&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.
-------
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
-------
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
-------
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.
-------
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
-------
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.
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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.
-------
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
-------
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
-------
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
-------
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.
-------
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.
-------
$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
-------
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
-------
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 +)
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
TO ADSORPTION
ro
BOTTOM
HIIIIMl'*
PRODUCTS
AIR WATER
INCINERATOR
NEUTRALIZED
WATER
Figure 6. Incineration section
-------
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
-------
A
WASTE VENT GASES
1
SCRUBBER
STORAGE
A
I
TANK
NaOH
WASTEWATER
1
ABSORPTION PIT
Figure 7. Absorption section,
74
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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 $300 per metric ton.
-------
Third, DCFRR for land-based Incineration at the unit disposal cost charged
by chlorolysls are presented. Again, it is shown that with the exception of
the CMW waste, the DCFRR for land-based incineration is lower than the corres-
ponding DCFRR for chlorolysis.
5.2 COMPARISON OF ENVIRONMENTAL IMPACTS
Data resulting from air quality simulations for constituents which have
counterparts in the three organochlorine waste disposal processes being consi-
dered in this report are summarized in Table 41. This table shows that there
are general differences in location and magnitude of expected maximum concen-
trations, as a result of the differences in emission rates and stack heights
used in air quality simulations. Because the most significant emissions from
chlorolysls are from process unit ventings, maximum concentrations are observed
close to the source. The only process unit for which this is not the case is
the incinerator at the chlorolysls plant. However, its contribution of
emissions is small, and the overall emission pattern of the units predominate.
Emission estimates for chlorolysls were obtained from the Hoechst-Uhde report
(Reference 3).
The data 1n Table 41 also highlight differences 1n the magnitude of air
contaminant concentrations produced by three processes. For land-based in-
cineration, the maximum ground level concentration of hydrogen chloride is
several orders of magnitude lower than the Threshold Limit Value (TLV) of
7 mg/m . The predicted concentrations of unburned wastes were conservatively
based on a destruction efficiency of 99.99$, 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
-------
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.
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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.
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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
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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
-------
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
-------
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
-------
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
-------
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)
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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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