1 1n plume could add to
   add rain problems.

•  Land-based Incineration, although relatively more expensive, 1s
   suited for the disposal of other types of liquid wastes as well
   as sludges, sol Ids, semi-sol Ids, and contaminated containers,
   with no restraints on the minimum quantity accepted for disposal.

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                         2.  LAND-BASED INCINERATION

2.1  GENERAL DESCRIPTION
     Land-based incineration is the predominant method for the disposal  of
organochlorine wastes in the United States at the present time.  In the  land-
based incineration process, organochlorine wastes are destroyed by controlled
oxidation at high temperatures, followed by efficient scrubbing of the furnace
gas effluent to remove the hydrogen chloride formed.  In addition to the
incinerator and the scrubbing system, the basic components of a land-based
incineration facility also include a stack for the dispersion of effluent
gases, tank farm for the storage of wastes, a stabilization lagoon system for
the treatment of wastewater generated from the scrubber system, and a landfill
area for the disposal of incinerator ashes.  Sludge from the wastewater  treat-
ment lagoon system will eventually be disposed of 1n an approved landfill area.

     For the purpose of comparative cost analysis and environmental  assessment,
the facility operated by Rollins Environmental  Services, Inc. and located at
Houston, Texas was selected as the model representative of land-based incine-
ration.  This is a centralized incineration facility extensively used for the
contract disposal of organochlorine wastes.  A brief description of the
Rollins incineration facility is provided in the following section.

2.1.1  The Rollins Incineration Facility
     The Rollins incineration system consists of a rotary kiln and a liquid
injection system, both feeding a common afterburner (Figure 1).  The main
burner Is for liquid wastes only and is of the vortex horizontal  type.   The
waste liquid burner flame temperature is approximately 1500°C.   The  rotary
kiln, equipped with a second burner, is 4.9 meters long and 3.2 meters in
diameter.  Flame temperature in the kiln is normally 1300°C.   The afterburner
dimensions are:  10.6 meters overall  length, 4.0 meters high, and 4.3 meters

                                     10

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               CONVEYOR
     FIBER PACKS
/SOLID WASTE
 FEED CHUTE
                                                                                             MIST ELIMINATOR
                                                                                                                EXIT GAS
ASH RESIDUE
SAMPLE
                   KILN EXIT DUCT

                      AFTERBURNER

                               HOT DUCT
                                 LODDBY
                                 (WASTE LIQUID BURNER)
                                                                                                                       SAMPLE
                                                                                                                       PORTS
      FEED WASTE LIQUID BURNERS
                                                                    HYDRATED LIME
                                                                    SLURRY FEED
                                                                                         DISCHARGE
                                                                                         SCRUBBER WATER
                      Figure 1.   Schematic of Rollins Environmental Services  Incinerator

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wide.  Afterburner temperature is typically 1300°C.  Overall retention time
of the Incinerator and afterburner is from two to three seconds at an average
temperature of 1400*C.  The total heat release rate 1s 100 GJ per hour (95
million Btu per hour).

     Solid wastes, usually packed in fiber drums, are fed into the rotary kiln
by a conveyor.  Liquid and sludges may also be pumped into the kiln.  Liquid
wastes that can be burned 1n the waste liquid burner are fed directly from
tanks into the burner.  The maximum liquid waste feed rate to the waste liquid
burner is 2.84 cubic meters per hour (750 gallons per hour), and the normal
feed rate is approximately 2.27 cubic meters per hour (600 gallons per hour).

     Both the kiln and the waste liquid burner are equipped with natural  gas
Igniters and gas burners for initial  refractory heat-up, flame stability, and
supplemental heat, if necessary.  Supplemental heat can also be provided  by
burning No. 2 fuel oil.

     As shown in Figure 1, the effluent gases from the incinerator are passed
through a duct into a wet venturl scrubber, absorption trays, and a mist  elimi-
nator before entering the stack.  The exhaust stack is 30 meters high.  Lime
1s injected into the scrubber water to neutralize the hydrogen chloride
absorbed.  Used scrubber water, typically containing 10,000 ppm calcium and
10,000 ppm chlorides, is discharged into settling ponds where it 1s analyzed
and further treated, if necessary, before final discharge.  Sludge is allowed
to settle in the ponds and will eventually be removed and disposed of in an
approved landfill area.

2.2  COST ANALYSIS
     Individual economic analyses were performed to determine the costs of
disposal  for five typical liquid organochlorine wastes at a centralized,
contract land-based incineration facility similar to the one operated by  Rollins
Environmental  Services at Houston, Texas.  The five wastes selected for econo-
mic analyses included a perchloroethylene waste, a hexachlorocyclopentadiene
waste, a mixed vinyl chloride monomer (VCM) and chlorinated solvent waste, a

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VCM waste, and a waste produced during the  manufacture  of  ally! chloride,
eplchlorohydrln, dlchloroethane. and vinyl  chloride  (hereafter referred to as
the combined manufacturing waste, or CMW).   The  mixed VCM  and chlorinated
solvent waste and the VCM waste were selected because both wastes are also
suitable feedstocks for chlorolysls, and the disposal costs  for these wastes
by land-based incineration can be readily compared with the  processing costs
for these wastes by chlorolysls.  The CMW waste  was  selected because the waste
composition and physical properties are representative  of  the average of
organochlorine wastes, and because the waste has been successfully  burned on
board the M/T Vulcanus.  The perchloroethylene and hexachlorocyclopentadlene
wastes were selected to examine the effects of chlorine content and heating
value on the cost of disposal.  As indicated by  selected properties of the
five organochlorine wastes given 1n Table 3, the perchloroethylene  waste  has
a higher chlorine content and a lower heating value  than the other  organo-
chlorine wastes.

     The economic analyses performed were divided into  capital  Investment cost,
annual operating costs, and unit disposal costs.

2.2.1   Capital  Investment
      The  capital investment cost  for  a centralized, land-based incineration
facility  to  dispose  of organochlorine wastes was estimated  based on equipment
cost  data  supplied by  Rollins  Environmental  Services,  Inc.  The major equipment
items  at  the Rollins  facility  include an incineration  system rated at 100 GJ
per  hour,  two feed pumps,  two  induced draft  fans, a venturi scrubber, a Flexi-
tray  absorber,  a 30  meter  stack,  tank farm for  the storage  of liquid wastes,
a  lime slurry tank,  and a  stabilization  lagoon  system.  At  an average liquid
waste feed rate of 2.27 cubic  meters  per hour (600 gallons  per hour), a total
of 23,420 metric tons  of organochlorine  wastes  could be incinerated at the
Rollins  facility per year, assuming that the incinerator  operates  at 330 days
per year  and 24 hours  per  day.
                                       13

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                                 TABLE  3.   ELEMENTAL COMPOSITION AND HEATING VALUE
                                           OF  ORGANOCHLORINE WASTES
Waste Characteristics
Elemental Composition
Carbon (wt %)
Hydrogen (wt %)
Nitrogen (wt %)
Sulfur (wt X)
Chlorine (wt %)
Oxygen (wt %)
Higher Heating Value"1"

CMW *
Waste

30.01
4.17
0.012
0.009
62.6
3.20
16,166 kJ/kg
(6,950 Btu/lb)
Perch! oro-
ethylene
Waste

20.90
0.12
—
--
78.98
—
6,862 kJ/kg
(2,950 Btu/lb)
Hexachloro-
cyclopentadiene
Waste

20.76
0.67
0.37
0.02
76.47
1.71
10,002 kJ/kg
(4,300 Btu/lb)
VCM &
Solvent
Waste

23.5
2.0
._
--
74.4
—
9,746 kJ/kg
(4,190 Btu/lb)
VCM
Waste

27.9
3.3
~
--
68.7
—
12,351 kJ/kg
(5,310 Btu/lb)
   This waste was produced during the manufacture  of ally!  chloride, epichlorohydrin, dichloroethane, and
   vinyl chloride.

*  The higher heating value or gross  heating value of a  substance  Is the heat evolved in its complete
   combustion under constant pressure at a temperature of 25°C  when all the water initially present as liquid
   in the substance and that present  in  the combustion products are condensed to the liquid state.  The net
   heating value is similarly defined, except that the final  state of  the water in the system after combustion
   is taken as vapor at 25°C.

Source:  Properties of the CMW waste  were obtained from  Reference  4.   Properties of the perchloroethylene
   waste were obtained from private communication  of a chemical company to C. C. Shin.  Properties of the
   hexachlorocyclopentadiene waste were  obtained from Reference 5. Properties of the VCM and solvent waste
   and the VCM waste were obtained from  Reference  3, except that heating values for these wastes were estimated
   from the heating values of the waste  components.

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     In the estimation  of the capital  investment  cost,  the major equipment
costs were adjusted to  March  1978 basis  using  the Chemical Engineering Plant
Cost Index.  The costs  of other portions of the incineration  facility and
associated labor costs  were estimated  using the method  of Happel  (Reference-5).
Land prices are not included  in the capital  investment  cost.  The total capital
investment cost for the land-based incineration facility, as  presented in
Table 4, is $4,592,600.  Approximately 65 percent of the capital  investment
cost can be attributed  to the installation cost for the incinerator.

2.2.2  Annual  Operating Cost
     The  annual operating costs for the disposal  of organochlorine  wastes at
a  land-based incineration facility consist of the costs of operating labor,
maintenance, utilities, overhead expenses, taxes  and insurance, and hydrated
lime.  The  operating labor costs were calculated based on the number of
personnel  assigned  to  operate  the Rollins incineration facility and at labor
rates  for the  Houston, Texas area.  The maintenance costs were based on
historical  maintenance cost  data furnished by Rollins Environmental Services,
Inc.   The utility cost includes the cost of electricity  to operate the pumps
and fans  and the cost  of  supplementary  fuel.  The amount of No. 2 fuel oil
needed was  estimated from the  heating value of the organochlorine waste fed.
For the Rollins incinerator, a heating  value of  18,600  kJ/kg (8,000 Btu/lb)
is necessary to provide  adequate heat release for either the waste or combi-
nation of waste plus auxiliary fuel.  Supplementary  fuel is therefore required
for any organochlorine waste with  heating  value  below  18,600 kJ/kg.  The
hydrated  lime  requirement was  calculated  based on  the  amount needed to neutra-
lize the  hydrogen  chloride formed  from  the incineration  of the organochlorine
waste. Costs  for  overhead expenses and taxes and  insurance have been included
at rates  prevalent in  the chemical  industry.

      The  annual  operating costs for the disposal  of  23,420 metric  tons per
year of the  CMW  waste  at a land-based incineration facility  is presented
 1n Table  5.  The net annual  operating cost 1s $2,345,700.  Because of the
 relatively high heating  value of the   CMW  waste,  the  cost of  fuel  oil amounts
 to only $123,500  per year.   For the disposal  of  other  organochlorine wastes,

                                      15

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                   TABLE 4.  CAPITAL INVESTMENT FOR A  CENTRAL  LAND-BASED  INCINERATION  FACILITY
Equipment
1-Venturi scrubber, absorber, pumps and stack
2- Induced draft fans, Including motors
2- Feed pumps
1-Tank farm, Including Hme slurry tank
Instruments (10% of equipment)
(Key Accounts)
Insulation (10% of key accounts)
Piping (45% of key accounts)
Foundations ( 4% of key accounts)
Buildings ( 4% of key accounts)
Structures ( 4% of key accounts)
Fire Protection (0.75% of key accounts)
Electrical (4.5% of key accounts)
Painting and Clean-up (0.75% of key accounts)
Subtotal
Installed Costs of Special Equipment
1-Incinerator, conveyor fed
1-Stabilization lagoon system
Equipment and Labor
Overheads (30? of Equipment & Labor)
Total Erected Cost
Engineering Fee (10% of Erected Cost)
Contingency (10% of Erected Cost)
Total Capital Investment
Size Estimated
Equipment
5,300 1pm $103,000
300 KW each 80,000
1,300 Iph each 5,100
3,040 cu.m. 133,000
$321,100
32,100
$353,200
35,300
158,900
14,100
14,100
14,100
2,600
15,900
2,600
$610,800
24 million Kcal/hr.
30,000 cu.m.

*
Costs
Labor

$ 32,100
4,800
$ 36,900
53,000
158,900
21 ,200
9,900
2,800
16,900
23,800
16,900
$340,300

Total

$ 951,100
1,900,000
93,000
$2,944,000
883,200
$3,827,200
382,700
382,700
$4,592,600
March 1978 basis.

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                              TABLE 5.    ANNUAL OPERATING COST
                              FOR DISPOSAL OF 23,420 METRIC TONS/YEAR OF
                              A REPRESENTATIVE ORGANOCHLORINE WASTE  AT A
                              CENTRAL LAND-BASED INCINERATION FACILITY

                  Item                                                             Cost,  $/Year


Chemicals
     Hydrated 11 me:  24,520 metric tons @ $35.00/metric ton                         $  858,200

Utilities
     Electric power:  9,980,000 Kw-hr @ $0.015/Kw-hr                                   149,700
     Fuel Oil:  9,500 bbl  @ $13.00 per bbl                                             123,500

Operating Labor
     Operator, 3 men per shift, $8.65/manhour                                          2
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 the  costs  of operating  labor, maintenance, overhead expenses, taxes and
 insurance,  and  electric power would  be  the same as those for the Shell waste,
 whereas  the costs  of  hydrated lime and  fuel oil would be dependent on the
 chlorine content and  heating value of the individual wastes.  The effects of
 these  variables on the  cost of waste disposal are addressed in the next
 section.

 2.2.3  Unit  Disposal Cost
     The method used for estimating the unit cost of disposal  of organo-
 chlorine wastes is based on the discounted cash flow (DCF)  technique.   In
 essence, this technique determines the annual  revenue during the plant life
 which will   generate a discounted cash flow equal  to the total  capital  invested
 for  the  plant.  In DCF analysis, all  future net income is discounted to a
 present  value depending on the discounted cash flow rate of return (DCFRR).
 In other words, the DCFRR is the interest rate at which present value  of all
 expenditures over  the life of the plant is equal  to the present value  of
 revenue.  Discounting can also be done on either an annual  or continuous
 basis.   For  the present situation, it is more reasonable to assume that
 transactions will   occur throughout the year and not in one  lump sum, and
 therefore continuous discounting is more representative of  the actual  flow of
 funds.   Plant life was assumed to be ten years.

     The calculation of discounted cash flow for the disposal  of 23,420 metric
 tons per year of the CMW waste at a land-based incineration facility is
 illustrated  in Table 6.  The calculation procedure follows  that described
 by Uhl (Reference  7), and the assumptions used are discussed in detail in
 Appendix A.  The calculation showed that at 15% DCFRR, an annual  cash  flow of
 $1,177,009 must be generated to offset the expenditures in  capital  investment,
working  capital  and startup cost.  As cash flow is the sum  of the net  profit
and depreciation,   the annual  revenue that must be derived can be found from:
         CF  =  D   +  (1 - t)  (S - C - D)
where:
         CF  =  Annual  cash flow
         D   =  Depreciation
                                     18

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                        TABLE 6.  CALCULATION OF DISCOUNTED CASH FLOW FOR THE DISPOSAL
                                  OF THE CMW WASTE BY LAND-BASED INCINERATION AT
                                  151 DISCOUNTED CASH FLOW RATE OF RETURN.
Time,
Year
-2 to 0
0
1
0 to 2
0 to 10
10
Item
Depreciable Investment
Working Capital
Interest on 30% of Total
Plant Cost at 102 Rate
Startup Cost
Cash Flow
Recover Working Capital
Investment Cash Flow Discounting
Factor
$4,592,600 1.1662
$ 636,069 1.0
- 0.5* ($307,796) 0.9048
- 0.5* ($229,630) 0.9286
10 ($1,177,009) 0.5179
- $ 636,069 0.2231
Discounted
Cash Flow
- $5,355,871
- $ 636,069
- $ 139,253
- $ 106,619
$6,095,886
$ 141,926
0
The actual cash flow for these two Items are reduced by 50% due to the effect on cash flow of Income tax.

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        S   =  Annual revenue
        C   =  Net annual operating cost
        t   =  Income tax rate
     Assuming  10 year straight time depreciation and an income tax rate of
 50%, the annual revenue that must be generated was calculated to be $4,240,488.
 For land-based incineration, no saleable products are generated and the annual
 revenue is derived completely from waste disposal charges.  The unit disposal
 cost was therefore obtained by dividing the annual revenue by the annual
 quantity of waste requiring disposal.  For the  CMW  waste, the unit disposal
 cost was calculated to be $181.06 per metric ton.

     To facilitate the computation of unit disposal costs for other organo-
 chlorine wastes, a general unit disposal cost equation has been derived based
 on Uhl's economic evaluation procedure (Reference 7).  The derivation of the
 unit disposal  cost equation and the assumptions involved are described in
 Appendix A.  The unit disposal cost equation is given as:
        Unit nisposal Cost ($/metric ton) =
where:
                                            C +  al + bW + cU - S1
        a, b, c are constants depending on the discounted cash flow
               rate of return and given in Table A-2.
        C   =  Net annual operating cost, $;
        I   =  Total plant investment, $;
        W   =  Working capital, $;
        U   =  Startup cost, $;
        S1  =  Annual revenue received from the sale of products
               generated from the processing of wastes, $;
        6   =  Annual quantity of waste disposed, metric tons.

     The unit disposal costs for the five organochlorine wastes at 15% DCFRR,
as given in Table 7, range from $181 to $212 per metric ton.  The higher
unit disposal cost for the perchloroethylene waste is the result of its
higher chlorine content and lower heating value.  The hydrated lime require-
ment is directly proportional to the chlorine content of the organochlorine
waste and was calculated from the reaction:
        2HC1   +  Ca(OH)2  -*•  CaCl2  +  2H20.
                                      20

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                       TABLE 7.  UNIT DISPOSAL COST FOR OR6ANOCHLORINE WASTES
                                 AT A CENTRAL LAND-BASED INCINERATION FACILITY
Item
Operating Cost
Hydrated lime
Electric power
Fuel Oil
Operating labor
Maintenance
Overhead expense
Taxes and insurance
>
Subtotal
Capital investment related i terns t
Working capital t
Startup costt
Unit Disposal Cost

$/Metric Ton Waste
CMH *
Waste

36.64
6.39
5.27
14.20
15.93
18.78
2.94
100.15
71.00
8.15
1 . 76
181.06
y
Perchloro-
ethylene
Waste

46.22
6.39
25.34
14.20
-15.93
18.78
2.94
129.80
71.00
9.54
1.76
212.10

Hexachloro-
cyclopentadiene
Waste

44.76
6.39
18.57
14.20
15.93
18.78
2.94
121.57
71.00
9.15
1.76
203.48

VCM &
Solvent
Waste

43.55
6.39
19.12
14.20
15.93
18.78
2.94
120.91
71.00
9.12
1.76
202.79

VCM
Waste

40.22
6.39
13.50
14.20
15.93
18.78
2.94
111.96
71.00
8.70
1 .76
193.42

This waste was produced during the manufacture of allyl  chloride,  epichlorohydrin,  dichloroethane, and
vinyl chloride.

The charges of capital investment related  items,  working capital and  startup  cost to  the  unit disposal
cost are based on ]5% discounted cash flow rate of return.

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With the assumption that all  the chlorine present 1n  the  organochlorlne waste
is converted to hydrogen chloride,  the hydrated lime  requirement,  at 60%  in
excess of the stoichiometric amount, is given as:
        Hydrated lime requirement  =  1.672 X weight  % Chlorine/100.
        (Metric ton/metric ton waste)
Thus, a 10% difference in the chlorine content of wastes  would  result  in  a
$5.85 difference in the unit disposal cost of these wastes.

     The supplementary fuel requirement for land-based Incineration was
calculated from the heating value of the organochlorine waste.   As indicated
in Table 7, the fuel cost for the disposal of the CMW waste  amounts to only
$5.27 per metric ton, or less than 3% of the unit disposal cost.  On the  other
hand, the fuel cost for the disposal of the perchloroethylene waste amounts
to $25.34 per metric ton, or 11.9% of the unit disposal cost.  Most organo-
chlorine wastes have higher heating values in the 9,300 to 14,000  kJ/kg  (4,000
to 6,000 Btu/lb) range, and the fuel cost for disposal would be from $10.00  to
$20.00 per metric ton of waste.  For wastes with known chemical composition,
the heating value can be estimated from its carbon, hydrogen, oxygen and
chlorine content by using the method of Handrick (Reference  8).  For two  wastes
with components of the same structural group (e.g., straight-chain hydro-
carbons), the higher chlorine content waste would also have  the lower  heating
value.  Thus, organochlorine wastes of high chlorine  content generally have
low heating values, and the unit disposal cost for these  wastes would  be
higher due to both the costs of hydrated lime and supplementary fuel.

     The effect of discounted cash flow rate of return on the unit disposal
cost of organochlorine wastes by land-based incineration  1s  summarized in
Table 8.  At 10% DCFRR, the unit disposal cost would  be approximately  $24 per
metric ton lower than at 15% DCFRR.  At 20% DCFRR, the unit  disposal cost
would be approximately $29 per metric ton higher than at  15% DCFRR.

     The unit disposal costs for organochlorine wastes calculated  using  the
cost model described in this study can also be compared with the actual
costs charged by contract waste disposal companies.  According  to  Rollins

                                     22

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       TABLE 8.  EFFECT OF DISCOUNTED CASH FLOW RATE OF RETURN
                 (DCFRR) ON UNIT DISPOSAL COST OF ORGANOCHLORINE
                 WASTES BY LAND-BASED INCINERATION
DCFRR


10%
12%
15%
18%
20%

CMW
Waste

157.31
166.28
181.06
197.52
209.46

Perchloro-
ethylene
Waste
187.87
197.03
212.10
228.85
241.00
$/Metr1c Ton Waste
Hexachloro-
cyclopentadiene
Waste
179.38
188.49
203.48
220.15
232.24

VCM &
Solvent
Waste
178.70
187.80
202.79
219.45
231.54
. — . — . —
VCM
Waste

169.47
178.52
193.42
209.99
222.01
Environmental  Services,  the unit  disposal  costs  for the CMW waste and the
perchloroethylene waste  would be  $183 per metric ton  ($0.90 per  gallon)  and
$215 per metric ton ($1.30 per gallon),  respectively.  These  costs  are  in
good agreement with the  calculated unit  disposal costs of $181 per  metric  ton
and $212 per metric ton  for the same two wastes, at  15%  DCFRR.   For the
disposal of liquid polychlorinated biphenyl  (PCB) wastes, Chem-Trol  Pollution
Services, Inc. of Model  City, New York,  quoted a unit disposal cost of  $220
per metric ton.  Liquid  PCB wastes have  an average chlorine content of
approximately 45 weight  percent and a low heating value  similar  to  that of
the perchloroethylene waste.  At 15% DCFRR, the unit disposal cost  for  liquid
PCB wastes was calculated to be approximately $205 per metric ton.   This again
shows that the cost of disposal of organochlorine wastes at a land-based
incineration facility can be calculated  with accuracy using the  cost model
described in this study, and by assuming 15% DCFRR.

     The unit cost for contract disposal of organochlorine wastes  at a  centra-
lized land-based incineration facility is not a function of waste  volume, as
long as the volume of waste requiring disposal  each time is  a minimum of a
tank truck.  In the calculation of the unit disposal cost, the capital  charges
                                      23

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and operating expenses can be simply prorated to the different organochlorine
wastes disposed during the year.  In other words, the unit disposal  cost is
based on the disposal of a total of 23,420 metric tons of organochlorine
wastes per year, and not on the disposal of large quantities of a specific
organochlorine waste.

2.3  ENVIRONMENTAL ASSESSMENT
     In order to determine the environmental  impact of land-based incineration
activities, analyses were performed to estimate the effect these activities
could have on air and water quality.  Gaussian diffusion and transport  models
were used to simulate the air quality expected changes and calculations were
made to characterize scrubber wastewater.   A  detailed description of the
simulation analysis is presented in Appendix  B.

     Air quality simulations were based on emissions and other data  obtained
at an incineration facility considered to  be  representative of a modern U.S.
commercial disposal facility capable of accepting organochlorine wastes.  (See
Section 2.1 for a description of the incinerator and scrubbing system).  Major
input parameters to the simulation model consist of effective stack  height (or
plume rise), wind speed and stability category.

     Plant operation parameters and characteristics were used to derive effec-
tive stack height.  Meteorological parameters (wind speed and stability cate-
gory) considered to be representative of conditions at a Houston site were
chosen.  A wind speed of 4.0 meters/second and "D" atmospheric stability
category were used.  It was assumed that all  plume constituents remain
airborne with no identifiable sinks at the ground level.

     No data were available describing emissions from the incineration  of
strictly defined organochlorine materials  at  a land-based facility.   However,
incineration tests had been performed on nitrochlorobenzene (NCB) at a
representative facility.  Emissions obtained  during these tests were used
for the air quality simulations for HC1, particulates and trace metals.
Emission rates for the unburned waste were estimated, based on the destruction

                                     24

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efficiency (>99.999%)  achieved  during  the  NCB  burn, and a  typical organochlo-
rlne waste feed rate of 3 metric tons/hour (Reference  9).   For the air simu-
lation analysis, however, H was assumed that  0.01% of the waste  feed was
emitted as uncombusted material.  Thus, results  are conservative  by at least
a factor of 10.  Emissions used in air quality simulation  are listed in
Table 9.  These emissions should be representative of  those generated from
the incineration of a typical organochlorine waste.

     Characterization of scrubber water was derived for emissions resulting
from the incineration of the CMW waste, which  has a chlorine content of  62.6
weight percent.  The scrubber solution used was assumed to be 3,200 liters
per minute of scrubber water and a 32% Ca(OH)2 solution.   At 60%  in excess of
the stoichiometric requirement, the amount of lime slurry  needed  was calculated
to be 193 liters per minute.  Total discharges of chlorides and calcium  were
estimated to be 1,880 kg per hour and 1,740 kg per hour,  respectively.
    TABLE 9.  STACK EMISSIONS USED FOR LAND-BASED AIR QUALITY SIMULATION
                             (ALL RATES IN Kg/Hr)
   HC1
Particulates
Trace Metals, Each
Unburned Wastes
  0.895
    1.03
     0.00069
      0.3
  Notes:  1)  Emission rates for HC1, partlculates, trace metals, and
              unburned wastes are all based on a dry volumetric flow
              rate of 68877 m3/hr.  Concentrations of HC1, partlculate
              and trace metals 1n the stack gases are 13 mg/m3, 15 mg/m3
              and 0.01 mg/m3, respectively.
          2)  Trace metals Include T1, N1 and Cr, each at the listed
              concentration level.  These concentrations are based on
              analysis of the .waste and not on stack gas measurements.
          3)  Emission estimates for unburned wastes were based on a
              99.99% destruction efficiency and a hypothetical waste
              feed rate of 3 metric tons/hr considered to be the average
              feed rate for CMW waste at one of the largest U.S. Incinerator.
                                       25

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     Selected air quality simulation and wastewater characterization  results
for land-based incineration activities are presented in  Table  10.  Air quality
data presented are the maximum ground level  concentrations  for stated meteo-
rological conditions.   Complete results of air quality simulations  (Appendix
B) give predicted ground level concentrations  at  various distances downwind
from the source.  The  maximum shown in Table 10 are predicted  to occur 3,000
meters from the source.

     The maximum HC1 concentration  is 536.6  nanograms/cubic meter or  0.0004
ppm.  This is four orders of magnitude less  than  the TLV of 5  ppm.  This con-
centration is also lower than the sensory threshold levels reported in the
literature (0.067 ppm) and is not known to have any adverse effects (Reference
12).  The most stringent of the National  Ambient  Air Quality Standards (NAAQS)
for particulates (60 yg/m  - annual  geometric  mean) is an order of magnitude
larger than the maximum predicted total  particulate concentration.
             TABLE 10.   SUMMARY OF AIR AND  WATER  QUALITY  EFFECTS
                        ASSOCIATED UITH LAND-BASED  INCINERATION
Air Quality(a)
HC1
•3
ng/m

536.6
Parti-
culates
ng/m3

617.6
Unburned
Wastes
ng/m3

179.9
Trace
Metals
ng/m3

0.41
Scrubber Water Quality^(mg/liter)

CMW Waste with 62.6%

Cl" Ca++
12,300 11,420
/ \
Chlorine10'

TDS
23,720
   (a)   Maxima from air quality  simulations:   effective  stack  height -
        96.5 meters, wind  speed  -  4.0  meters/second,  ground  surface
        reflectivity =  1.0 and atmosphere  stability = D.  These maxima
        occur 3,000 meters downwind  from the  source.
   (b)   TDS levels  of scrubber water depend primarily on  percentage
        chlorine composition  of  the  incoming  wastes and  type of scrubber
        solution used.   Concentrations in  mg/liter.
   (c)   Scrubber solution  is  32% Ca(OH)2.
                                     26

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     It should also be stressed that tests showed no emission  of unburned
wastes from the stack, and the emissions rate used In the model  was  based  on
a 99.99% destruction efficiency.  The calculated destruction efficiency, based
on the detection limit of analytical instrumentation, was 99.999%.   Therefore,
the predicted concentrations of unburned wastes are conservative.

     Water quality impacts will be reflected in the need for additional  down-
stream treatment and 1n possible adverse effects of heavy metals and high  TDS.
Possible adverse effects Include direct impacts on treatment plant  processes
(e.g., process upsets and/or receiving water bodies if these materials  were
not removed by the treatment process), and indirect effects of any  trace
metals or unburned waste that might be associated with the sludges  resulting
from treatment.

     All effluent streams (stack gas, spent scrubbing solution, sludge,
clinker, bottom ash, and treated scrubbing solution) have the  potential  of
adversely affecting the soil.  Impacts on the soil can be manifested in
several ways, ranging from no adverse effects to contamination of the soil,
vegetation, and groundwater.

     The combustion products which are entrained in the stack  gases will
eventually be removed from the atmosphere, as previously discussed, and will
come Into contact with the soil or surface water.  The effects and inter-
actions of these contaminants with surface water has been previously discussed,
and their Interaction with the soil will  be addressed 1n the discussion of
residue handling.

     Clinker and any bottom ash formed will contain primarily inorganic
carbonaceous compounds.  Less  than  3% of  the total weight of carbonaceous
compounds will be trace compounds,  Including heavy metals.  Because of the
presence of these heavy metals, these solids should be disposed of in land-
fills  approved for  hazardous wastes.
                                      27

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     Spent scrubbing solution, 1f sent to an on-site settling tank or pond,
will generate two streams.  One stream will  be the clear liquid effluent  which
may be suitable for sending to municipal  treatment facilities.  The other
stream will be sludge or solid residue from  the settling process,  which,
because 1t will contain heavy metals and perhaps some organlcs, should be
disposed of In an approved landfill.

     Spent scrubber solution may not be treated on-s1te, but rather disposed
of directly Into the municipal sewage system.   This will result in sludges
generated by the municipal treatment process containing heavy metal  contami-
nants which will be landfllled and, depending  on the destruction efficiency
of the incinerator, the liquid effluents  could potentially contain small
amounts of organochlorlne wastes.  However,  if destruction efficiencies are
kept at the levels achieved on test burns, (it 1s expected that regulatory
controls will ensure that 1s the case), no unburned wastes will be expected
in the scrubber wastewater.

     Effects of the contaminants once deposited onto or into the soil  vary as
a function of the type and porosity of the soil, the weather conditions,  and
the mobility of the Individual contaminants  (Reference 13).   Some  contami-
nants, for example, selenium (HSeOT & SeOo"),  are relatively mobile In the
                                                -H-           ++          -H-
soil, while metal  cations, for example, Iron (Fe  ), zinc (Zn  ),  lead (Pb   ),
and copper (Cu  )  are moderately mobile 1n the soil.

     The magnitude of any of these effects cannot be determined accurately
using available data.  If the concentration  of heavy metals and unburned
wastes in waste scrubber water 1s found to be too high, then additional treat-
ment may be required.  If these high concentrations are found in wastewater
treatment sludges, then the chosen disposal  method for the solids  will have
to ensure that air and water resources are not contaminated.
                                     28

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Malfunction Potential
     The functional analysis of an Incineration facility for a  land-based
operation Indicates that most components of the system are 1n a "series"
configuration; each series component must be adequately functioning  to  avoid
degraded performance.   A few process components may be 1n a "parallel"  con-
figuration, allowing a switch-over to another component upon detection  of
problems with the on-stream component.  Waste feed line filters will usually
have two or more units 1n parallel, and even feed pumps may be  "spared"
(duplicated) 1f plant processing rates are determined to be especially
critical.  Multiple burners in an Incinerator are not considered to  be
redundant components, because the loss of any burner will result in  degraded
performance.  Waste feed and wastewater spills and leaks can be caused  by
material corrosion, valve packing and pump seal deterioration,  liquid level
control failure, or manual errors.

     A  listing of some possible operational malfunctions at a land-based
incineration facility is given in Table 11.  The largest hazardous spill
possibility exists in the storage tank and transfer area.  All  of this  area
in a facility should be paved, diked, and drained to a catch basin with
pumped  return to the storage tanks.  Absorbent material should be ready to
use for clean-up 1n the event of a  leak or failure 1n other parts of the
system,

     The other major failure cause  could come from incinerator malfunctions,
such as burner flameout, leading to a toxic vapor discharge.  Well-designed
combustion controls provide a large amount of protection against these
potential  problems.
                                      29

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            TABLE  11.   POTENTIAL OPERATIONAL MALFUNCTIONS AT A LAND-BASED INCINERATION FACILITY
Operation
Tank Filling
Possible Malfunction
1. Overfill on level Intelock failure
2. Leakage due to pump seal, valve
Consequence
Waste spill
Small waste spill
Waste Transfer
 through Pump
 and Filter
Waste Injection
 to Incinerator
Incineration
Stack Gas
 Scrubbing
Wastewater
 Treatment
     packing material corrosion, etc.
 3.  Inclusion of unauthorized waste by sub-
     version of quality control procedures

 1.  Leakage due to pump seal, material
     corrosion, etc.
 2.  Filter plugging
1. Nozzle plugging (low flow detection)
2. Atomization air loss on air blower
    failure

1. Burner flame loss (flame-out) due to
    loss of fuel pressure, loss of primary
    combustion air, coking, or water slug
    1n feed
2. Improper fuel rate
3. Improper air/fuel ratio
4. Injection into a cool combustion zone
    on startup

1. Scrubbing solution circulating pump falls
2. Weak scrubbing solution

3. Pump, valve, or tank leaks


1. Chemical addition pump fails
2. Pump, valve, or tank leaks
                                                                      Possible incineration difficulties
Small waste spill


None if filters switched on high pump
 discharge pressure measurement

Temporary shut-down

Failure to combust, toxic vapor dis-
 charge, liquid accumulation

Transient toxic vapor discharge prior
 to automatic shutdown on flame loss
 detection (or low combustion temper-
 ature.  A water layer in the tank can
 be isolated by conductivity measure-
 ment interlock to the waste feed pump)
Excess waste product in discharge

Inefficient combustion

Inefficient combustion
High HC1 concentration in stack gases
Not much change, even water scrubbing
 is very effective for HC1  removal
Scrubbing solution spill  (no conse-
 quence if water is used  for scrubbing)

Low pH discharge
Small  wastewater spill

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                           3.   AT-SEA  INCINERATION
3.1   GENERAL DESCRIPTION
     Incineration of combustible chemical wastes on  board specially designed
vessels has been practiced off European  coasts  since 1971.  This technology
for disposal of toxic chemical  wastes  was demonstrated off U.S. coasts for the
first time between October 1974 and February 1975, sanctioned by a permit
granted by the U.S. Environmental  Protection Agency  (EPA) under the authority
of the Marine Protection, Research, and  Sanctuaries  Act  of 1972, as amended.
A total of 16,800 metric tons of organochlorine wastes were incinerated  during
this first series of burns.  The organochlorine wastes disposed were  produced
during the manufacture of ally! chloride, epichlorohydrin, dlchloroethane, and
vinyl chloride monomer at Shell Chemical Company's Deer  Park, Texas plant.

     A second incineration program, again burning  organochlorine wastes  from
Shell Chemical Company's Deer Park, Texas plant,  took place  in March  and April
1977 under U.S. EPA Special Permit No. 750D008E.   The burn  zone was located in
the Gulf of Mexico and 18,000 metric tons of organochlorine wastes were  incin-
erated.  A third burn started in July and ended in September  1977  in  a Pacific
Ocean burn zone west of Johnston Atoll where 10,400  metric  tons of U.S.  Air
Force stocks of Herbicide Orange were incinerated under  U.S.  EPA  Research  and
Special Permits No. 770DH001R and 770DH001S.

     In all three U.S. programs, wastes were burned on board  the  M/T  Vulcanus,
owned by Ocean Combustion Services, B.V., of the Netherlands.  A  brief des-
cription of the M/T Vulcanus is provided in the following section.

3.1.1  The M/T Vulcanus
     The M/T Vulcanus, originally a cargo ship, was converted in 1972 to a
chemical tanker  fitted with  two large incinerators  at the stern.   The double

                                     31

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hull vessel meets all applicable requirements of the Inter-governmental
Maritime Consultative Organization (IMCO) concerning transport of dangerous
cargo by tanker.  Her crew numbers 18; twelve to operate the vessel  and  six
to operate the incinerators.  Two diesel  engines drive the single propeller
to give cruising speeds of 10 to 13 knots.  Waste is carried in 15 tanks,  the
walls and bottoms of which form the inner hull and bottom.  The space between
the two hulls is used for ballast.  Ballast tanks may be filled with sea water
and emptied independently as required to trim and balance the ship.   Tanks
range in size from 115 to 574 cubic meters, with an overall  waste capacity of
3503 cubic meters.  Filling of tanks is accomplished through a manifold  on
deck using a dockside loading pump.  During normal operation the waste tanks
can be discharged only through the incinerator feed system.   There is, however,
provision for discharging the cargo into the ocean if an emergency arises  that
requires protection of the crew.  Information applicable to  the M/T  Vulcanus
is given in Table 12.

     Waste is burned on board the M/T Vulcanus in two identical, refractory-
lined furnaces located at the stern.  Each incinerator consist of two main
sections, a combustion chamber and a stack, through which the combusting gases
pass sequentially.  This dual chamber configuration, which is characteristic
of most high intensity combustion systems, uses the first chamber for internal
mixing and initial combustion and the second for adequate residence  time and
to complete combustion.

     Combustion air is supplied by large  fixed speed blowers with a  rated
maximum capacity of 90,000 cubic meters per hour for each incinerator.  Ad-
justable vanes are incorporated in the combustion air supply system  to control
air feed rate.  They are normally left fully open, however,  no instrumentation
to monitor air volumetric flow is installed.

   Liquid wastes are fed to the combustion system by means of electrically
driven pumps.   Upstream of each burner supply pump is a device (Gorator) for
reducing solids in the waste to a pumpable slurry.  The Gorator also acts  as
a mixing pump by recirculating waste to the cargo tanks.
                                     32

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              TABLE 12.   M/T VULCANUS, GENERAL INFORMATION
Length overall,  m
Breadth, m
Draft, maximum,  m
Deadweight (DWT), metric tons
Speed, knots
                3
Tank capacity, m
Number of tanks

Tank coating

Loading equipment

Hose connection, diameter, cm

Safety equipment

Waste to be processed
Incinerators
Per Incinerator:
  Overall height, m
  Combustion chamber
    OD, m
    ID, m
  Stack (top)
    OD, m
    ID, m
  Waste feed (max), metric tons/hr
  Combustion air (max), m3/hr
  Burners (Vortex type)
  Volume, m
  Residence time, sec
101.95
14.40
7.40
4,768
10-13
3,503
15,              -
from 115 to 574 nT
No coating in tanks, pipes, pumps,  etc.
All equipment consists of low carbon
steel
Not available, but can be placed on
board, if required
10.2, 15.2,
and 20.3
Specially designed for this task and 1n
accordance with latest regulations  of
IMCO, Scheepvaart-Inspectie (The Hague)
Must be liquid and pumpable.  May con-
tain solid substances in pieces up to
5 centimeters 1n size.  Must not attack
mild steel
10.45

5.5
4.8

3.8
3.4
12.5
90,000
3
120
1.0 at 1500°C  (calculated)
                                   33

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     Three vortex-type burners are located at the same level  on  the  periphery
of each furnace near Its base.  They are of a rotating cup,  concentric  design
and deliver waste or fuel oil  through a central  tube to an atomlzatlon  nozzle,
where 1t meets high velocity air delivered through an annulus.   Three-way
valves on each Incinerator burner provide either waste feed,  fuel  oil feed,
or a shutoff condition.   Waste and fuel oil  cannot be valved  into  a  burner
simultaneously; however, alternate burners could be operated  with  fuel  and
waste to achieve higher combustion temperatures  if necessary, depending on the
relative heat contents of the  fuel oil  and waste.

3.2  COST ANALYSIS
     For at-sea incineration of organochlorlne wastes, definitive  cost  data
are not available at the present time to estimate capital  investment cost  and
annual operating costs with accuracy.  The discussion on cost of disposal  Is,
therefore, mostly based on prices charged by Ocean Combustion Services, B.V.
and SBB Stahl-Und Blech-Bau Ltd.

3.2.1  Capital Investment
     Under contract to the Maritime Administration of the U.S.  Department  of
Commerce, Global Marine Development Inc. of Newport Beach, California is
currently (July 1978) conducting a program titled "A Study of the  Economics
and Environmental Viability of a U.S. Flag Toxic Chemical  Incineration  Ship".
As part of this ongoing study, preliminary estimates for the capital invest-
ment cost of modifying a World War II T2 tanker to an at-sea Incineration
vessel have been obtained.  For a 150 meter  (500 ft) long ship  capable  of
loading 12,000 metric tons of toxic chemical waste, and equipped with six
Incinerators (five to be operated simultaneously and one as  standby) with  a
combined burn rate of 95 metric tons per hour, Global Marine estimated  that
the capital investment cost would be $10.4 million.  The M/T Vulcanus has  a
load capacity about one-third that of the Global Marine design, and the capital
Investment cost would probably be in the $4 million to $6 million  range.
                                     34

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3.2.2  Annual Operating Cost
     The annual operating costs  for at-sea  incineration  of  organochlorine
wastes consist of the costs of operating crew,  maintenance, fuel  for  the ship
and for waste incineration, overhead expenses,  and  taxes and insurance.  For
the incineration ship in the Global Marine  study, preliminary estimates have
Indicated that the net annual operating cost would  be $9,8  million.   The net
annual operating cost was computed with the following assumptions:
     •  2 weeks per year for ship maintenance and repair.
     •  A utilization factor of 75% for the remaining 50 weeks per
        year, I.e., the incineration ship would either be burning
        wastes, or 1n transit to pick up wastes or  to reach the
        burn zone, or in the process of waste loading for 6,300
        hours per year.
     0  Disposal of 350,000 metric tons of waste per year.   This
        1s equivalent to incinerator operating time of 3,684 hours
        per year.

      Details on the breakdown of the operating costs are not available from
Global Marine  at the present time.

3.2.3  Unit  Disposal Cost
      For disposal  of organochlorine wastes on board the M/T Vulcanus, Ocean
Combustion Services, B.V.  quoted a March 1978 price of  175 Dutch Gilders  per
metric ton of  waste. With  an exchange  rate of 1 Dutch Gilder » 0.4598 U.S.$,
the  unit disposal  cost  1s  U.S.$80.47 per metric ton of  waste.  For organo-
chlorine wastes with heating values below 11,720 kJ/kg  (5,040 Btu/lb), there
 Is an additional  fuel  surcharge.   To  bring  the  M/T Vulcanus  from Europe to
 the United  States, the minimum  quantity of waste requiring disposal  would be
 two shiploads, or approximately 8,200 metric tons.  A discount of 5  to 10%
 1s allowed  1f the quantity of waste to be  disposed 1s 1n excess  of two ship-
 loads.  The M/T Vulcanus is also available for charter  at  35,000 Dutch Gilders
 (U.S.$16,100) per day.

      The charter cost for the M/T Vulcanus was slightly lower in 1977.  For
 the disposal of 10,400 metric tons of Herbicide Orange, the U.S. A1r Force

                                       35

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paid a charter rate of $13,500 per day when not burning, and $15,000 per day
during incineration.  The total charter cost for the Herbicide Orange Inciner-
ation program was approximately $2.6 million, or $250 per metric ton of waste.
For this specific case, the unit disposal cost was considerably higher because
of the remoteness of the burn zone, special preparations required in the hand-
ling of the Herbicide Orange, and contingency planning.   The total  burn time
was 714 hours, or approximately 30 days (Reference 15).   Thus, the cost asso-
ciated with the actual burn was only $450,000.  More than 80 percent of the
total cost of disposal was due to demurrage charges for  travelling to Gulfport,
Mississippi, and then to Johnston Atoll in the Pacific Ocean and back to
Europe.  However, some savings was achieved because the  empty Vulcanus was  in
the Gulf area at the time and did not have to travel all the way from Europe.

     The Matthias III, owned by SBB Stahl-Und Blech-Bau  Ltd., is not in active
service.  As of March 1978, however, price quotes for the disposal  of liquid
organochlorlne wastes were available.  The disposal cost for liquid organo-
chlorine wastes on board the Matthias III was given as follows:

              Waste Volume                     Disposal  Cost (f.o.b.)
     <5,000 metric tons per year                 $75 per metric ton
     5,001 to 10,000 metric tons per year        $65 per metric ton
     10,001 to 40,000 metric tons per year       $50 per metric ton
     >40,000 metric tons per year                $45 per metric ton

These costs were comparable to the disposal costs charged by Ocean Combustion
Services, B.V.

     For the five typical  liquid organochlorine wastes selected for cost
analysis for land-based incineration, the unit disposal  costs by at-sea Incin-
eration are given In Table 13.  These unit disposal costs are based on prices
charged by Ocean Combustion Services, B.V., and a fuel surcharge of $2.16 per
GJ (equivalent to $13.00 per barrel) has been added to wastes with heating
values below 11,720 kJ/kg  (5,040 Btu/lb).
                                     36

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              TABLE 13.   UNIT  DISPOSAL  COST  FOR ORGANOCHLORINE
                         WASTES  BY AT-SEA  INCINERATION
       Waste Type                                      Unit Disposal Cost,
                                                       $/Metric Ton Waste

  CMW Waste                                                   80.47
  Perchloroethylene Waste                                     90.96
  Hexachlorocyclopentadlene Waste                             84.18
  VCM & Solvent Waste                                         84.73
  VCM Waste                                                   80.47
     The unit disposal  cost for organochlon'ne wastes  by  at-sea  Incineration
can also be calculated  using the preliminary  capital  Investment  cost  and  net
annual operating cost figures provided by Global  Marine.   Assuming  10 year
straight line depredation and an income tax  rate of  50%, the  unit  disposal
cost for organochlorlne wastes using the Global Marine Incineration ship  was
calculated to be $40.86 per metric ton, at 1555 DCFRR.   This  unit disposal cost
1s much lower than that for the M/T Vulcanus  because  of the  larger  loading
capacity of the ship, the higher burning rate of  the  shipboard incinerators,
and the assumption of a high utilization factor.   The quantity of waste to be
disposed per year on board the Global  Marine  incineration ship was  assumed to
be 350,000 metric tons, which represents 74 percent of the total  estimated
organochlorlne wastes produced in the United  States in 1978.   Other types of
liquid organic wastes as well as aqueous wastes contaminated with organics
could also be disposed  of by shipboard incineration.   The portion of  chemical
wastes that are potential candidates for at-sea incineration could  thus be
several times that of the liquid organochlorine wastes requiring disposal.

     Because of the preliminary nature of the Global  Marine  cost estimates,
the unit disposal costs based on prices charged by Ocean  Combustion Services,
B.V. will be used for cost comparison purposes.
                                      37

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3.3  ENVIRONMENTAL ASSESSMENT
     Analysis of environmental impacts for at-sea incineration activities were
based on the results of models used to estimate effects of plume constituents
on air and ocean water quality.  Details of the air quality simulations are
presented in Appendix B.

     Major input parameters for air quality simulation are effective stack
height (or plume rise), wind speed, and stability category.  Values for these
parameters selected for use in simulators are considered to be generally repre-
sentative of conditions likely to occur under real world circumstances.  In
general, simulations were based on information obtained in connection with the
incineration of  CMW  wastes on board the M/T Vulcanus in March 1977 (Reference
4).  Effective stack height calculations were based on data obtained during
this burn.  The wind speed and atmospheric stability category used were
selected after review of measured and statistical data for shore locations in
the general vicinity of a burn zone located off the Gulf Coast.  (Measured
wind speed data are not available for the proposed off-shore site, therefore,
data from the nearest shore-based meteorological stations were used instead.)

     Wind speed (i.e., speed of the diffusing layer) is an input parameter
which significantly influences predicted downwind pollutant concentrations.
Generally, increasing wind speed decreases downwind concentration.  When an
incinerator ship is moving, the relative wind speed, as measured at the stack,
may be greater than the speed of the diffusing layer.  However, relative
wind speed was not used as an input to the diffusion modeling performed here.
This is because the materials emitted will assume the average speed of the
diffusing layer shortly after they are discharged to the atmosphere.  One
result of this is that downwind concentrations near the source may be lower
(due to the additional mechanical turbulence from the ship velocity) than
estimated in this study.  Downwind concentrations will also tend to be de-
creased by the fact that a moving source distributes its emissions into a
larger volume of air per unit time (i.e., if the relative wind speed is
greater than that of the diffusing layer).
                                     38

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     The diffusion model  employed  assumed  that  the  chemical  species  emitted
remain airborne and are not removed  from the  atmosphere  by either chemical or
physical processes.  There are a variety of technical  arguments against this
assumption.  For example, particulate matter  will be  removed by gravity, and
there will  undoubtedly be acid-base  interactions  between airborne droplets of
ocean water and HC1.  However, the data required  to take pollutant-marine
boundry layer interactions into account is unavailable.

     Wastes processed during the M/T Vulcanus burn  were  produced from  the
manufacture of ally! chloride, epichlorohydrin, dichloroethane and  vinyl
chloride (the CMW waste).  Composition of  the waste is given in Table  14.
Elemental analysis of a typical organochlorine  waste  is  shown in Table 15.

     Emission rates used for the at-sea incineration  are shown in Tables  16
and 17.  These estimates were made assuming feed  rate and emissions  character-
istics of the M/T Vulcanus furnaces.  Emissions data  for particulates  were not
obtained during the March 1977 burn.  However,  data were available  describing
waste composition and emissions of various inorganic  constituents.   These
data were converted to mass emission rates and  summed in order to derive  an
estimate of expected particulate emissions.  The "summed inorganics" column
of Table 17 presents the results of  this  derivation.   It should  be  noted  that
these results compare favorably with the  analysis data indicating a loss  on
ignition value of 99.8% for the CMW  waste  (Reference  4).

     Estimation of the effects of at-sea  incineration on ocean water quality
were generally obtained by using a diffusion model  to identify the  ocean  area
affected by the incinerator's plume  and  determination of the water  concen-
trations of plume constituents.  The concentrations were determined by assuming
that all of the material in the plume dissolved in  a  prescribed  depth  of  the
affected water area.

     Selected air quality simulation and  water quality effects  for  at-sea
incineration activities are presented in  Table 18.   Air quality  data represent
maximum sea level concentrations.   Complete air quality simulation  results
                                      39

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      TABLE 14.  ANALYSIS OF ORGANOCHLORINE WASTE BURNED AT-SEA
                            (The CMW Waste)
•  Physical
   Characteristics:
Loss on Ignition, %                99.8
Gross Thermal Content, Btu/lb       6,950
Specific Gravity                    1.28
0  Elemental
   Analysis:
Element

Carbon
Hydrogen
Nitrogen
Sulfur
Halogens as chlorine
  Composition, %

      30.01
       4.17
       0.012
       0.009
      62.60
•  Other
   Constituents
Element
Concentration, ppm
t  Organic
   Composition:
Si                                  >500
P                                 50 - 500
Ti                                50 - 500
Ca                                  >25
Br                                  Trace

                                 Est. Cone.
Compound                          (% w/W)

1,2,3-Trichloropropane              18
Dichloropropenes (3)                11
Dichloropropane                     18
Trichloroethane                     12
1,2-Dichloroethane                  10
1,1-Dichloroethane                   0.9
Dichloropropanol                     6.2
Chloropropene (Ally! Chloride)       5.7
Chloropropanes (2)                   5.8
Chloroethane                         0.6
Trichloromethane (Chloroform)        0.5
Tetrachlorobutenes (2)               2.4
Acrolein (Propenal)                  0.2
Chlorobenzene                        3.3
Bis(2-Chloroethylether)              1.9
Unidentified Chloro- and
  Oxychloro-Compounds                3
Water                                0.5
Source:  Reference 4
                                 40

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              TABLE 15.  ELEMENTAL ANALYSIS OF CMW WASTE.



Carbon
Hydrogen
Oxygen
Chlorine

Copper
Chromium
Nickel
Zinc
Lead
Cadmi urn
Arsenic
Mercury
BURN 1
% by weight
29
4
4
63
(Parts per million)
0.51
0.33
0.25
0.14
0.05
0.0014
<0.01
<0.001
BURN II

29.3
4.1
3.7
63.5

1.1
0.1
0.3
0.3
0.06
0.001
<0.01
<0.002
       Source:  Reference 16.
          TABLE 16.   EMISSION  RATES  USED  FOR AT-SEA AIR  QUALITY
                     SIMULATION:   HC1  AND UNBURNED WASTES
  Average Waste
    Feed Rate
  Destruction
Efficiencies, %
     Emissions Rate, gm/hr
   HCT
Unburned Wastes
22 metric tons/hr
 (22X106 gm/hr)
     99.99
(max. observed)

     99.96
(min. observed)
14.16X10
                                             14.16X10'
                                                     6
    2.2X10W
                  8.8X10V
Notes:  1)  Data are for both furnaces of the M/T Vulcanus.

        2)  HC1 emission rate assumes a 62.6% chlorine content 3
            1n the waste, and a volumetric flow rate of 8700 Nm /hr
            of HC1 1s discharged from both stacks.
                                   41

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              TABLE 17.   EMISSION RATES  USED FOR AT-SEA  AIR
                         QUALITY SIMULATION:  INORGANICS
                         (All  units in kg/hr)
Summed Inorganics       	Specific  Elemental  Constituents
  Low      High         CuTZn      AsTCoPb/TI       N1Cr


  53        72           0.7        0.1         0.4        2        4
Notes:  1)  Data are for both furnaces of the M/T Vulcanus.
        2)  Data on the concentration ranges of inorganics  in  the
            wastes and in stack emissions were collected and converted
            to mass emission rates.   These rates were  summed for all
            Inorganics, and are considered to represent estimates  of
            expected particulate emissions for the at-sea incineration
            of CMW wastes.
        3)  When two elements are listed, the noted emission rates are
            for each constituent.
        TABLE 18.  SUMMARY OF MAJOR AIR AND WATER QUALITY EFFECTS
                   ASSOCIATION WITH AT-SEA INCINERATION

            Air Quality (ug/m3)|a|Water Quality (ppb)

 HC1   Inorganics^5'   Unburned'0'   Copper^ '      HC1    Unburned   Copper
                         Wastes                           Wastes


4422       22.49          2.75         0.22        197      0.09      .04
(a)  Maxima for stipulated meteorological conditions:  effective stack
     height = 125.5 meters, wind speed = 4.0 meters/second, surface
     reflectivity = 1.0 and stability category = D.
(b)  Based on summation of inorganic constituents in wastes; provides
     an estimate of particulate concentrations.
(c)  Based on lowest observed destruction efficiency (99.96%).
(d)  Copper is the metallic waste constituent with the highest  emission
     rate.  Zinc's emission rate was equivalent to that of copper.
                                    42

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which give predicted concentrations  at various  distances  downwind  from  the
source are presented 1n Appendix B.

     The HC1 concentrations in the plume are expected to  be high because  there
1s no scrubbing of the combustion gases.  Due to Its  buffering  capacity,  one
cubic meter of ocean water is capable of neutralizing 80  gm of  HC1  (80,000  ppb)
(Reference 17).  Thus, a 197 ppb contribution of HC1  from plume touchdown
would never be detected by a pH change.

     During a 1974.burn of CMW waste onboard the M/T  Vulcanus,  water samples
were obtained in the vicinity of plume touchdown (Reference 16).   Analysis  of
these samples showed no significant difference in pH  and  copper (the most
abundant heavy metal constituent of the waste) as compared with samples from
control areas.  Organochlorine wastes were undetected at  the 0.5  ppb level.

     A Threshold Limit Value  (TLV) of 7 mg/m3 has been established for HC1.
This level  represents the maximum allowable HC1 concentration for humans 1n a
work area.  Excursions beyond this level for periods  greater than 15 minutes
result 1n either intolerable  irritation, or chronic or Irreversible tissue
damage (Reference  11).  The maximum sea level HC1 concentration of 4.4 mg/m
predicted as a result of at-sea  Incineration is below this TLV.  It 1s also
noticed that sea level plume  impact is  for short durations and at different
points in the water.

     The predicted maximum ambient unburned waste concentration is an order of
magnitude larger than the  corresponding ground  level  parameters for the  land-
based facility.  More detailed  Information Is required to  determine the  extent
to which this  emission 1s  combined with partlculate matter that may be a
component of the combustion  gases, or whether 1t 1s  in the gaseous state.
 If associated  with gravity settleable particulates,  the  Impact of the  un-
 burned waste will  be felt  mostly In  the water  environments.  If the emission
 1s gaseous  and the plume stays aloft  for  extended periods, then the Impact of
 the unburned wastes will  be felt In  downwind areas.   Information  on the  size
                                      43

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distribution of the particulate matter emitted is  required to  answer  questions
about whether this material  will be removed directly by gravity,  or whether
it will remain suspended and possibly serve as condensation nuclei.   Under
the latter set of conditions particulate matter (which could contain  unburned
wastes and heavy metals) could have adverse effects  whenever washout  does
occur.

     Biological specimens (phytoplankton and zooplankton)  were also taken
during the 1974 burn (Reference 16).  Examination  of chlorophyll-a  (an  indica-
tor of phytoplankton activity) levels, and adenosine triphosphate (ATP)  levels
in the specimen showed no deleterious or subtle adverse Impacts.

     A series of biological  tests were also associated with the March 1977
burn.  Laboratory experiments with various concentrations  of CMW waste  culmi-
nated with the following results (Reference 19):
     t  Seven of 14 fish (fundulus Grandis) exposed  to 74  ppm  of CMW  waste
        died within 41 hours.  Death was apparently  due to respiratory  com-
        plications.
     •  At a concentration of 7.4 ppm, no effect on  fish mortality was  noted.
     t  Enzyme systems (catalase and P-450) of fish  exposed to 1.0 ppm  showed
        a marked response.
The P-450 enzymes are located in the liver and are required for the metabolism
of foreign chemicals introduced into an organism.   The response noted (an
increase in the P-450 activity) reflects the presence of a foreign material
that has to be metabolically altered prior to excretion.   This effect is seen
as an indication of a potential problem.

     In addition to the laboratory tests, the same fish species was exposed  to
the plume of the M/T Vulcanus during incineration.  Exposure was accomplished
by using a device called a biota! ocean monitor (BOM), which allows specific
organisms to be exposed under field conditions and then retrieved.  The BOM
tests showed an elevation in the activity of P-450 enzymes. However, when
exposed fish were left in clean water for a few days, the  enzyme activity  re-
verted to those of control organisms.

                                     44

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     It was concluded that the overall  effects  were  localized and temporary,
and do not represent drawbacks to the use  of at-sea  Incineration for organo-
chlorine waste disposal  (Reference 19).

     Metals are present In liquid organochlorlne wastes;  they will  appear  1n
the stack gases (and thus the plume)  as partlculate  matter.  The quantity  of
metal salts or metal oxides 1n the plume is  Independent of combustion  efficiency
and 1s directly proportional  to the metal  content of the  waste  Itself.   Control
of the metal content of the waste, which 1s  accepted for  at-sea incineration
where the effluent gases are not scrubbed, becomes the responsibility  of
regulatory agencies to ensure that wastes  with  unacceptably high metal  content
are not approved for burning at sea.   Control must be implemented  by restric-
tions based on the air and water quality requirements. Metal  content  permitted
in waste thus becomes a function of the plume model  and of the  at-sea  inciner-
ation, e.g., dilution In the plume, feed rate of waste, total  combustion air
and the speed of the incineration ship.

Malfunction  Potential
      A  listing  of some possible operational malfunctions during an at-sea
 Incineration  operation 1s shown 1n Table  19.   The greatest possibility of
 spills  1s  during  loading.  Hatches are open, samples are being taken, and
 exposed flex  lines are under pressure.  An additional source of contamination
 1s  the  bllgewater from the pump room.  Historically this material contains
 some of the pumped cargo.  Bilges must not be pumped into channels, at dock-
 side or at sea.   This would be a procedural violation.  Provision must be
 made to dispose of the bilge, possibly through the Incinerator, where 1t can
 be  burned  with  fuel.

      If flameout  occurs  as the result of  a slug of non-combustable material
 (e.g.,  water) entering the waste feed lines and passing through one or more
 burners, subsequent Incoming waste will be vaporized.  Vaporization will
 occur due  to  the  latent  heat 1n the  Incineration.  This vapor will be emitted
 directly to the atmosphere.  To prevent this failure mode, a positive and
                                      45

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                TABLE 19.  POTENTIAL OPERATIONAL MALFUNCTIONS
                           DURING AN AT-SEA INCINERATION OPERATION
  Operation
   Possible Malfunction
    Consequence
Tank Filling
Waste Transfer
 through Pump
 and Filter
Waste Injection
 to Incinerator
Incineration
1.  Overfill  on level
    interlock failure

2.  Leakage due to pump seal,
    valve packing material
    corrosion, etc.
3.  Inclusion of unauthorized
    waste by subversion of
    quality control  procedures

1.  Leakage due to pump seal,
    material corrosion, etc.

2.  Deliberate bypassing of
    Incinerator (ocean
    operations)
3.  Filter plugging
1. Nozzle plugging (low
    flow detection)

2. Atomization air loss on
    air blower failure
   Burner flame loss (flame-
    out) due to fuel loss of
    pressure, loss of
    primary combustion, air,
    coking, or water slug In
    feed
                    2. Improper fuel  rate


                    3. Improper air/fuel  ratio

                    4. Injection into a cool
                        combustion zone on
                        start-up
Waste spill

Small waste spill
                                                     Possible incineration
                                                      difficulties
Small waste spill


Waste spill
None if filters switched
 on high pump discharge
 pressure measurement

Temporary shut-down

Failure to combust, toxic
 vapor discharge, liquid
 accumulation

Transient toxic vapor dis-
 charge prior to automatic
 shutdown on flame loss
 detection (or lower combus-
 tion temperature. A water
 layer in the tank can be
 isolated by conductivity
 measurement interlock to
 the waste feed pump)
Excess waste product in
 discharge

Inefficient combustion
Inefficient combustion
                                      46

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rapid waste feed shutoff system must  be  available.   Such a  system or device
should rely on direct sensing of the  burner flames  (ultra-violet or Infrared
detectors) rather than secondary measurements which may have an Inherent lag
before response to a flameout.

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                               4.   CHLOROLYSIS
4.1  GENERAL DESCRIPTION
     Chlorolysis, or chlorinolysls, 1s a process for converting organochlorlne
wastes to perch! oroethylene, trfchloroethylene and carbon tetrachlorlde as
useful products.  In the chlorolysls process, excess chlorine 1s added  at
temperatures In the 400° to 600°C range, so that the carbon-carbon bonds of
hydrocarbons can be broken and the molecular fragments  can react with chlorine
to form chlorinated hydrocarbons of shorter chain length (Reference 20).
Typical reactions In the chlorolysls process are:
C2H3C13
C4H6C12
c4ci6
+ 4C12
+ ioci2
+ 5C12
-»• 2CC14 H
H- 4CC14 H
H- 4CC14
H 3HC1
i- 6HC1

     According to Shiver (Reference 21), the U.S.  patent literature Indicates
that Dow Chemical, Diamond Shamrock, and Pittsburgh Plate Glass have developed
chlorolysis processes suitable for the conversion  of C-j  through C., hydro-
carbons to chlorinated solvents.  In addition, Farberwerke Hoechst AG, the
German affiliate of Hoechst-Uhde Corporation of New Jersey, has patented a
chlorolysls process to manufacture carbon tetrachlorlde from organochlorlne
wastes.

     The operating characteristics of the four chlorolysis processes are
summarized in Table 20.   Of these four chlorolysis processes, the Hoechst-
Uhde process 1s the only one that has some capability of handling aromatic
hydrocarbon feedstocks.  This is because when chlorolyzing benzene and alkyl
benzenes, hexachlorobenzene is formed as an intermediate which is reacted only
above 500°C (Reference 20), and the lower reactor operating temperatures of the
Diamond Alkali and Pittsburgh Plate Glass chlorolysls processes do not appear
                                     48

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      Process
     Developer
     Dow
     Chemical
     Diamond
     Alkali
vo
     Pittsburgh
     Plate
     Glass
     Hoechst
     Uhde
                         TABLE 20.  OPERATING CHARACTERISTICS OF CHLOROLYSIS PROCESSES
   Feedstock
C], C2, Cs hydro-
carbon products &
their partially chlo-
rinated derivatives.

Ethylene dlchloride.
Ethylene dichloride
and other C2
chlorohydrocarbons.
 CT  to  Ce organo-
 chlorine compounds.
Operating
Conditions
                                                            Product Yield
                                            600°C
400°C,
using
Fuller's
earth as
catalyst in
fluid bed
400°C, oxy-
chlorinatlon
in a fluid
bed catalytic
reactor
94-95% of perchloro-
ethylene and carbon
tetrachloride, 6% of
hexachlorobenzene.

90% yield of perchlo-
roethylene and
trichloroethylene; the
balance estimated to be
hexachl oroethane,
hexachlorobutadiene,
hexachlorobenzene,
tetrachl oroethane ,
pentachl oroethane .

85% yield of trichloro-
ethylene and perchloro-
ethylene; the balance
probably carbon oxides,
and chl orohydrocarbons
such as hexachloro-
butadiene and
hexachl orobenzene .
 600°C and
 20 MPa
     yield of carbon
tetrachloride per pass.
Heavy ends consist
chiefly of hexachloro-
benzene .
                                                                        Comments
                                          Hexachlorobenzene is one
                                          of the hard to treat
                                          wastes.
The tetrachloroethane &
pentachloroethane can be
recycled and pyrolized
to trichloroethylene.
The hexachlorobutadiene
& hexachlorobenzene are
expected to be residues
from this process.
Relatively low yield to
useful products.  The
hexachlorobutadiene and
hexachlorobenzene formed
are expected to be
residues from this
process.


Very high overall yield
to carbon tetrachloride
1f the presence of oxy-
genated chlorohydrocarbons
in the feedstocks is
limited.  The hexachloro-
benzene formed can be
recycled to extinction.
         The information source for the Dow Chemical,  Diamond  Alkali  and  Pittsburgh  Plate  Glass  processes
         Is  Reference 21. Information on the Hoechst-Uhde  process was obtained  from  Reference  3.

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to be adequate to convert the hexachlorobenzene to useful  products.   Also,
with the exception of chlorinated alkanes, chlorolysls  of chlorinated hydro-
carbons 1s favored at higher reactor pressures.  Chlorolysls  of chlorinated
aromatic hydrocarbons 1n the Hoechst-Uhde reactor, at 20 MPa, 1s therefore
more thermodynamlcally favorable.  For the same reasons, the  Hoechst-Uhde
process 1s the only chlorolysls process that does not produce organochlorlne
residues in sizable quantities, as all wastes Initially produced can  be
recycled to extinction.

     The Hoechst-Uhde process is the chlorolysis process considered  in the
present study.  A demonstration plant producing 8,000 metric  tons per year of
carbon tetrachlorlde has been in operation in Frankfurt, Germany since Novem-
ber 1970.  More recently, a commercial plant producing 50,000 metric  tons per
year of carbon tetrachloride has been on stream at the same site since 1977,
and two chlorolysls plants have been sold to the Soviet Union.  A detailed
description of the Hoechst-Uhde chlorolysls process is provided 1n Section  4.3.

     Theoretically, most organochlorine wastes could be used  as feedstocks
for the Hoechst-Uhde chlorolysls process.  Suitable feedstocks include those
residues from the production of vinyl chloride monomer, chloromethanes,
propylene oxide, ally! chloride, perchloroethylene, as well as residues from
benzene chlorination.  The presence of other elements besides carbon, hydro-
gen, and chlorine, however, could lead to problems in regard  to product
handling and corrosion.  Particulate matter, for example, poses a significant
mechanical problem in the operation and maintenance of control equipment.
The presence of small amounts of sulfur is extremely corrosive to any nickel-
containing material.  With this 1n mind, the sulfur content of the feedstock
must be kept below 25 ppm.  This is achievable in practice by dilution of the
sulfur feedstock with other feedstock which can be processed  in a given
amount of time.

     The effects of nitrogen and/or phosphorus in combination in the  feedstock
are unknown at this time.  To guard against the possible formation of nitrogen
trichloride (NC13) and phosphorus trichloride  (PClg), chlorolysis feedstocks
are analysed to assure that no nitrogen and/or phosphorus are present.  Neither

                                      50

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compound 1s desirable as nitrogen trichloride 1s  explosive  and  phosphorus
trichloride is pyrophoric.   The emissions which might be generated  include
N02. and P20g dependent upon combustion conditions.

     In summary,  acceptable feedstocks  for chlorolysis  should be  free of
particulates.  The sulfur content should not  exceed  25  ppm.  The  feed stream
should not contain nitrogen or phosphorus. To Hm1t the reaction temperature
to the maximum reactor design temperature of  620°C,  an  additional restriction
of a maximum of 5 percent aromatic hydrocarbons,  calculated  as  benzene, was
placed on the Hoechst-Uhde design.  In  an industry survey,  Shiver has shown
that available organochlorine wastes suitable as  chlorolysis feedstocks Include
23,000 to 27,000 metric tons per year of vinyl chloride monomer residue and
19,500 metric tons per year of chlorinated solvent waste (Reference 21).
Geographically, these wastes are generated primarily at Gulf Coast  locations
from Corpus Christi, Texas to New Orleans, Louisiana (Reference 3).  The
concentration of these wastes along the Gulf  Coast indicates that a Houston,
Texas location would be suitable for the cost analysis  and  environmental
assessment of the Hoechst-Uhde chlorolysis process.

4.2  COST ANALYSIS
     The cost analysis performed was based on estimates provided in the
Hoechst-Uhde report (Reference 3).  The two wastes for which cost data  are
available include a mixed vinyl chloride monomer (VCM) and  chlorinated  solvent
waste and a vinyl chloride monomer (VCM) waste.   The first  waste, considered
by Hoechst-Uhde as the base case, contains 60 percent by weight of VCM  residues,
and 40 percent by weight of chlorinated solvent  wastes.  According  to the
experience of Hoechst AG with various organochlorine wastes, 40 percent  is
the maximum quantity of solvent wastes  which can be  mixed with VCM residues.
The reason for the limitation is material problems caused by the requirement
that feed chlorine would have to be heated up to a temperature in excess  of
250°C.  The second waste, produced during the manufacture of vinyl  chloride
monomer, consists of 33 percent by weight of  light ends and 67 percent  by
weight of heavy ends distillate.  Selected properties of these two organo-
chlorine wastes have been previously given in Table  3.

                                     51

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     The discussion on cost analysis is divided into capital  investment cost,
annual operating costs, and unit disposal  costs.

4.2.1  Capital Investment
     The capital investment cost for a chlorolysis  plant processing  25,000
metric tons per year of organochlorine waste,  as  estimated  in the  Hoechst-Uhde
study, was $25,496,900 for the first half of 1977 (Reference  3).   Adjusted  to
March 1978 basis using the Chemical  Engineering Plant Cost  Index,  the  total
capital investment cost was estimated to be $27,210,000.

     The capital investment cost estimated by Hoechst-Uhde  was based on a
new plant location with a clear and level  site 1n the Gulf  Coast area.  It
was also assumed that foundations can be installed with conventional spread
footings and that a pumping station would not be required to  provide cooling
water to the plant.  Land costs and all startup costs were  also excluded.

4.2.2  Annual Operating Costs
     The annual operating costs for the chlorolysis of organochlorine  wastes
consist of the costs of chemicals, utilities, operating labor, maintenance,
overhead expenses, taxes and insurance, and process royalty.   The  raw  material
and operating requirements for the chlorolysis of the mixed VCM and  solvent
waste and the VCM waste were obtained directly from the Hoechst-Uhde study
(Reference 3).  The net annual operating costs for the mixed  VCM and solvent
waste and the VCM waste, as presented in Tables 21 and 22,  are $16,011,800
and $19,881,800, respectively.

     The difference in the net annual operating costs for the chlorolysis of
the two organochlorine wastes is due to the difference 1n the process  chlorine
requirement.  For the mixed VCM and solvent waste, 68,000 metric tons  per
year of chlorine are needed to convert 25,000 metric tons per year of  waste
to 75,000 metric tons per year of carbon tetrachloride and  17,850  metric  tons
per year of hydrogen chloride.  For the VCM waste, 93,800 metric  tons  per
year of chlorine are needed to convert 25,000 metric tons per year of  waste
                                      52

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               TABLE 21 .  ANNUAL OPERATING COST FOR PROCESSING 25,000 METRIC TONS/YEAR OF A
                         MIXED VINYL CHLORIDE MONOMER AND SOLVENT WASTE AT A CHLOROLYSIS PLANT
                       Item
                                                                                    Cost,  $/Year
en
        Chemicals
     Chlorine:  68,000 metric tons @ $150/metric ton
     20% Caustic:  14,500 metric tons @ $30/metric ton
     Methane:  134,500,000 ft3 
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         TABLE 22.  ANNUAL OPERATING COST FOR PROCESSING 25,000 METRIC TONS/YEAR
                    OF VINYL CHLORIDE MONOMER WASTE AT A CHLOROLYSIS PLANT

                 Item                                                               Cost, $/Year

Chemicals

     Chlorine:  93,800 metric tons @ $150/metric ton                                $  14,070,000
     20% Caustic:  14,500 metric tons 6 $30/metric ton                                  435,000
     Methane:  134,500,000 ft3 0 $2/1000 ft3                                            269,000
Utilities

     Electric power:  25,600,000 Kw-hr @ $0.015/Kw-hr                                   384,000
     Steam:  52,000 metric tons @ $4/metric ton                                         208,000
     Cooling water:  3.9 x 109 gallons @ $0.01/1000 gallons                              39,000
Operating Labor

     Operator, 10 men/shift, $8.65/manhour                                              755,700
     Direct supervision, 4 men, $12.12/manhour                                          100,800
Maintenance

     Maintenance labor, 2% of Total  Plant Cost                                          544,200
     Maintenance supply, 2% of Total  Plant Cost                                         544,200
Direct Overhead

     (30% of Operating Labor and Supervision)                                           257,000
General Plant Overhead

     (50% of Operating and Maintenance Labor and 3% of Total  Plant  Cost)                1,516,700
Taxes and Insurance

     (1.5% of Total Plant Cost)                                                         408,200

Royalty                                                                                 350,000
Net Annual  Operating Cost                                                           $ 19,881,800

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to 88,500 metric tons  per year of carbon  tetrachlorlde and  30,000 metric tons
per year of hydrogen chloride.

     At a carbon tetrachlorlde selling  price  of  $300  per metric ton, and a
hydrogen chloride selling price of $50  per metric  ton, the  annual revenue
derived from the sale  of these two products would  be  $23,392,500 from the
chlorolysls of the mixed VCM and solvent  waste,  and $28,050,000 from the
chlorolysls of the VCM waste.  Thus,  the  cost associated with the higher
process chlorine requirement could be more than  offset by higher product
credits.

4.2.3  Unit Disposal Cost
     As discussed in the cost analysis  for land-based incineration,  the method
used for estimating the unit disposal cost of organochlorine wastes  is based
on the discounted cash flow technique.   Calculation of discounted cash flow
for the chlorolysls of the mixed VCM and solvent waste is  illustrated  in Table
23.  The calculation procedure follows  that  described by Uhl (Reference 7),
and the assumptions used are discussed  in detail in Appendix A.   It  showed
that at 15% DCFRR, an annual cash flow of $7,023,300  must be generated to
offset the expenditures In capital investment, working capital  and  startup
cost.  With a net annual operating cost of $16,011,800,  and assuming 10 year
straight line depreciation and an income tax rate  of 50%, the annual  revenue
that must be generated was calculated to be  $27,337,400.  As the  annual  revenue
obtained from the sale of carbon tetrachlorlde and hydrochloric acid was  cal-
culated to be $23,392,500, the additional revenue to be  derived from waste
disposal charges would be $3,944,900.  Unit  disposal  cost 1s, therefore,  $157.79
per metric ton.

     The calculation of discounted cash flow for the  chlorolysis  of the VCM
waste is shown 1n Table 24.   At 15% DCFRR,  the annual cash flow  and the
annual revenue that must be generated were calculated to be $7,114,500 and
$31,389,800, respectively.  For the VCM waste, the annual  revenue obtained  from
the sale of carbon tetrachlorlde and hydrochloric  acid was  calculated to  be
                                      55

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en
                               TABLE 23.  CALCULATION OF DISCOUNTED CASH FLOW FOR CHLOROLYSIS
                                          OF MIXED VINYL CHLORIDE MONOMER AND SOLVENT WASTE
                                          AT 15X DISCOUNTED CASH FLOW RATE OF RETURN
Time,
Year
-2 to 0
0
1
0 to 2
0 to 10
10
Item Investment Cash Flow
Depreciable Investment $ 27,210,000
Working Capital $ 4,100,607
Interest on 30% of Total n ,* /* i 090 R-IA\
Plant Cost at 10% Rate ' °'b ($'.823,614)
Startup Cost - 0.5* ($ 1,360,500)
Cash Flow 10 ($ 7,023,290)
Recover Working Capital - $ 4,100,607
Discounting
Factor
1.1662
1.0
0.9048
0.9286
0.5179
0.2231
Discounted
Cash Flow
- $
- $
- $
- $
$
$

31,732,194
4,100,607
825,037
631 ,689
36,374,558
914,969
0
       *
          The actual cash flow for these two items are reduced by 50% due to the effect on cash flow of income tax.

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tn
                                      TABLE 24.  CALCULATION OF DISCOUNTED CASH FLOW FOR
                                                 CHLOROLYSIS OF VINYL CHLORIDE MONOMER WASTE
                                                 AT 15% DISCOUNTED CASH FLOW RATE OF RETURN
Time,
Year
-2 to 0
0
1
0 to 2
0 to 10
10

Item Investment Cash Flow
Depreciable Investment $ 27,210,000
Working Capital $ 4,708,303
Interest on 30% of Total n •»* fi 1 ft?1? 6141
Plant Cost at 10% Rate °'5 I*1'823'614'
Startup Cost - 0.5* ($ 1,360,500)
Cash Flow 10 ($ 7,114,446)
Recover Working Capital - $ 4,708,303

Discounting
Factor
1.1662
1.0
0.9048
0.9286
0.5179
0.2231

Discounted
Cash Flow
- $
- $
- $
- $
$
$

31,732,194
4,708,303
825,037
631 ,689
36,846,659
1,050,564
0
       *  The actual cash flow for these two Hems are reduced by 50% due to the effect on cash flow of Income tax.

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$28,050,000.  Thus, the additional  revenue to be derived  from  waste  disposal
charges would be $3,339,800.   The unit disposal  cost  for  the VCM waste  1s,
therefore, $133.59 per metric ton.

     Unit disposal costs for  organochlorlne wastes  can  also be more  readily
calculated using the unit disposal  cost equation described 1n  Appendix  A.
In Table 25,  the different cost elements that contribute to the unit dis-
posal costs for the mixed VCM and solvent waste and the VCM waste  at a
chlorolysis plant are presented.  It is seen that the unit disposal  cost  1s
very dependent on the carbon  tetrachlorlde sales credit.

     The  CMW  waste, the perch!oroethylene waste,  and  the hexachlorocyclo-
pentadiene waste considered in the cost analysis of land-based and at-sea
incineration are not, strictly speaking, suitable feedstocks for the chloro-
lysis process.  The sulfur contents for the  CMW waste and the hexachloro-
cyclopentadlene waste are 90  ppm and 200 ppm, respectively, both exceeding
the 25 ppm sulfur limit.  The perchloroethylene waste contains 9.2 percent  by
weight of chlorinated benzene, exceeding the 5 percent  by weight limit  for
aromatics.  However, all three wastes can be blended with VCM  wastes to meet
the chlorolysis feedstock acceptability criteria.  For  comparison  purposes,
the unit disposal costs for these three organochlorine  wastes  at 15£ DCFRR
were estimated to be $196 per metric ton for the CMW  waste,  $136 per  metric
ton for the perchloroethylene waste, and $196 per metric  ton  for the
hexachlorocyclopentadiene waste.  For the  CMW  waste and the  hexachloro-
cyclopentadiene waste, the presence of oxygen leads to  formation of  carbonyl
chloride and a lower yield of carbon tetrachlorlde.  The  carbonyl  chloride
obtained 1s assumed to be sent to the incineration  unit for disposal and  not
recovered as a product.  The  higher unit disposal cost  for  these two wastes
Is the direct result of the lower carbon tetrachlorlde  yield.

     The pronounced effect of carbon tetrachlorlde  selling  price on  the unit
disposal costs for the mixed  VCM and solvent waste  and  the  VCM waste 1s
Illustrated In Figure 2.  At  15% DCFRR, it is seen  that the unit disposal
cost would Increase to $248 per metric ton for the  mixed  VCM  and solvent  waste
                                     58

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                            TABLE 25.  UNIT DISPOSAL COST FOR ORGANOCHLORINE
                                       WASTES AT A CHLOROLYSIS PLANT
01
Item
Operating Cost
Chlorine
Caustic
Methane
Electric power
Steam
Cooling Water
Operating Labor
Maintenance
Overhead expense
Taxes and Insurance
Royalty
Subtotal
Capital Investment Related Items
Working Capital
Startup Cost
Sales of Carbon Tetrachloride
Sales of Hydrochloric Add
$/Metric
VCM and
Solvent Waste

408.00
17.40
10.76
15.36
8.32
1.56
34.26
43.53
70.95
16.33
14.00
640.47
394.06
49.21
9.76
- 900.00
- 35.71
Ton Waste
VCM Waste

562.80
17.40
10.76
15.36
8.32
1.56
34.26
43.53
70.95
16.33
14.00
795.27
394.06
56.50
9.76
- 1,062.00
60.00
        Unit Disposal  Cost
157.79
                                                                                             133.59

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500
              280        290         300         310        320

            SELLING PRICE FOR CARBON TETRACHLORIDE, $/METRIC TON
330
        Figure 2.  Effect of carbon tetrachlorlde  selling price and
                  discounted cash flow rate of return (DCFRR) on unit
                  disposal  cost of crganochloHne wastes by chlorolysls,
                                    60

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and $240 per metric ton for the VCM waste,  if the  selling  price  for carbon
tetrachloride falls to $270 per metric ton.   On  the  other  hand,  the unit dis-
posal cost would decrease to $68 per metric ton  for  the  VCM and  solvent waste
and $27 per metric ton for the VCM waste, if the selling price for carbon
tetrachloride rises to $330 per metric ton.  Thus, the unit disposal  cost  for
organochlorine wastes by chlorolysis is extremely sensitive to the selling
price for carbon tetrachloride.

     The effect of discounted cash flow rate of return on the unit disposal
cost of organochlorine wastes by chlorolysis is also illustrated in  Figure 2.
At 12% DCFRR, the unit disposal cost would be approximately $84  per  metric ton
lower than at 152 DCFRR.  At 18% DCFRR, the unit disposal cost would be
approximately $93 per metric ton higher than at 1595 DCFRR.

     The results of cost analysis  have indicated that the economic viability
of the chlorolysis process  is totally dependent on the selling price for carbon
tetrachloride.  As discussed in the  Hoechst-Uhde report (Reference 3), the
total volume of carbon tetrachloride produced 1s estimated to be about 400,000
metric tons per year.  About 80% of  the carbon tetrachloride produced is used
in the manufacture of Freon-11  and 12  for refrigeration and propel1 ant usage.
The  use of  fluorocarbon  aerosol propellents,  however, has  already been reduced
by 50% due  to the  current  concern  about  the  depletion of  the ozone layer
attributed  to the  C^  fluorocarbons.   In  the  Hoechst-Uhde  analysis, the produc-
tion level  for  carbon tetrachloride  Is expected to  be stabilized  at  about
310,000 metric  tons  per  year,  partly by  adjustments  in  the product mix of
plants  that coproduce carbon  tetrachloride with  either  perchloroethylene or
methylene  chloride and chloroform.  For  a  chlorolysis plant processing 25,000
metric  tons of  organochlorine wastes per year,  the  volume of carbon  tetra-
chloride  produced  would  be 75,000 to 100,000 metric tons  per year, depending
on the  carbon content of the  feedstock.  This volume of carbon  tetrachloride
represents  24 to  33% of  the projected stabilized  market,  a level  which cannot
be readily absorbed without causing major  pertubations  1n the pricing  structure.
                                       61

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 4.3   ENVIRONMENTAL ASSESSMENT
 4.3.1   Emissions Characterization for Chlorolysls
      The  chlorolysis plant, as designed by Hoechst-Uhde Corp., consists of a
 pretreatment  section for the treatment of all wastes entering the unit; a
 reactor section where the treated residues are converted into hydrogen chlor-
 ide  (HC1) and carbon tetrachloride (CCl^), a distillation section for the
 separation of reaction products, and an incineration section for the disposal
 of remaining  residues.  An absorption unit is used for the elimination of all
 waste gases containing chlorine gas (C^) and HC1 for normal and emergency
 shut-down situations.  A simplified flow diagram is shown in Figure 3.

      The wastes used in this process are characterized by their production
 processes.  The vinyl chloride wastes are unique in that they contain hydro-
 gen whereas the solvent wastes do not.  This occurs because of the higher
 degree  of chlorination and higher temperature required to make chlorinated
 solvents.  Typical analyses of the waste fractions are shown in Table 26.

      The components in these wastes range from C-j through Cg organochlorine
 compounds.  They are all suitable feeds for the chlorolysis process.  A normal
 feed  rate for a chlorolysis unit is a mixture of 60 percent by weight vinyl
 chloride waste and 40 percent by weight solvent wastes.   The description 1s
 based upon a  25,000 metric tons per year process.  Emission estimates for the
 chlorolysis process were obtained from the Hoechst-Uhde  report (Reference 3).

 Pretreatment Section (See Figure 4)
     The pretreatment for light ends  consists of adsorbers  with a regeneration
 system.  The wet light ends are passed through the adsorption unit with the
 dried organics flowing into a holding tank.   The regeneration system, consist-
 ing of a scrubber and a separator,  renews one adsorber while the other is
 being charged.  Any residue from the  separator is sent to the incineration
unit for disposal.   The distillate  is sent to a holding  tank.

     In the pretreatment for heavy  ends,  the  waste residues  are separated from
the  tarry  residues  and soot.   The system  contains evaporators,  a separator,

                                     62

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CO





LIGHT EWS
|

ttWKI


t








some*





scrju





UTO> I
1


f


)
— .
*
t~EJ
—* L-
,craK.

L
	 T
[



                            Figure 3.  Flow diagram for the  Hoechst-Uhde chlorolys^ls  process.
                                              (Emission sources are Indicated by  +)

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TABLE 26.  ANALYSES OF VINYL CHLORIDE MONOMER AND
           CHLORINATED SOLVENTS WASTE FRACTIONS
Light Ends (Vinyl Chloride Monomer)
Chloroethylene
Chloroethane
Di Chloroethylene
Trichloromethane
Chlorobutadiene
Dichloroethane
Carbon Tetrachloride
Benzene
Trichloroethylene
TOTAL
Heavy Ends (Vinyl Chloride Monomer)
Di Chloroethylene

Chlorobutadiene
Dichloroethane
Carbon Tetrachloride
Dichloropropane
Tri chloroethane
Dichloropropene
Dichlorobutene
Trichloropropene
Chlorobenzene
Tetrachloroethane
Di chlorobenzene
TOTAL
Solvents
Hexachloroethane
Hexachlorobutadiene
Hexachl orobenzene

C2H3C1
C2H5C1
run
s **O 0
CHC13
C4H5C1
C2H4C12
cci4
C6H6
C2HC13


C9H9C19
L C C
C4H5C1
C2H4C12
cci4
C3H6C12
C2H3C13
C3H4C12
C4H6C12
C4H6C13
C6H5C1
C2H2C14
C6H4C12


c2ci6
c4ci6
C6C16
Percent by Weight
10.9
3.8
4.5
9.9
14.5
30.4
16.9
6.2
2.9
100.0
Percent by Weight
0.5

2.7
2.2
0.7
1.7
56.6
2.7
26.0
6.7
2.8
2.3
1.1
100.0
Percent by Weight
25.0
65.0
10.0
       TOTAL
100.0
                            64

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      Cl,
              ADSORBER
SCRUBBER
                                                    SEPARATOR
  LIGHT  ENDS
HEAVY  ENDS
                                       CONDENSER
                                     HOLDING
                                       TANK
                                                           DRUM
                   YlllllllMIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIVIIIIIIItlllllllllllimilll
 SOLVENTS
              SEPARATOR
      CONDENSER
                                                           DRUM
TO

REACTION
                                                                                      ABSORPTION
                                                                                        TO
                    liiiiiiiiiiiiiiiiiiiiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiniuiiiimimiiiiO*
                                                                                   INCINERATION
                                Figure  4.    Pretreatment section
                                                 65

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condensers, collection drums and sealing drums.  A distillation process
operating under a vacuum is used to minimize the thermal load (this helps
avoid polymerization and coking).  Surface condensers are employed to minimize
the production of contaminated wastewater.  Small amounts of uncondensed
organic components are transferred into the sealing drum where they are routed
to the incineration unit.  The drum vents approximately 6 kilograms per hour
of air with traces of heavy ends.  For corrosion protection, small amounts of
ammonia (NH3) are fed into the drum to obtain a slightly alkaline solution.

     In the pretreatment for solvents, the residues are separated from the
sooty solid materials and polymers by use of a distillation system.  As above,
there is a vent to the atmosphere which yields approximately 6 kilograms per
hour of air with traces of solvents.  From this system, the residue from the
evaporator as well as the wastewater from the receiving drum is sent to the
incineration unit.  The distillate is transferred into the reactor holding
drum.

     Pretreatment of the waste material appears essential for effective
operation of the chlorolysis process.  Excess moisture, particulate matter,
contamination products and certain elements must be removed or diluted before
entering the reactor.  Light ends may contain a maximum of 0.1 percent dis-
solved water.  Heavy ends and solvents may contain soot, coking products,
polymer or undesirable elements which are not converted quantitatively to carbon
tetrachloride (CC14) and hydrogen chloride (HC1).  The non-volatile organlcs
and particulate matter tend to accumulate.  These particulates pose a signi-
ficant mechanical  problem in the operation and maintenance of control equipment.
They usually consist of fine carbon particles and catalyst fragments.  The
mere size of these particles makes conventional filtration difficult.  There-
fore, the evaporation method is more suitable for removal of these particles.
The component hexachlorobenzene (CgClg) contained in the solvent residue Is
not totally soluble at ambient temperature.  To maintain its solubility, the
hold tank must be  kept in a narrow temperature range.
                                      66

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Reaction Section (See Figure 5)

     Chlorolysis is a recycling process.   The by-product residues of the varied
chlorination processes are recycled into  the feed stream in order to convert
them into carbon tetrachloride and hydrogen chloride.   More than 99 percent of
the chlorine in the feed streams is converted to carbon tetrachloride and hydro-
gen chloride.  The by-products are recycled to extinction.

     Chlorolysis reactions are all exothermic.  Reactions take place at tem-
peratures up to 600°C with pressures of 18.1 MPa absolute.   The heat of reac-
tion is sufficient for adiabatic reaction with the temperature controlled by
the amount of chlorine produced.  Temperatures must not exceed 620°C due to
material limitations.  Exact reaction conditions are dependent upon the residue
composition.  The following equations illustrate some characteristic oxidations;
CHC13 H
C2H4C12 H
C6H6 <
C6C16 H
i- C12
H 5 C12
H 15 C12
i- 9 C12
+ CC14 H
* 2 CC14 H
* 6 CC14 H
-»• 6 CCK
4
i- HC1
(• 4 HC1
i- 6 HC1

Hexachlorobenzene is formed as an intermediate product when benzene (CgHg)
and alkylbenzenes are chlorolyzed.   Hexachlorobenzene only reacts above
500°C.

     Chlorine, the light ends distillate, the heavy ends distillate, the sol-
vent distillate, and the recycled residues are fed into a reactor.  The primary
sections of the reactor are heated, initiating reactions and compensating for
any heat losses.  The final reactor section functions as a quench section.
The reaction products are quenched from 600°C to 500°C by the injection of
carbon tetrachloride (recycled from the "pure" CC14 column).  The products are
cooled further by a reduction in pressure, via a pressure relief valve, as a
result of the Joule-Thomson effect, before entering the distillation section.
                                       67

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01
00
                                                               t
         FROM CL2

        TO CL2

        TO INCINERATION














REACTOR

(

t











HEAVY ENDS
COLUMN

t



iiiiiini


m*m^mt^^^
HC1
COLUMN
t
1
RAW CC14
COLUMN
\

f
PURE CC1.
COLUMN *
-» 1
TANK
1
MURIATIC
ACID


A
|«-NaOH
i- — ~~~ 	
1 *• TANK
1 NaOH , 	
                                                                                                                      WASTEWATER
                                                                                         ABSORBER
                                                                                    I

                                                                                    I
                                                                                                                      WASTEWATER
                                                                                TO ABSORPTION
                                           Figure  5.  Reaction and  distillation section.

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Distillation Section (See Figure 5)
     From the reactor, the product stream enters  a  heavy  ends  column  to  continue
the reaction process.   Unconverted hexachlorobenzene and  hexachloroethane
(C2C16) are separated and recycled back into the  primary  reactor.   Other pro-
ducts recycled include carbonyl  chloride (COC12)  and iron chloride  (FeClJ.
The formation of carbonyl chloride occurs when there are  feedstock  compounds
containing oxygen.  The iron chloride is surplus  catalyst.   Small amounts  of
soot also are recycled into the  reactor.  Carbon  dioxide  (CCL) as well as  car-
bonyl chloride are formed from the oxygen containing feedstock.  Gaseous
hydrogen chloride, C12, CCl^, and small amounts of COC12» and C02  are discharged
as overhead product Into a "raw" carbon tetrachloride column.

     In the "raw" carbon tetrachloride column, the  products undergo further
separation.  The bottom product consisting of carbon tetrachloride, carbonyl
chloride, small amounts of bromine and traces of chlorine,  hexachlorobenzene,
and hexachloroethane enters a "pure" carbon tetrachloride column.   Overhead
products from the "raw" carbon tetrachloride column (HC1, C02, CK. and  COC12)
are drawn off and sent to the HC1 column.  As overhead product, HC1 is drawn
off this column with small amounts of C02 and stored at the plant  for further
use.  Compounds vented from this column are shown 1n Table 27.  Chlorine,  con-
taining traces of carbonyl chloride and carbon tetrachloride 1s drawn off  as
a side stream from the HC1 column.  This stream along with fresh chlorine  from
storage Is recycled Into the reactor feed.  The bottom product from the  HC1
column (a mixture of carbonyl chloride, carbon tetrachloride and chlorine) 1s
             TABLE 27.  EMISSIONS FROM THE HC1 COLUMN CHLOROLYSIS
                        PROCESS, BASED UPON 25,000 METRIC TONS/YEAR

                   Compound                     Emission Rate

                     HC1                          4.28 kg/hr
                     C12                          0.43 gm/hr
                     CC14                         0.21 gm/hr
                     COC12                        0.21 gm/hr
                                       69

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sent to the incineration unit.   (If the carbonyl  chloride  were  to  be  used  In
an isocyanate process, It would need to be rectified.   As  the quantity  obtained
is minimal, it is not economical  to provide a column and a storage vessel  with
a filling device equipped with  the safety facilities required for  this  hazardous
substance.)  The HC1  column system is designed with a buffer volume surge
capacity of approximately three hours of operation.

     The bottom products from the "raw" CC14 column are sent to the "pure"
CC14 column where they are distilled into pure carbon tetrachloride.  A portion
of the distilled carbon tetrachloride is pumped into a holding  vessel,  with the
remainder sent to storage.  The stored carbon tetrachloride is  used as  needed,
for the quenching operation in  the final reactor sections.  Also recycled  into
the reactor from the CCl^ column are small quantities of bromine,  chlorine,
carbonyl chloride, hexachlorobenzene and hexachloroethane.  Small  amounts  of
uncondensed components (usually CC14, C12, HC1, COC12, Br) are  fed into an
absorber where purification is  achieved by scrubbing with  a 20  percent  NaOH
solution.  The vented emissions from this absorber are shown in Table 28.  The
bottom product from the absorber is separated into wastewater and  carbon tetra-
chloride streams.  The wastewater stream, lighter than the carbon  tetrachloride
stream, flows to the incineration unit while the CC14 is passed through driers
before re-entering the pure CC14 column.  The wastewater stream will  contain
the various trace metals which were present in the feedstock.   Most will remain
as residue in the pit.  Any bromine present as impurity in the  feedstock will
be discharged in the wastewater from the Incineration pit  as traces of  sodium
bromide (NaBr) and sodium hypobromite (NaOBr).
           TABLE 28.  EMISSIONS FROM THE NaOH ABSORBER CHLOROLYSIS
                      PROCESS, BASED UPON 25,000 METRIC TONS/YEAR
                 Compound                     Emission Rate,
                                                  mg/hr
                   HC1                             30.0
                   COC12                           10.0
                   CCK                           500.0
                                     70

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Incineration Section  (See  Figure  6)
     All  pretreatment chlorinated tars which  cannot  be used In the chlorolysls
process as well  as all  wastewater streams  contaminated with traces of chlori-
nated hydrocarbons are sent to the incineration  unit.  The waste streams contain
chlorinated hydrocarbons (C, H, Cl,  0) with possible traces of bromine, Iron,
copper and aluminum compounds.  Combustion air and water  also are fed into the
combustion chamber.  Incineration takes  place in the temperature range of
1250°C.  Under optimum conditions, the major  products resulting from combustion
are C02,  HC1, and H20.   Trace inorganics present in  the feedstock also will be
found 1n  the combustion products.

     Factors which Influence the combustion process  are the chlorine content
and the oxygen content of the Incoming waste  streams as well as the quantity
of water required.  A high chlorine  content 1n the waste  streams results in a
low heating value for the wastes.  A waste stream with a  60 percent to 70
percent chlorine content has a heating value  range of 8,400 kJ/kg  (3600 Btu/lb)
to 16,800 kJ/kg (7200 Btu/lb).  Proper combustion of the  wastes 1s difficult
when the heating value is below 12,600  kJ/kg  (5400 Btu/lb).  Therefore, sup-
plemental fuel Is needed for combustion.  This  supplement may  be either fuel
oil mixed with the Incoming waste stream or a separate  gas  burner.
                                        i
     The combustion product 1s a gaseous mixture of No*  02,  HC1, C02»  CO,  C12>
and H20.  Temperature and residence time of the reactants 1n  the incinerator
also are critical parameters.  High temperatures permit  short residence time,
provided that complete combustion (greater than 99 percent)  of the chlorinated
hydrocarbons Is assured with the minimum formation of free chlorine.   These
results are achieved by a residence time greater than three seconds  in the
combustion  zone and by the  Introduction of a  relatively large quantity of
water.  It  is necessary to  add water to the waste streams having a high  heat-
ing value to regulate the combustion temperature.  For this  reason,  the  smaller
wastewater  streams are combined with additional  water to reduce the combustion
temperatures from approximately  2000°C  to approximately 1250°C.   (Temperature
reduction also 1s needed to protect the materials used in the combustion  cham-
ber.)  The  ratio of hydrogen  chloride to chlorine also increases with rising

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                                                                                             TO ADSORPTION
ro
                    BOTTOM
                  HIIIIMl'*
                   PRODUCTS
                            AIR      WATER
INCINERATOR
                                                                                                         NEUTRALIZED
                                                                                                           WATER
                                                         Figure 6.   Incineration  section

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temperature as the destruction  of chlorinated  hydrocarbons  is  improved at high
temperatures.   Excessive oxygen affects  the  reactions as  the free  chlorine
content in the exhaust gas is  increased.   A  lack  of oxygen  results  in the
formation of soot.  An excess  of water also  suppresses  the  formation of free
chlorine.

     The exit gases from the combustion  unit are  discharged through a cooler
to a quench system and a scrubbing system.  In the  quench system,  the tempera-
ture of the gases is lowered from approximately 1000°C  to approximately 100°C
by the injection of recycled hydrochloric  acid.  The quench gas  is  fed to the
scrubber, where HC1 is absorbed.  Emissions  from  the scrubber  are  143 gm per
hour of HC1.  Additional HC1 is collected  in the  bottom portion  of the scrubber.
From here, a portion of the HC1 is recycled  to the  quench system (see above)
with the remainder neutralized in a pit  and  sent  to storage.   If there were
perfect combustion in the incinerator, no  free chlorine would  be formed so that
the HC1 could be removed thoroughly with water.  With  incomplete combustion,
Clg may be emitted in ppm quantities if  the  off-gas is  washed  only with water.
To prevent the venting of excessive quantities of C^  to the atmosphere, a
small amount of caustic soda is added to the wash water, to enhance removal of
the HC1 formed as well as to eliminate most  C12 traces.  With  caustic added,
the wastewater effluent may contain sodium chloride (NaCl), sodium hypochlorite
(NaOCl), sodium hydroxide (NaOH), sodium carbonate  (Na2C03), sodium bromide
(NaBr), and sodium hypobromite (NaOBr).  Sodium bromide and sodium hypobromite
are present because of the presence of trace amounts of bromine  1n the feed-
stock.  Typical discharges are shown in  Table  29.

Absorption System  (See Figure 7)
     An absorption unit 1s provided to treat the  waste vent gases  which contain
chlorine, hydrogen chloride, and carbonyl  chloride.  Waste  gases are  released
during a plant shutdown as a result of the pressure relief  needed in  the safety
valve.  Gases also are released when filters are  changed.  The absorption  units
consist of four stages in which absorption takes  place 1n liquid scrubbers  by
redrculatlon of a 20 percent NaOH solution.  The reactions taking place  are
exothermic, therefore, cooling units follow the scrubber.  Compounds  vented
                                      73

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                           A
WASTE VENT GASES
  1
SCRUBBER
STORAGE
                                                   A
                            I
TANK
                                       NaOH
                                                       WASTEWATER
                                              1
                                            ABSORPTION PIT
                      Figure 7.  Absorption section,
                               74

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 TABLE 33.  TOTAL AIR EMISSIONS FROM
            THE CHLOROLYSIS PROCESS
Pollutant
CC14
coci2
HC1
ci2
so2
Emission Rate
67.01 gm/hr
42.82 gm/hr
4.42 kg/hr
31 .03 gm/hr
3.00 gm/hr
TABLE 34.  TOTAL WASTEWATER DISCHARGES
           FROM THE CHLOROLYSIS PROCESS
           UNDER NORMAL FLOW CONDITIONS
Pollutant
Emission Rate,
    kg/hr
  NaCl

  NaOH

  NaOCl
     700

 2.0 to 4.0

       1
                   77

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                            TABLE 35.  POTENTIAL OPERATIONAL  MALFUNCTIONS  AT A CHLOROLYSIS  PLANT
                 Operation
            Possible  Malfunction
       Consequence
        Waster Transfer to Holding Tank
        Waste Transfer to Pretreatment
00
        Incineration
        Scrubbing
1)  Overfill                                   Waste  Spill
2)  Leakage Due to Seals, Packings, Corrosion  Waste  Spill
1)  Leakage Due to Seals, Corrosion
2)  Filter Plugging

1)  Flameout
2)  Improper Fuel Rate
3)  Improper Air/Fuel Ratio
4)  Injection into Cool  Combustion Zone on
    Startup
1)  Circulating Pump Failure
2)  Pump, Valve or Tank Leak
Waste Spill
None if switched on High
Discharge Pressure Overflow
to Absorption Section
Toxic Vapor Discharge
Excess Water in Discharge
Inefficient Combustion
Inefficient Combustion
High HC1 Concentrations in
Vent Gas Solution Spill

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 TABLE 33.  TOTAL AIR EMISSIONS FROM
            THE CHLOROLYSIS PROCESS
Pollutant
cci4
coci2
HC1
ci2
so2
Emission Rate
67.01 gm/hr
42.82 gm/hr
4.42 kg/hr
31.03 gm/hr
3.00 gm/hr
TABLE 34.  TOTAL WASTEWATER DISCHARGES
           FROM THE CHLOROLYSIS PROCESS
           UNDER NORMAL FLOW CONDITIONS

Pollutant                Emission Rate,
                             kg/hr


  NaCl                        700

  NaOH                    2.0 to 4.0

  NaOCl                         1
                   77

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                            TABLE 35.   POTENTIAL OPERATIONAL MALFUNCTIONS AT A CHLOROLYSIS PLANT
                 Operation
            Possible Malfunction
       Consequence
        Waster Transfer to Holding Tank    1)  Overfill
                                          2)  Leakage Due to Seals, Packings, Corrosion
        Waste Transfer to Pretreatment     1)  Leakage Due to Seals, Corrosion
                                          2)  Filter Plugging
00
        Incineration
        Scrubbing
1)  Flameout
2)  Improper Fuel Rate
3)  Improper Air/Fuel Ratio
4)  Injection into Cool Combustion Zone on
    Startup
1}  Circulating Pump Failure

2)  Pump, Valve or Tank Leak
Waste Spill
Waste Spill
Waste Spill
None if switched on High
Discharge Pressure Overflow
to Absorption Section
Toxic Vapor Discharge
Excess Water in Discharge
Inefficient Combustion
Inefficient Combustion
High HC1 Concentrations in
Vent Gas Solution Spill

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most likely consequence of a malfunction would be a waste spillage.   Spill
potentials are greatest in the storage and transfer areas.  As  these are
potentially hazardous substances, the storage/transfer area  should  be paved
and diked with a catch basin to return these materials to a  storage  tank.

4.3.2  Environmental Impact Analysis
     Emission estimates described in the previous section were  used  as inputs
for analytical procedures designed to assess impacts of these emissions on
air and water quality.  Expected impacts on air quality were determined via
the use of air quality simulation models.  Estimations of water quality and
other Impacts were determined via a process of comparing estimated  mass
emission rates with known and potential environmental effects of the constit-
uent In question.

     Air quality simulations were performed for a variety of emission sources
within the plant.  Process units and corresponding emission  constituents are
listed in Table 36.

     Estimates of emission rates for identified constituents were made in
accordance with procedures described earlier in this report. These estimates
served as inputs to the air quality simulation model.  Simulations  were
performed for each constituent and process unit listed 1n Table 36.
               TABLE 36.  SUMMARY OF CHLOROLYSIS PROCESS UNITS
                          AND EMISSION CONSTITUENTS
               Process Unit              Emission Constituents
               HC1 Column                CHI, C12, CC14,
               NaOH Absorber             HC1 , CC14, COC12
               Incineration Unit         HC1
               Absorption Unit           C12, CC14> COC12
               Absorption Tank           SO,
                                      79

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     Other parameters which served as inputs to the air quality simulation
were effective stack height, wind speed and stability category.  Information
was not available to permit an analytical derivation of effective stack heights
for the process units considered.  Therefore, an effective stack height of
5 meters was assumed for ground level units, and the physical height of the
incinerator was used to simulate air quality resulting from emissions from
that source.  Simulations were based on a wind speed of 4 meters per second
and a stability category of D.  These meteorological parameters are considered
to be representative of the general conditions observable at the hypothetical
Houston site.

     Selected results of the air quality simulations are presented in Table 37.
The values listed were obtained by taking the predicted ground level concen-
tration for each process unit-constituent pair, and summing these concentrations
for those constituents which were emitted by more than one process unit.
Appendix B provides details of the simulation and presents results of air
quality simulations performed for differing distances downwind from the source.

     The largest emissions associated with the chlorolysis process were due to
venting and fugitive emissions from sources closest to ground level.  Conse-
quently, the highest concentrations are expected to occur close to the source.
All concentrations listed in Table 37 are predicted to occur at the closest
downwind location for which simulations were run (100 meters).

     In general, the predicted air concentrations are low with respect to
potentially adverse acute effects on exposed human and biological  populations.
Threshold Limit Values (TLV's) for constituents listed in Table 36 are pre-
sented in Table 38.  These TLV's are generally two to four orders of magnitude
higher than predicted maximum constituent concentrations attributable to all
process units (Table 37).  There is even a greater difference between the
predicted levels and other levels (listed in Table 38) known to produce
assorted toxic effects 1n man and other organisms.   Because highest predicted
ground level  concentrations occur close to the source, plant personnel  comprise
the population most at risk.
                                     80

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               TABLE  37.  SUMMARY OF AIR QUALITY SIMULATION
                          RESULTS FOR A CHLOROLYSIS PLANT

                                                Maximum Ground
               Pollutant                     Level Concentration,
                                                    yg/m3

           Hydrogen  Chloride, HC1                     1435
           Chlorine, C12                                10
           Carbonyl  Chloride, COC12                     14
           Carbon TetrachloHde, CC1,                   22
           Sulfur Dioxide, S02                           1
     Hexachlorobenzene (HCB)  1s  a waste  by-product of most of the chlorolysls
processes currently 1n use (Reference  21).   However, the Hoechst-Uhde process
1s capable of converting HCB  to  the  process  end  product,
     Emissions from manufacturing,  storage  and  transport of HCB containing
materials resulted 1n livestock contamination within  a  100 square mile area of
Louisiana (Reference 24).   This Incident prompted  EPA to establish  an enfor-
ceable tolerance level for HCB 1n livestock products  (Reference 24).  Another
damage Incident Involving  HCB occurred 1n Turkey.   During the  1950's, 5000
sustained HCB poisoning following 1ngest1on of  contaminated grain.  Symptoms
produced by Ingesting this material Included liver deterioration, acute  skin
sensitivity and blistering, excessive hair  growth, and  for some Individuals,
tremors, convulsion and death (Reference 24).   TLV data was not available for
this compound, but the Information provided above  Indicates that any emission
of this material deserves  close scrutiny.

     There were no data available describing emission of  particulate matter
from the chlorolysls process.  Such material may be emitted from the Inciner-
ator, but the absence of data on its quantity and  nature  prevents  discussion
of expected impacts.  However, it should be mentioned that the use  of a
scrubber should keep such emissions at a relatively low level.

                                      81

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00
ro
                             TABLE  38.  THRESHOLD LIMIT VALUE AND TOXICITY DATA
                                       FOR SELECTED COMPOUNDS EMITTED FROM THE
                                       HOECHST-UHDE CHLOROLYSIS PROCESS
Compound
Hydrogen Chloride,
HC1
Chlorine,
ci2
Carbonyl Chloride,
COC1 g
Carbon Tetrachlo-
ride, CC14
Sulfur Dioxide
TLV
(mg/m )
7
3
0.2
65
13
LC50
(ppm)
3124
Rat/30 min.
293
Rat/1 hr.
780
Human


TCLO
(ppm)

15
Human, PUL

20
Human, CNS

LD50 TLm96
(mg/kg) (ppm)

< 1
Carp

1770 10-100
Rat, Oral PTaice

       Source:   Based  on  information obtained  from References 22 and 23.

       Abbreviations used:
       TLV   :   Threshold limit  value acceptable  levels for 8 hour/day occupational exposure.
             :   Lethal  air  concentration  for 50%  of test animals.
             :   Lowest air  concentration  capable  of producing a toxic effect.
       LD5Q  :   Lethal  dose for  50% of  test animals.
       TLm96 :   Water  concentration of  a  constituent which kills 50% of aquatic test animals
                  in 96 hours  of exposure.

       PUL   :   Pulmonary effect.
       CNS   :   Central nervous  system  effect.

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     The constituents  of the liquid  and  solid waste  streams from the chlorolysls
process were listed 1n Tables 29,  31,  and  32.   In addition, It 1s expected that
trace elements such as copper, Iron, aluminum,  and various heavy metals are
present 1n small  quantities.  Data from  Hoechst-Uhde do  not Indicate the
presence of these trace elements  1n  the  effluent streams.  Therefore, It was
assumed that trace elements  are present  1n small quantities as contaminants.

     As indicated in the tables,  the waste effluent  streams are primarily liquid,
Any solid emissions would be contained in  the liquid effluent as dissolved
and/or suspended particles.

     The liquid effluents will be discharged to a municipal sewage  system after
pretreatment.  Any residual  organic  and  trace element constituents  will most
likely be concentrated 1n the sludges  generated by the municipal treatment
system.  The sludges will probably be  landfUled, and the effects of any con-
taminants deposited onto or into  the soil  will  vary  as a function of the type
and porosity of the soil, the weather  conditions, and the mobility  of the
Individual contaminants.  Both organochlorine compounds  and various trace
elements (e.g., lead and copper)  have  been found  in  sanitary  fill leachates
(Reference 26), so 1t will be necessary  to minimize  these types of  constituents
1n the chlorolysls effluents to avoid  eventual  transfer  to the  land.

     The Resource Conservation and Recovery Act of  1976  (RCRA)  requires that
the Administrator of the Environmental Protection Agency promulgate standards
applicable to owners of hazardous waste  treatment,  storage, and disposal
facilities.  These standards Include requirements for operating methods, and
practices, location and design of facilities, and contingency plans for
minimizing unanticipated damage from treatment, storage, or disposal of
hazardous waste.  In that the chlorolysls  processes  Involve the treatment of
hazardous wastes, it is likely that  these  facilities will be  covered by such
regulations.  Therefore, procedures  will be instituted to ensure that all
process residues will  be handled in  a  way  which Is  environmentally  acceptable.
                                      83

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          5.  COMPARATIVE COST ANALYSIS AND ENVIRONMENTAL ASSESSMENT

5.1  COST ANALYSIS COMPARISON
     The capital investment costs and the unit costs for the disposal  of
liquid organochlorine wastes by land-based incineration, at-sea incineration,
and chlorolysis are compared in Table 39.  As discussed previously, costs for
land-based incineration were based on a centralized facility similar to the
one operated by Rollins Environmental Services in Houston, Texas.   Costs for
at-sea incineration were based on the M/T Vulcanus.  Costs for chlorolysis
were based on the Hoechst-Uhde design of a chlorolysis plant located on the
Gulf Coast.  Unit disposal costs presented for land-based incineration and
chlorolysis were calculated at 15% discounted cash flow rate of return.

     As noted from Table 39, chlorolysis requires the highest capital  Invest-
ment cost because of the complexity of the plant design to produce saleable
products.  In terms of unit disposal  costs, land-based incineration is
considerably more expensive than at-sea incineration, mainly due to the cost
of hydrated lime needed for the neutralization of hydrochloric acid, and the
higher unit costs for capital related charges and operating labor.  The
capital investment costs and annual operating costs are similar for a  land-
based incineration facility and for an Incineration ship, but the  unit costs
are lower for the incineration ship because of the larger volume of organo-
chlorine wastes disposed each year.

     The unit cost of disposal  of organochlorine wastes by chlorolysis is
dependent on the carbon tetrachloride selling price.  At the base  case of
carbon tetrachloride selling at $300 per metric ton, the unit disposal costs
by chlorolysis are $33 to $116 per metric ton higher than the corresponding
unit disposal costs by at-sea incineration.  As compared with land-based
incineration, chlorolysis is less expensive for the disposal of the
                                     84

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CD
                                           TABLE 39.  COST COMPARISON FOR DISPOSAL
                                                      OF ORGANOCHLORINE WASTES
Disposal
Method
Land- based
Incineration
At-sea
Incineration
Chlorolysls



Capital
Investment
Cost
$ 4,592,600
$ 4,000,000-
$ 6,000,000
$27,210,000
CC14 e $270 per
CC14 £ $300 per
CC14 e $330 per
Annual Volume
of Waste
Disposed,
Metric Tons
23,420
ff
25,000
metric ton
metric ton
metric ton
Unit
CMW Perch! oro-
Waste ethyl ene
Waste
181 212
BO

302 216
196 136
90 56
M^^H^^H^^^^M^B^K^^B^M^HV^VMMMBHB^iHH
Disposal Cost, $/Metr1c
Hexachioro-
cyclopentadlene
Waste
203
84

271
196
121
Ton
VCM and
Solvent
Waste
203
85

248
158
68

VCM
Waste
193
80

240
134
27
         Annual volume of waste disposed 1s  based  on an  Incinerator  feed  rate  of
         23 metric tons per hour and 3,000 hours of Incinerator  operation per  year.

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perch!oroethylene waste,  the hexachlorocyclopentadiene waste,  the mixed VCM
and solvent waste and the VCM waste,  but more expensive  for  the disposal of the
CMW waste.  Chlorolysls becomes a less  attractive option for the disposal of
the CMW waste and the hexachlorocyclopentadiene waste because  of the  presence
of oxygen 1n these wastes, leading to the formation  of carbonyl chloride and
a lower yield for carbon tetrachloride.  The carbonyl chloride formed 1s dis-
posed of by Incineration.  The alternative of purifying  carbonyl chloride for
usage as feedstock in an isocyanate process 1s not considered  in the  present
study.

     At a carbon tetrachloride selling  price of $330 per metric ton,  the unit
costs of disposal of organochlorine wastes by chlorolysls are  competitive with
corresponding disposal costs by at-sea  Incineration. In general, disposal by
chlorolysls is favored over at-sea Incineration for  organochlorine  wastes with
higher carbon content and lower hydrogen and oxygen  content, such as  the
perchloroethylene wastes, the mixed VCM and solvent  waste, and the  VCM waste.
This is because carbon present 1n the organochlorine waste is  converted  1n the
chlorolysis process by the addition of chlorine, at  $150 per metric ton, to a
higher priced commodity, carbon tetrachloride, at $330  per metric ton.  In
contrast, hydrogen present in the organochlorine waste  1s converted in the
chlorolysls process by chlorine, at $150 per metric  ton, to  a  lower priced
commodity, hydrogen chloride, at $50  per metric ton. Similarly,  the  oxygen
present is converted in the chlorolysis process to carbonyl  chloride  with no
byproduct value.

     At a carbon tetrachloride selling price of $270 per metric ton,  the unit
costs of disposal of organochlorine wastes by chlorolysls are  higher  than
corresponding disposal costs by land-based Incineration.

     In Figure 2, the effect of carbon tetrachloride selling price  on the
unit disposal cost of the mixed VCM and solvent waste and the  VCM waste  1s
depicted graphically.  It is seen that at a carbon tetrachloride  selling price
of around $285 per metric ton, chlorolysls becomes less  attractive  than  land-
based incineration for the disposal of these two organochlorine wastes from
the cost standpoint.  At a carbon tetrachloride selling  price  of around  $315

                                     86

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per metric ton, chlorolysls becomes Increasingly cost competitive with  at-sea
Incineration for the disposal  of these two organochlorine  wastes.  Thus,  a
fluctuation In carbon tetrachloride selling price of ± 5 percent from the base
price of $300 per metric ton could determine whether chlorolysis is  the least
expensive or the most expensive option for the disposal  of organochlorine
wastes among the three methods compared here.

     The economics of disposal of organochlorine wastes by the three alterna-
tives can also be compared in a different fashion.  The unit disposal costs
for land-based Incineration and chlorolysls could be assumed to be  the  same
as that for at-sea incineration, and the calculated discounted cash  flow  rate
of return (DCFRR) can be compared.  Similarly, DCFRR for land-based  Incinera-
tion at the unit disposal cost charged by chlorolysls can  be calculated,  and
compared with the DCFRR for chlorolysls.  Comparison of DCFRR 1s possible
except in the case of at-sea incineration, where reliable financial  data  are
not available to perform DCFRR calculations.

     In Table 40,  the calculated DCFRR for land-based incineration and
chlorolysls are compared.  First, DCFRR for chlorolysls at the unit disposal
cost charged by land-based incineration are presented.  The comparison  of
DCFRR shows that, with the exception of the CMW waste, a higher rate of return
on Investment can be realized from the disposal of organochlorine wastes  by
chlorolysls than by land-based Incineration.

     Second, DCFRR for land-based Incineration and chlorolysls at the unit
disposal  cost charged by at-sea Incineration are  presented.   In this case,
the comparison of DCFRR shows that land-based Incineration cannot be cost
competitive with at-sea Incineration, because the net operating cost for land-
based Incineration, without taking Into account any return on investment, is
higher than the unit disposal costs charged  for at-sea  Incineration.  The
DCFRR for land-based incineration are, therefore, all less than Q%.  For
chlorolysls, the charges for  the disposal  of organochlorine wastes only  re-
present a fraction of the  total annual revenue.   By  lowering  the DCFRR to the
10.8 to 13.455 range, chlorolysls can  be made to be cost competitive with at-
sea Incineration for the disposal of  organochlorine wastes.

                                      87

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                      TABLE 40.  COMPARISON OF DISCOUNTED CASH FLOW RATES OF RETURN
                                 FOR THE DISPOSAL OF ORGANOCHLORINE WASTES
00
00
Disposal
Method
Land- based
Incineration
At-sea
Incineration
Chlorolysis
Waste Type
CMW Waste
Perch! oroethylene Waste
Hexachlorocyclopentadiene
VCM and Solvent Waste
VCM Waste
CMW Waste
Perchloroethylene Waste
Hexachlorocyclopentadiene
VCM and Solvent Waste
VCM Waste
CMW Waste
Perchloroethylene Waste
Hexachlorocyclopentadiene
VCM and Solvent Waste
VCM Waste
Unit Disposal
Cost,
S/Metric Ton
181
212
Waste 203
203
193
80
91
Waste 84
85
80
196
136
Waste 196
158
134
DCFRR *
Land-Based
Incineration
15.0 %
15.0 %
15.0 %
15.0 %
15.0 %
< 0
< 0
< 0
< 0
< 0
17.8 %
< 0
13.5 %
4.7 %
< 0

Chlorolysis*
14.2 %
17.5 %
15.3 %
16.5 %
17.0 %
10.8 %
13.4 %
10.8 %
12.4 %
13.2 %
15.0 *
15.0 %
15.0 %
15.0 %
15.0 %
        Reliable financial data are not available to compute the DCFRR for at-sea incineration.

        For chlorolysis DCFRR calculations, the carbon tetrachloride selling price is assumed
        to be  $300 per metric ton.

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     Third,  DCFRR for land-based  Incineration at the unit disposal cost charged
by chlorolysls  are presented.   Again,  it  is  shown that with the exception of
the CMW waste,  the DCFRR for land-based incineration is lower than the corres-
ponding DCFRR for chlorolysis.

5.2  COMPARISON OF ENVIRONMENTAL  IMPACTS
     Data resulting from air quality simulations for constituents which have
counterparts in the three organochlorine  waste  disposal processes being consi-
dered in this report are summarized in Table 41.  This table shows that there
are general  differences in location and magnitude of expected maximum concen-
trations, as a result of the differences  in  emission rates  and  stack heights
used in air quality simulations.   Because the most  significant  emissions  from
chlorolysls are from process unit ventings,  maximum concentrations are observed
close to the source.  The only process unit  for which  this  is  not the case  is
the incinerator at the chlorolysls plant.  However, its  contribution of
emissions is small, and the overall emission pattern of  the units  predominate.
Emission estimates for chlorolysls were obtained from  the Hoechst-Uhde  report
(Reference 3).

     The data 1n Table 41 also highlight differences  1n  the magnitude  of air
contaminant concentrations produced by three processes.   For land-based in-
cineration, the maximum ground level concentration of hydrogen chloride is
several orders of magnitude lower than the Threshold Limit Value (TLV)  of
7 mg/m  .  The predicted concentrations of unburned wastes were conservatively
based on a destruction efficiency of 99.99$, whereas no emission of unburned
wastes  from the  stack was detected  in actual tests.  Emissions from land-based
incineration are, therefore, lower  than those expected to cause significant
impacts.

     For at-sea  incineration,  emissions of  hydrogen chloride are greater than
those from the other  two  processes  because  of the absence of scrubbers.
However, the maximum  ambient concentration  of hydrogen chloride, at 4.4 mg/m3,
is  still below the TLV.   The predicted maximum ambient level of unburned
wastes,  based on  a destruction efficiency of 99.99*, is 0.69 ug/m3.  Analysis
                                      89

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                               TABLE  41.   COMPARABLE GROUND LEVEL/SEA LEVEL CONCENTRATIONS OF EMISSIONS    *
                                          FROM LAND-BASED  INCINERATION, AT-SEA INCINERATION AND CHLOROLYSIS
Distance
(Meters)
100
200
300
400
500
600
700
800
900
1.000
2,000
3,000
4,000
5,000
6,000
7,000
8,000
9,000
10,000
20,000
30,000
Land-Based At-Sea
Indner- Inciner-
ation ation

—
.01
.03
.06
.15
.50
.54
.49
.43
.37
.32
.28
.24
.22
.09
.05
HC1» yg/m3
1
.10
.84
8.09
25.43
144.67
2,082.66
2,849.86
4,422.80
4,389.32
4,116.79
3,777.38
3.438.65
3,124.50
2,843.01
1,318.93
781.14
i^^^^—J.i i
Cnloro-
lysis
Land-Based
Inciner-
ation
At-Sea
Inciner-
ation
Chloro-
lysis
Unburned Waste, yg/m3
,434.60
529.93
264.34
178.05
127.06
89.95
74.89
56.10
48.51
39.98
14.98
8.25
5.40
3.89
2.97
2.37
1.95
1.63
1.39
0.51
0.28
—
—
.01
.02
.05
.16
.18
.16
.14
.12
.11
.09
.08
.07
.03
.02
—
—
—
. ...
.02
.32
.60
.69
.68
.64
.59
.53
.49
.44
.20
.12
1
22.46
8.30
4.13
2.78
1.98
1.39
1.16
0.87
0.75
0.61
0.23
0.12
0.08
0.04
0.04
0.03
0.02
0.02
0.01
—
---
Land -Based
Inciner-
ation
Inciner-
ation
lysis*
Other Inorganics, yg/m3
—
.01
.04
.07
.17
.55
.62
.56
.49
.42
.37
.32
.28
.25
.10
.06
---
...
.04
.13
.74
10.59
19.58
22.49
22.32
20.93
19.21
17.48
15.89
14.46
6.71
3.97
25.76
9.51
4.75
3.19
2.27
1.60
1.33
1.00
0.85
0.70
0.26
0.15
0.09
0.07
0.05
0.04
0.03
0.03
0.02
—

Indner- Indner- lysis
ation ation
Trace Metals (T1,N1,Cr), ng/m3
I
.03
.06
.12
.33
1.11
1.23
1.14
.99
.84
.75
.63
.57
.51
.21
.12
.04
.38


3.65 <
11.49 *~
«c
65.39 o
941.31
1 ,740.05 °
1,999.01
1 ,983.87
1 ,860.69
1,707.30
1.554.19
1,412.20
1,284.98
596.13







353.06
                         111

Detailed Information on the emission rates, meteorological  conditions, and  stack  heights used in the '^quality simulation
calculations 1s presented In Appendix B.   Fugitive emissions were  not mcluded  in  the emission rate estimates.

Other Inorganics for chlorolysls is sum of C12,  S02 and  COC12  ground level  concentrations.

-------
of ocean water samples obtained in  the vicinity of  plume  touchdown  has shown
that there was  no significant difference  1n pH and copper  (the most abundant
heavy metal constituent of the waste burned) as compared  with  samples from
control areas.  Organochlorlne wastes were not detected at  the 0.5  ppb level.
It may, therefore, be concluded that emissions from at-sea  Incineration  are
not expected to cause major environmental  Impacts.

     For chlorolysls, the predicted maximum ground  level  concentrations  of
hydrogen chloride, chlorine, carbonyl chloride, carbon tetrachloride, and
sulfur dioxide are all several orders of magnitude  lower  than  their respective
TLV's.  Emissions from chlorolysls are lower than those from at-sea Inciner-
ation, and also lower than those from land-based Incineration  with  the
exception of hydrogen chloride emissions.   Environmental  impacts  associated
with the chlorolysls process should, therefore, be  lower  than  those associated
with the other two disposal processes.

     Table 42 presents wastewater discharge rates for land-based  incineration
and the chlorolysls process.  This Information indicates  that  much  greater
water quality Impacts (1n terms of TDS) may result from land-based  inciner-
ation, than would be expected from the chlorolysls  process.  It should  also
be pointed out that although there are no direct wastewater discharges  from
at-sea incineration, the spill potential may be higher than the other two
disposal processes, especially during the loading operation when hatches are
open, samples are being taken, and exposed  flex lines are under pressure.
       TABLE 42.  COMPARISON OF WASTEWATER EMISSIONS FROM LAND-BASED
                  INCINERATION, AT-SEA INCINERATION AND CHLOROLYSIS
Pollutant
Cl"
Na+
Ca++
Organics
Land-Based
Incineration
(kg/hr)
1,880
1,740
Negligible
At-Sea
Incineration
No discharge
No discharge
No discharge
No discharge
Chlorolysls
(kg/hr)
425
277
—
Negligible
                                     91

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5.3  INTEGRATION OF ANALYSIS RESULTS
     The results of the present study have Indicated that at-sea Incineration,
at $80 to $91 per metric ton, 1s the least costly option for the disposal
of liquid organochlorine wastes.  Chlorolysis has a cost advantage over land-
based Incineration for the disposal of most organochlorine wastes, and can be
made to be cost competitive with at-sea incineration 1f a DCFRR 1n the 10.8%
to 13.4% range 1s considered to be acceptable.  On the negative side, the
economic attractiveness of chlorolysis 1s very dependent on the selling price
for carbon tetrachloride.  Because of the uncertain market demand for carbon
tetrachlorlde, there is a higher risk factor associated with capital  Invest-
ment in a chlorolysis plant.

     From the environmental impact standpoint, maximum downwind concentrations
of inorganic chloride and organochlorine species and particulates emitted from
land-based incineration and chlorolysis are all several orders of magnitude
lower than their respective Threshold Limit Values (TLV's) or are within air
quality standards.  Wastewater discharges from both disposal processes have
high TDS.  For at-sea incineration, maximum downwind concentrations of all
species emitted are less than their TLV's, and water quality 1s not measurably
impacted.  All three disposal processes can, therefore, be considered as
environmentally acceptable.  The chlorolysis process, however, has an apparent
ecological advantage in that chemical wastes are recycled to yield saleable
products.  The results should be an environmental credit for an emission
that can be avoided, related to the quantities of carbon tetrachlorlde that
would not have to be manufactured by the chemical industry.

     In terms of environmental  risks associated with operational malfunctions,
the greatest spill possibility at a land-based incineration facility exists 1n
the storage tank and transfer.   The greatest spill possibility related to at-
sea incineration occurs during loading.  The other major failure cause for
both land-based and at-sea incineration could come from Incinerator malfunc-
tions, such as burner flameout.   By comparison, the Hoechst-Uhde chlorolysis
design 1s considerably more complex from an equipment standpoint.  Increased
complexity generally leads to increased reliability problems, but the use of

                                    92

-------
redundant equipment and maintenance  surveillance  associated with general
chemical  plant practice will  minimize  equipment failure problems.

     Aside from cost and environmental  consideration,  land-based Incineration
has greater versatility 1n handling  different  types  of wastes.  At  a  land-
based Incineration facility,  the rotary kiln system  can be used to  handle
sludges, solids, semi-solids  and contaminated  containers  as well as liquid
wastes.  Also, the minimum quantity  of waste accepted  for disposal  at any one
time could be a SB-gallon drum or less.  Unit  disposal costs  are generally
charged on a cost sharing basis.  At-sea Incineration  1s  applicable to the
disposal of liquid organic wastes as well as aqueous wastes contaminated with
organlcs.  The acceptability of burning sol Ids at-sea, on the other hand,
remains to be demonstrated.  For at-sea Incineration,  another restriction Is
that the minimum quantity of waste to be disposed would  be one or  two ship-
loads at a time.  This means that a  storage depot for  waste collection would
have to be set up 1f at-sea Incineration 1s to become  an  available option for
the disposal of small quantities of wastes.  Disposal  by chlorolysls 1s limited
to organochlorlne wastes relatively free of partlculates, with sulfur content
less than 25 ppm, containing no nitrogen or phosphorus,  and a maximum of 5
percent aromatic hydrocarbons.  Only approximately 10  percent of the organo-
chlorlne wastes generated 1n the U.S. are available and  considered as suitable
feedstocks for chlorolysls.

     Overall, 1t may be concluded that land-based Incineration,  at-sea Incin-
eration, and chlorolysls are all viable options for the disposal  of liquid
organochlorlne wastes.  Chlorolysls should be considered 1f suitable feedstocks
are available and the selling price for carbon tetrachlorlde  remains relatively
stable, mainly because  1t is a  recycling process that conserves  resources  and
causes minimum environmental Impact.  At-sea incineration is  cost-effective
for the disposal of large quantities of  liquid organochlorlne wastes, and the
environmental risks are considered to  be acceptable.  Land-based Incineration,
although relatively more expensive, 1s suited for the disposal of other types
of liquid wastes as well as  solid wastes, with no restraints on the minimum
quantity accepted for disposal.
                                      93

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                               6.   REFERENCES


 1.  Russel, R.R. and J.A.  Mraz, Hydrochloric Acid Recovery  from  Chlorinated
     Organic Waste in Industrial Process  Design for Pollution  Control.  Vol.  5.
     American Institute of Chemical  Engineers, New York.   1974.

 2.  Paige, S.F., L.B. Baboolal, J.E.  Cotter, H.J. Fisher, K.H. Scheyer, A.M.
     Shaug, R.C.  Tau and C.F.  Thorne.   Environmental  Assessment - At-Sea and
     Land-Based Incineration of Organochlorine Wastes.   EPA-600/2-78-087.
     Report prepared by TRW, Inc.  for the U.S. Environmental Protection Agency.
     May 1978.

 3.  Chlorolysls  Applied to the Conversion of Chlorocarbon Residues  Possibly
     Containing Oxygenated Analogs.   Draft final  report  prepared  by  Hoechst-
     Uhde Corporation for the U.S.  Environmental  Protection  Agency.  October
     1977.

 4.  Clausen, J.F., H.J. Fisher, R.J.  Johnson, E.L. Moon,  C.C. Sh1h, R.F.
     Tobias and C.A. Zee.  At-Sea  Incineration of Organochlorine  Wastes Onboard
     the M/T Vulcanus.  EPA-600/2-77-196.  Report prepared by  TRW, Inc. for the
     U.S. Environmental Protection  Agency.  September 1977.

 5.  Destroying Chemical Wastes in  Commercial Scale Incinerators  - Phase II.
     Final Report.  Report prepared by TRW, Inc.  and Arthur  D. Little,  Inc.
     for the U.S. Environmental Protection Agency.  November 1977.

 6.  Happel, J. and D.G. Jordan.  Chemical Process Economics.  2nd Ed.  Marcel
     Dekker, Inc.  New York, 1975.   511  p.

 7.  Uhl, V.W.  A Standard Procedure of Economic  Evaluation  for Pollution
     Control  Operations.  Draft report prepared for the  U.S. Environmental
     Protection Agency.  November  1977.

 8.  Reid, R.C. and T.K. Sherwood.   The Properties of Gases  and Liquids.  2nd
     Ed.  McGraw-Hill Book Company,  New York.  1966.   646  p.

 9.  TRW, Inc.  Destroying Chemical  Wastes in Commercial Scale Incinerators,
     Facility Report No. 6, Rollins  Environmental  Services.  Report  prepared
     for the Office of Solid Waste  Management Programs,  U.S. Environmental
     Protection Agency.  June  1977.   NTIS No. PB  270897.

10.  Standards Applicable to Owners  and Operators  of Hazardous Waste Treatment,
     Storage, and Disposal  Facilities.  Draft RCRA Regulations.   U.S. Environ-
     mental Protection Agency.  March  24, 1978.
                                     94

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11.  Committee on Medical  and Biological  Effects of Environmental Pollutants:
     Chlorine and Hydrogen Chloride.   National Academy of Sciences.  1976.

12.  Stahl, Q.R.   A1r Pollution  Aspects of  Hydrochloric Add.  Report prepared
     by Litton Systems,  Inc.  for the  National A1r  Pollution Control Adminis-
     tration.  September 1969.   NTIS  No.  PB 188067.

13.  Fuller, W.H.  Movement of Selected Metals, Asbestos, and Cyanide 1n Soil:
     Application  to Waste Disposal  Problems.  EPA  600/2-77-020.  U.S. Environ-
     mental Protection Agency, Cincinnati,  Ohio.   April 1977.

14.  Van Vleet, E.S. and J.G. Qulnn.   Input and Fate of Petroleum Hydrocarbons
     Entering the Providence River  and Upper Narrangansett Bay from Wastewater
     Effluents.  Environmental Science and  Technology, 11(12):  1086-1092.
     November 1977.

15.  Ackerman, D.G., H.J.  Fisher, R.J. Johnson, R.F. Maddalone, B.J. Matthews,
     E.L. Moon, K.H. Scheyer, C.C.  Shlh,  and R.F.  Tobias.  At-Sea Incineration
     of Herbicide Orange Onboard the  M/T  Vulcanus.  EPA-600/2-78-086.  Report
     prepared by  TRW, Inc. for the  U.S. Environmental Protection Agency.
     April 1978.

16.  Wastler, T.A., C.K. Offutt, C.K.  Fitzslmmons, and P.E. Des Rosiers.
     Disposal of  Organochlorine  Wastes by Incineration at Sea.  EPA-430/9-75-014.
     Division of  011 and Special Materials  Control, Office of Water and
     Hazardous Materials,  U.S. Environmental Protection Agency.  July 1975.

17.  Grasshoff, K., Kiel University,  Extract from  his report on:  "Possible
     Effects of Burning  Chlorinated Hydrocarbons At-Sea" as Included In
     Appendix N of Final Environmental Statement:  Disposition of Orange
     Herbicide by Incineration,  Department  of the  Air Force, November 1974.

18.  American Conference of Governmental  and Industrial Hygienists, TLV -
     Threshold Limit Values for  Chemical  Substances and Physical Agents in
     the Workroom Environment with  Intended Changes for 1973.

19.  TerEco Corporation, A Report on  the  Philadelphia Dumpsite and Shell
     Incineration Monitorlngs, Box  2848,  College Station, Texas, undated.

20.  Physical, Chemical  and Biological Treatment Techniques for Industrial
     Wastes.  EPA SW-148C.  Report  prepared by Arthur D. Little, Inc. for the
     U.S. Environmental  Protection  Agency.  1977.

21.  Shiver, J.K.  Converting Chlorohydrocarbon Wastes by Chlorolysis.
     EPA-600/2-76-270.  October  1976.

22.  American Conference of Governmental  and Industrial Hygienists.  Documen-
     tation of the Threshold Limit  Values for Substances in Workroom Air.
     3rd Ed.  1971.
                                     95

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23.  National  Institute of Occupational  Safety and  Health.   Registry of Toxic
     Effects of Chemical  Substances.   1976 Edition.

24.  U.S. Environmental Protection Agency.  Hazardous  Waste  Disposal Damage
     Reports.   EPA/530/SW-151.3.   Office of Solid Waste  Management  Programs.
     1976.

25.  Helmke, P.A., R.D. Koons,  P.J. Schomberg, and  O.K.  Iskandar.   Determin-
     ation of Trace Element Contamination of Sediments by Multielement
     Analysis  of Clay-Size Fraction.   Environmental  Science  and Technology.
     11(10):  984-989.   October 1977.

26.  Khare, M. ancTN.C. Dondero.   Fractionation and Concentration from Water
     of Volatiles and Organics  on High Vacuum System:  Examination  of Sanitary
     Landfill  Leachate.  Environmental Science and  Technology.  11(8): 814-819.
     August 1977.

27.  Pojasek,  R.B.  Stabilization, Solidification of Hazardous Wastes.
     Environmental Science and  Technology, 12(4): 382-386.   April 1978.
                                     96

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                                 APPENDIX A

                             CALCULATION OF  UNIT
                  COST OF DISPOSAL OF ORGANOCHLORINE WASTES


     The method used for estimating the unit cost  of disposal of organochlorine

wastes is based on the discounted cash flow  (DCF)  technique.  In essence,  this

technique determines the annual  revenue during  the plant  life which will

generate a discounted cash flow equal to the total capital  invested for  the

plant.  In DCF analysis, all future net income  is  discounted to a  present  value

depending on the discounted cash flow rate of return  (DCFRR).  Discounting can

also be done on either an annual or continuous  basis.   For the present situa-
tion, it 1s more reasonable to assume that transactions will occur throughout
the year and not in one lump sum, and therefore continuous discounting is  more

representative of the actual flow of funds.

     The DCF method used to derive the unit  disposal  cost equation follows the

procedure described by Uhl  (Reference A-l).   The basis for the  analysis include
the following:

     •  10 year plant life with no salvage value at the end of
        life of the plant.

     t  Straight line method to calculate annual  depreciation.

     t  Negligible land cost.

     •  Startup cost  1s expensed  uniformly during  the  first year
        of operation  and not treated  as capital investment.  Also,
        startup cost  is assumed  to be 555 of  total  plant cost.

     •   Interest on construction  is  considered as  an operating
        expense at the  end  of the first year.  Also, Interest is
        charged on only the fraction  of the  construction cost that
        corresponds to  the  debt  fraction of  the total  capitaliza-
         tion for the  company.  This  is assumed to be 30%.  Interest
         1s at  10% rate.

     •  Working capital  1s  assumed to be 15% of annual revenue.

      •  Annual  revenue  and  operating cost are  assumed  to  be
         constant during the plant life.


                                       97

-------
     t  Income tax rate is 50%.

     •  Uniform continuous discounting factors  are  used  for
        depreciable investment,  startup cost, and cash flow.

     •  Instantaneous continuous discounting  factors  are used
        for interest during construction (a one-time  expense at
        the end of the first year)  and for  recovery of working
        capital (at the end of 10 years).
Definition of Terms
I    =  Total plant cost, $. Because interest during construction  and  start-
        up costs are expensed, this is also the total  depreciable  Investment.

W    =  Working capital, $.

U    =  Startup cost, $.

C    =  Net annual  operating cost, $.

S    =  Annual revenue, $.

D    =  Annual depreciation, $.   With  10 year straight line  depreciation,
        D = 0.1 I.

CF   =  Annual cash flow, $.

t    =  Income tax  rate  =0.5.

G    =  Annual quantity of organochlorine waste disposed,  metric tons.

R    =  Discounted  cash flow rate of return.


Annual Cash Flow

CF   =  D  +  (1 -  t) (S - C - D)
     =  0.11  +  0.5 (S - C - 0.11)
     =  0.5S  -  0.5C  +  0.051                  (A-l)


Interest During Construction

     It is assumed  that interest  is paid on 30% of the total  plant cost,

or 0.31.  The interest factor to  be applied is found from  the following

schedule to be 0.2234.  Interest  is paid at the end of the first year

(Reference A-l).

                                    98

-------
   Years Before           Project         Interest Factor       Weighted
     Start-Up          Expenditure       at 1 yr. at 10%       Interest
   	          Schedule         Cost Interest         Factor
Second (-2 to -1)           50%       X       1.2846      =      0.6423
First (-1 to 0)             50%       X       1.1623      =      0.5811
                                                               1.2234
     The actual  interest payment  is  0.2234 X 0.3 I = 0.06702 I.

Calculation of Unit Disposal  Cost
     From the calculations  summarized  in Table A-1, Total Discounted Cash Flow
-(e2R-l) I/2R - W - 0.030321  I - 0.5  (1 - e"R) U/R +  (1 - e"10R) CF/R
+ e"10R W  =  0                                                          (A-2)
     Substituting the value of CF from equation  (A-1)  Into equation (A-2)
and simplifying
                  2p                                          P
     S  =  C + ( 6   "J  I  °-Q606?2R  .  Q  n  T  l  £RU  I  ^X~ U        fA 31
                                                                 u        A"3)
                            i  . o                      i
                            i  — e                      I  —  e
or   S  =  C + al + bW + cU                                              (A-4)
where
            90
     a  -  e   * »•»««« R -  ' - 0.1                                    (A-5)
                1 - e"IUK
     b  -  2R                                                            (A-6)
 Therefore
      Unit  Disposal Cost  _  C+al+bW+cU-S'
        ($/metric ton)              6
(A-8)
      The  values of the constants a, b and c at different discounted cash flow
 rates of  return are  given in Table A-2.  S' is the annual revenue derived
 from the  sale  of  products generated from the processing of wastes.
                                    99

-------
Simplified Calculation of Unit Disposal  Cost

     With the additional  assumptions  that the startup cost U  is  equal  to  5%

of the investment I, and  the working  capital W is  equal  to 15% of the  annual

revenue S, equation (A-4) can be further simplified  to:


     S  =  a + 0-05 c r        1     r -  « I  + e  C                     (A Ql
     5     1 - 0.15 b l   1  - 0.15 b  L    ot i  + e  t                     (A-9)
Therefore

     Unit Disposal  Cost  _  a I +  3 C - S'
       ($/metric ton)     ~      G
(A-10)
     The values of the constants a and e at different discounted  cash  flow
rates of return are also given in Table A-2.  Equation (A-10)  is  used  in
calculation of the unit cost for the disposal  of organochlorine wastes.
                                REFERENCE

A-l.  Uhl, Vincent W.  A Standard Procedure of Economic Evaluation for
      Pollution Control Operations.  Draft Report prepared for the U.S.
      Environmental Protection Agency.  November 1977.
                                    100

-------
                               TABLE A-l.   CALCULATION OF  DISCOUNTED CASH  FLOW
Time,
Year
-2 to 0
0
1
0 to 2
0 to 10
10
Item Investment Cash Flow
Depreciable Investment I
Working Capital W
Interest on 30* of Total -0.5* X 0.067021
Plant Cost at 10% Rate
Start-up Cost -0.5* U
Cash Flow 10 CF
Recover Working Capital - W
Discounting
Factor
(e2R - 1)/2R
1.0
e-0.1
(1 - e"R)/R
(1 - e"10R)/10R
e-10R
Discounted
Cash Flow
- (e2R - 1) I/2R
- W
-0.030321 I
-0.5 (1 - e"R) U/R
(1 - e"10R) CF/R
e-10R W
The actual cash flow for these two items so designated are reduced by 50%
due to the effect on Cash Flow of income tax.

-------
TABLE A-2.  VALUE OF CONSTANTS UTILIZED
            IN THE CALCULATION OF UNIT
            DISPOSAL COST BY THE DCF METHOD
DCF Rate
of Return
10X
12*
152
18%
20%
a
0.25985
0.29857
0.36205
0.43222
0.48283
b
0.20
0.24
0.30
0.36
0.40
Value of Constants
c
0.15054
0.16182
0.17930
0.19735
0.20964
a
0.27565
0.31811
0.38850
0.46732
0.52480
0
1.03093
1.03734
1.04712
1.05708
1.06383
                     102

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                                 APPENDIX  B
                    AIR QUALITY SIMULATION METHODOLOGY

     A computer simulation of air quality  impacts that  would result from
at-sea incineration, land-based incineration and the chlorolysis process was
performed using the most representative set  of physical parameters and
meteorological conditions that could be determined from the available data.
In this appendix the formation of the model  is presented and the inherent
limitations of the analysis are discussed.  The values  of the input data are
given and the results of a sensitivity analysis performed for two parameters
are shown.  The results of the air quality  simulation are presented and the
air impacts associated with at-sea and land-based incineration  and chloro-
lysis are briefly  discussed.
TECHNICAL APPROACH
     Downwind concentration of gaseous pollutants can be simulated with a
conventional  Gaussian diffusion  plume model which assumes a continuous  point
source of strength  Q.  The basic equation used  in the  calculation  is:
                                                                      20
                                                                in    (•  ~\
x (x.y§2) a  - Q— - exp [- y/2 or] {exp [  -  (z-h)2
                       a2
                      + exp [ -(z+h)2/2   a  2 ]>                  (B-l)
                      a
                                              2
 where x(*,y,z)  is  the concentration  downwind from the  source  at  x,y,z;  Q  is
 the continuous  point source strength (i.e.,  emission rate); h is the  effective
 stack height; u is the mean wind speed;  and  a  and o   are the horizontal  and
 vertical  standard  deviations of the  plume.   In the above formulation  the  x-axis
 is aligned with the mean wind speed, the y-axis is in  the crosswind direction,
 and the z-axis is  in the vertical.
      To obtain the downwind concentration at ground level, equation (B-l)
 simplifies to
                                      103

-------
     When gases and particulates are released from a point source they are
carried downwind and are dispersed by atmospheric turbulence.   Particulates
will have an additional downward component of velocity at their terminal
velocity, v .   As the gases or particulates approach the ground a fraction
will be deposited on the surface or on vegetation by direct sedimentation,
inertial impaction, adsorption, chemical  reaction and other mechanisms.   This
removal causes the downwind flux of airborne gases or particulates to decrease.
In the conventional Gaussian plume model  described in Equation (B-l), no
account is made for gravitational settling of particulates or for deposition
mechanisms.
     Overcamp  (Reference B-l) has proposed a modification of the Gaussian plume
model  for the  deposition of fine and heavy particulates and gases.  It combines
a downward-sloping plume to account for settling and the assumption of a  con-
stant  deposition velocity.  The general equation for the concentration is
                                                          V ¥
                                     °
                     a                y
                -i-   a{x'}  exp [-(z+h - -^-)2/2 oz2] }             (B-3)
where a{x'}  could be considered as that fraction of the plume that is reflect-
ed at the surface and  a{x'} is defined as

           '
                   vs + vd + (uh-v) (Bl)-1 (da;/dx)               -

where vd is the deposition velocity and vs is the terminal  settling velocity.
For a gas that is perfectly reflected at the ground, a is unity.   It should
be noted that x' is the point where the plume image streamline passes through
the ground plane.  An implicit equation for x' is
                 z+h -  f   = (h -
                                                                   (B-5)

     The air quality simulation results presented in this report were not able
to incorporate particulate settling or deposition mechanisms due to the un-
availability of specific data.  Particle size and the characteristics of the
surface, among other parameters, would need to be known before settling and
deposition could be included in the analysis.  Therefore, ground-level
                                   104

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downwind concentrations  were  calculated  from  Equation  (B-2) using the most
representative set of physical  parameters  and meteorological conditions that
could be determined from the  available data.
     A word needs to be  said  about the diffusion  and transport of pollutants
over large bodies of water.   It has been long known that  the turbulence spec-
trum (and hence the diffusion)  over water is  different from that over land
(References B-2 and B-3) at comparable stabilities.  Raynor et a.  (Reference
B-4) reported diffusion  observations at  sea which showed  little spreading and
marked departure from the standard Pasqulll-Gifford curves.  This apparently
occurs for two reasons.   First, the ocean surface is a dynamic one  in contrast
to the static land surface.  Therefore,  the roughness  height,  ZQ, which among
other parameters determines the turbulence intensity,  becomes  a  function of the
stage of wave development.  Kitaigorodskil (Reference  B-5) derived  expressions
from determining an "equivalent sand roughness" element,  z ,  of  the sea surface.
This value was found to be dependent on  the Reynold's  number  at  the surface.
Second, density stratification over water 1s  controlled not only  by heat flux
but also by water vapor flux because of the Intense evaporation  which  takes
place at the water surface.  Monln (Reference B-6) has taken  this  into  account
by redefining the stability parameter, L, 1n terms of the latent  heat  of vapor-
ization, the Bowen ratio and the L which would occur over land.
     Gifford  (Reference B-7) suggested in principle a method  for obtaining  the
equivalent Pasquill-Gifford stability over water.  He suggested  that the zs and
L over water be first found, then  the equivalent Pasqulll-Gifford turbulence
level be found from either Golder's  (Reference B-8) or Smith's (Reference  B-9)
nomograms.  Using values characteristic of the ocean, 1t was  found that L  could
range anywhere between  20-40%  of  its  "equivalent over-land" value, confirming
the greater stability of the air mass over the ocean.
     PortelH  (Reference B-10) recently reviewed the subject  of diffusion  over
water.  The turbulence  intensity of  the atmosphere over the ocean was found to
depend on  (1) the temperature  difference between the air and the ocean surface,
and  (2) the roughness of the ocean surface.  It was difficult, however, to
obtain quantifiable results  (In particular for o  and a  ) over the ocean which
could be compared with  the equivalent land values.  Therefore, in this report,
the at-sea values for these diffusion parameters were assumed to be the same
as the corresponding land values.
                                     105

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LIMITATIONS OF THE ANALYSIS
     There are a series of inherent problems and other factors which could
have significant effects on the nature and applicability of results from this
type of simulation analysis.  In this section these problems and factors will
be identified and measures taken (if any) to mitigate their effects will be
described.
     The first problem involves inter-facility variations of those factors
that affect effective stack height.  Factors of importance include the follow-
ing:
     (1)  The physical height of the stack's terminus above ground level (or
          sea level for ships)
     (2)  The ambient temperature lapse rate, effluent velocity, temperature
          of the effluent, and stack radius.
     Numerical studies (e.g., see the sensitivity analysis performed in a
later section of this appendix) have shown that ground level concentrations
are strongly dependent on effective stack height.  There is no simple way of
designing this analysis to reflect these individual differences; therefore,
the results in this report should be viewed as approximate concentrations
expected to occur under the conditions imposed by a set of specified input
parameters.
     A second problem relates to differences in the meteorological conditions
that may exist at individual facilities.  Predicted ambient concentrations are
strongly dependent on the selected meteorology.  Atmospheric mixing over the
ocean is generally conceded to be less than that over land, but the exact
quantities are not yet known.  As with the previous problem, there is no way
of determining meteorological conditions that would be universally represen-
tative of at-sea and land-based conditions.  However, information is presented
in the model input sections of this appendix which shows that the selection of
meteorological parameters is validated to some extent by available data.  The
simulation was performed under a set of conditions which were considered to be
the most representative of the land-based and at-sea facilities.  It was
assumed that these conditions would persist over long averaging times (on the
order of 24 hours), even though such a persistence is highly unlikely.  In
                                   106

-------
addition, other special  meteorological  circumstances  (fumigation,  looping  and
trapping) may also be conducive to high pollution build-ups  especially  around
the land-based site.
     Another level of difficulty stems  from a void in our knowledge  of  aerosol
scavenging and chemical  reaction of pollutants in the atmosphere.  Hydrogen
chloride by virtue of its deliquescent  nature, can be expected  to  be absorbed
by moisture typically present in marine environments.  HC1 may  also  combine
with other salt complexes and condensation nucleii present over the  ocean.
Similarly, unburned wastes and total organics may themselves enter into chem-
ical reactions with marine aerosols or, at the very least, provide nucleation
centers  (condensation nucleii) for droplet formation.  A determination  of  the
consequences of the types of chemical reactions and the resulting  scavenging
of combustion products is beyond the scope of this study.  However,  in  this
analysis it is assumed that no scavenging takes place.
MODEL INPUT
     The inputs to the diffusion model  used for the air quality simulation in
this report were  the following:
     •   Emission  or discharge rate
     •   Effective stack height
     •   Atmospheric stability category
     t   Wind speed
     The emission rates used as inputs to the model are shown in Table  B-l(a)
for at-sea and land-based incineration and in Table B-l(b) for the chlorolysis
process.  The emission rates for at-sea and land-based incineration were
obtained from actual test data measured during operation of the incinerator
(References 4, 5, 9 and 11).  Emission rates for the chlorolysis process were
obtained from Reference 3.
     The physical stack height of the  land-based incineration facility is 30
meters.  The approximate distance of the top of the stack above the waterline
for the  at-sea facility is 15 meters.  Effective stack height values were cal-
culated  to be 96.5 meters for the land-based  facility and 125.5 meters for  the
at-sea facility.  For the chlorolysis  process, the physical  stack height  of 40
                                   107

-------
meters in the Hoechst-Uhde design was used as the effective stack height for
the incineration unit (Reference 3).  A value of 5 meters was used as the
effective stack height for all other units that discharged emissions  because
these are all emissions from process unit ventings.
             TABLE B-l(a).  EMISSION RATES USED FOR AIR QUALITY SIMULATION
                            FOR AT-SEA AND LAND-BASED INCINERATION3
        Constituent
               Emission Rate (kg/hr)
At-Sea Incineration       Land-Based  Incineration
   HC1
   Unburned Wastes
   Inorganics
14.16 X 10°
 8.8 (99.96% DEC)
 2.2 (99.99% DEC)
72.0

53.0
0.895
0.3
Participates
F
Cr
Ni
Ti
Pb
Cu
Zn
As
Co

1.0
4.0
2.0
0.4
0.4
0.7
0.7
0.1
0.1
1.03

6.9 X 10"4
6.9 X 10"4
6.9 X 10"4





    Emission rates are based on sampling and analysis data obtained at two
    operating facilities (References 4, 5, 9 and 11).  See Sections 3 and 4
    of this report for a detailed description of how emissions were deter-
    mined.

    The magnitude of this emission is determined by the use of combustion
    efficiency for the at-sea facility and detection limits for the land-
    based facility.  See Sections 3 and 4 of this report.
   •»
   'DE  =  Destruction Efficiency
                                    108

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TABLE B-l(b).  EMISSION RATES USED FOR AIR QUALITY
               SIMULATION FOR THE CHLOROLYSIS  PROCESS
NaOH Absorber

Incineration Unit

Absorption Unit

Absorption Tank
HC1 Column

Inerts
cci4
coci2
HC1
Inerts
HC1
Inerts
ci2
coci2
cci4
so2
HC1
ci2
cci4
coci2
10 kg/hr
0.5 gm/hr
0.01 gm/hr
0.03 .gm/hr
2737 kg/hr
142.6 gm/hr
1250 kg/hr
30.6 gm/hr
42.6 gm/hr
66.3 gm/hr
3.0 gm/hr
4.28 kg/hr
0.43 gm/hr
0.21 gm/hr
0.21 gm/hr
                       109

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     Table B-2 shows the annual  percent frequency of  Pasquill  categories  for
all wind directions and speeds at seven cities  across the  United  States.  The
D stability (neutral) is the most commonly occurring, while  the A category
(highly unstable) is the least.   All  simulations  were performed for  neutral
(Class D) atmospheric stabilities.
     TABLE B-2.  ANNUAL PERCENT FREQUENCY  OF PASQUILL  STABILITY
                 CATEGORIES FOR ALL WIND DIRECTIONS AND SPEEDS

Pasquill Stability Category

Birmingham, Alabama
Tucson, Arizona
Los Angeles, Calif.
Miami, Florida
Chicago, Illinois
New York, New York
Philadelphia, Pa.
A
1
2
0
0
1
0
0
B
7
10
4
5
5
3
5
C
12
14
15
14
11
10
11
D
44
33
48
42
55
67
51
E
36*
41*
13
39*
12
13
14
F


19

17
6
18

indicates E and F categories combined.  (After Reference B-ll).
     A mean wind speed of 4.0 meters per second was used in all  simulations.
Table B-3 summarizes average wind speeds and directions for three on-shore
sites closest to the North Atlantic area under consideration as  a site for
at-sea incineration.  Averages at these three sites were 4.0 meters per
second at Trenton, 4.6 meters per second at Newark and 4.8 meters per second
at Atlantic City.  The value of 4.0 meters per second was selected because
the use of this value would result in higher ground level concentrations.
(See Sensitivity Analysis in the next section of this Appendix).   Table B-4
shows the average wind speed and direction for Houston over a period of 32
years.  The average over 32 years was 4.8 m/s while for 1969 the average was
3.5 m/s.  Again a value of 4.0 m/s (rather than 4.8 m/s) was selected as this
would result in higher ground level concentrations.
                                   no

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         TABLE B-3.  AVERAGE WIND SPEEDS (METERS/SECOND)  AND
                     PREVAILING WIND DIRECTION FOR THREE  COASTAL AREAS
Atlantic City3
Speed Direction
Meters/ Second
January
February
March
April
May
June
July
August
September
October
November
December
AVERAGES
5.3
5.5
5.6
5.5
4.9
4.3
4.1
3.9
4.2
4.4
5.1
5.1
4.8
WNW
W
WNW
S
S
S
S
S
ENE
W
W
WNW
S
Newark
Speed Direction
Meters/Second
5.0
5.2
5.4
5.1
4.5
4.2
3.9
3.9
4.0
4.2
4.6
4.8
4.6
NE
NW
NW
WNW
SW
SW
SW
SW
SW
SW
SW
SW
SW
Trenton
Speed Direction
Meters/Second
4.4
4.6
4.8
4.6
4.0
3.8
3.5
3.4
3.5
3.7
4.1
4.2
4.0
NW
NW
NW
S
S
S
S
S
S
N
SW
NW
S
a Represents 16 years of data (1955-1970)
b Represents 31 years of data (1940-1970)
c Represents 32 years of data (1939-1970)

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     TABLE B-4.  AVERAGE WIND SPEED AND DIRECTION  AT  HOUSTON,  TEXAS

Houston
1931-1963 1969
Speed Direction Speed
(m/sec) (m/sec)
January
February
March
April
May
June
July
August
September
October
November
December
5.3
5.4
5.7
5.8
5.2
4.6
3.9
3.8
4.1
4.4
5.0
5.1
NNW
SSE
SSE
SSE
SSE
SSE
S
SSE
SSE
ESE
SSE
SSE
4.8
51.
5.4
4.5
3.7
3.0
2.4
2.5
2.2
3.3
2.6
3.1
Direction
(degrees)
110
70
40
150
130
150
180
130
80
90
10
90
AVERAGE
4.8
SSE
3.5
120
Wind direction for 1931-1963 is prevailing direction  while  that  for  1969  is
resultant direction.
                                   112

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SENSITIVITY ANALYSIS
     The purpose of this sensitivity analysis  is  to  describe  the manner  in
which predicted ground level  concentrations  vary  in  response  to changes  in
key input parameters.  For the purpose of this analysis  an emission  rate of
6050 grams/hour was used.
     Ground level concentration as a function  of  three effective  stack heights
is shown in Figure B-l.  At an effective stack height, h,  of  10.0  meters and
a wind speed, u, of 0.5 meters/second, a peak  concentration of 3040  yg/m
occurs at 0.5 km downwind.  As h is doubled to 20 m, concentration is re-
                 3
duced to 810 yg/m  but now occurs further downwind at 0.9 km.  Increasing
the effective stack height to 30.0 m further reduces the ground level maxi-
                             3
mum concentration to 267 yg/m  which now occurs even further  downwind at 2.0
km.  An increase in the effective stack height by a factor of two causes ap-
proximately a four-fold decrease in ground level  concentration and increasing
the effective stack height by a factor of three causes approximately a 12-fold
decrease in ground level concentration.  This demonstrates the strong in-
fluence of effective stack height on ground level concentration.
     The dependence of  concentration on wind  speed  is shown  in Figure B-2.
Increasing wind  speed  by a factor of 2 reduces ground level  concentration by
exactly one-half.  This may  be  inferred directly from Equation (B-l)  in which
concentration  is inversely proportional to wind speed.
                                      113

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  3000.
  2400.
   1800
X
   1200.
        0
1000
2000         3000

       x (meters )
4000
5000
6000
         Figure  B-l.  Ground level concentration as a function  of downwind
                     distance at three effective stack heights,  h.   Emission
                     rate is 6.05 kg/hr.
                                      114

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3000
             j=0.5 meters/second
2400 . -
                                                                    00       6000
                                       x (meters)
           Figure B-2.
Ground level  concentration as a function of downwind
distance at three wind speeds, u.  Emission rate
is 6.05 kg/hr.
                                     115

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SIMULATION RESULTS
     Simulation of ambient air quality effects  associated with  at-sea  incin-
eration, land-based incineration, and the chlorolysis  process was  performed
using the model and inputs described in previous sections and the  results  are
shown in Tables B-5 through B-12.
Land-Based Incineration
     The highest ground level concentration for land-based incineration can
be expected from particulates.  Table B-5 shows a maximum of 0.62 yg/m  occur-
ring at 3 km downwind for D stability.  Unburned wastes from land-based in-
cineration appear small.  At 3 km downwind the concentration is 0.18 ug/m
for D stability.


 At-Sea  IjTcineratioji
      As shown  in  Tables  B-6 and  B-7, the highest  predicted  concentrations from
 at-sea  incineration are  due to HC1  emissions.   A  maximum of 4.42  mg/m  occurs
 at 4  km downwind  for D  Stability.
      The ambient  levels  for unburned wastes  from  at-sea  incineration  are  much
 lower than  for HC1.  This is due to a lower  emission  rate for  unburned waste
 as compared to that for HC1.  In turn, the differences in emission  rates  are
 related to  1)  the relatively high combustion efficiency  of the incinerator,
 and 2)  the  fact that scrubbers are not used  for at-sea incineration.   There-
 fore, all  HC1  produced  is emitted while unburned  waste emissions  are  assumed
 to be,  and  in  fact are, combustion efficiency limited.  The maximum concen-
                                                         3
 tration for unburned waste is calculated to  be 2.75 yg/m  at 4 km downwind
 for D stability.
 Chlorolysis Process
      The simulation results for  the chlorolysis process  are shown in  Tables
 B-8 through B-12.  The maximum ground level  concentration for  all emissions
 from each unit except the incineration unit  occurs at the source with concen-
 tration decreasing as distance from the source increases.  Because the incin-
 eration unit has a stack height  of 40.0 meters, the maximum ground level  con-
 centration of emissions from the incineration unit occurs at 700 meters down-
 wind from the source.
                                      116

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     In Table B-13 the same emissions from each  process  (I.e.,  CCl^  from the
NaOH absorber, CCl^ from the absorption unit,  and CCl^ from the HC1  column)
have been summed and the totals are shown.  It 1s assumed that  emission con-
centrations are additive.  The maximum concentration for the summed  emissions
occurs at the source with concentration decreasing as distance  from  the source
Increases.
                                     117

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TABLE B-5.  RESULTS OF AIR QUALITY SIMULATION FOR LAND-BASED INCINERATION:
            HC1, TRACE METALS, UNBURNED WASTE AND PARTICULATES3
Distance Downwind
From Facility
(Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
HC1,
(ng/m3)
.00
.00
.00
.00
.07
2.88
9.20
31.03
57.47
148.08
477.06
536.61
489.52
425.73
367.13
317.79
277.36
244.06
216.52
90.42
51.90
Trace Metals
(Ti,N1 & Cr.ea)
(ng/m3)
.00
.00
.00
.00
.00
.00
.01
.02
.04
.11
.37
.41
.38
.33
.28
.25
.21
.19
.17
.07
.04
Unburned
Waste
(ng/m3)
.00
.00
.00
.00
.02
.96
3.09
10.40
19.26
49.63
159.91
179.87
164.09
142.70
123.06
106.52
92.97
81.81
72.58
30.31
17.40
Participates
(ng/m3)
.00
.00
.00
.00
.08
3.31
10.59
35.71
66.14
170.41
549.02
617.55
563.36
489.95
422.51
365.72
319.19
280.87
249.18
104.05
59.73
 Simulation parameters were:
Effective Stack Weight = 96.5 meters
Wind Speed = 4.0 meters/second
D stability
                                   118

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TABLE B-6.  RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION:

             HC1, UNBURNED WASTES AND INORGANICS8

Distance Down-
wind From Ship
(Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
GROUND LEVEL CONCENTRATION
Unburned Wastes
HCK h(ug/nr) h
(ng/mj) 99.96* DED 99.99* DED
.00
.00
.00
.00
.00
.10
.84
8.09
25.43
144.67
2082.66
2849.86
4422.80
4389.32
4116.79
3777.38
3438.65
3124.50
2843.01
1318.93
781.14
.00
. .00
.00
.00
.00
.06
.00
.01
.02
.09
1.29
1 2.39
2.75
2.73
2.56
2.35
2.14
1.94
1.77
.82
.49
.00
.00
.00
.00
.00
.00
.po
.00
.00
.02
.32
.60
.69
.68
.64
.59
.53
.49
.44
.20
.12
Inorganics
(iig/m3)
High Low
.00
.00
.00
.00
.00
.00
.00
.04
.13
.74
10.59
19.58
22.49
22.32
20.93
19.21
17.48
15.89
14.46
6.71
3.97
.00
.00
.00
.00
.00
.00
.00
.03
.10
.54
7.80
14.41
16.55
16.43
15.41
14.14
12.87
11.69
10.64
4.94
2.92
 aS1mu!at1on parameters were:  Effective Stack Height - 125.5 meters
                               Wind Speed • 4.0 meters/second
                               D stability
 bDE « Destruction efficiency
                                        119

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TABLE B-7.  RESULTS OF AIR QUALITY SIMULATION FOR AT-SEA INCINERATION:
            SELECTED TRACE ELEMENTS^

Downwind Distance
From Ship (Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
Ground
F
(ng/m3)
.00
.00
.00
.00
.00
.01
.06
.57
1.80
10.22
147.08
271.08
312.34
309.98
290.73
266.76
242.84
220.66
200.78
93.14
55.17
Level Concentration
Cu/Zn
(ng/m3)
.00
.00
.00
.00
.00
.01
.04
.40
1.26
7.15
102.96
190.32
218.64
216.99
203.51
186.73
169.99
154.46
140.54
65.20
38.62
Pb/Ti
(ng/m3)
.00
.00
.00
.00
.00
.00
.02
.23
.72
4.09
58.83
108.75
124.94
123.99
116.29
106.71
97.14
88.26
80.31
37.26
22.07
 Simulation parameters were:
Effective Stack Height = 125.5 meters
Wind Speed =4.0 meters/second
D stability
                                   120

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TABLE B-7 (Continued)

Downwind Distance
From Ship (Meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
As/ Co
(ng/m3)
.00
.00
.00
.00
.00
.00
.00
.06
.18
1.02
14.71
27.19
31.24
31.00
29.07
26.68
24.28
22.06
20.08
9.32
5.52
Ground Level Concentration
Cr
(ng/m3)
.00
.00
.00
.00
.00
.03
.24
2.28
7.18
40.87
588.32
1087.53
1249.38
1239.92
1162.93
1067.06
971.37
882.63
803.11
372.58
220.66
Ni
(ng/m3)
.00
.00
.00
.00
.00
.01
.12
1.14
3.59
20.43
294.16
543.77
624.69
619.96
581.47
533.53
485.68
441 .31
401.56
186.29
110.33
                  121

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        TABLE  B-8.  RESULTS OF AIR QUALITY SIMULATION FOR CHLOROLYSIS
                   PROCESS:  EMISSIONS FROM NaOH ABSORBER3
Downwind Distance
From Facility (meters)
100
200 .
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
Inerts
Ug/m3)
3351 .84
1238.16
617.24
415.08
295.74
208.59
173.34
129.50
111.80
91.88
34.15
18.76
12.27
8.82
6.74
5.36
4.41
3.70
3.17
1.14
.62
ecu
(ng/m-3)
167.59
61.91
30.86
20.75
14.79
10.43
8.67
6.47
5.59
4.59
1.71
.94
.61
.44
.34
.27
.22
.19
.16
.06
.03
COC12
(ng/m 3)
3.35
1.24
.62
.42
.30
.21
.17
.13
.11
.09
.03
.02
.01
.01
.01
.00
.00
.00
.00
.00
.00
HC1 ~
(ng/mj)
10.06
3.71
1.85
1.25
.89
.63
.52
.39
.34
.28
.10
.06
.04
.03
.02
.02
.01
.01
.01
.00
.00
aSimulation parameters were:
Effective Stack Height - 5.0 meters
Wind Speed = 4.0 meters/second
D stability
                                   122

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TABLE B-9.  RESULTS OF AIR QUALITY  SIMULATION  FOR
            CHLOROLYSIS PROCESS:   EMISSIONS  FROM
            INCINERATION UNIT3

Downwind Distance
From Facility (meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
Ground Level
Inerts
(mg/m3)
.00
.02
3.04
7.45
9.14
12.89
13.46
12.98
12.76
12.72
6.82
4.23
2.93
2.17
1.70
1.37
1.14
.96
.83
.30
.17
Concentration
HC1
(yg/m3)
.00
.00
.16
.39
.48
.67
.70
.68
.66
.66
.36
.22
.15
.11
.09
.07
.06
.05
.04
.02
.01

   Simulation parameters were:   Effective  Stack  Height  =  40.0 meters
                                 Wind Speed =4.0 meters/second
                                 D stability
                              123

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        TABLE  B-10.
RESULTS OF AIR QUALITY SIMULATION  FOR CHLOROLYSIS
PROCESS:  EMISSIONS FROM ABSORPTION UNIT9
Downwind Distance
From Facility (meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
Inerts
(mg/m3)
418.98
154.77
77.15
51.89
36.97
26.07
21.67
16.19
13.97
11.48
4.27
2.35
1.53
1.10
.84
.67
.55
.46
.40
.14
.08
Ground Level
Cl23
10.26
3.79
1.89
1.27
.90
.64
.53
.40
.34
.28
.10
.06
.04
.03
.02
.02
.01
.01
.01
.00
.00
Concentration
coci2
(yg/m 3)
14.28
5.27
2.63
1.77
1.26
.89
.74
.55
.48
.39
.15
.08
.05
.04
.03
.02
.02
.02
.01
.00
.00
cci4
22.22
8.21
4.07
2.75
1.96
1.38
1.15
.86
.74
.61
.23
.12
.08
.06
.04
.04
.03
.02
.02
.01
.00
Simulation parameters were:
         Effective Stack Height =5.0 meters
         Wind Speed =4.0 meters/second
         D stability
                                   124

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TABLE B-ll.  RESULTS OF AIR QUALITY SIMULATION FOR CHLOROLYSIS
             PROCESS:  EMISSIONS FROM ABSORPTION TANK3

Downwind Distance
From Facility (meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
Ground Level Concentration
so2
(ug/m3)
1.01
.37
.19
.12
.09
.06
.05
.04
.03
.03
.01
.01
.00
.00
.00
.00
.00
.00
.00
.00
.00

  aSimulat1on parameters were:  Effective Stack Height »  5.0 meters
                                Wind Speed » 4.0 meters/second
                                D stability
                               125

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     TABLE B-12.
RESULTS OF AIR QUALITY SIMULATION FOR CHLOROLYSIS PROCESS:
EMISSIONS FROM HC1  COLUMN3
Downwind Distance
From Facility (meters)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
HC1
1434.59
529.93
264.18
177.66
126.58
89.28
74.19
55.42
47.85
39.32
14.62
8.03
5.25
3.78
2.88
2.30
1.89
1.58
1.35
.49
.39
Ground Level
(ng/m3)
144.13
53.24
26.54
17.85
12.72
8.97
7.45
5.57
4.81
3.95
1.47
.81
.53
.38
.29
.23
.19
.16
.14
.05
.03
Concentration
cci4
(ng/m3)
70.39
26.00
12.96
8.72
6.21
4.38
3.64
2.72
2.35
1.93
.72
.39
.26
.19
.14
.11
.09
.08
.07
.02
.01
coci2
(ng/m3)
70.39
26.00
12.96
8.72
6.21
4.38
3.64
2.72
2.35
1.93
.72
.39
.26
.19
.14
.11
.09
.08
.07
.02
.01
aSimulation parameters were:
            Effective Stack Height = 5.0 meters
            Wind Speed =4.0 meters/second
            D stability
                                    126

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              TABLE  B-13.   GROUND LEVEL CONCENTRATIONS OF EMISSIONS FROM A CHLOROLYSIS PLANT*
ro
CC1
Downwind Distance 4
From Facility (meters) (yg/m3)
100
200
300
400
500
600
700
800
900
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
20000
30000
22.46
8.30
4.13
2.78
1.98
1.39
1.16
.87
.75
.61
.23
.12
.08
.06
.04
.04
.03
.02
.02
.01
.00
Ground Level Concentration
HC1 C12 COC12
(yg/m3) (yg/m3) (yg/m3)
1434.60
529.93
264.34
178.05
127.06
89.95
74.89
56.10
48.51
39.98
14.98
8.25
5.40
3.89
2.97
2.37
1.95
1.63
1.39
.51
.28
10.40
3.84
1.92
1.29
.91
.65
.54
.41
.34
.28
.10
.06
.04
.03
.02
.02
.01
.01
.01
.00
.00
14.35
5.30
2.64
1.78
1.27
.89
.74
.55
.48
.39
.15
.08
.05
.04
.03
.02
.02
.02
.01
.00
.00
so2
(ng/m3)
1.01
.37
.19
.12
.09
.06
.05
.04
.03
.03
.01
.01
.00
.00
.00
.00
.00
.00
.00
.00
.00
Inerts
(mg/m3)
422.33
156.03
80.80
59.76
46.41
39.17
35.30
29.30
26.84
24.29
11.12
6.60
4.47
3.28
2.55
2,05
1.69
1.42
1.23
.44
.25
  aValues obtained by adding the concentrations of the same emissions from each process.

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                                 REFERENCES


B-l    Overcamp, T.J., A General  Gaussian  Diffusion - Deposition Model for
       Elevated Point Sources.   J.  Appl. Meteor.,  15. 1976, pp. 1167-1171.

B-2    Slade, D.H., Atmospheric Diffusion  Over Cheseapeake Bay, Monthly
       Weather Rev., 90, pp.  217-224.

B-3    Van Der Hoven, I., Atmospheric  Transport and Diffusion at Coastal
       Sites.  Nuclear Safety,  £, 1967,  pp.  490-499.

B-4    Raynor, G.S., P. Michael,  R.M.  Brown, and S. Seth-Raman.  A Research
       Program on Atmospheric Diffusion  from an Oceanic Site.  American Meteor.
       Society Symposium on Atmospheric  Diffusion  and Air Pollution, Santa
       Barbara, California, Sept. 9-13,  1974, pp.  289-295.

B-5    Kitalgorodskil, S.A.,  The Physics of  Air-Sea Interaction, 1970.  Trans.
       from Russian and pub!. by Israel  Program for Scientific Translations,
       1172-50062, Jerusalem, 1973, v  and  237 pp.

B-6    Monln, A.S., The Atmospheric Boundary Layer.  Annual Review of Fluid
       Mechanics, 2, 1970, pp.  225-250.

B-7    Gifford, F.A., Turbulent Diffusion-Typing Schemes.  A Review, Nuclear
       Safety, Vol. 17, No. 1,  1970, pp. 25-43.

B-8    Golder, D., Relations  Among Stability Parameters 1n the Surface
       Boundary Layer.  Meteor. 3_,  1972, pp. 47-58.

B-9    Smith, F.B., A Scheme  for Estimating  the Vertical Dispersion of a
       Plume from a Source Near Ground Level.  Proc. of the Third Meeting of
       the Expert Panel on Air  Pollution Modeling, NATO-CCHS Report No. 14,
       Brussels, 1972.

B-10   Portelli, R.V., A Brief  Summary of  Scientific Literature Dealing with
       Diffusion over Water.   Presented  at the Meeting on Incineration At-Sea,
       London, England, March 21-25, 1977.

B-ll   Holzworth, G.C., Climatological Aspects of  the Composition and
       Pollution of the Atmosphere. World Meteorol. Organization Tech.
       Note No. 139, 1974.
                                    128

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                               TECHNICAL REPORT DATA
                         (Please read Instructions on The reverse before completing)
 REPORT NO.
 EPA-600/2-78-190
                          2.
                                                     3. RECIPIENT'S ACCESSION" NO.
 TITLE ANDSUBT.TLE Comparative Cost Analysis and
 environmental Assessment for Disposal of
Organochlorine Wastes
                                5. REPORT DATE
                                 August 1978
                                6. PERFORMING ORGANIZATION CODE
 AUTHOR(s)C.C.Shih, J.E. Cotter, D.Dean, S.F.Paige,
E. P. Pulaski, and C. F. Thome
                                                     8. PERFORMING ORGANIZATION REPORT NO.
 PERFORMING ORGANIZATION NAME AND ADDRESS
TRW, Inc.
One Space Park
Redondo Beach, California  90278
                                10. PROGRAM ELEMENT NO.
                                1AB606
                                11. CONTRACT/GRANT NO.

                                68-02-2613, Task 12
 2. SPONSORING AGENCY NAME AND ADDRESS
 EPA,  Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC  27711
                                13. TYPE OF REPORT AND PERIOD COVERED
                                Task Final; 5-6/78
                                14. SPONSORING AGENCY CODE
                                  EPA/600/13
 5.SUPPLEMENTARY NOTESIERL-RTP project officer is Ronald A. Venezia, Mail Drop 62,
919/541-2547.
 e. ABSTRACT rpne rep0rt compares the costs and environmental impacts associated with
the disposal of liquid organochlorine wastes by land-based incineration, at-sea incin-
eration, and chlorolysis at a Houston, Texas, location. All three methods are viable
options for the disposal of these wastes. At typical unit disposal costs of #80 to #91
 per metric ton, at-sea incineration is the least costly option. Comparable costs are
  Sl to #212  per metric ton at a centralized land-based incinerator, and #134 to #158
per metric ton by the Hoechst-Uhde chlorolysis process if suitable feedstocks are
available. Environmentally, maximum ground level concentrations of inorganic
chlorine and organochlorine species and particulates emitted from land-based incin-
erators and chlorolysis are all several orders of magnitude lower than their  respec-
tive Threshold Limit Values (TLVs) or are within air quality standards.  The only
wastewater  problem identified for both disposal processes is discharges  with high
total dissolved solids. For at-sea incineration, the maximum sea level concentration
of hydrogen chloride is 4.4 mg/cu m and below its TLV of 7 mg/cu m. The maximum
sea level concentration of unburned wastes is several orders of magnitude lower than
the TLV of  most organochlorine compounds. Water quality is not measurably impacted
by  at-sea incineration.
 7.
                             KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
                                          b.lDENTIFIERS/OPEN ENDED TERMS
                                               COSATI Field/Group
 Pollution
 Chlorine Organic
   Compounds
 Chlorine Inorganic
   Compounds
 Waste Disposal
 Dust          	
Organic Wastes
Chlorine
Cost Comparison
Assessments
Incinerators
Sea Water
Hydrogen Chloride
Pollution Control
Stationary Sources
Organochlorines
Environmental Assess-
   ment
At-sea Incineration
Particulate
13 B

07C

07B

11G
14A
14B

08J
 18. DISTRIBUTION STATEMENT

 Unlimited
                     19. SECURITY CLASS (This Report)
                     Unclassified
                                                                   21. NO. OF PAGES
                              129
                     20. SECURITY CLASS (Thispage/
                     Unclassified
                                              22. PRICE
EPA Form 2220-1 (9-73)
                                      129

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