xvEPA
United States
Environmental
Agency
Office of
Toxic Substances
Washmston, DC 20460
January 1980
EPA-560 13-30 002
Tox ic SubsTdnces
Materials Balance for
Methyl Chloroform
Level II
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FINAL REPORT
LEVEL II MATERIALS BALANCE
METHYL CHLOROFORM
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF PESTICIDES AND TOXIC SUBSTANCES
TASK NO. 3
Contract No. 68-01-5793
Michael Callahan - Project Officer
C. Richard Cothern - Task Manager
Prepared by:
JRB ASSOCIATES, INC.
8400 Westpar.k Drive
McLean, Virginia 22102
Project Manager: Karen Slimak
Task Leader: Michael Katz
Contributing Writers: Timothy McCartin
Le-Tan Phuoc
Terry Shannon
Kathy Wagner
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THE FINAL REPORT PRESENTED HEREIN RESULTED FROM
A LEVEL II MATERIALS BALANCE STUDY ON METHYL
CHLOROFORM. THE RESULTS WERE BASED ON AN ANALYSIS
OF ALL AVAILABLE INFORMATION RELEVANT TO THE MATERIALS
BALANCE. UNCERTAINTIES AND FURTHER DATA REQUIREMENTS,
INCLUDING SITE SAMPLING, ARE IDENTIFIED. THE
GENERATION OF NEW DATA THROUGH MONITORING IS NOT
WITHIN THE SCOPE OF THIS STUDY.
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MATERIALS BALANCE LEVELS
Materials balance studies are performed at three levels or depths
of study and effort. In general the study of a chemical proceeds se-
quentially through these three levels. Particular chemicals are assign-
ed to be studied at one of the levels on the basis of availability of
information. The three levels are described below.
Level I:
A LEVEL I MATERIALS BALANCE requires the lowest level of effort
and involves a survey of readily available information for construct-
ing the materials balance. Ordinarily, many assumptions must be made
in accounting for gaps in information; however, all are substantiated
to the greatest degree possible. Where possible the uncertainties in
numerical values are given, otherwise they are estimated. Data gaps
are identified and recommendations are made for filling them. A Level
I materials balance relies heavily on the EPA's Chemical Information
Division as a source of data and references involving readily available
information. Most Level I MB's are completed within a 3-6 week period;
CID literature searches generally require a 2 week period to complete.
Thus the total time required for completion of a Level I materials
balance ranges from 5-7 weeks.
Level II:
A Level II MATERIALS BALANCE involves a greater level of effort-,
including an in-depth search for all information relevant to the
materials balance. The search includes all literature, (concentrating
on primary references), contacts with trade associations, other agencies,
and industry to try to uncover unpublished information, and possibly site
investigations. Uncertainties and further data needs are identified in
the Level II report. Recommendations for site sampling needs for Level
III are also identified.
Level III:
A Level III study requires generation of new data through monitoring
and other means. IE builds on the Level II literature searches and re-
views of industrial production data by filling in data gaps through site
visits and necessary monitoring. The data generated in this type of study
are intended to be statistically valid and have known confidence values.
The goal is a study upon which regulations or legal proceedings may be
based.
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TABLE OF CONTENTS
List of Tables
List of Figures
Abstract ix
Executive Summary x
1.0 Introduction 1-1
2.0 Production of Methyl Chloroform 2-1
2.1 Global Production 2-6
2.2 Production of Methyl Chloroform from Vinyl Chloride 2-9
2.2.1 Production 2-9
2.2.2 Emissions to Air 2-10
2.2.3 Emissions to Water 2-22
2.2.4 Emissions to Air Due to Wastewater Treatment 2-24
2.2.5 Emissions to Land 2-26
2.2.6 Emissions to Air Due to the Incineration
Disposal Method 2-27
2.2.7 Multimedia Environmental Losses 2-28
2.3 Production of Methyl Chloroform from Ethane 2-30
2.3.1 Production 2-30
2.3.2 Emissions to Air 2-32
2.3.3 Emissions to Water 2-r38
2.3.4 Emissions to the Air Due to Wastewater
Treatment 2-40
2.3.5 Emissions to Land 2-41
2.3.6 Emissions to the Air Due to the Incineration
Disposal Method 2-42
2.3.7 Multimedia Environmental Losses 2-43
2.4 Vinylidene Chloride Process
2.4.1 Production 2-45
2.4.2 Emissions to Air 2-46
2.4.3 Emissions to Water 2-54
2.4.4 Emissions to Land 2-57
2.4.5 Multimedia Environmental Losses 2 58
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Page
2.5 Indirect Production of Methyl Chloroform by
Chlorination 2-60
2.6 Production of Methyl Chloroform from Natural Sources 2-63
2.7 Stockpiles 2-64
2.7.1 Introduction 2-64
2.7.2 Quantity Stockpiled 2-64
2.8 Imports 2-67
3.0 Uses and End Products 3r-l
3.1 Metal Cleaning 3^2
3.1.1 Use of Methyl Chloroform in Metal Cleaning 3^2
3.1.2 Quantification of Methyl Chloroform Used in 3^2
Metal Cleaning
3.1.3 Emissions from Cold Cleaning Operations 3r-10
3.1.4 Emissions from Open Top Vapor Degreasers 3-18
3.1.5 Emissions from Conveyorized Vapor Degreasers 3-24
3.1.6 Emissions from Conveyorized Non-Boiling 3-26
Degreasers
3 27
3.1.7 Multimedia Environmental Losses
3.2 Aerosol Products 3-30.
3.2.1 Quantification of Methyl Chloroform Used in 3-30
Aerosol. JPfoducts _. ... - _. .--
3.2.2 Use of Methyl Chloroform in Aerosol Products 3-30
3.2.3 Use and Emissions of Methyl Chloroform in 3-r31
Household Aerosol Products
3.2.4 Use and Emissions of Methyl Chloroform in 3-35
Automotive Products
3.2.5 Use and Emissions of Methyl Chloroform in 3-37
Coatings and Finishes
3.2.6 Use and Emissions of Methyl Chloroform in 3-39
Personal Care Products and Pesticide Products
3.2.7 Multimedia Environmental Losses 3-41
3.3 Adhesives 3-43
3.3.1 Quantification of Methyl Chloroform Used in 4-43
Adhesives
ii
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3.3.2 Use of Methyl Chloroform in the Adhesives Industry
3.3.3 Use and Emissions of Methyl Chloroform in
Solvent Based Adhesives
3.3.4 Use and Emissions of Methyl Chloroform in Water
Based Adhesives
3.3.5 Multimedia Environmental Losses
3.4 Textiles
3.4.1 Use and Quantification of Methyl Chloroform Used
in Textiles
3.4.2 Emissions of Methyl Chloroform from the Production
of Textiles
3.4.3 Multimedia Environmental Losses
3.5 Drain Cleaners and Septic Tank Cleaners
3.5.1 Use of Methyl Chloroform in Drain and Septic
Tank Cleaners
3.5.2 Quant if ite^-'on of Methyl Chloroform Used in Drain
and Septic Tank Cleaners
3.5.3 Multimedia Environmental Losses
3.6 Paints
3.6.1 Emissions to Air
3.6.2 Emissions to Water
3.6.3 Emissions to Land
3.6.4 Multimedia Environmental Losses
3.7 Inks
3.7.1 Emissions to Air
3.7.2 Emissions to Water and Land
3.7.3 Multimedia Environmental Losses
3.8 Miscellaneous Uses of Methyl Chloroform
3.8.1 Catalyst Preparation
3.8.2 Film Cleaning
3.8.3 Pharmaceuticals
3.8.4 Leather Tanning and Finishing
3.9 Exports
3.9.1 Exports of Methyl Chloroform
3.9.2 Method of Export
.3.9.3 Trends in the Export of Methyl Chloroform
3-44
3-47
3.57
3-63
3-65
3-65
3-65
3-75
3-77
3-77
3-78
3-80
3-86
3-86
3-87
3-88
3-89
3-91
3-91
3-92
3-93
3-95
3-96
3-97
3-101
3-107
3-115
3-115
3-116
3-117
iii
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4.0 Disposal and Destruction of End-Products 4-1
4.1 Contamination of End-Products 4-1
4.2 Summary of Disposal/Destruction of End-Products 4-2
5.0 Summary of Environmental Releases of Methyl Chloroform 5-1
6.0 Summary of Uncertainties 6-1
7.0 Data Gaps and Recommendations 7-1
7.1 Vinylidene Chloride Method 7-1
\
7.2 Vinyl Chloride Process 7-2
7.3 Ethane Process 7-3
7.4 Metal Cleaning 7-4
7.5 Aerosols 7-5
7.6 Adhesives 7-6
7.7 Textiles 7-7
7.8 Paints 7-7
7.9 Inks 7-8
7.10 Septic Tank Cleaners and Drain Cleaners 7-8
7.11 Catalyst Preparation 7-8
7.12 Film Cleaning 7-9
7.13 Leather Tanning 7-9
8.0 Discussion of National Academy of Science Study:
STRATOSPHERIC OZONE DEPLETION BY HALOCARBONS
8.1 Comparison of Production Estimates 8-1
8.2 Discussion of Estimates for Ozone Depletion 8-3
References R-l
Appendices
A - Process Description A-l
B - Legislation Effecting the Use of Methyl Chloroform B-l
C - Metal Cleaning C-l
D - Products Containing Methyl Chloroform D-l
E - Physical Properties of Methyl Chloroform E-l
F - Breathing and Working Losses F-l
iv
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LIST OF TABLES
Table Page
2.1-1 Worldwide Production of Methyl Chloroform 2-6
2.1-2 Methyl Chloroform Production Capacity for Plants
Outside the United States (103 kkg/year) 2-7
2.2-1 Selected Physical Properties of Vinyl Chloride,
1,1-Dichloroethane and Methyl Chloroform 2-14
2.2-2 Uncontrolled Emissions Due to Storage and Handling 2-16
2.3-1 Estimates of Total Uncontrolled VOC Emissions from a
Model Plant Producing Methyl Chloroform from Ethane 2-33
2.3-2 Estimated Composition of Distillation Vent Gas from
Model Plan Producing Methyl Chloroform from Ethane 2-34
2.3-3 Storage Tank Data for Methyl Chloroform (Ethane Feed)
Model Plant 2-37
2.5-1 Concentrations of Volatile Chlorinated Organics Before
and After Chlorination 2-61
2.7-1 Stockpiles of Methyl Chloroform 2-66
3.1-1 Estimates of Use of Methyl Chloroform in Solvent 3-5
Degreasing
3.1-2 Major Control Variables for Cold Cleaners 3-11
3.1-3 Efficiencies of Control Options in Controlling 3-12
Solvent Losses from Cold Cleaners
3.1-4 Control Variables - Open Top Vapor Degreasers 3-=20
3.3-1 Adhesive Subcategories 3-45
3.3-2 Summary of Uncertainties for Environmental Release from 3-53
Vessel Cleaning
3.3-3 Summary of Uncertainties for Environmental Releases from 3.51
Vessel Cleaning
3.4-1 Subcategories of the Textile Industry 3-67
3.9-1 U. S. Export of Methyl Chloroform 3-115
3.9-2 U. S. Exports of Methyl Chloroform 3-118
4.2-1 Disposal and Destruction of End Products 4-3
4.2-2 Summary of Methyl Chloroform Landfilled Over 5 Year 4-4
Period
6.0-1 Summary of Uncertainties 6-2
8.1-1 Estimated Global Production of Methyl Chloroform from 8-r3
1977-1982 Using Three Possible Scenarios
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TABLES
Table Page
C-l Use of Solvent Degreasing Among Metal Working SIC
Categories C-l
C-2 Summary of Uncertainties for Waste Solvent C-10
C-3 Summary of Uncertainties for Waste Solvent from C-17
Vapor Degreasing
C-4 Summary of Uncertainties for Waste Solvent from . C-22
Conveyorized Vapor Degreasers
C-5 Summary of Uncertainties for Waste Solvent from C-28
Conveyorized Vapor Degreasers
D-l List of Products Containing Methyl Chloroform D-l
D-2 Registered Pesticides Containing Methyl Chloroform D-3
F-l Assumptions Used in Breathing and Working Loss Rate
Calculations F-2
vi
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LIST OF FIGURES
Figure Page
ES-1 Summary of Materials Balance for Methyl Chloroform (1978) xiii
2.0-1 Locations and Plant Capacities of the Production Plants of
Methyl Chloroform 2-2
2.0-2 Location of Dow Chemical Company Methyl Chloroform
Production Plant (Vinyl Chloride Process) 2-3
2.0-3 Location of PPG Industries, Inc. Methyl Chloroform
Production Plant (Vinylidene Chloride Process) 2-4
2.0-4 Location of Vulcan Materials Company Methyl Chloroform
Production Plant (Ethane Process) 2-5
2.2-1 Flow Diagram for Production of Methyl Chloroform
from Vinyl Chloride 2-12
2.2-2 Multimedia Environmental Losses from the Vinyl Chloride-
based Production Process 2-29
2.3-1 Flow Diagram for Production of Methyl Chloroform
from the Ethane Process 2-31
2.3-2 Multimedia Environmental Losses from the Ethane-based
Production Process 2-44
2.4-1 Derived Flow Diagram of the Production Process from
Vinylidene Chloride . . . 2-47
2.4-2 Multimedia Environmental Losses from the Vinylidene
Chloride-based Production Process 2-59
2.5-1 The Haloform Reaction 2-62
3.1-1 Geographic Distribution of the Metalworking Industry 3.3
3.1-2 Overall Summary of Materials Balance for Methyl Chloroform 3-4
in Metal Cleaning
3.1-3 Production Trends for Methyl Chloroform and 3-8
Trichloroethylene
3.1-4 Points of Emission from a Cold Cleaning Operation 3-10
3.1-5 Multimedia Environmental Losses of Methyl Chloroform 3-14
from Cold Cleaning
3.1-6 Geographic Distribution of Methyl Chloroform from Cold 3-17
Cleaning Operations
3.1-7 Points of Emission from an Open Top Vapor Degreaser 3-18
3.1-8 Multimedia Environmental Losses of Methyl Chloroform from 3-21
Open Top Vapor Degreaser
3.1-9 Geographic Distribution of Methyl Chloroform Losses from 3-25
Vapor Degreasing
vii
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Page
3.1-10 Multimedia Environmental Losses of Methyl Chloroform from 3-24
Conveyorized Vapor Degreasers
3.1-11 Multimedia Environmental Losses from Methyl Chloroform from 3-27
Conveyorized Nonboiling Degreasers
3.1-12 Overall multimedia Environmental losses for Methyl Chloroform 3-28
from Metal Cleaning
3.2-1 Flow Diagram and Multimedia Environmental Losses of Methyl 3-32
Chloroform from Aerosols
3.2-2 Multimedia Environmental Losses of Methyl Chloroform from 3-42
the Production and Use of Aerosols
3.3-1 Geographic Distribution of Adhesive Industries 3-46
3.3-2 Multimedia Environmental Losses of Methyl Chloroform from 3-56
Solvent Based Adhesives
3.3-3 Multimedia Environmental Losses of Methyl Chloroform from 3-58
Water Based Adhesives
3.3-4 Total Multimedia Environmental Losses from the Formulation T.AA
and Use of Adhesives
3.4-1 Flow Diagram of the Methyl Chloroform Used in Textiles 3-66
3.4-2 Multimedia Environmental Losses of Methyl Chloroform from 3-76
Text iles
3.5-1 Multimedia Environmental Losses of Methyl Chloroform 3-81
from Septic Tank Cleaners and Drain Cleaners
3.6-1 Multimedia Environmental Losses of Methyl Chloroform from 3-90
Traffic Paints
3.7-1 Multimedia Environmental Losses of Methyl Chloroform from 3-94
the Ink Industry
3.8-1 Multimedia Environmental Losses of Methyl Chloroform from 3-100
Film Cleaning
3.8-2 Typical Process for Extraction of Medicinal Chemicals 3-103
3.8-3 Multimedia Environmental Losses of Methyl Chloroform from- 3-106
Pharmaceutical Processes
3.8-4 Flow Diagram for the Chrome Tanning Process 3-108
3.8-5 Flow Diagram for a Typical Leather Tanning Process 3-109
3.8-6 Multimedia Environmental Losses of Methyl Chloroform in the 3-114
Tanning Industry
A-l Flow Diagram for Methyl Chloroform from Vinyl Chloride A-3
A-2 Flow Diagram for Methyl Chloroform from Ethane A-7
A-3 Derived Flow Diagram of the Production Process from
Vinylidene Chloride A-ll
viii
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ABSTRACT
A Level II materials balance for methyl chloroform was performed.
Using 1978 data, the results of this materials balance included emission
factors, the equations required to calculate environmental releases, and
multimedia environmental losses for each production process and end use.
Assumptions used to calculate the environmental losses were analyzed and
an uncertainty was given to each.
Recommendations were developed to close data gaps. These recommendations
identified monitoring requirements and sites and suggested those end uses
for future studies.
This report was submitted in fulfillment of Contract Number 68-01-5793,
Task No. 3 by JRB Associates, Inc. under the sponsorship of the United States
Environmental Protection Agency.
ix
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EXECUTIVE SUMMARY
This Level II materials balance reports emissions of methyl chloroform
resulting from the production and use of this substance. A volatile organic
»
compound, methyl chloroform is used primarily for metal cleaning (66 percent),
as a vapor depressant in aerosols (7 percent), and for adhesive formulations
requiring a solvent (7 percent). Methyl chloroform usage had been increasing
steadily until 1976. Because of questions concerning its human health effects
as a suspected carcinogen and its impact on the stratosphere, the Occupation
Health and Safety Agency and the Environmental Protection Agency are con-
sidering placing restrictions on its use. These potential restrictions have
inhibited the growth of methyl chloroform usage during the past few years.
The materials balance is presented for 1978 quantities of methyl
chloroform. Estimates of environmental losses were derived using industry
trends and information from industrial contacts and literature searches.
In 1978, an estimated 284,000 kkg of methyl chloroform were produced
by three processes with different starting materials: vinyl chloride (Dow),
ethane (Vulcan), and vinylidene chloride (PPG). These processes constitute
63 percent, 28 percent, and 9 percent respectively, of the total 1978
production. In 1979, PPG Industries, Inc. placed their vinylidene chloride
process in reserve status and began producing methyl chloroform using
vinyl chloride as the raw material. The releases to the environment
from these production processes are discussed and calculated in Chapter 2
and summarized in Figure ES-1. Air emissions from various process vents,
storage, handling, fugitive losses, aeration during waste water treatment,
and the incineration of heavy-end wastes were estimated to be 176 kkg.•
Effluent emissions from the production of methyl chloroform totaled 0.29 kkg
for 1978. Emissions to land from these processes were 0.004 kkg.
Quantities produced, but not sold were assumed to be placed in
stockpiles. Stockpiles represented 17,500 kkg or approximately 6.2 percent
-------
of total production in 1978. Emissions from stockpiles were included in the
total emissions from product storage.
Imports of methyl chloroform were not identified during our literature
search nor were any suggested during phone conversations with industry
sources. Our analysis found no sources of natural or indirect production.
The quantity of methyl chloroform exported in 1978 was 18,000 kkg (6.3
percent of total production). Table 3.9-1 lists the quantities exported
to foreign countries.
There were no consumptive uses of methyl chloroform in 1978. Methyl
chloroform had been used by Dow to produce vinylidene chloride but this process
was terminated in 1974. Secondary contamination of other products was not
found and is considered unlikely.
Noneonsumptive uses (and the approximate percentage of methyl chloro-
form production used by each) were: metal cleaning (66.1 percent),
aerosols (7.0 percent), adhesives (7.0 percent), textiles (1.0 percent),
paints (1.8 percent), inks (1.0 percent), drain cleaners (0.5 percent),
film cleaning (0.1 percent), Pharmaceuticals (0.1 percent), leather tanning
(0.1 percent) and other unspecified miscellaneous uses (2.8 percent)
(primarily miscellaneous solvent-cleaning applications). Emissions from
each nonconsumptive use are identified in Figure ES-1.
Metal cleaning was the primary end use of methyl chloroform and also
the primary source of emissions. Emissions to air, land, and water from
metal cleaning operations totaled 159,500, 22,200, and 975 kkg respectively.
Air emissions resulting from metal cleaning represent almost 75 percent of
the total air emissions for all sources. Water and solid waste emissions from
metal cleaning are greater than 40 and 84 percent, respectively, of the total
emissions in these categories.
XI
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Two major uses, adhesives and aerosols, each account for approximately
7 percent of the annual production of methyl chloroform. Air emissions from
these uses were nearly identical (17,400 and 18,100 kkg) but solid waste
and water emissions differed significantly. For adhesives, 919 kkg were
lost through solid waste and 329 kkg in water effluent. For aerosols,
almost 1900 kkg were lost in solid wastes, yet because of the formulation
process and end use, no quantifiable amount of methyl chloroform was
released to waste waters.
Total emissions from nonconsumptive uses were 213,000 kkg to the air,
26,200 kkg in solid wastes, and 2,400 kkg in water effluent.
Waste disposal and destruction accounted for 4,700 kkg of the total
methyl chloroform produced. Metal cleaning was the largest source of methyl
chloroform landfilled or incinerated (4,200 kkg or 91 percent of the total).
Of the production processes, waste disposal and destruction for vinylidene
chloride were proportionately higher than for the other two processes. This
is due to the greater level of control technology assumed for this process.
This report contains many estimates, including some for important
numbers. The quantities of methyl chloroform in minor end uses will be
required for meaningful emissions estimates. Data gaps are identified
in Chapter 7, which also gives our recommendations for filling them.
xii
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ES-1 Summary of Materials Balance for Methyl Chloroform (1978)
Sources
Consumptive
Use
Nonconsumptlve
Use
Secondary
Uses
Storage/Waste
Dlspoi*!
Air
TO TIlB ^'pyipnnmrtnr (t'
Solid Was Woter
3.58x10
75.5
-5
0.00364
17,500
4200
57.3
177
145
284,000 18,000 248,500
(+7Z,-5J!) (+ 10X) (+10Z.-7X)
94.5
67,4
3.58x10
13.7
159,500
18,100
17,400
2920
4950
2780
278
124
218
104
28.4
6730
0.133
0.115
0.00383
0,043
22,200
1890
919
17.5
100
57
303
20.7
2.23
829
975
329
1.94
1..08x10"
919
1.88
76
22,200 213,300 26,300 2,300
(+27X.-37Z) (+2U.-30Z) (+9U,.99>:) (+71JI.-72X)
1017 kkg of Methyl Chloroform used In adheslves are reclaimed and sold as waste solvent
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1.0 INTRODUCTION
This report was prepared in response to a task order from the U.S.
Environmental Protection Agency (EPA) for a Level II materials balance
study on methyl chloroform. The study is primarily concerned with the
flow and releases of methyl chloroform from its production to its end
uses.
In order to provide EPA a material balance report on methyl chloro-
form, available information was thoroughly and carefully analyzed. In
most cases where changes in recent years have made published data
obsolete, industrial sources were contacted to obtain updated information.
Thus, the results generated in this report are more applicable to a
Level II than to a Level I materials balance. In some cases where data
could not be obtained, estimates were provided based on available
information on similar processes.
This study also presents an analysis of the National Academy of
Sciences (NAS) report on methyl chloroform in the stratosphere. Since
methyl chloroform has been identified as an ozone-depleting agent, a
comparison of the results of our study with the Academy's has been
provided. The differences between the reports with respect to the
future stratospheric Impact of methyl chloroform are highlighted.
This report contains numerous calculations resulting in numbers
that are not directly additive. These values are the result of always
rounding to three (3) significant figures.
1-1
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2.0 PRODUCTION OF METHYL CHLOROFORM
The quantity of methyl chloroform produced in 1978 was reported as
284,000 kkg (+7%, -5%) (USITC, 1978). This figure is based on the
amount of product reported to the International Trade Commission by eech
producer. The upper and lower bounds presented in Sections 2.2.1, 2.3.1
and 2.4.1 form the basis for the uncertainty of the overall production
figure. Methyl chloroform was reported to be produced by 3 different
methods: a) the vinyl chloride method, b) the ethane method and c) the
vinylidene chloride method. The percentages of methyl chloroform
produced by each method are, respectively, 63 percent, 9 percent, and 28
percent. The following sections will present an in-depth discussion of
each process. Figures 2.0-1 - 2.0-4 shows the locations of methyl
chloroform production sites in the United States.
Natural production sources have not been identified and indirect
sources, such as chlorination of public water, were not found to contribute
significantly ( ^.001 per cent) to the total production.
2-1
-------
Name and Location
Production Plant
Dow Chemical Co., Freeport TX
PPG Industries Inc., Lake Charles LA
Vulcan Materials Co., Geismar LA
1978
Plant Capacity
(kkg)
204,000
136,000
29,500
1979
Plant Capacity
(kkg)
340,000
136,000
93,000
Figure 2.0-1 Locations and Plant Capacities of the Production Plants
of Methyl Chloroform
Source: EPA, 1979a
2-2
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DOU CHEM ^L COMPANY
GULF CF MEX GO
Residential
«TA O Emission Source
— Highway
~~ Railroad
O Plant Proper
Industrial
Marsh
Air Site
Soil Site
Water Site
Sediment Site
Figure 2.0-2 Location of Dow Chemical Company
Methyl Chloroform Production Plant
(Vinyl Chloride Process)
2-3
-------
: ^^^55?
-------
MANUFACTURING
GULFOF.MEX
V
•figure 2.0-4 Location of Vulcan Materials Company
Methyl Chloroform Production Plant
(Ethane Process)
2-5
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2.1 GLOBAL PRODUCTION
Table 2.1-1 shows worldwide emissions of methyl chloroform from
1974-1978. These estimates were made by the Corporate Product Depart-
ment of Dow Chemical (Neely and Agin, 1978) and exclude any methyl
chloroform produced in the Soviet Union and other Iron Curtain countries.
As judged from a previous Dow publication (Neely and Plonka, 1978),
total worldwide production may be about 3 to 6 percent greater than
total annual emissions.
Table 2.1-1 Worldwide Production of Methyl Chloroform
(1)
Year
1974
1975
2
Global Releases
(103 kkg)
363
365
U.S.
Production
(103 kkg)
268
208
Production
Outside U.S.
(103 kkg)
95
157
U.S. Production
as a Percent of
Global Releases
74
60
1976
416
261
155
63
1977
427
287
140
67
1978
477
284
194
59
USSR and Iron Curtain Countries not included.
Neely and Agin, 1978. These figures represent emissions
rather than production; production may be 3 to 6 percent
higher than total emissions.
U.S. Tariff Commission, 1978
EPA, 1979a.
2-6
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Table 2.1-1 indicates that production of methyl chloroform is increasing
less rapidly in the United States than in other countries. Although
still producing more than half of the world supply, the United States
contributes a signficiantly smaller percentage than it did in the early
1970's.
The capacities of several foreign plants for which information was
available are listed in Table 2.1-2.
Table 2.1-2 — Methyl Chloroform Production Capacity for Plants
•j
Outside the United States (10 kkg/year)
Country 1971
Japan - Tao Gosei 18
Central Kagaku 6
Kanto Denka 12
Toya Sad a 12
Asahi-Dow
Ashi-Penn
Mitsubishi
Europe - Dow
England
1975
18
6
12
12
40
1977
18
6
12
12
40
180
1979
36
6
12
12
40
20
160
180
1501
Source
PROMPT, 1979
PROMPT, 1979
PROMPT, 1979
PROMPT, 1979
PROMPT, 1979
PROMPT, 1979
McCracken, 1979
McCracken, 1979
McCracken, 1979
This plant is proposed but will not necessarily be on line by 1979.
This list is evidently not inclusive: Table 2.1-1 indicates
that 1975 production outside the United States was 157,000 kkg, but
plant capacities listed in Table 2.1-2 account for only 88,000 kkg or
2-7
-------
56 percent of the total produced outside the United States. The large
increase in production outside the United States between 1977 and 1978
is probably attributable to the Dow-Europe plant.
Table 2.1-1 shows that total global releases for 1978 increased by
13 percent, while U.S. production remained stable. Foreign production
increased from 140,000 kkg in 1977 to 194,000 kkg in 1978, a 33 percent
increase in one year. Although production of 194,000 kkg of methyl
chloroform is within the known capacity of foreign plants (Table 2.1-2),
it is unlikely that European market conditions could create such a
significant increase in demand. Thus, it is evident that the 1979
global releases suggested by Neely and Agin are overestimated.
To improve the accuracy of global production figures for methyl
chloroform, information will be required from foreign countries with
production facilities.
2-8
-------
2.2 PRODUCTION OF METHYL CHLOROFORM FROM VINYL CHLORIDE
2.2.1 Production
Methyl chloroform (1,1,1-trichloroethane) can be produced by the
vinyl chloride method. The main reactions involved in this process
include the hydrochlorination of vinyl chloride into 1,1-dichloroethane
in the presence of a catalyst and then the chlorination of 1,1-dichloroethane
into methyl chloroform. The chemical reactions are presented below
(Hydroscience, 1979):
CH2 = CHC1
Vinyl
Chloride
CH3 - CHC12
+ HC1 +
Hydrogen
Chloride
+ ci2
•s
Catalyst
CH, - CC1,
x^ j J
CH3 - CHC12
1 , 1-dichloroethane
1,1-dichloroethane Chlorine Methyl Chloroform
An average yield rate of 98 percent is achieved with this method (EPA
1979a; Mannsville Chemical Products, 1978). Unconverted materials are
either recycled within the process, used as raw materials in other
processes, or wasted. A more detailed discussion of this process is
presented in Appendix A.
According to MRI (EPA, 1979a), the Dow Chemical Company produced
181,000 kkg of methyl chloroform in 1976 using vinyl chloride as a raw
material. This represented approximately 63 percent of the total U.S.
production quantity, but one percent below 1975. The methyl chloroform
plant capacity of Dow also represented 63 percent of the total in 1976.
By 1979 though, Dow accounted for less than 60 percent of the plant
capacity due to extensive plant expansion by their competitors, Vulcan
and PPG (EPA, 1979a).
2-9
-------
Assuming that the percentage of Dow's market capture remained steady,
we estimate the 1978 market share to be 63 percent. Therefore, the
1978 Dow methyl chloroform production can be estimated as follows:
Production from 1978 Total U.S. Percent Market
Vinyl Chloride = Production of x Capture of
Method Methyl Chloroform Process
179,000 kkg = (284,000 kkg) (0.63)
The uncertainty of this number is +6% and -7%. The upper bound assumes
the Dow market share is equivalent to its percentage (65.2 percent) of
total U.S. methyl chloroform production capacity prior to plant expansion
by all three producers (EPA, 1979a). The lower bound assumes the Dow
market share is equivalent to its percentage (59.8 percent) of the total
U.S. 1979 methyl chloroform production capacity after all three producers
had completed their proposed plant expansions (EPA, 1979a). The confidence
placed on the estimated Dow production for 1978 is primarily due to the
consistency of the various market shares reported by MRI covering the
previous 10 years (EPA, 1979a).
Prior to 1977, Dow Chemical Company and the Ethyl Corporation
produced methyl chloroform using vinyl chloride as the raw material.
During 1976, Ethyl ceased the production of methyl chloroform (EPA,
1979a). In September 1979, Vulcan Materials Company began operating a
new methyl chloroform production facility. The new facility, using
vinyl chloride as the raw material, will become Vulcan's primary source
of methyl chloroform production. Since all calculations here are being
performed with 1978 data, methyl chloroform produced from vinyl chloride
at the Vulcan facility will not be included. The equations presented
below will enable readers to estimate emissions from the Vulcan facility
using future data.
2.2.2 Emissions to Air
Storage vents, handling and fugitive losses were identified as
the most significant locations for methyl chloroform air releases.
2-10
-------
Secondary sources of air emissions included wastewater treatment and the
incineration of residues (Hydroscience, 1979).
Figure 2.2-1 represents the flow diagram for the production of
methyl chloroform from vinyl chloride. A discussion of the losses using
this flow diagram is presented in the following sections.
2.2.2.1 Emissions to Air From the Light Ends Column (Vent AI)
According to MRI and TRW, "trichloroethane" is emitted to the air
during the production of methyl chloroform from vinyl chloride (EPA,
1979a; TRW, 1975). The configuration of the "trichloroethane",
either 1,1,1-trichloroethane (methyl chloroform) or 1,1,2-trichloro-
oethane, was not identified. These emissions were identified in the
hydrochlorination reactor vent gases. However, Hydroscience did not
suggest that any methyl chloroform emissions were released from this
reactor or columns associated with the reactor.
Since the TRW and MRI reports disagree with the emissions estimated
by Hydroscience, an analysis of the hydrochlorination reactor, heavy
ends column and light ends column was performed.
If the quantities of methyl chloroform (or "trichloroethane") and
1,1-dichloroethane were present in the vent gases as proposed by MRI and
TRW (0.009 kkg methyl chloroform/kkg and 0.0085 kkg dichloroethane/kkg
of methyl chloroform produced), then the hydrochlorination reactor would
have to produce approximately a 50-50 mixture of the two organic compounds
(EPA, 1979a; TRW, 1975). However, the hydrochlorination process is
known to convert vinyl chloride to 1,1-dichloroethane at an efficiency
greater than 98 percent (EPA, 1979a; Mannsville Chemical Products,
1978). Therefore, it is highly improbable that methyl chloroform releases
could be so high.
Assuming that methyl chloroform (MC) and dichloroethane (DCE)
were measured in the vent gases at a ratio of 9:8.5, the percentage of
methyl chloroform formulated by hydrochlorination can be calculated as
follows:
2-11
-------
to
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01) OO
Figure 2.2-1 Flow Diagram of the Production Process from
Vinyl Chloride
(Hydroscience, 1979)
-------
Relative TRW/MRI Estimated , TRW/MRI Total Compound
Quantity kkg/kkg of Methyl Estimated MC Vapor
of = Chloroform/DCE _._ and DCE kkg/kkg _._ Pressure
Selected Produced ' of Methyl ' at 40°C
Compound Chloroform
Produced
Relative
Quantity of = 0.009 kkg/kkg 4- (0.009 kkg/kkg + 0.0085 kkg/kkg) -=- 275*
Methyl
Chloroform (MC)
Relative Quantity = 0.0085 kkg/kkg 4- (0.0175 kkg/kkg) 4- 400*
of DCE
MC = 1.869 DCE = 1.215
Percentage of MC = 1.869 . nnv ,n ,„
(1.869 + 1.215) x 100% = 6°'6/°
Percentage of DCE = K215 x 10Q% = 39>4%
These calculations suggest that methyl chloroform would comprise over
60 percent of the product formulated in the hydrochlorination reactor.
However, the second step of the vinyl chloride process chlorinates
1,1-dichloroethane at 400°C to produce methyl chloroform (EPA, 1979a;
Hydroscience, 1979). Thus, even in the presence of a catalyst (Fed,) ,
the 30-40°C hydrochlorination reaction could not produce any significant
quantities of methyl chloroform. Also, the estimate given by TRW and
MRI precludes the presence of vinyl chloride, an unlikely possibility
(EPA, 1979a; TRW, 1975).
Hydroscience estimates that the composition of the light ends
column consists of 0.1 weight percent of vinyl chloride, 2.5 weight
percent of 1,1-dichloroethane and 97.4 weight percent of other non-organic
gases (Hydroscience, 1979). Using these weight percents, vinyl chloride
and 1,1-dichloroethane represent 4 percent (0.1 4- 2.6) and 96 percent
(2.5 4- 2.6), respectively, of the volatile organic compounds present
in the vent gases. These percentages are consistent with the known
conversion rate of vinyl chloride to 1,1-dichloroethane (98 percent)
2-13
-------
identified previously (EPA, 1979a; Mannsville Chemical Products,
1978). The most likely reason for the higher percentage of vinyl
chloride (4 percent rather than 2 percent) in the vent gases is its
lower molecular weight, boiling point and density. Also, the volatility
(vapor pressure) of vinyl chloride is significantly higher than that of
1,1-dichloroethane (see Table 2.2-1).
TABLE 2.2-1
SELECTED PHYSICAL PROPERTIES OF VINYL CHLORIDE,
1,1-DICHLOROETHANE AND METHYL CHLOROFORM
Molecular Weight
Boiling Point (°C)
Density
Vapor Pressure
(at 40°C, 1 Atra)
Vinyl
Chloride
62.50
-13.4
0.9106
N/A
1,1-Dichloro-
ethane
98.96
57.3
1.1757
400 mm
Methyl
Chloroform
133.42
74.1
1.339
275 mm
Source: CRC, 1972
Note: Vapor Pressure of Methyl Chloroform Calculated by Linear Inter-
polation between 100 mm, 1 atra, 20.0°C and 400 mm, 1 atm, 54.6°C.
It should be noted that Hydroscience does not identify methyl chloroform
as a product from the hydrochlorination reactor nor as a light ends
column vent gas. Again, this is consistent with the first step of the
vinyl chloride process.
Although methyl chloroform in the light ends column reported by MRI
and TRW has been discounted and was not identified by Hydroscience, it
may nevertheless be present in trace quantities (EPA, 1979a; TRW, 1975;
Hydroscience, 1979). If methyl chloroform is present, the quantity
could not exceed the 4 percent unreacted vinyl chloride identified
2-14
-------
by Hydroscience (Hydroscience, 1979). Assuming it is produced, the
relatively (to vinyl chloride) high boiling point (74.1°C) and low vapor
pressure (275 mm at 40°C, 1 atm) would minimize the quantity of gaseous
methyl chloroform present in the light ends column. Since the vinyl
chloride to 1,1-dichloroethane process temperature is 30-40°C, methyl
chloroform and 1,1-dichloroethane would be liquids, whereas vinyl
chloride would be a gas (boiling point: -13.4°C).
Therefore, we estimate that 1 percent of the 4 percent vinyl
chloride identified by Hydroscience in the light ends column vent gases
is methyl chloroform. Our confidence in this number is represented by a
±25% uncertainty. Dow Chemical Company has reported the use of a wet
scrubber on the distillate column vent gases (Dow, 1978). Methyl chloro-
form is almost insoluble in water (1300 ppm) and therefore, the efficiency
of the scrubber is limited to approximately 25 percent (±50%) (Appendix E;
CRC, 1972). The primary removal agent is entrainment. Trapped methyl
chloroform eventually evaporates during wastewater treatment. The
quantity of methyl chloroform released by the light ends column or any
step in the process can be calculated as follows:
Methyl Annual Production Volatile Organic
Chloroform = of Methyl Chloroform x Compound x
Air Emissions by the Vinyl Chloride Uncontrolled
Process Emission Factor
Fraction of Methyl Emission
Chloroform in x 1 - Control
Volatile Organic Efficiency
Compounds
(1) Assume MRI and TRW values - Total VOC = .0175 kkg/kkg
(EPA, 1979a; TRW, 1975)
Methyl Chloroform = 179,000 kkg x .0175 kkg/kkg x (4% x 1%) x (1 - 25%)
= 0.940 kkg
(2) Assume Hydroscience value - Total VOC » .00019 kkg/kkg
(Hydroscience, 1979)
Methyl Chloroform = 179,000 kkg x .00019 kkg/kkg x (4% x 1%) x (1 -25%)
= .0102 kkg
2-15
-------
Since we have more confidence in the values estimated by Hydro-
science (see previous discussion), the proposed emission is 0.2 kkg.
The uncertainty of this value is -1-370% (MRI/TRW estimate and the upper
bound of total production) and -95% (Hydroscience estimate and the lower
bound of total production). The accuracy and error given this estimate
have little significance because the upper bound or maximum emission
represents only 0.0005 percent of the total quantity of methyl chloroform
produced by the vinyl chloride process.
2.2.2.2 Emissions to the Air From Product Storage and Handling
(Vents B, C. & D)
Uncontrolled emissions of volatile organic compounds (VOC's) to the
air from product storage and the loading of tank cars and trucks and
other transport containers in the vinyl chloride process are estimated
in Table 2.2-2.
TABLE 2.2-2
UNCONTROLLED EMISSIONS DUE TO STORAGE AND HANDLING
Source
Figure 2.2-1 -
Vent Designation
Ratio of Volatile Organic
Compound (VOC) Emissions
Per Quantity of Methyl
Chloroform Produced
Storage Vents
o Intermediate Storage
o Product Storage
Handling - loading tank,
trucks and cars, etc.
B
C
D
0.05 kkg/10J kkg*
1.19 kkg/103 kkg*
0.61 kkg/103 kkg
Source: Hydroscience, 1979; EPA, 1977c.
* See Appendix F
2-16
-------
a) Air Emissions from Intermediate Storage (Vent B)
As discussed in Section 2.2.2.1 above, it is unlikely that
measurable quantities of methyl chloroform could be found in the
intermediate storage of 1,1-dichloroethane. However, the preceding
analysis does suggest that small quantites of methyl chloroform may be
present after the hydrochlorlnation of vinyl chloride. There is a
mechanical refrigeration unit (MRU) on the storage tank vents (Dow,
1978).
A summary of the assumptions used to calculate air emissions from
intermediate storage are presented below:
1) 1978 production = 179 x 103 kkg (+6%, -7%) (EPA, 1979a and
Section 2.2.1)
2) Uncontrolled emission rate for VOC from intermediate storage =
0.05 kkg/103 kkg (±25%)(Hydroscience, 1979)
The storage tank loss uncertainty is ±25% due to the following
assumptions. The uncontrolled emission factor proposed by Hydroscience
(Hydroscience, 1979) is based on a fixed roof tank which is half full.
Diurnal temperature variations heat and thereby expel gases during
daylight hours while cooling and drawing in air during darkness. These
variations cause continuous vent losses during storage. The larger the
air space above the liquid, the greater the daily losses are. Therefore,
floating roof and non-vented storage tanks are sometimes employed.
Additional losses occur during filling and drawdown; these are
also called working losses. These losses are the result of tank venting
required to perform each procedure. Losses from this working phase are
primarily dependent on throughput, loading method and the vapor pressure
of the liquid.
2-17
-------
Hydroscience assumed a temperature of 27°C for calculating the
vapor pressure of methyl chloroform (Hydroscience, 1979). Submerged
filling was assumed since it is commonly employed for volatile liquids.
The emission factor proposed by Hydroscience is a combination of
the breathing losses (diurnal heating and cooling) and working losses
(throughput). Assuming a normal throughput of 1 to 2 turnovers per
week, breathing and working loss contributions to the emission factor
are approximately equivalent.
If the tank is 75 or 25 percent full, the breathing losses vary by
±30%. Therefore, breathing losses are estimated to be accurate to
±30%, assuming the tank is half filled. Working losses are estimated to
be accurate to ±20% due to fluctuations in the average temperature. A
change of ±10°C will alter the losses by ±20 percent. Averaging the two
losses and their errors translates into an overall ±25% error.
3) Fraction of methyl chloroform in the VOC - 0.04 percent
(±25%) (Section 2.2.2.1)
4) Mechanical Refrigeration Unit (MRU) control efficiency =
85 percent (±5%)
The uncontrolled emission of methyl chloroform to the air from this
source is:
Air Emissions = 179 x 103 kkg x 0.05 kkg/103 kkg x (4% x 1%) x (1 - 85%)
= 0.000537 kkg
The uncertainty of this value is ±49%.
b) Air emissions from Product Storage (Vent C)
-------
Emissions from product storage tank will be 100 percent methyl
chloroform. The storage tanks are provided with an MRU on the vents
(Dow, 1978).
A summary of the assumptions used to calculate air emissions from
methyl chloroform product storage are presented below:
3
1) 1978 production = 179 x 10° kkg (+6%, -7%) (EPA, 1979a and
Section 2.2.1)
2) Uncontrolled emission rate for VOC from product storage =
1.19 kkg/103 kkg (±25%) (Hydroscience, 1979)
3) Fraction of methyl chloroform in the VOC = 100 percent
4) Mechanical Refrigeration Unit (MRU) control efficiency =
85 percent (±5%)
Therefore, the annual uncontrolled emission of methyl chloroform
from product storage is:
179 x 103 kkg x 1.19 kkg/103 kkg x 100% methyl chloroform x (1-85%)
= 32.0 kkg
The uncertainty of this estimate is ±42% (see subsection (a)
above).
c) Losses Due to Handling Techniques (Vent D)
Estimated air emissions are based on the submerged loading of
methyl chloroform, at 27°C, into railroad tank cars and tank trucks
(Hydroscience, 1979). Since the product being handled is raw methyl
chloroform, we have assumed the VOC releases to be 100 percent product.
A MRU is used during handling at the Dow Chemical Company facility (Dow,
1978).
2-19
-------
A summary of the assumptions used to calculate air emissions
from losses due to handling techniques are presented below:
1) 1978 production = 179 x 103 kkg (+6%, -7%) (EPA, 1979a and
Section 2.2.1)
2) Uncontrolled emission rate for VOC from losses and handling
storage = 0.61 kkg/103 kkg (+30%, -10%) (Hydroscience, 1979)
3) Fraction of methyl chloroform in the VOC - 100 percent
4) Mechanical Refrigeration Unit (MRU) control efficiency =
80 percent (±5%)
Annual air emissions of methyl chloroform are:
179 x 103 kkg x 0.61 kkg/103 kkg x 100% methyl chloroform x (1-85%)
= 16.4 kkg
This emission quantity is presented with an uncertainty of +45%
-35%. The uncertainties for the total methyl chloroform production and
the MRU are given above (see (a)). The uncontrolled air emission factor
used by Hydroscience is predominatly dependent on the bulk liquid temperature.
This temperature was assumed to be 27°C. A variation of +3°C or -5°C
will account for a difference of +30% and -10%, respectively, in the
emission factor. These errors were used to calculate the overall uncertainty
for product handling.
The Freeport plant, Texas Division of Dow Chemical Company, estimated
the annual evaporative losses of methyl chloroform due to product storage
and handling at 41.4 tons or 37.6 kkg (Dow, 1978). The sum of the
product storage and handling losses calculated above is 48.4 kkg. This
represents a difference of only 22 percent between the Dow measurements
and calculations and those presented in this report.
2^20
-------
2.2.2.3 Emissions Due to the Distillation (Steam Stripping) of Methyl
Chloroform (Vent A,,)
MRI and TRW estimated the loss of methyl chloroform from the dis-
tillation vent to be 0.0005 kkg/kkg of product (EPA, 1979a; TRW, 1975).
Using the quantity produced by Dow in 1978, the annual air emission of
methyl chloroform from this vent is:
179,000 kkg x 0.0005 kkg/kkg x 100% methyl chloroform x (1-25%)
= 67.1 kkg
The uncontrolled emission factor estimated by Hydroscience is 0.19
kkg VOC/ 10 kkg of methyl chloroform (Hydroscience, 1979). The VOC's
are assumed to be 100 percent methyl chloroform. According to Dow, a 25
percent (±50%) efficient wet scrubber is used to control emissions from
this source (Dow, 1978). The annual emission of methyl chloroform to
the air is:
179 x 103 kkg x 0.19 kkg/103 kkg x 100% x (1 - 25%) = 25.5 kkg
The discrepancy between the 67.1 kkg (EPA, 1979a; TRW, 1975) and the
25.5 kkg (Hydroscience) values is probably due to the method of measuring
the total air emissions from this part of the process. The EPA and TRW
reports seem to include all air emissions from vent and wastewater
stream. Therefore, the proposed emission of methyl chloroform from the
distillation column vent is 25.5 kkg with an uncertainly of +160%, -15%.
The +160% assumes the EPA and TRW value is correct and therefore is used
as the upper bound. The -15% assumes minimum Dow market capture and
maximum scrubber efficiency.
2.2.2.4 Fugitive Emissions (Vent E)
Sources of fugitive emissions within the production facilities
include process pumps, compressors, process valves, and pressure-relief
devices (Hydroscience, 1979).
-------
A summary of the assumptions used to calculate air emissions
from fugitive losses are presented below:
1) 1978 production = 179 x 103 kkg (+6%, -7%) (EPA, 1979a and
Section 2.2.1)
2) Uncontrolled emission rate for VOC from fugitive losses
=0.37 kkg/103 kkg (Hydroscience, 1979)
3) Fraction of methyl chloroform in the VOC = 100 percent
4) Emission Control Efficiency = 90 percent (±5%) (Hydroscience,
1979). Fugitive emissions are controlled through careful
detection and correction of major leaks.
The emission of methyl chloroform to the air from fugitive emis-
sions is:
179 x 103 kkg x 0.37 kkg/103 kkg x 100% x (1 - 0.9) = 6.62 kkg
The uncertainty of this emission quantity is estimated at ±50%
due to the following reasons: 1) it is estimated 100 percent of the
VOC's is methyl chloroform; 2) the variability in leak detections and
corrections; 3) maintenance procedures; and (4) Dow methyl chloroform
production.
2.2.3 Emissions to Water (F)
Stream stripping of wastewater (Figure 2.2-1, emission F) is a
source of VOC emissions.
2-22
-------
A summary of the assumptions used to calculate emissions from wastewater
treatment are presented below:
1) 1978 production = 179 x 103 kkg (+6%, -7%) (EPA, 1979a and
Section 2.2.1)
2) Uncontrolled emission rate for VOC for wastewater treatment
= 0.001 kkg/103 kkg (Hydroscience, 1979)
3) Fraction of methyl chloroform in the VOC = 100 percent
4) No emission control devices are included on the wastewater stream
The emissions to water are:
179 x 103 kkg x .001 kkg/103 kkg x 100% x (1-0%) = 0.179 kkg
Another method for calculating the total water emissions is to use
the EPA monitored level of methyl chloroform in the controlled aqueous
effluent near the Dow plant. According to reported monitoring data, the
levels of methyl chloroform ranged from 0.8 to 119 ppb by weight. We
will assume the controlled aqueous effluent is 35 ppb methyl chloroform
by weight, with an1uncertainty of ±50% (EPA, 1977a). This is an EPA
composite of available monitoring data (EPA, 1977a).
Based on typical daily water discharges from chemical plants
similar in size to Dow's, we estimate that the water discharge of this
plant is approximately 2 million gallons per day. The uncertainty of
this figure is ±25%.
Using the above assumptions, the quantity of methyl chloroform in
the controlled effluent discharge of the vinyl chloride based process
can be calculated by multiplying the following factors:
A) 2,000,000 gpd of water discharges (±25%)
2-23
-------
B) Operating days per year = 330 days/year
(±5% due to typical chemical plant down-time (Hydro-
science, 1979))
C) Water density at 25°C = 1 kg/liter
D) 3.785 liters/gallon
E) Concentration of methyl chloroform in the effluent =
_q
35 x 10 kg methyl chloroform/kg of water (±50%)
3
Water emissions = 2 x 10 gallons/day x 330 days/year x
1 kg/liter x 3.785 liter/gallon x 35 x 10~9 kg/kg =
87.4 kg or 0.0874 kkg
The estimates calculated using Hydroscience and EPA collected data
represent a likely range for methyl chloroform residing after wastewater
treatment. The range (0.0874 - 0.179 kkg), although quite large on a
relative scale, represents an insignificant portion (< 0.0001 percent)
of the total methyl chloroform released to the environment.
For purposes of the materials balance, we estimate that the average
of the two values, or 0.133 kkg, is the annual discharge. The uncertainty
of this estimate is ±35% due to the uncertainty of the Hydroscience
emission factor, total production of methyl chloroform by Dow daily
water discharge quantities, annual days of operation, and inaccuracies
in the EPA monitoring data and composite value.
2.2.4 Emissions to Air Due to Wastewater Treatment
During the wastewater treatment phase, volatile organic compounds
(VOC's), such as methyl chloroform, trapped in aqueous effluent may be
emitted to the air during aeration. We assume that 99 percent of the
trapped methyl chloroform evaporates prior to being treated and the
remaining 1 percent is treated. Thus, of every 100 parts of methyl
2-24
-------
chloroform in the aqueous effluent, 99 evaporate prior to water treat-
ment, while the remaining part enters the treatment system. The error
of the treated portion is +100%, -50% due to the insolubility in water
(1300 ppm, Appendix E) and to the entrainment, not dissolution, of
methyl chloroform in water.
Of the 1 percent treated, we assume that 5 percent is removed
(evaporates, biodegrades, or is reformulated) during treatment and 95
percent is released intact in the controlled aqueous effluent. The
assumption is based on the following:
o Methyl chloroform is not very soluble in water (1300 ppm -
Appendix E)
o Biodegradation of methyl chloroform does not readily occur
(Section 2.6)
o Chlorination of waste water does not remove (nor does it produce)
any significant quantity of methyl chloroform. Also, indirect
production of methyl chloroform does not readily occur.
(Section 2.5)
The quantity removed from the controlled aqueous effluent is presented
with an uncertainty of ±50%. The uncertainty represents an estimate
based on the method of wastewater treatment and the likelihood of
evaporation, biodegradation and reformulation during the treatment
process. Therefore, the total quantity of methyl chloroform emitted to
the air from process wastewater can be calculated as follows:
100% 99%
(0.133 kkg) x 95% x 1% 13.9 kkg
2-25
-------
where: 0.133 kkg = the quantity of methyl chloroform released to the water;
(Section 2.2.3);
100%/95% = the ratio of the percentage of methyl chloroform that
enters the treatment system and the unreacted percentage
discharge into the control water effluent;
99%/l% = the ratio of the percentage of methyl chloroform released
to the air prior to treatment and the percentage of this
chemical that enters the treatment system.
The overall uncertainty of this figure is +107% and -62%. Although
the proposed error is large, the estimated upper bound for wastewater
treatment air emissions is only 0.02 percent of the methyl chloroform
produced by Dow.
2.2.5 Emissions to Land (G and H)
Residue quantities (labeled G and H on Figure 2.2-1) disposed in
landfills or incinerated are the only sources of methyl chloroform solid
waste occurring at the plant (Hydroscience, 1979).
Solid waste is comprised of catalyst residues and organic wastes.
They are estimated to contribute less than 0.1 percent to the total
uncontrolled VOC emission rate at the model plant (Hydroscience, 1979).
Hydroscience aggregates the loss due to landfill disposal and incineration
into one number. For this analysis, we are assuming that half the
Hydroscience emission rate will be considered to result from landfill
disposal. The remaining half is incinerated and the ash is landfilled.
A summary of the assumptions used to calculate this factor are presented
below:
1) 1978 production = 179 x 103 kkg (+6%, -7%) (EPA, 1979a;
Section 2.2.1)
2-26
-------
2) Uncontrolled emission rate for VOC's based on 50 percent of the
residues being landfilled and 50 percent being incinerated = .0005
kkg/10 kkg (Hydroscience, 1!
wastes could be landfilled).
kkg/10 kkg (Hydroscience, 1979) (±100% - all or none of the solid
3) Fraction of methyl chloroform in the VOC =0.04 percent
(±25% - see Section 2.2.2.1 - emissions from points G and H in Figure
2.2-1 occur prior to the probable formulation of methyl chloroform).
4) No environmental controls are used during the landfill of sludge.
The calculation for this emission is:
Land emission = 179 x 103 kkg x .0005 kkg/103 kkg x 0.04% x (1-0%)
= 3.58 x 10~5 kkg.
The uncertainty of this emission factor is estimated to be +103%
-100%. This large uncertainty is mainly due to the 50/50 landfill to
incineration estimate. Again, since the emission is so small
—8
«2 x 10 percent), large uncertainties have little significance.
2.2.6 Fjnissions to Air Due to the Incineration Disposal Method
The remaining 50 percent of the residues identified above are
incinerated at the plant. Methyl chloroform, a volatile organic compound
which is unstable at high temperatures, decomposes easily when incinerated.
In addition, the process formulation temperature (approximately 400°C)
is much lower than typical incineration temperatures (1000-1200°C).
Therefore, we can assume a 95 percent destruction of the waste materials
is achieved through incineration. The remaining 5 percent is released
to the air. We also assume that there are no emission controls on the
flue gases released by the incineration (Hydroscience, 1979). The high
temperatures involved in the incineration process (1000-1200°C) precludes
2-27
-------
any quantifiable amount of methyl chloroform remaining in the ash residue.
The fraction of methyl chloroform in the solid wastes from emission
points G and H is 0.04 percent (see Section 2.2.2.1).
Assumptions used to calculate the emission factor are:
1) 1978 production = 179 x 103 kkg (+6%, -7%) (EPA, 1979; Section 2.2.1)
2) Uncontrolled emission rate of residues (based on 50 percent of
residues being incinerated) = 0.0005 kkg/103 kkg (±100% - all
or none may be incinerated) (Hydroscience, 1979)
3) Fraction of methyl chloroform in VOC residues = 0.04 percent
(±25% - see Section 2.2.2.1)
4) Incinerator efficiency = 95 percent destruction (±4% -
see discussion above)
Air emissions = 179 x 103 kkg x 0.0005 kkg/103 kkg x 0.0004 x (1 - 0.95)
= 1.79 x 10~6 kkg
The composite uncertainty of this emission figure is +131% and -100%.
Incinerator air emissions of methyl chloroform represents approximately
_Q
10 percent of the total Dow methyl chloroform production.
2.2.7 Multimedia Environmental Losses
Figure 2.2-2 shows multimedia environmental losses of methyl
chloroform from its production using the vinyl chloride process.
2-28
-------
Ni
I
NJ
1.79x10 kkg
, -100%)
Air
Incinerator
6.62 kkg
(+ 50%)
Air
/ v
Emission
control device
Air
74.1 kkg
,-57%)
Air
13.9 kkg
^(+107%,-62%)
Air
Methyl chloroform
production process
from vinyl chloride
179,100 kkg
Water
5
.3.58x10 kkg v,
Land
Waste water
treatment
process
179,000 kkg (+6%,-7%)
Production
Landfilled
.58x10 kkg
(+103%,-100%)
Landfilled
0.133 kkg
(+ 35%)
Water effluent
Figure 2.2-2 Multimedia Environmental Losses from the
Vinyl Chloride-based Production Process
-------
2.3 PRODUCTION OF METHYL CHLOROFORM FROM ETHANE
2.3.1 Production
Methyl chloroform is produced by the noncatalytic chlorination of ethane,
This process is summarized by the following fractions (Hydroscience, 1979):
+c i + n
OU-CH., ^2. CH -CH_C1 2^
-HCK
(ethane) (ethyl chloride)
CH -CHC1 2 CH.CCU
J -HC1 ' J J
(1 , 1-dichloroethane) (1,1, 1-trichloroethane)
A flow diagram, representing this process for a model plant is
shown in Figure 2.3-1 (Hydroscience, 1979). The model plant is based on
an annual production capacity of 29,500 kkg (8760 hours of operation).
According to Key and Standifer, this is the reported capacity of the
Vulcan Materials Company plant at Geismar, Louisiana, the only company
presently using the ethane process for the production of methyl chloroform
(Hydroscience, 1979). The Hydroscience model plant flow diagram was
used due to the lack of other available information on the Vulcan process.
The quantity of methyl chloroform produced in 1976 by the ethane
process was 26,100 kkg or 9 percent of the total production (EPA, 1979a).
Assuming that the percentage obtained for 1976 is also applicable for
1978, the quantity of methyl chloroform produced by the this method can
be estimated by multiplying the 1978 total methyl chloroform production
by 9 percent:
284,000 kkg x 0.09 = 25,500 kkg.
This quantity was verified by verbal communication with Mr. Herb McGowan
of Vulcan Materials Company (H. McGowan, 1979).
2-30
-------
to
CO
ij
FUGITIVE
FV-AUT
•C3UEUC.M
ocxuuu
FK.CM
OIC.Hl.CCO- REOOvE.1V
Figure 2.3-1 Flow Diagram of the Production Process
from Ethane
(Hydroscience, 1979)
-------
Also, since Vulcan began operation of a new 63,500 kkg production
facility in 1979, we can assume the old facility was operating near capacity.
This was typical of both the Dow and PPG expansion planning (EPA, 1979a).
Downtime ranges from 5 to 15 percent annually depending on the age and
maintenance of the plant and the chemical produced. Thus, the uncertainty
of the above estimate is +2,000 kkg (95% x 29,500 kkg = 28,000 kkg) and
-1,000 kkg (85% x 29,000 kkg = 25,000 kkg). The errors are +10%, -2%.
2.3.2 Emissions to Air
At the production site, uncontrolled emissions of volatile organic
compounds (VOC's) to the atmosphere have been quantified from the following
four sources:
1) plant process (distillation vents),
2) product storage and handling,
3) overall fugitive plant emissions, and
4) waste treatment (Hydroscience, 1979).
These emission rates are presented in Table 2.3-1 (Hydroscience,
1979). In order to calculate emissions at the site for these sources
the following formula is used:
Methyl Chloroform
Air emissions (kkg) = 1978 production of methyl chloroform by
3
the ethane process (10 kkg)
x volatile organic compound uncontrolled emission
•j
factor (kkg/10 kkg of production)
x fraction of methyl chloroform in VOC
x (1 - emission control efficiency*)
Quantities obtained using the above formula together with assumptions
used in calculating these emissions from the four sources are discussed
below.
*If applicable
2-32
-------
Table 2.3-1 — Estimates of Total Uncontrolled VOC Emissions from
a Model Plant Producing Methyl Chloroform from Ethane3
Source
Distillation vents
Storage vents
Recycle storage
Product storage
Handling
Fugitive
Secondary
Wastewater treatment
Incineration of residues
and/or landfill
Total
Vent
Designation
(Fig.III-2)
A
B
C
D
E
F
G,H
VOC
Ratio
(g/kg)b
0.21
0.06C
0.98C
0.61
1.69
0.001
0.001
3.4
Emissions
Rate
(kg/hr)
0.7
0.19°
3.3°
2.1
5.7
0.004
0.01
11.6
Uncontrolled emissions are emissions from a process for which there are no
control devices other than those necessary for economical operation.
g of emission per kg of methyl chloroform produced.
Q
see Appendix F
Source: Hydroscience, 1979
2-33
-------
2.3.2.1 Plant Process
The only significant process emission occurs when gas is vented at
the distillation-column reflux condenser vents (labled A in Figure 2.3-1)
(Hydroscience, 1979). The combustion of vent gas is employed to control
emissions at the model plant (Hydroscience, 1979). Assumptions used to
estimate methyl chloroform loss from these vents are:
1) 1978 production = 25.5 x 103kkg (+10%, -2%) (EPA, 1979a; McGowan,
1979; Section 2.3.1)
3
2) uncontrolled emission rate =0.21 kkg/10 kkg (Hydroscience, 1979)
3) fraction of methyl chloroform in VOC (see Table 2.3-2) = 0.67 (±25%)
(Hydroscience, 1979)
4) efficiency of incineration as control device = 95 percent. (±4%)
(Hydroscience, 1979 and Section 2.2.6)
Using the above information in the formula described in the previous
section, air emissions are calculated as follows:
Air Emissions = 25.5 x 103 kkg x 0.21 kkg/103 kkg x 0.67
x (1 - .95) = 0.179 kkg
Table 2.3-2 — Estimated Composition of Distillation Vent Gas
from Model Plant Producing Methyl Chloroform from Ethane
Component
Methyl chloroform
Ethylene dichloride
Nitrogen, oxygen
Total
Composition
(wt %)
35
17
48
100
Weight Percent
Volatile Organic
Compounds
67
33
—
100
Source: Hydroscience, 1979
2-34
-------
The composite uncertainty of the emission factor is estimated to be
±84%. The primary reason for this uncertainty is the variance in the
effeciency attributed to the vent gas incinerator. For example, a two
percent decrease in the emission control efficiency increases the air
emission by 40 percent.
Air emissions (93% efficient incinerator) = 25.5 x 10 kkg x
0.21 kkg/103 kkg x 0.67 x (1-.93) = .251 kkg
Increased Air Emission = .251 kkg/.179 kkg = 1.40
2.3.2.2 Product Storage and Handling
VOC emissions result from the intermediate storage (labeled B in
Figure 2.3-1 ), product storage (labeled C in Figure 2.3-1) and the loading
of tank cars and trucks (label D in Figure 2.3-1). Handling and storage
emissions are controlled by a refrigerated vapor recovery system (Hydro-
science, 1979; D. Phillips, 1979). Assumptions used to calculate methyl
chloroform air emissions from product storage and handling are:
1) 1978 production - 25.5 x 103 kkg (+10%, -2%) (EPA, 1979a;
McGowan, 1979; Section 2.3.1)
2) Uncontrolled VOC emission rates from Table 2.3-1 (Hydroscience,
1979; Appendix F; Section 2.2.2.2):
A) Intermediate storage = 0.06 kkg/10 kkg (±20%)
3
B) Product storage =0.98 kkg/10 kkg (±20%)
C) Handling - 0.61 kkg/103 kkg (+30%, -10%)
3) Based on the suggested turnover volume identified in Table 2.3-3
(Hydroscience, 1979),
A) Intermediate Storage = 20% (±25%)
B) Product storage = 100%
C) Handling = 100%
2-35
-------
4) Efficiency of vapor recovery system = 85 percent (±5% (Hydroscience,
1979 and Section 2.2.2.2)
Therefore, the calculations for storage and handling emissions are:
A) Intermediate storage
Air emissions (kkg) = 25.5 x 103 kkg x 0.06 kkg/103 kkg x 0.20
x (1 - .85)
= 0.0459 kkg (+47%, -39%)
B) Product storage
Air emissions = 25.5 x 103 kkg x 0.98 kkg/103 kkg x 1.00
x (1 - .85) = 3.75 kkg (+40%, -39%)
C) Handling
Air emissions = 25.5 x 103 kkg x 0.61 kkg/103 kg x 1.00
x (1 - .85)
= 2.33 kkg (+46%, -35%)
Total handling and storage emissions = 0.04 kkg + 3.75 kkg + 2.33 kkg
= 6.13 kkg
The uncertainty of the sum of the emission factors is estimated to
be +61%, -52%.
Uncertainties for storage and handling emission rates are the
same as those identified in Section 2.2.2.2. Emission rates for inter-
mediate and product storage represent only "working" losses because the
storage tanks identified by Hydroscience are not normally vented (Hydro-
science, 1979). This is typical of smaller tanks. Thus, breathing
losses should not be present at Vulcans methyl chloroform storage facility.
Since loading and unloading does requre venting, estimated working
losses are presented and an uncertainty of ±20 percent has been given to
these values (See Section 2.2.2.2 and Appendix F).
2-36
-------
The fraction of methyl chloroform in intermediate storage releases
is a function of the number of tank turnovers and the quantity per
turnover. Calculations suggest that the quantity of methyl chloroform
transferred represents 20 percent of the total for intermediate storage.
Product storage and handling air emissions are assumed to contain 100
percent methyl chloroform.
Table 2.3-3 — Storage Tank Data for Methyl Chloroform
(Ethane Feed) Model Plant
Contents
Number of tanks
3
Tank size (m)
Turnovers per year
Bulk temperature (°C)
Intermediate
1,1 Dichloro-
ethane
4
55
11
27
Tank
Intermediate
Crude, Methyl
chloroform
2
29
44
27
Product
Refined, Methyl
chloroform
4
174
73
27
Source: Hydroscience, 1979
2.3.2.3 Overall Fugitive Plant Emissions
Fugitive VOC emissions (labeled E in Figure 2.3-1) have been
estimated (Hydroscience, 1979) based on the average number of process
pumps, compressors, process values, and pressure relief valves handling
VOC at the model plant. Assumptions used in the calculation include:
A) 1978 production = 25.5 x 103 kkg (+10, -2%) (EPA, 1979a; McGowan,
1979; Section 2.3.1)
B) Uncontrolled VOC emission rate = 1.69 kkg/103 kg (±20%) (Hydro-
science, 1979; Table 2.3-1)
2-37
-------
C) Fraction of methyl chloroform in VOC (fugitive emission
composition is estimated to be comparable to the composition
of the vent gases, see Table 2.3-1) = 67 percent (±25%) (Section
2.3.2.1)
D) Efficiency of control device (detection and correction of
major leaks) = 90% (±5%) (Hydroscience, 1979).
The calculation of methyl chloroform air emissions are:
Air emissions = 25.5 x 103 kkg x 1.69 kkg/103 kg x 0.67 x (1 - .90)
= 2.89 kkg
The uncertainty of the emission factor is estimated to be +60%
-59% . The uncertainty is due to the variability in leak detection
capability and maintenance procedures. A plant inspection would be
required to ascertain the adherence to leak detection and correction
procedures. The overall fugitive emission uncertainty (especially the
upper bound) seems consistent with good economic operation.
2.3.3 Emissions to Water
Steam stripping of wastewater (labeled F in Figure 2.3-1) is a
source of VOC emissions. Assumptions used in calculating methyl chloroform
water emissions are:
1) 1978 production = 25.5 x 103 kkg (+10%, -2%) (EPA, 1979a;
McGowan, 1979; Section 2.3.1)
2) Uncontrolled emission rate for wastewater treatment = 0.001
kkg/103 kg (Hydroscience, 1979)
3) Fraction of methyl chloroform in VOC (maximum value assumed) =
100%
2-38
-------
4) No control device used due to low concentrations.
The emissions to water are:
3 3
Water emissions = 25.5 x 10 kkg x .001 kkg/10 kkg x 1.00
= .0255 kkg
Another method for calculating the total water emissions uses
the EPA monitored level of methyl chloroform in the controlled aqueous
effluent near the Vulcan plant. According to reported monitoring data,
the levels of methyl chloroform ranged from 2 - 16,500 ppb by weight
(EPA, 1977a). We will assume the average controlled aqueous effluent
(composite of EPA monitoring data) is 169 ppb methyl chloroform by
weight; with an uncertainty of ±50% (EPA, 1977a).
Based on typical daily water discharges from chemical plants similar
in size to Vulcan's, we estimate that the water discharge of this plant
is approximately 300,000 gallons per day. The uncertainty of this
figure is ±25%.
Using the above assumptions, the quantity of methyl chloroform in
the controlled effluent discharge of the ethane based production process
can be calculated by multiplying the following factors:
A) 300,000 gallons of water discharged per day (±25%)
B) Operating days per year =
on'*nn iffi x 365 davs - 316 davs (+10%. -2 %>
-------
Total methyl chloroform in controlled effluent discharge =
300,000 gallons/day x 316 days/year x 1 kg/liter x
3.785 liter/gallon x 169 x 10~9 kg/kg = 60.6 kg or 0.0606 kkg
The Hydroscience and the EPA. effluent monitoring data estimates
represent the likely range of methyl chloroform remaining after wastewater
treatment. The range, although quite large on a relative scale, represents
an extremely minor portion ( •<. .0002 percent) of the total methyl chloro-
form produced at the Vulcan facility.
For the purposes of the materials balance, we estimate that the
average of the two calculated emissions, or 0.0430 kkg, is the annual
discharge. The uncertainty of this estimate is ±41 percent based on the
uncertainty of the Hydroscience emission factor, daily water discharge
quantities and inaccuracies in the EPA monitoring data.
2.3.4 Emissions to the Air Due to Wastewater Treatment
During the wastewater treatment phase, volatile organic compounds
(VOC's), such as methyl chloroform, trapped in the aqueous effluent may
be emitted to the air due to the aeration process in the treatment
system. We assume that 99 percent of the trapped methyl chloroform
evaporates prior to being treated and the remaining 1 percent is treated
by the system. Thus, of every 100 parts of methyl chloroform in the
aqueous effluent, 99 evaporate prior to water treatment, while the
remaining part enters the treatment system. The estimated uncertainty
is +100% -50% (see Section 2.2.4). Of the 1 percent treated, we assume
that 5 percent of the methyl chloroform is removed during treatment of
activated sludge and 95 percent is released intact in the controlled
aqueous effluent (see Section 2.2.4). The 95 percent represents the
calculated emission of methyl chloroform to water in the preceding
section. Therefore, the total quantity of methyl chloroform emitted to
the air from process water can be calculated as follows:
(0.0430 kkg) ( 100% ) (99% ) =4.48 kkg
95% 1%
2-40
-------
Where:
0.0430 kkg = the amount of methyl chloroform released to the water
by the wastewater treatment system.
100%/95% = the ratio of the percentage of methyl chloroform that
enters the treatment system and the untreated percentage
discharged into the controlled water effluent.
99%/l% = the ratio of the percentage of methyl chloroform
released to the air prior to treatment and the
percentage of this chemical that enters the treatment
system.
The overall uncertainty of this figure is +109% and -66% due to the
uncertainty of the evaporation rate and the removal efficiency of the
treatment system.
2.3.5 Emissions to Land
Residue quantities (labeled G and H in Figure 2.3-1) disposed in
landfills are the only source of VOC solid waste estimated to occur at
the model plant (Hydroscience, 1979). Assumptions used to calculate the
emission factor are:
1) 1978 production = 25.5 x 103 kkg (+10%, -2%) (EPA, 1979a;
McGowan, 1979; Section 2.3.1)
2) Uncontrolled emission rate (based on 50 percent of the residues
being landfilled and 50 percent being incinerated = .0005
kkg/103 kkg (±100%) (Hydroscience, 1979; Section 2.2.5)
2-41
-------
3) Fraction of methyl chloroform in VOC = 30 percent (±50%). The
fraction was estimated by assuming
o the weight of the residues from emissions labeled G and H
were equal.
o 50 percent of the spent catalyst is methyl chloroform.
o 10 percent of the solid wastes from the quench column is
methyl chloroform.
A ±50% uncertainty has been assigned to this value. It is unlikely
that the fraction of methyl chloroform is greater than 45 percent, nor
less than 15 percent of the total VOC residues.
4) No control device used due to low concentrations.
The calculation for this emission is:
Quantity of methyl
Led = 2!
0.00383 kkg
chloroform landfilled = 25.5 103kkg x .0005 kkg/103 kkg x 0.30
The uncertainty of the land emission is estimated to be +112%,-100%.
It is primarily due to the assumption that 50 percent of the residues
are landfilled.
2.3.6 Emissions to the Air Due to the Incineration Disposal Method
The remaining 50 percent of the residue is incinerated at the
plant. We assume a 95 percent destruction of the waste materials is
achieved through incineration, with the remaining 5 percent being released
to the air. We also assume that there are no emission controls on the
flue gases released by the incinerator. The high temperature involved
in the incineration process precludes any quantifiable amount of methyl
chloroform remaining in the ash residue.
2-42
-------
Assumptions used to calculate the emission factor are:
1) 1978 production = 25.5 x 103 kkg (+10, -2%) (EPA, 1979a;
McGowan, 1979; Section 2.3.1)
2) Uncontrolled emission rate of residues (based on 50 percent of
residues being incin
1979; Section 2.2.5)
3
residues being incinerated) = .0005 kkg/10 kkg (±100%) (Hydroscience,
3) Fraction of methyl chloroform in VOC residues = 30 percent
(±50%) (Section 2.3.5 above)
4) Incinerator efficiency = 95 percent destruction (±4%) (see
Section 2.2.6)
Air emissions = 25.5 x 103 kkg x 0.0005 kkg/103 kkg x 0.30 x (1 - 0.95)
= 0.000191 kkg
The uncertainty of this emission figure is +138 percent and
-100 percent due to the percentage of the emission factor estimate
portioned to incineration, the assumption of no control on the emission
from the incinerator, and the efficiency of the incinerator.
2.3.7 Multimedia Environmental Losses
Figure 2.3-2 shows multimedia environmental losses of methyl chloroform
from its production using the ethane process.
2-43
-------
0.000191 kkg
(+138%,-100%)
Air
Incinerator
2.89 kkg
(+60%,-59%)
Air
Emission
control device
Air
6.31 kkg
(+61%,-52%)
Air
4.48 kkg
(+109%,-66%)
Air
Methyl Chloroform
production process
from ethane
25,500 kkg
0.00383 kkg
Land
Water
Waste water
treatment
process
25.500 kkg
Production
0.00383 kkg
(+112%,-100%)
Landfilled
Landfilled
0.0430 kkg
(+ 41%)
Water effluent
Figure 2.3-2 Multimedia Environmental Losses from the
Ethane-based Production Process
-------
2.4 VINYLIDENE CHLORIDE PROCESS
2.4.1 Production
Methyl chloroform can be produced by the vinylidene chloride method.
The main reaction involved in this process is the hydrochlorination of
vinylidene chloride in the presence of a Fed- catalyst. It is represented
as follows:
CH2 = CC12 + HC1 FeC13 ^ C
An average yield rate of 98 percent or more is achieved with this
method (EPA, 1979a; Mannsville Chemical Products, 1978). Unconverted
materials are usually recycled or wasted. A more detailed discussion of
this production process is presented in Appendix A.
Until late 1978, Pittsburgh Plate Glass (PPG) produced methyl
chloroform by the vinylidene chloride method (SRI, 1975; EPA, 1979a;
PPG, 1979; GPS, 1978). By January 1979, the new production method was
operating at full capacity. The vinylidene chloride plant presently fills
any requirements in excess of those supplied by the new process. Therefore,
in 1979, the production of methyl chloroform by the vinylidene chloride
method will be approximately 25,000 kkg. Information on this newly
developed production process was unavailable at the time this report was
prepared. Informed sources have suggested that the new process probably
uses vinyl chloride as a raw material .
Since this report presents a material balance of methyl chloroform
for the year 1978, it is appropriate to calculate the quantity of methyl
chloroform produced from vinylidene chloride in 1978.
According to Midwest Research Institute (MRI) , the quantity of
methyl chloroform produced in 1976 by the vinylidene chloride method
2-45
-------
(EPA, 1979a) was estimated at 79,500 kkg or 28 percent of the total
production. Assuming that the percentage obtained for 1976 is also
applicable for 1978, the quantity of methyl chloroform produced by this
process can be estimated as follows:
Production from 1978 Total U.S. Percent Market
Vinylidene Chloride = Production of Methyl x Capture of
Method Chloroform Process
79,500 kkg = (284,000 kkg) x (0.28)
This figure has an uncertainty of +0% and -14%. The +0% error is due to
the known maximum operating capacity of the PPG Lake Charles plant (EPA,
1979a) . In 1976, the maximum plant capacity was achieved thus verifying
this figure as an actual upper limit (EPA, 1979a) . The lower limit
(-14%) assumes PPG has expanded plant capacity to meet their future
expected percent of the market; that is, 24 percent (EPA, 1979a; Mannsville
Chemical Products, 1978; CEH, 1979). This percentage is also consistent
with the lower limit for operating days per year; or 310 days (Hydroscience,
1979; Section 2.2.3).
2.4.2 Emissions to
According to MRI, methyl chloroform is not emitted to the air from
the vinylidene chloride process (EPA, 1979a) . We speculate that some
emissions to the air from this process must exist.
With little available information on the vinylidene chloride method
and by using information obtained on the vinyl chloride-based production
process (a similar process) (Hydroscience, 1979), we arrived at a derived
flow diagram which probably represents the actual production process of
methyl chloroform from vinylidene chloride. This derived flow diagram
is presented in Figure 2.4-1. According to the derived flow diagram,
methyl chloroform emissions to the air can occur from the following
possible sources: 1) the hydrochlorinator vent; 2) the methyl chloroform
column vent; 3) storage and handling techniques; and 4) fugitive emissions
2-46
-------
1
Hydrochlorination
reactor vent
NJ
Vinylidene
Chloride
HC1
FeCl3
catalyst
Hydrochlorinator
reactor
X_^
VjMRU ;
/
Recycle*
_J
| Catalyst
„„ A filter
Distillation
column vent
g
9
H
0
O
r
s.
/
0
•H
i •»
H |
H 3
•H H
•P 0
01 O
•H
Q
___^_^^_
>
I
.
\l
Recycle
^ — ''
Heavy ends
Fugitive
emissions
Miscellaneous
waste water
sources
Product
storage
Tank loading
and unload ing
Figure
Derived Flow Diagram of the Production Process from
Vinylidene Chloride
-------
Since there is no information on the emissions of methyl chloroform
to the air from the vinylidene chloride based production process, we
assume that the use of emission factors obtained for similar emission
sources in the ethane and vinyl chloride-based production processes
are applicable for the calculation of the emission quantities of methyl
chloroform from the vinylidene chloride method.
Emissions are calculated with and without environmental control
devices. Both calculations are presented in this report to account for
the lack of available environmental control information. For each
source of emission, the most probable type of control technology is
indicated. Also, an evaluation of the likelihood that PPG uses the
indicated control technology is performed.
Total multimedia environmental losses (Figure 2.4.2) are calculated
by assuming that PPG uses appropriate emission control technologies.
In order to calculate emissions at the production site, the following
formulae are used.
Uncontrolled
Methyl Chloroform
Emissions
1978 Productions of Methyl
Chloroform by the Vinylidene
Chloride Process
Volatile Organic
Compound Uncontrolled
Emission Factor
Controlled
Methyl Chloroform =
Emissions
Fraction of Methyl
Chloroform in VOC
Uncontrolled
Methyl Chloroform
Emissions
1-Emission
Control
Efficiency
2.4.2.1 Emission to Air From the Hydrochlorinator Vent (Vent A.)
Process emissions occur when gases are released from the hydro-
chlorination reactor vent (A ). Although it is unlikely, PPG may not
use an emission control device on the hydrochlorination reactor.
2-48
-------
Therefore, it is assumed that these vent gases are controlled with a
mechanical refrigeration unit (MRU). The controlled emission is included
in the total multimedia environmental losses.
Assumptions used to estimate the loss of methyl chloroform from the
hydrochlorination reactor vent are:
1) 1978 Production = 79,500 kkg (+0%, -14%) (EPA, 1979a; Hydro-
science, 1979; and Section 2.4.1)
2) Uncontrolled VOC emission factor = 2 kkg/10 kkg (+350%, -90%)
The emission factor was estimated using vinyl chloride and ethane process
emission rates for both hydrochlorination reactor vents (.00019 kkg/kkg
and .00021 kkg/kkg) (Hydroscience, 1979) and the TRW/MRI estimate for
the vinyl chloride process (0.009 kkg/kkg) (TRW, 1975; EPA, 1979a). The
proposed estimate reflects a greater confidence in the Hydroscience
report (Hydroscience, 1979). The upper and lower bounds of the emission
factor are the TRW/MRI and Hydroscience estimates.
3) fraction of methyl chloroform in VOC = 98 percent (+1%, -8%)
The yield rate of methyl chloroform from vinylidene chloride
is 98 percent (EPA, 1979a; Mannsville Chemical Products, 1978).
An upper bound of 99 percent is possible (although not likely) and
an economic lower bound is approximately 90 percent.
4) Vapor recovery system (MRU) effeciency = 85 percent (±5%) (Hydroscience,
1979; Section 2.2.2.2)
2-49
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Using the above information in the formulae described in the
previous section, uncontrolled and controlled air emissions are calculated
as follows:
Uncontrolled Air Emissions = 79,500 kkg x .002 kkg/kkg x 0.98 = 156 kkg
Controlled Air Emissions = 156 kkg x (1 - 0.85) = 23.4 kkg
The uncertainty assigned to the controlled air emission is +352%
and -97%. The large uncertainty is due primarily to the large variance
in the emission factor. It should be noted that the upper bound of this
contplled emission represents less than 0.2 percent of the methyl chloroform
produced by the vinylidene chloride process. Even if the hydrochlorination
reactor vent is not equipped with an emission control, the estimated
upper limit contributes less than 0.9 percent of the methyl chloroform
produced by this process. In either case, the quantities released are
not significant.
2.4.2.2 Emissions to the Air from the Distillation Column
It is estimated that 0.0005 kkg per kkg of methyl chloroform produced
is released to the air from the methyl chloroform distillation column in
the vinyl chloride-based production process (EPA, 1979a). If this
emission factor is also applicable for the vinylidene chloride-based
production process, then the following can be used to calculate the
uncontrolled and controlled emissions:
1) 1978 production 79,500 kkg (+0%, -14%) (Section 2.4.1)
2) Uncontrolled VOC emission factor = 0.0003 kkg/kkg product
(+67%, 33%) (See 2.4.2.1 - uncontrolled VOC emission factor).
The upper bound is the TRW/MRI estimate (0.0005 kkg/kkg) and
the lower bound is the Hydroscience estimate (0.0002 kkg/kkg)
(EPA, 1979a; TRW, 1975; Hydroscience, 1979).
2-50
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3) Fraction of methyl chloroform in VOC = 100%
4) Vapor Recovery System (MRU) efficiency = 85% (±5%) (Hydroscience,
1979; Section 2.2.2.2)
The uncontrolled and controlled emissions to the air are calculated
as follows:
Uncontrolled Air Emission = 79,500 kkg x 0.0003 kkg/kkg x 1.00 = 23.9 kkg
Controlled Air Emission = 23.9 kkg x (1 - 0.85) = 3.59 kkg
As shown on Figure 2.4-1, it is assumed that the distillation
column has a mechanical refrigeration unit. This type of emission
control is typical of volatile organic compound processes. Therefore,
the controlled air emission is included in the multimedia environmental
losses. The uncertainty of the estimated emissions is +75%, -49%.
Again, the uncertainty given to the distillation column emission is
large. But, as noted earlier, although the range of estimated emissions
is large, the relative quantity of methyl chloroform released to the
quantity produced is not significant ( < .01 percent).
2.4.2.3 Emissions to the Air from Product Storage and Handling Techniques
Uncontrolled emission of methyl chloroform to the air from product
storage and loading of tank cars and trucks in the vinyl chloride-based
production process is estimated at 1.19 g/kg and 0.61 g/kg of methyl
chloroform produced respectively (Hydroscience, 1979; Appendix F). The
facility operated by PPG is probably similar to that of Dow. Thus, tank
sizes should be similar to those of Dow, although not as many are
required. Assuming similar tank sizes, the above emission factors are
also applicable for the vinylidene.chloride method. Emissions of methyl
chloroform from the above sources can be calculated using the following
assumptions:
2-51
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1) 1978 production = 79,500 kkg (+0%, -14%)(see Section 2.4.1)
2) Uncontrolled VOC emission factors (See Section 2.2.2.2)
a) product storage = 0.00119 kkg/kkg (±25%)
b) handling techniques = 0.00061 kkg/kkg (+30%, -10%)
3) Fraction of methyl chloroform in VOC = 100 percent
4) Vapor Recovery System (MRU) efficiency = 85 percent (±5%)
a) emissions of methyl chloroform from storage tanks (Vent C)
The uncontrolled and controlled emissions to the air from this source
are calculated below:
Uncontrolled Air Emissions = 79,500 kkg x 0.00119 kkg/kkg x 1.00
94.6 kkg
Controlled Air Emissions =94.6 kkg x (1 - 0.85) = 14.2 kkg
The uncertainty of the controlled estimate is +41%, -44%. Vented
storage tanks often have refrigeration systems to control diurnal and
working losses. The controlled estimate has been included in the
multimedia environmental losses of methyl chloroform.
b) Handling losses (Vent D)
The uncontrolled and controlled emissions to the air due to product
handling are calculated below:
Uncontrolled Air Emissions = 79,500 kkg x 0.00061 kkg/kkg x 1.00
- 48.5 kkg
Controlled Air Emissions = 48.5 kkg x (1 - 0.85) = 7.27 kkg
2-52
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The uncertainty of the controlled estimate is +45%, -37%. Refrigeration
of vapors is required for the economic transfer of VOC's. The controlled
emission of methyl chloroform due to handling is included in the multimedia
environmental losses.
2.4.2.4 Emissions to the Air from Other Fugitive Sources Within the
Production Plant
Sources of fugitive emissions within the production facilities
include process pumps, compressors, process values, and pressure relief
devices (Hydroscience, 1979). According to the Hydroscience report,
fugitive emissions of methyl chloroform from the vinyl chloride-based
production process are estimated at 0.37 g/kg of methyl chloroform also
applicable for the vinylidene chloride method, then the fugitive emissions
of methyl chloroform can then be calculated using the following assumptions:
1) 1979 production = 79,500 kkg (+0%, -14%)
2) Uncontrolled VOC emission factor = 0.00037 kkg/kkg (±20%)
3) Fraction of methyl chloroform in VOC = 100 percent
4) Emission control efficiency = 90 percent (±5%)
The total uncontrolled fugitive emissions are equal to:
Uncontrolled Air Emissions = 79,500 kkg x 0.00037 kkg/kkg x 1.00 = 29.4 kkg
Assuming that a 90 percent control efficiency could be achieved in
fugitive emission sources by the detection and correction of major
leaks, the controlled fugitive emission quantity is calculated below:
Controlled Air Emissions =29.4 kkg x (1 - 0.9) = 2.94 kkg
The uncertainty of this controlled emission quantity is estimated
at +54% and -56% due to the following reasons: 1) it is estimated that
2-53
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100 percent of VOC is methyl chloroform; 2) the variability in leak
detections and corrections; and 3) maintenance procedures. The controlled
emission estimate is included in the multimedia environmental losses
because minimizing fugitive losses improves overall system efficiency.
2.4.3 Emissions to Water
Waterborne emission of methyl chloroform discharged by the vinylidene
chloride production method is estimated in the range of "ppb" in aqueous
effluent waste streams (EPA, 1977a). The quantity of methyl chloroform
present in this stream is not mentioned in the study done by MRI (EPA,
1979a).
According to the reported monitoring data near sites of methyl
chloroform production (EPA, 1977a), the level of methyl chloroform
present in the controlled aqueous effluent of the PPG plant (which
produces methyl chloroform by the vinylidene chloride method) ranged
from 5 to 180 ppb by weight. We then assume that the weighted composite
concentration of methyl chloroform in the controlled aqueous effluent
is 120 ppb by weight with an uncertainty of ±50% (EPA, 1977a). Based on
the typical daily water discharge of chemical plants of the size of the
PPG plant, we estimate that the daily water discharge of this process is
1 million gallons per day. The uncertainty of this figure is ±25%.
Using the above assumptions, the quantity of methyl chloroform
emitted to the water in the controlled effluent discharged by vinylidene
chloride-based production process can then be calculated by multiplying
the following factors:
1) the quantity of water discharged per day = 1 million gallons
(±25 percent)
2) the number of operating days per year = 330 days (±5%) (Section
2.2.3)
2-54
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3) the density of water at 25°C = 1 kg/1
4) the conversion factor from gallon to liter = 3.785 1/gal
5) the concentration of methyl chloroform in the water effluent
= 120 ppb (±50%)
Water Emissions =
(1,000,000 fSL) (330 4lZ2.)(i JES. )( 3.7851 )(120 x 10"9 £&) = 150 kg or 0.15 kkg.
day year 1 gal kg
Wastewater losses (labeled F in Figure 2.4-1) were identified as a
source of VOC emissions by Hydroscience (Hydroscience, 1979). Assumptions
used in calculating emissions to water are:
1) 1978 production = 79,500 kkg (+0%, -14%)
2) Uncontrolled VOC emission rate for wastewater treatment =
3
0.001 kkg/10 kkg (Hydroscience, 1979) this value was assumed
by Hydroscience to be typical of all water discharges during
the production of methyl chloroform
3) Fraction of methyl chloroform in VOC (maximum value assumed)
= 100 percent
4) No control device used due to low concentrations
The uncontrolled emission of methyl chloroform is:
Water Emissions = 79.5 x 103 kkg x 0.001 kkg/103 kkg x 1.00
= 0.0795 kkg
Assuming the average value from the effluent discharge and Hydro-
science calculations, the 1978 emission of methyl chloroform is 0.115
kkg. The uncertainty of this emission is ±31 percent. This assumes the
alternative methods for calculating the water emission represents the
upper and lower bounds.
2-55
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2.4.3.1 Emission to the Air Due to the Wastewater Treatment
During the wastewater treatment phase, volatile organic compounds
(VOC's) such as methyl chloroform, trapped in the aqueous effluent may
be emitted to the air due to the aeration process in the treatment
system. We assume that 99 percent of the methyl chloroform trapped in
the untreated aqueous effluent is released prior to being treated. The
remaining 1 percent is treated by the system. Thus, of every 100 parts
of methyl chloroform in the aqueous effluent, 99 evaporate prior to
water treatment, while the remaining part enters the treatment system.
The error of the treated portion is +100%, -50% (Section 2.2.4). Of the
1 percent treated, we assume that 5 percent methyl chloroform is removed
during treatment and 95 percent is released intact in the controlled
aqueous effluent. The quantity removed from the controlled aqueous
effluent is presented with an uncertainty of ±50% (Section 2.2.4). This
95 percent methyl chloroform is represented by the calculated emission
to water in the preceding section. Therefore, the total quantity of
methyl chloroform emitted to the air from process wastewater can be
calculated as follows:
(0.115 kkg)
100%
99%
12.0 kkg
Where:
0.115 kkg
100%/95%
the amount of methyl chloroform released to the
water by the wastewater treatment system (Section
2.4.3)
the ratio of the percentage of methyl chloroform
that enters the treatment system and the untreated
percentage discharged into the controlled water
effluent (see Section 2.2.4)
the ratio of the percentage of methyl chloroform
released to the air prior treatment and the percentage
of this chemical that enters the treatment system.
(see Section 2.2.4).
2-56
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The uncertainty of this figure is +106% and -60% due to the uncertainty
of the evaporation rate and the removal efficiency of the treatment
system. Although the proposed error is large, the estimated upper bound
for wastewater treatment air emissions is only 0.04 percent of the
methyl chloroform produced by PPG.
2.4.4 Emissions to Land
According to the MRI report (EPA, 1979a), a heavy-ends waste stream
containing at the maximum of 0.1 percent (or 0.001 kkg/kkg of methyl
chloroform produced) of methyl chloroform is discharged by the vinylidene
chloride-based production process. It is also reported that this heavy
ends waste stream is disposed of in an incinerator (EPA, 1979a).
2.4.4.1 Emission to the Air Due to the Incineration Disposal Method
Information on the incineration disposal method of the heavy end
waste stream is not available. We assume that a 95 percent (±4%) destruction
of the- waste materials is achieved by incineration. The remaining 5
percent is assumed to be emitted to the air during the disposal cycle.
We also assume that there is no emission control on the flue gas released
by the incinerator. As mentioned above, Midwest Research Institute has
estimated that the emission factor of methyl chloroform from the heavy-
end waste streams of the vinylidene chloride process is 0.001 kkg/kkg of
product (EPA, 1979a). This estimate should be considered as an upper-
limit of the calculation of the emission from this source.
Based on the above assumptions, the emission quantity of methyl
chloroform to the air from the incinerator can then be calculated using
the following assumption:
1) 1978 production = 79,500 kkg (+0%, -14%)
2) uncontrolled emission factor from heavy-end waste stream
= 0.001 kkg/kkg
3) fraction of methyl chloroform in VOC = 100 percent
2-57
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4) the incinerator efficiency = 95 percent (±4%) (Section 2.2.6)
Air Emission = 79,500 kkg x 0.001 kkg/kkg x 100 x (1 - 0.95) = 3.98 kkg
The uncertainty of this value is +80%, -81%.
2.4.4.2 Emission to Land
There was no mention in the literature of direct emission of methyl
chloroform containing wastes to land (EPA, 1979a; Hydroscience, 1979).
We estimate that the amount of methyl chloroform produced from the
incinerator ash is not quantifiable.
2.4.5 Multimedia Environmental Losses
Figure 2.4-2 shows multimedia environmental losses of methyl chloroform
from its production using the vinylidene chloride process. Total multimedia
environmental losses are calculated by assuming that PPG uses the appropriate
available control technology.
2-58
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Ni
I
Ul
3.98 kkg
(+80%,-81%)
Air
Incinerator
2.94 kkg
(+54%,-56%)
Air
Emission
control device
48.5 kkg
K365
Air
A12.0 kkg
(+106%,-60%)
Air
Methyl chloroform
production process
from vinylidene
chloride
79,600 kkg
Water
Waste water
treatment
process
75.5 kkg
Land
79,500 kkg (+0%,-14%)
Production'
\x
kkg
Land
0.115 kkg
(+ 31%)
Water efflue'
Figure 2.4-2 Multimedia Environmental Losses from the Vinylidene
Chloride-based Production Process
-------
2.5 INDIRECT PRODUCTION OF METHYL CHLOROFORM BY CHLORINATION
No evidence was found to support the indirect production of methyl
chloroform resulting from the chlorination of wastewater or drinking
water. The major pathway for the formation of volatile halogenated
organics in chlorinated waters is the haloform reaction with humic and
fulvic acids. The pattern of this reaction requires the successive
replacement of hydrogen by chlorine on a carbon alpha to a carbonyl
group followed by hydrolysis to produce CHX- and a carboxylate (see Figure
2.5-1) (Jolley, 1978). This reaction mechanism does not result in the
formation of methyl chloroform.
Analysis of drinking water and treated wastewater before and after
chlorination have shown that methyl chloroform concentrations decrease as
a result of chlorination, undoubtedly because of evaporative losses.
In one such analysis, secondary treated wastewater from the Metro-
Denver treatment plant was analyzed for chlorinated organics before and
after chlorination. Chromatograms from headspace analysis of wastewater
showed increased concentrations of chloroform; concentrations of tri-
chloroethylene and tetrachloroethylene remained about the same and
concentrations of methyl chloroform decreased (Sievers, 1978).
Bellar (Jolley, 1978) analyzed wastewater from several cities before
and after chlorination. The results for volatile aliphatic hydrocarbons
are summarised in Table 2.5-1. The concentrations of methyl chloroform
decreased during the chlorination process (as a result of evaporation)
while concentrations of methylene chloride, chloroform, 1,1,2-trichloro-
ethylene and 1,1,2,2-tetrachloroethylene increased as a result of
chlorination (Jolley, 1978).
2-60
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TABLE 2.5-1 - Concentrations of Volatile Chlorinated Organics Before
and After Chlorination (jug/1)
Before Before After
Compound Treatment Chlorination Chlorination
methylene chloride 8.2 2.9 3.4
chloroform 9.3 7.1 12.1
methyl chloroform 16.5 9.0 8.5
1,1,2,2-tetrachloroethylene 6.2 3.9 4.2
1,2,1-trichloroethylene 40.4 8.6 9.8
Source: Jolley, 1978
2-61
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R-<
.. OH"
slow'
R-C=
(HOX
fast
fast
fast
H*
fast
0&
-C=CX2J
(HOX
fast
JCHX3|* R-C-OH ^ H20
fast
0
R-C—CX3
Figure 2.5-1 The Haloform Reaction
Source: Jolley, 1978
2-62
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2.6 PRODUCTION OF METHYL CHLOROFORM FROM NATURAL SOURCES
Information on the production of methyl chloroform from natural sources
is not available. We have extensively searched for additional information on
this subject, but this information does not exist at all in the literature.
Therefore, in this report we assume that the occurrence of methyl chloroform
produced from natural sources is very small until future studies indicate
differently.
2-65
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2.7 STOCKPILES
2.7.1 Introduction
Data for U.S. production and sales of methyl chloroform suggests
that various quantities are placed in and retrieved from stockpiles
annually. This data is presented in Table 2.7-1.
We assumed that the quantity of methyl chloroform to be added or
subtracted from stockpiles was the difference between the total U.S.
annual production and the total sales. Internal plant transfers of
methyl chloroform for use as a raw material in other processes is not
included in the production figures (Woodward, 1979). According to Mr.
Woodward of Dow, the methyl chloroform produced (at least by Dow Chemical
Company) does not become a raw material for other processes (Woodward,
1979).
2.7.2 Quantity Stockpiled
Stockpiles of methyl chloroform are not reported and sales information
for 1978 was not available. Therefore, the quantity of methyl chloroform
placed-in (retrieved-from) stockpiles must be calculated using historical
information.
As presented in Table 2.7-1, the percent of production stockpiled
has varied from an 11.8 percent addition to a 4.2 percent reduction.
The 10 year average shows a 5.1 percent rate of methyl chloroform added
to stockpiles. Between 1972-1975, regulations restricting the use of
trichloroethylene in California and other states and market expansion
increased the demand for methyl chloroform. Also, in 1975, the Ethyl
Corporation closed down their methyl chloroform production plant. These
actions produced a shortage of plant capacity and required withdrawals of
methyl chloroform from stockpiles. By 1977, the three present manufactures
were operating at over 90 percent of their plant capacity (EPA, 1979a)
2-64
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and had new additions under construction. The total 1977 production had
exceeded sales by 11.8 percent, thereby providing a new increase to
stockpiles.
To estimate the quantity of methyl chloroform stockpiled in 1978,
2- and 10-year averages were used as a likely range. The 1976 and
1977 2-year average provides an upper bound based on an expanding market
during heavy U. S. industrial growth. The 10-year average provides a
lower bound and represents a long-term market growth trend. 1978 stockpiles
are:
7 ?y 4. s \°/
x 284,000 kkg = 17,500 kkg
The uncertainty of this number of +10%, -20% due to methyl chloroform
market growth, plant additions, and economic health.
The total quantity of methyl chloroform stockpiled between 1966 and
1978 represents approximately a 5 month supply. Economic conditions in
1978 and the length of time required to rebuild a damaged production facility
suggest that this may be an optimum quantity in stockpiles.
2-65
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Table 2.7-1 — Stockpiles of Methyl Chloroform
Year
Total Production
Quantity
kkg
1960-
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976 •
1977
1978
NA
110,179
NA
135,808
147,102
166,154
169,919
199,902
248,754
268,350
208,112
286,358
287,945
284,000
Sales
kkg
NA
113,263
122,335
130,681
135,580
148,508
154,813
176,449
256,827
261,136
216,912
278,919
254,061
NA
Percent of Production
Stockpile
kkg*
NA
(3084)
NA
5127
11522
17646
15106
23953
(8073)
7214
(8800)
7439
33,884
NA
10 year average
2 year average
Stockpiled
NA '
(2.8%)
NA
3Qa/
. O/b
7.8%
10.6%
8.9%
11.7%
(3.2%)
2.7%
(4.2%)
2.6%
11.8%
NA
5.1%
7.2%
Source: EPA, 1979(a)
*Reductions in stockpile quantity shown in parenthesis ( ).
2-66
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2.8 IMPORTS OF METHYL CHLOROFORM
Information with regard to the importation of methyl chloroform to
the U.S. was not available. However, due to surplus quantities (approximately
6 percent of the annual production) and excess U.S. plant capacity present in
the industrial sector importation of methyl chloroform is expected to be
negligible (EPA, 1979a).
2-67
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3.0 Use and End Products
Methyl chloroform was not used consumptively as an intermediate in
the synthesis of any organic chemicals in 1978. Until 1974, about
27,000 kkg methyl chloroform was used in the production of vinylidene
chloride but this process is no longer used.
Methyl chloroform is used in several non-consumptive applications
which favor the use of chlorinated solvents. The uses and their environmental
releases described in this section include:
o Metal cleaning
o Aerosols
o Adhesives
o Textiles
o Drain and septic tank
cleaners
o Paints
o Inks
o Catalyst preparations
o Film cleaners
o Pharmaceuticals
o Leather tanning and finishing
The status of methyl chloroform as a solvent for various end-uses
is changing as a result of OSHA regulations and existing or potential
regulations concerning ozone formation in the troposphere and ozone
depletion in the stratosphere. Appendix B discusses the Impact of
existing or potential regulations on industrial uses of chlorinated
solvents.
The assumptions and estimations used to determine environmental
losses and destruction of methyl chloroform from various end-uses are
detailed in this chapter. Because of the very high evaporation rate of
methyl chloroform, any losses to wastewater are assumed to be mostly
evaporated before stream discharge. Evaporation of methyl chloroform
from land and water disposal are discussed further in Chapter 4.
3-1
-------
3.1 METAL CLEANING
3.1.1 Use of Methyl Chloroform in Metal Cleaning
This section quantifies methyl chloroform losses in solvent
degreasing operations. Solvent degreasing is widely performed in an
estimated 49,000 (±4,600) plants within eight SIC categories included in
the metal working industry, (Dow, 1976; Dresser, 1979). Methyl chloroform
is commonly used in three applications — manufacturing cold cleaning,
open top vapor degreasing, and conveyorized degreasing. Appendix C-l
includes a description of the metal working industry and the major
solvent degreasing operations. Solvent degreasers are assumed to be
geographically distributed in a manner similar to the metal working
industry as a whole. Figure 3.1-1 shows the distribution of metal
working plants (Metalworking Data Bank, 1972).
A summary of methyl chloroform materials balance for solvent
degreasing operations is shown in Figure 3.1-2. The following discussion
details the rationale and calculations for these estimates. Because of
the detailed calculations required to estimate losses of methyl chloroform
from this industry, many of the calculations have been appendicized.
3.1.2 Quantification of Methyl Chloroform Used in Metal Cleaning
Use of methyl chloroform varies with the type of metal cleaning
operations. Simple petroleum distillates are the most widely used
solvents in cold cleaning operations. Based on EPA data and contacts
with an industry selling cold cleaners, 70 to 80 percent of all cold
cleaners are used for maintenance operations (EPA, 1977b; G. Pendelton,
1979). There is little opportunity to recover solvents in simple maintenance
cold cleaning and consequently less expensive petroleum solvents are
generally used. Manufacturing cold cleaners are often required for high
quality cleaning. Again, petroleum distillate fractions dominate due
to lower cost, but solvent blends with chlorinated solvents and pure
chlorinated hydrocarbons, including methyl chloroform, are also used.
Vapor degreasing operations use halogenated solvents almost exclusively
because they are non-flammable and are much heavier than air. The practice
3-2
-------
3.1-1 Geographic Distribution of Metal Working Industry
Source: Metalworking Data Bank
-------
623 kkg .
(+772,-85%)
Incinerated
Air
45,700 kkg
56,300 kkg
187,700 kkgx
(+39%,-2%)
(+39%,-2%)
Cold
cleaning
28,600 kkg
(+58%,-29%)
247 kkg Destroyed during
-^ (+77%,-59%)carbon regeneration
Water
Land
8530 kkg (+43%,-33%)
7600 kkg (+46%,-29%)
159 kkg
(+51%,-52%)
Incinerated
Air
8940 kkg
'(+47%,-46%)
77.0 kkg Destroyed during
—^ (+ 69%) carbon regeneration
Water
(+34%,-32%)
546 kkg (+ 35%)
Land. 863 kkg (+52%,-47%)
Metal cleaning
1580 kkg
(+37%, -76%)'
Incinerated
Air
70,600 kkg
"(+42%,-41%)
91.700 kkg
131.400 kkg
(+11%,-21%)
(+35%,-39%)
619 kkg
(+68%,-95%)'
Incinerated
39,300 kkg
(+35%,-39%)
Open top
vapor
degreasers
609 kkg Destroyed during
(+66%,-65%)carbon regeneration
8470 kkg (+38%, -74%)
10,500 kkg (+38%, -74%)
286 kkg Destroyed during
—^ (+62%,-64%)carbon regeneration
2000 kkg (+60%,-61%)
3270 kkg (+69%,-93%)
Figure 3.1-2 Overall Summary of Materials Balance for
Methyl Chloroform in Metal Cleaning
3-4
-------
of solvent substitution to obtain State Implementation Plan approval has
led to the widespread substitution of methyl chloroform for trichloroethylene.
Although methyl chloroform is not a perfect substitute for trichloroethylene
(methyl chloroform has problems with zinc and aluminum and cannot be
applied where there is excessive water) (Rehm, R., GCA, 1979), decreased
use of trichloroethylene has led to an increased use of methyl chloroform.
There are several independent estimates of the quantities of
methyl chloroform used in degreasing operations from 1974 through 1977.
These data have been used to project 1978 estimates. Table 3.1-1 summarizes
the estimated use of methyl chloroform in degreasing. Appendix C-l
discusses these and other estimates in further detail.
Table 3.1-1 Estimates of Use of Methyl Chloroform in Solvent Degreasing
Estimated
Consumption of
Methyl Chloro-
form in Solvent
Degreasing
(kkg/yr)
214,000
Source of Annual
Year of Consumption Growth
Estimate Estimate Rate
1976 EPA, 1979 5-7%
1978 Source of
Estimate Growth Rate
(kkg/yr) Estimate
235,935 SRI (1978);
to Hugh Farber,
245,009 Dow Chem. (79)
162,000
(+10%, -0%)
1974
QAQPS
1977
4%
189,500
±10,-0
Roy George,
QAQPS, 1979
177,000
CEH, (78)
1977 Based on
EPA Estimate
5-7
186,000
to
189,000
SRI (1978);
Hugh Farber,
1978
3-5
-------
The 1977 estimate made by SRI was considered the most accurate
figure from which to estimate 1978 use, since it is the most recent
estimate available. This estimate, ranging from 186,000 kkg to 189,000
kkg, is also consistent with an estimate based on 1974 data from OAQPS,
once the annual growth rate was taken into account (EPA, 1977b;
George, R. 1979f). Based on other estimates available to OAQPS, the
1974 data is considered accurate to +10% and -0% (See Appendix C-l for
other estimates).
The 1976 estimate of 214,000 kkg was thought to be high because it
corresponds to' an annual growth rate of 9 to 13 percent from 1974 to
1976. Based on several 1974 estimates shown in Appendix C.I, total
methyl chloroform production increased by only 2 percent over the same
period (EPA, 1979a).
We estimate that 187,700 kkg of methyl chloroform was used in metal
cleaning in 1978. This estimate is considered accurate to +11% and -2%
because of the close agreement with the estimate made by OAQPS and to
account for the uncertainty suggested by OAQPS data in Appendix C-l.
While the use of methyl chloroform in the metal cleaning industry
is estimated to be increasing at 5-7 percent per year, growth is slower
in cold cleaning as compared to vapor degreasing. The number of cold
cleaning operations has increased from 122 million units in 1974 (EPA,
1977b) to 135 million units in 1978 (SRI, 1978). This corresponds to
approximately 3 percent growth per year. Seventy to eighty percent of
the cold cleaning operations are maintenance cleaners which rarely use
methyl chloroform or other halogenated solvents (Pendelton, G. 1979;
EPA, 1977b). Approximately 30 million cold cleaners are manufacturing
units, which are more likely to use halogenated solvents. In contrast,
the number of open top vapor degreasers (32,000) (SRI, 1978) increased
at a rate of 10 percent annually since 1974 when 22,000 units were
reported (EPA, 1977b). A growth rate of only about 5 percent was
projected for vapor degreasers between 1976 and 1980 (EPA, 1979f).
3-6
-------
Efforts were made to determine how much of the 187,700 kkg of
methyl chloroform consumed in metal cleaning operations was used for
cold cleaning and how much was used in vapor degreasing. Contacts were
made to methyl chloroform producers and manufacturers of metal cleaning
equipment. Many of the contacts indicated that they were only "guessing"
or that the split between vapor degreasers and cold cleaners was difficult
to determine. Under these circumstances it was decided to use the
results of the Dow survey of solvent metal cleaning operations conducted
in 1974 to estimate the respective quantities of methyl chloroform used
by cold cleaners and vapor degreasers. The results of the survey were
used and adjusted to account for the growth rate of cold cleaning and
vapor degreasing units and the effect of solvent substitution for
trichloroethylene.
The results of the Dow Survey suggested that in 1974, 36 percent of
the methyl chloroform consumed in metal cleaning was used for cold
cleaning and 64 percent was used for vapor degreasing. Accounting for a
growth rate of 3 percent and 10 percent for cold cleaning and vapor
degreasing, respectively and for the effects of solvent substitution,
JRB estimates that 30 percent of the methyl chloroform was used in cold
cleaning and 70 percent in vapor degreasing. In accounting for the
growth rate it was necessary to assume that use of methyl chloroform
increased in proportion to the increased number of units. Appendix C-2
details the calculations used to determine this split. Based on this
distribution, the quantity of methyl chloroform used in cold cleaning
and vapor degreasing is determined as follows:
Cold Cleaning:
Total Methyl Percent of Total Total Used
Chloroform Used Used in Cold = in Cold Cleaning
in Metal Cleaning Cleaning
(187,700 kkg) (0.3) = 56,300 kkg
3-7
-------
Jo
10J
275 '
225
175 -
125
Trichloroethylene
1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977
Figure 3.1-3 Production Trends for Methyl Chloroform and
Trichloroethylene
-------
Vapor Degreasing;
Total Methyl Percent of Total Total Used
Chloroform Used Used in Vapor = Vapor Degreasing
in Metal Cleaning Degreasing
(187,700 kkg) (0.7) = 131,400 kkg
The decision to use the results of the Dow survey as a basis for
determining the split between cold cleaning and vapor degreasing was
based on the following factors:
o The Dow survey results were the only actual survey results
available.
o Although the survey was based on users with 20 employees or
more, these results are probably representative for methyl
chloroform. The high cost of this solvent precludes its use
among many small operations.
o The results of the estimate based on the Dow survey are in
good agreement with estimates being used by GCA Technology, a
contractor for the OAQPS. GCA estimates that one-third of the
methyl chloroform was used in cold cleaning and two-thirds was
used for vapor degreasing the Dow survey, was also the basis
for this estimate (Rehm, R., GCA, 1979).
o Finally Mansanto estimated that in 1974, 45 percent of the
methyl chloroform was used for cold cleaning and 35 percent
for vapor degreasing (EPA, 1977b). Accounting for solvent
substitution and the growth rate, approximately 39 percent and
61 percent would have been used for cold cleaning and vapor
degreasing in 1978. This estimate is in reasonably good
agreement with our estimate, based on the Dow survey.
Detrex estimated the split at 59 percent and 41 percent for vapor
degreasing and cold cleaning, respectively (MRI, 1979). This estimate
of percent distribution differs most significantly from the JRB estimate.
3-9
-------
If Detrex's estimate is more representative of methyl chloroform usage,
JRB's estimate of 56,300 kkg for cold cleaning may be low by 37 percent
and the estimate of 131,400 kkg for vapor degreasing may be high by 21
percent. Accounting for an uncertainty estimate of +11% and -2% for the
total methyl chloroform used in metal cleaning, our overall uncertainty
estimates are +39% and -2% for cold cleaning and +11% and -21% for vapor
degreasing.
3.1.3 Emissions from Cold Cleaning Operations
3.1.3.1 Sources of Emissions From Cold Cleaning Operations
Figure 3.1.-4 shows points of emission from a typical cold cleaning
operation.
Bath Agitation Spray
evaporation^
tVV '
^ /
Cold cleaning
\
\
Waste solvent
Carry-out
Figure 3.1-4 Points of Emission from a Cold Cleaning Operation
Waste solvent may contribute 40 to 60 percent of total solvent
evaporative losses where reclamation is not practiced (EPA, 1977b).
Operations using halogenated solvents are more likely to recover waste
solvent because of the high cost of chlorinated solvents (EPA, 1977b).
It is often the case, however, that methyl chloroform is used in
3-10
-------
mixtures with less costly solvents. It was estimated that at the time
of the Dow survey in 1974 that only about 20 percent of cold cleaning
operations were recycling solvents; but this practice has been steadily
increasing (Richards, D., Dow 1979). The National Solid Waste Management
Association estimated that 30 - 40 percent of the solvent used in cold
cleaning is reclaimed (NSWM, 1980). JRB assumes that 30 percent of the
methyl chloroform was reclaimed in 1978. The remaining waste solvent is
disposed of by flushing, landfilling or incineration.
Depending upon control practices, evaporative losses from spray and
agitation and losses from carry out are highly variable. For highly
volatile solvents, such as methyl chloroform, room ventilation and use
of a cover are the most critical factors in determining solvent losses
from evaporation.
Table 3.1-2 summarizes the major control variables influencing
solvent losses.
Table 3.1-2 Major Control Variables for Cold Cleaners
Loss Control
Evaporation o Room ventilation
o Surface area of the tank
o Use of cover; manual vs. automatic
o Freeboard height
o Use of carbon adsorption
Carry-out o Racks for draining parts
o Use of internal drainage
o Time allotted for drainage
Waste-Solvent o Reclamation practices
Because of the variability in emission controls and in the type of
metal cleaning application, there is no "typical" cold cleaner nor
"typical" annual emission rate. Table 3.1-3 shows results of several
test runs using cold cleaners, with and without various controls. The
results clearly indicate the wide variability in solvent losses depending
upon the controls used and the type of equipment.
3-11
-------
Figure 3.1-3 Efficiencies of Control Options in Controlling Solvent
Losses From Cold Cleaners
U)
I
Surface
Unit Area
Kleer-Flo m2
Model 90 0.97
Kleer-Flo
Model 90 0.97
Gray Mills
SL-32 0.33
Baron
Blakeslee 1.1
HD425
(operated
in cold mode)
Control
Air
Draft
Decreased
from
85m/mln
to
27a/nin
Emissions
Without
Control
kkg/hr/n2
(kkg/yr)*
2.8
(U.2)
With
Control
kg/hr/m2
(kkg/yr)*
1.0
(4.0)
Percent
Control
Efficiency Solvent
64% Perechloro-
ethylene
Comment
Evaporation
Losses
Only
Air Draft Maintained
Cover
Increased
Freeboard
0.27-0.50
Solvent
Reclamation
2.8
(11.2)
0.2
(0.8)
93% Perechloro-
ethylene
at 83-85m/min
Evaporation Losses
Only
Air Draft 52-57m/min
1.2
(5.8)
0.14
(.16)
0.8
(3.2)
0.04
(.16)
34% Perechloro-
ethylene
1.1.1
70% Trichloro-
ethane
Evaporation Losses
Only
Waste Solvent Losses
Only
*Based on 250 day/yr; 16 hr/day.
Source: Dow, 1976
-------
Emissions of Methyl Chloroform from Cold Cleaning
Total emissions from cold cleaning operations were estimated in
Section 3.1.1 to be 56,300 kkg. This estimate includes losses from non-
boiling conveyorized degreasers which are considered in section 3.1.2.4.
Total losses from conveyorized non-boiling degreasers have been estimated
at 10,600 kkg based upon the assumptions discussed in Appendix C-3.
Total losses from all other cold cleaners are estimated as follows:
Total Cold Losses from Non-Boiling Losses from
Cleaning Losses - Conveyorized Degreasers = Non Conveyorized
Cold Cleaners
(56,300 kkg) - (10,600 kkg) = 45,700 kkg
Although emission rates vary widely, annual average emissions have
been estimated for the study. We assumed there were 1.35 X 10 cold
cleaners in 1978 and 30 percent of these are manufacturing units; which
are more likely to use halogenated solvents (EPA, 1977b). Based on the
Dow survey, we estimate that 18 percent of the manufacturing cold cleaners
use methyl chloroform (Dow, 1976). The total number of cold cleaning
units using methyl chloroform is estimated as follows:
Total Number Percent Which Percent Using Total Number
of Cold Cleaners are Manufacturing Methyl = of Cold Cleaners
Units Chloroform Using Methyl
Chloroform
(1.35 x 106) (0.3) (0.18) = 72,900 units
Emissions per unit are estimated by dividing the total methyl
chloroform used by the number of units.
45,700 kkg/72,900 units = 0.63 kkg/unit
Using JRB derived estimates, annual emissions approximate 0.63
kkg/unit. The OAQPS has estimated typical emissions from a manufacturing
cold cleaner at 0.5 kkg/unit (EPA, 1977b). This emission rate, however,
was based on an average for all solvents, not only methyl chloroform.
JRB's estimate of 0.63 kkg/unit/yr is within 20 percent of the estimate
made by OAQPS (EPA, 1977b).
3-13
-------
Total methyl chloroform emissions to air, water and land are shown
in Figure 3.1-5.
623 kkg,)
(+77%,-85%)
Incinerated
A5,700 kkg
(+39Z.-2Z)
Cold
cleaning
V, 28,600 kkg
(+58%,-29%)
Air
247 kkg
(+77%,-59%)
8530 kkg
(+43%,-33%)
7600 kkg
Destroyed during
regeneration
Water
Land
(+46%,-29%)
Figure 3.1-5 Multimedia Environmental Losses of Methyl Chloroform
from Cold Cleaning*
*Numbers may not add due to rounding
Losses were calculated for the 72,900 cold cleaning units which
used 45,700 kkg methyl chloroform in 1978.
Detailed calculations for these emissions are presented in Appendix
C-4. The assumptions used to calculate these multimedia environmental
releases are:
o Solvent Reclamation
JRB estimated that 30 percent of the methyl chloroform is
reclaimed at 90 percent efficiency. Although solvent recovery
services are more efficient in reclaiming solvent, many of the
operations are equipped with their own stills which operate at
lower efficiency. It was also assumed that 25 percent of the
still bottoms (172 kkg) were incinerated at 95 percent efficiency
and the remaining 75 percent (517 kkg) were landfilled.
Although some reclamation services incinerate all the still
bottoms (Solvent Recovery Service of the Northeast, 1979)
there are currently very few approved incinerators for chlorinated
hydrocarbons.
3-14
-------
o Waste Solvent:
The remaining 70 percent of the waste solvent (16,100 kkg) was
disposed of by landfilling, flushing or by incineration. The
Dow survey suggested that unreclaimed waste solvent was
disposed of as follows:
o Incineration 3 percent (±5%)
o Landfilling 44 percent (+15%, -5%)
o Flushing 53 percent (+5%, -15%)
Although several contacts were made in an effort to update this
information, no reliable estimates were obtained. One large manufacturer
of metal cleaning equipment indicated that most of his clients landfilled
their solvent, although flushing was also common. An Effluent Guidelines
Survey of the metal cleaning industry suggested that 79 percent of the
plants discharged waste solvent to the sewer and only 21 percent, landfilled
the waste (Dresser, 1979). However, the number of operations surveyed
and made available to JRB was too small to generalize from (only 14
plants).
Atmospheric Losses;
Direct atmospheric emissions from bath evaporation, agitation,
spray and carry-out were estimated to be the difference between the
total solvent losses from cold cleaning and the waste solvent losses.
Total Methyl Losses from Waste Total
Chloroform - Still Bottoms + Solvent = Atmospheric
Losses from Losses Emissions
Cold Cleaning
(45,700 kkg) - (16,100 kkg + 689 kkg) = 28,900 kkg
Only about 1.5 percent of the operations use activated carbon to recover
atmospheric losses and the efficiency of recovery is about 60 percent
(Dow, 1976). As Appendix C-4 indicates this practice reduces direct
atmospheric losses by about 260 kkg to 28,600 kkg.
3-15
-------
As Figure 3.1-5 indicates 63 percent of the solvent is emitted
directly to the air. Approximately 2 percent of the solvent is destroyed
during incineration or carbon regeneration and 16 percent of the waste
solvent was determined to be landfilled. No information was available
on the quantities of landfilled wastes that are properly containerized
and air emissions from land disposal of waste solvent cannot be estimated.
The remaining 19 percent of the solvent is discharged, mainly to municipal
treatment systems. It is assumed that 95 percent of the methyl chloroform
(8100 kkg) evaporates before stream discharge.
The overall uncertainties for the estimates of multimedia releases
must account for uncertainties related to: (1) the total quantity of
methyl chloroform used in metal cleaning (187,700, +11% and -2%); (2)
the quantity used in cold cleaning verses vapor degreasing (56,300 kkg,
+39% and -2%; (3) the quantity of unreclaimed waste solvent generated
and the means of disposal of the waste solvent (Appendix C-4); and (4)
the quantity of still bottoms generated and the means of disposal
(Appendix C-4). The estimated overall uncertainty factors for the
quantities shown in Figure 3.1-5 based on the above individual uncertainties
are +43 and -33 percent for water, +46 and -29 percent for land, +77
and -85 percent for the quantity incinerated and +58 and -29 percent for
emissions to air.
The major factor contributing to these large uncertainties is the
uncertainty related to the amount of methyl chloroform used in cold
cleaning as compared to vapor degreasing.
Figure 3.1-6 shows the geographic distribution of cold cleaning
operations based on Dow survey (1976) and the total annual emissions for
each geographic area. Control technologies were assumed to be similar
for each geographic area. Emissions are largely concentrated in the
northeast and midwest where 65 percent of all cold cleaning operations
are located.
3-16
-------
OJ
I
1900 kkg
SOUTHWEST
% = % of total cold cleaners
kkg = kkg lost annually per area
34%
15,200 kkg
9.5%
4200 kkg
Figure 3.1-6 Geographic Distribution of Methyl Chloroform from Cold Cleaning
-------
3.1.4 Emissions from Open Top Vapor Degreasers
It was estimated in Section 3.1.1 that 131,000 kkg methyl chloroform
were lost in 1978 from the operation of vaporized degreasers. Seventy
percent of these losses are attributable to open top vapor degreasers
(OTVD) and 30 percent to conveyorized vapor degreasers (CVD).
(131,000 kkg) (0.7) =
(131,000 kkg) (0.3) =
91,600 kkg
from OTVD
39,300 kkg
from CVD
Roof vent '
Open top
vapor
degreaser
Diffusion/convection
Carry-out
Waste-solvent
Figure 3.1-7 Points of Emission from an Open Top Vapor Degreaser
This section deals with emissions from OTVD only. Figure 3.1-7
shows points of emission from an OTVD. Solvent reclamation is much more
widely practiced for OTVD operations than for cold cleaning. Because of
better waste solvent control practices, a smaller proportion of the
solvent losses are due to waste solvent and liquid carry-out. Most of
the emissions are those which diffuse out of the degreaser.
3-18
-------
Table 3.1-4 summarizes the major control variables influencing
solvent losses by diffusion and convection and the percent control
efficiency observed under test runs. The extent to which some control
practices are used is not well know. It is known, however, that most
vapor degreasers do recycle waste solvent. As indicated previously, the
results of the Effluent Guidelines Survey for Mechanical Products found
that 73 percent of solvent degreasing operations recovered waste solvent
(Dresser survey, 1979). A contact with Phillips Incorporated indicated
that approximately 75 percent of all vapor degreasers are equipped with
stills (Raquat, D., 1979). This estimate was also in agreement with an
estimate made by NSWMA (1980). It is estimated that about 1.5 percent
of all open top vapor degreasers use activated carbon and 12 percent are
equipped with refrigerated chillers (Dow, 1976; Raquat, D. 1979). The
extent to which covers are used to control emissions is not known. Open
top vapor degreasers range in size from a table-top model with dimensions
of 0.3m x 0.6m up to degreasers which are 36m long and 2m wide. Because
of the wide variability in sizes of degreasers and in the types of
solvent control options, there are no typical units nor typical emission
rates.
Emissions from OTVD
The number of OTVD which use methyl chloroform was estimated from
the Dow Survey and adjusted for solvent substitution (Dow, 1976). Using
this data, an estimated 30 percent of the 32,000 OTVD use methyl chloroform.
Number of Percent Using = Total Number
OTVD Methyl Chloroform of Units Using
(32,000 units) (30) - 9,600 units
The average unit loss of methyl chloroform is estimated from the
following expression.
Total Methyl Chloroform Average
Losses from OTVD = Annual Loss
[No. of OTVD] Per Unit
91,700 kkg = 9.55 kkg/unit
9,600
3-19
-------
Table 3.1-4 Control Variables - Open Top Vapor Degreasers
Control
Cover
Regrigerated
Freeboard
Chiller
Refrigerated
Freeboard
£ Chiller
o and Cover
Pneumatic
Cover
Regf igerated
Freeboard
Chiller
and Cover
Carbon
Adsorption
Freeboard
Height
(quiet air)
Solvent
Losses
No Control
kg/m /hr
1.72
1.72
1.72
0.78
0.67
2.9
0.46
(.5) = ratio
Solvent
Losses with Percent
Control Efficiency
kg/m /hr
0.91 47%
1.24 28%
0.55 60%
0.49 37%
0.57 15%
1.05 65%
0.25 46%
(.75) = ratio
Surface
Area
2
m
1.67/
1.2
1.2
1.67/
1.2
5.3
3.8
5.9
0.4
Surface
Used
Methylene
Chloride
Methylene
Chloride
Methlene
Chloride
Methyl
Chloroform
Methyl
Chloroform
Trichloro-
ethylene
Methyl
chloroform
Type
Degreaser
Crest
Ultrasonics
Crest
Ultrasonics
Crest
Ultrasoncis
Detrex
DUS-800-S
Detrex
DUS-800-S
Blakeslee
D-95-9
Detrex
2D500-E
-------
This estimate is in good agreement with an estimate made by OAQPS
that an average of 9.5 kkg solvent are emitted from uncontrolled OTVD.
Total methyl chloroform losses to air, water and land are summarized
in Figure 3-8. Detailed calculations for these estimates are included
in Appendix C-5.
1380 kkg
(+37%,-76%)
Incinerated
91,700 kkg
(+35%,-39%)
Open top
vapor
degreasers
70,600 kkg
^(+42%,-41%)
Air
609 kkg _> Destroyed during
(+66%,-65%) regeneration
8470 kkg
(+20%,-21%)
10,500 kkg
(+38%,-74%)
Water
Land
Figure 3.1-8 Multimedia Environmental Losses of Methyl Chloroform
from Open Top Vapor Degreasers*
*Numbers may not add due to rounding
Losses were estimated for 9,600 OTVD units which emitted a total of
0
91,700 kkg methyl chloroform in 1978 or 9.55 kkg per unit.
In order to derive the estimates for.multimedia releases shown in
Figure 3.1-8, the following assumptions were made:
3-21
-------
1) Still Bottoms
It has been estimated that 20-25 percent of the total virgin
solvent becomes waste solvent in OTVD operations (EPA, 1977b). The
estimated 20,600 kkg waste solvent includes both still bottoms and
unreclaimed waste solvent. Based on information from the Effluent
Guidelines Survey, the NSWMA, and from Phillips, Inc, an estimated 75
percent of the OTVD operations are equipped with distillation equipment
for solvent recovery (EPA, 1979; NSWMA, 1980; Raquat, D., 1979). Methyl
chloroform losses in still bottoms, 4750 kkg, were estimated by assuming
that 75 percent of the solvent is reclaimed at 90 percent efficiency.
The disposal of still bottoms was assumed to be the same as for cold
cleaning operations; 25 percent are incinerated and 75 percent are
landfilled.
2) Unreclaimed Waste Solvent
The quantity of unreclaimed still bottoms (15,800 kkg) was estimated
by assuming that 25 percent of the operations do not practice solvent
recovery. The disposal of unreclaimed waste solvent was assumed to be
the same as for cold cleaning; 3 percent was incinerated, 44 percent was
landfilled and 53 percent was flushed. These estimates were based on
the Dow Survey (Dow, 1976)
3) Direct Atmospheric Losses
Direct atmospheric emissions, determined to be 70,500 kkg, were
estimated as the difference between total losses from OTVD and losses
from waste solvent.
Total Unreclaimed Still Total
Methyl Chloroform - Waste + Bottoms = Atmospheric
Losses Solvent Emissions
(91,700 kkg) - (15,800 kkg + 4750 kkg) = 71,200 kkg
This quantity was then adjusted to account for an estimated 1.5 percent
of the operations using carbon adsorption of about 60 percent efficiency.
(Dow, 1976). The practice of using carbon adsorption reduced emissions
by 641 kkg and actual atmospheric losses were estimated at 70,500 kkg.
3-22
-------
Figure 3,1-8 indicates that approximately 77 percent of the annual
methyl chloroform used in open top vapor degreasers is emitted directly
to the atmosphere. An estimated 9 percent is discharged to municipal
treatment systems and approximately 8000 kkg of this quantity or 95
percent reaches the atmosphere by evaporation before stream discharge.
Approximately 11 percent of the solvent is disposed of to land. No
information was available on how these wastes are containerized and
therefore no estimate of air emissions can be made. The remaining 3
percent of the solvent was incinerated or destroyed during activated
carbon regeneration.
The overall uncertainties for the quantities shown in Figure 3.1-8
are a function of the following individual uncertainties:
1) The total quantity of methyl chloroform used in solvent
degreasing (187,700 kkg, +11% and -2%)
2) The total methyl chloroform used for vapor degreasing (131,400
kkg, +11% and -21%)
3) Uncertainties related to the quantities of still bottoms
generated and the final disposal methods for the still bottoms (see
Appendix C-5)
4) Uncertainties related to the quantities of unreclaimed waste
solvent generated and the final disposal of the waste solvent (see
Appendix C-5)
5) Uncertainty related to air emissions (70,500 kkg, +42/-41
percent)
Based on these individual uncertainties our overall uncertainty
estimates are: +42 and -41 percent for releases to air; +20 and -21
percent for the quantity discharged; +38 and -74 percent for the quantity
released to land, +37 and -76 percent for the quantity incinerated and
+66 and -65 percent for the quantity destroyed during carbon regeneration.
3-23
-------
Figure 3.1-9 shows the percent distribution of open top vapor
degreasers in various geographic regions and the corresponding methyl
chloroform losses (Dow, 1976). Methyl chloroform losses are estimated
by assuming control technology and disposal techniques are similar
throughout all geographic regions.
3.1.5 Emissions from Conveyorized Vapor Degreasers
There are an estimated 5,000 conveyorized degreasers, 85 percent of
which are vapor degreasers (EPA, 1977b). Based on the Dow survey
(1976), it is assumed that 30 percent use methyl chloroform. Solvent
emissions from conveyorized vapor degreasers are similar in source to
those described for open top degreasers. However, enclosures common for
these degreasers reduce emisssions from natural air drafts or fans.
Also, the conveyorized design usually eliminates most poorer degreaser
operations and major drag out sources. Although conveyorized degreasers
emit more methyl chloroform than do OTVD or cold cleaners, they actually
emit less solvent per part cleaned.
Annual emissions to air, water and land are shown in Figure 3.1-10.
Detailed calculations are included in Appendix C-6. Estimates were made
assuming 1,280 conveyorized vapor degreasers and annual methyl chloroform
losses of 39,300 kkg. It was assumed that 85 percent of conveyorized
vaporized degreasers practiced solvent recovery. All other estimates
were the same as those made in determining losses from vapor degreasing.
61$ kkg
(+68Z.-95Z)
Incinerated
39,300 kkg
(+35Z.-39Z)
Conveyorized
vapor
degreasers
33,200 kkg
(+35Z.-39Z)
Air
286 kkg
(+62Z.-64Z)
2000 kkg
(+60Z.-617.)
3270 kkg
Destroyed during
regeneration
Water
(+69Z.-93Z)
, Land
Figure 3.1-10 Multimedia Environmental Losses of Methyl Chloroform
from Conveyorized Vapor Degreasers*
*Numbers may not add due to rounding
3-24
-------
U)
% = total vapor degreasers
kkg = kkg lost annually per area
37%
33,000 kkg
FAR WEST i7.3%
5300 kkg
23%
2000 kkg
. SOUTHWEST
Figure 3.1-9 Geographic Distribution of Methyl Chloroform Losses from Vapor Degreasing
-------
Because solvent recovery is widely practiced in the operation of
conveyorized degreasing, waste solvent is minimal and most of the
solvent losses are directly to the atmosphere.
Figure 3.1-10 indicates that 84 percent of the methyl chloroform
was emitted to air, less than 3 percent was destroyed by incineration or
during carbon regeneration, 5 percent was discharged and about 8 percent
was landfilled. It was assumed that 95 percent of the quantity discharged
(1900 kkg) was emitted to air before stream discharge. No estimate was
made for releases to air from landfilled waste solvent.
As was indicated for cold cleaners and vapor degreasers, the
overall uncertainty estimates are a function of several individual
uncertainties. Accounting for these individual uncertainties, overall
uncertainties are as follows: +60 and -61 for the quantity discharged;
+69 and -93 for the quantity landfilled; +68 and -95 percent for the
quantity incinerated; +35 and -39 percent for the quantity released
directly to air and +62 and -64 percent for the quantity destroyed
during carbon regeneration.
3.1.6 Emissions from Conveyorized Non-boiling Degreasers
Non-boiling degreasers are not designed to prevent solvent losses
as adequately as conveyorized vapor degreasers. OAQPS estimated that a
typical non-boiling conveyorized degreaser, (CND) loses nearly twice as
much solvent as a conveyorized vapor degreaser. (EPA, 1977b) Points of
emission are the same as from OTVD.
Figure 3.1-11 shows annual losses of methyl chloroform from non-
boiling conveyorized degreasers. Losses were calculated based on 225
units with total annual losses of 10,600 kkg or 47 kkg per unit (see
Appendix C-7 for detailed calculations).
3-26
-------
159 kkg
(+51%,-52%)
Incinerated
10,600 kkg
(+34%,-32%)
^8940 kkg
(+47%,-46%)
Mr
77.0 kkg
Conveyorized
nonboiling
degreasers
(+ 69%)
546 kkg
. Destroyed during
' regeneration
Water
(+ 35%)
863 kkg
Land
(+52%,-47%)
Figure 3.1-11 Multimedia Environmental Losses of Methyl Chloroform
from Conveyorized Nonboiling Degreasers*
*Numbers may not add due to rounding
Eighty-four percent of the methyl chloroform is emitted directly to
the atmosphere, 5 percent is discharged to municipal sewers and 8
percent is landfilled. Two percent is destroyed during the incineration
of still bottoms and 1 percent is destroyed during carbon regeneration.
The uncertainties for the environmental releases or destruction are
calculated using the same factors as those for conveyorized vapor degreasers.
The overall uncertainties are: +47 and -46 percent for releases to air;
±35 percent for releases to water; +52 and -47 percent for releases to land;
+34 and -32 percent for the quantity incinerated and ±69 percent for the
quantity destroyed during regeneration.
3.1.7
Multimedia Environmental Losses
Figure 3.1-12 shows the sum of the multimedia environmental losses
from cold cleaning and vapor degreasing.
The overall uncertainty for air emissions for metal cleaning was
calculated as follows:
3-27
-------
CO
187,
(+11%
2980 kkg
(+109%, -100%)
Incinerated
700 kkg
,-2%)
\
/
.141,000 kkg
T+44%,-30%)
Air
1220 kkg
Metal
cleaning
(+119%, -100%)
Destroye
regene
. 18,
d during
ration
500 kkg
1 (+76%, -72%)
19,500 kkg
(+76%, -72%) H
Water
975 kkg
\
/
(+86%, -82%)
Air
volitalization
Water
22,200 kkg
Land
(+91%,-100%)
Figure 3.1-12 Overall Multimedia Environmental Losses for
Methyl Chloroform from Metal Cleaning
-------
Upper Bound:
subtract the lower limit of all other environmental
losses from the upper limit of the total quantity
of methyl chloroform used in metal cleaning.
(Total) 187,700 kkg (±11%)
(Regeneration) 1,220 kkg (-100%)
(Landfilled) 22,200 kkg (-100%)
(Water) 19,500 kkg (-72%)
(Incinerated) 2,980 kkg (-100%)
208,300 kkg
(0)
(0)
(5,500)
(0)
202,800 kkg
Upper Bound =
Lower Bound:
202.800 kkg
141,300 kkg
1.44 or +44%
subtract the upper limit of all other environmental
losses from the lower limit of the total methyl
chloroform used in metal cleaning.
(Total)
(Regeneration)
(Landfilled)
(Water)
(Incinerated)
187,700 kkg (-2%)
1,220 kkg (+119%)
22,200 kkg (+91%)
19,500 kkg (+76%)
2,980 kkg (+109%)
183,900 kkg
(2,700)
(42,400)
(34,300)
(6,200)
98,300 kkg
Lower Bound = 1 - 98,300 kkg = 0.30 or -30%
141,300 kkg
The total quantity of air emissions from metal cleaning is 160,000
kkg. This figure includes 18,500 kkg of methyl chloroform (95 percent of
19,500 kkg) which volatilizes readily from waste water.
3-29
-------
3.2 AEROSOL PRODUCTS
3.2.1 Quantification of Methyl Chloroform Used in Aerosol Products
Methyl chloroform is used as a solvent and a vapor depressant agent
in many aerosol products. The quantity of methyl chloroform consumed in
this category is not reported annually. It is estimated that about
18,000 kkg of this chemical was used in 1976 in the aerosol manufacturing
industry (SRI, 1978; Chemical Marketing Reporter, 1977). Stanford
Research Institute estimated that a 5 percent increase per year over 1976
could be expected for the consumption of methyl chloroform due to the ban
of chlorofluorocarbon—based aerosol products from the consumer market
(SRI, 1978). This would amount to a more than 10 percent increase in
1978 over 1976 consumption for aerosol uses. In that case, the total
consumption of methyl chloroform in 1978 can be estimated by multiplying
the quantity consumed in 1976 by the rate of increase.
Methyl Chloroform x Rate of Increase = Total Consumption
Consumed in 1976 of Methyl Chloroform
in 1978
(18,000 kkg) (1.05)2 - 20,000 kkg
The uncertainty of this figure is -±20% due to the uncertainty in
the trend of aerosol consumption and the uncertainty of the total
quantity consumed.
3.2.2 Use of Methyl Chloroform in Aerosol Products
Of the total quantity of methyl chloroform used in aerosol manufacture,
5,000 kkg is estimated to be consumed in the production of household
products, automotive products, and coatings and finishes registered under
the regulation of the Consumer Product Safety Commission (CPSC) (Battelle,
1979). The remaining 15,000 kkg is assumed to be consumed in the use of
aerosols for personal care products (which are registered with the Food and
Drug Administration (FDA)) and pesticide products (under the jurisdiction
3-30
-------
of the U.S. Environmental Protection Agency (EPA)). Information on the
breakdown of different types of personal care products was not available
in the literature. Because the use and formulation of these aerosol products
are all similar, we can assume that the emission of methyl chloroform from
aerosols is not affected by the lack of information on personal care
products. Appendix D lists the registered pesticide products containing
methyl chloroform (EPA Pesticide Files).
The following sections describe each methyl chloroform aerosol manu-
facturing process and the use of these aerosol products. Figure 3.2-1
shows a flow diagram of the use of methyl chloroform for aerosol products.
3.2.3 Use and Emissions of Methyl Chloroform in Household Aerosol Products
Methyl chloroform has been identified as a solvent used in many
household aerosol products. JRB estimates that 60 percent of the total
methyl chloroform consumed for products under the jurisdiction of CPSC is
used in formulation of household products. This estimate is based solely
on a 1975 estimate of the number of aerosol products used in household
products as compared to the number used in coatings and finishing and
automotive products. (Kirk-Othmer, 1971).
Based on this estimate, the quantity of methyl chloroform used in
this category is calculated using the following equation.
Total Methyl Chloroform Percent Used in =• Total Methyl Chloroform
Used in CPSC Registered Household Products in Household Products
Products
(5,000 kkg) (0.6) = 3,000 kkg
The uncertainty for the percent methyl chloroform used in household
products is ±30%. Accounting for an uncertainty of ±20% for total
methyl chloroform used in aerosol products, the overall uncertainty
estimate is ±36%.
3-31
-------
OJ
to 20,000 kkfi
(+ 20%)
Air
75 Kkg A
(+41X)
Household 3000 kkg % Pormul.Mnr 2,930 kkg
products . ,,„. •
Air
12.5 kkg A
<+ 41%)
Automotive 500 kkg ^ formulation
yiuJuclb - ,+ 36jj) '
Air
37.5 kkgf 1320
(j; 41%) (+ 4
Coatings and 1500 kkg ,FonBul.M(M, 1460 kkg
finishings (+~36Z)
"54i» AT
Personal care products .,- QQQ . , 1
and pesriride ' \jFnrmulat--fnn
products (+ 36%) |
Air
2640 kkgA
(+ 41%)
_i End uses
1
Landfilled 293 kk(> (+ 99%)
Air
439 kkg ,A
(+ 41%)
487 kkp
Air
kkg "
1%)
_i End uses
-
_j End uses
1 48.8 kkg
Landfilled (+ 992)
LandTilled 146 kkg (+ 99%)
13,200 kkg^
(+ 41%)
14,600 kkg
End uses
7
L
and fll fed
1400 kkg
Figure 3.2-1 Flow Diagram and Multimedia Environmental
Losses of Methyl Chloroform from Aerosols
-------
Methyl chloroform has been identified in the following household
products (Battelle, 1979):
-Adhesives
-Dusting aid
-Anti-static spray
-Leather and suede products
*shoe polish formulation
*suede cleaner and conditioner
-Spot remover
-Fabric protector/water repellant
-Metal cleaner/protective polish
-Exhaust fan and hood cleaner
-Mattress refresher
-Teflon renewal
-Miscellaneous
The chemical ingredient list of each product is shown in Appendix D.
3.2.3.1 Emissions to the Environment Due to the Formulation of Household
Products
There is little information on the emission of methyl chloroform in
the production of household aerosols. According to Johnson, it is estimated
that the loss to the air during the formulation phase of aerosols can be as
much as 2 to 3 percent of the consumption quantity (Johnson, 1979; Anthony,
1979) . We feel that this percentage represents a good estimate of the
emissions based on available information concerning the method used to fill
aerosol cans. Thus, the total emission of methyl chloroform to the air
during the production phase of household aerosols can be calculated as
follows:
Quantity of Methyl Percent Lost = Quantity of Methyl
Chloroform in During Chloroform Lost
Household Products Formulation During Formulation
(3,000 kkg) (0.025) - 75.0 kkg
Emissions to land and water from production are estimated to be
negligible due to the particular physical properties of methyl chloroform.
Because this chemical is only slightly soluble in water (0.44g/100 ml @ 20° C)
3-33
-------
and is readily evaporated, we assume that all annual environmental
emissions of methyl chloroform are to the air.
The uncertainty estimate for releases from formulation of household
products is ±20%. The overall uncertainty is ±41% to account for possible
deviations in the total quantity of methyl chloroform used in aerosols
and the percent used in household products.
The quantity of methyl chloroform in aerosol products is estimated to
be the difference between total methyl chloroform used in this cateogry
and releases during formulation.
Quantity of Methyl Quantity Released to = Quantity Present
Chloroform for Air During Formulation in Household Aerosol
Household Products Products
(3000 kkg) - (75 kkg) - 2,930 kkg
3.2.3.2 Emissions to the Environment Due to Use of Household Aerosol
Products
Based on typical consumer usage of aerosols, we assume that 90 percent
of the contents of an aerosol package is used up and the remaining 10
percent remains in the package which will end up in municipal landfills.
The following expression is used to calculate the amount of methyl
chloroform emitted to the air from the consumer use of aerosols:
Quantity of Methyl Percent Emitted = Quantity Emitted
Chloroform in to Air to Air
Household Products
(2930 kkg) (0.9) = 2,640 kkg
The overall uncertainty of this estimate is ±41%. This accounts
for uncertainties related to total methyl chloroform used for aerosol
products, the percent used for household products and the percent emitted
to air, which has an uncertainty estimate of ±5%.
3-34
-------
The remaining 10 percent is retained in aerosol containers and is
disposed in landfills as residue.
Quantity of Methyl Percent Retained in = Amount Disposed
Chloroform in Containers to Landfills
Household Products
(2930 kkg) (0.1) = 293 kkg
With an uncertainty of ±90% for the percent of methyl chloroform
retained in aerosol cans, the overall uncertainty for the quantity
released to land is ±99%.
3.2.4 Use and Emissions of Methyl Chloroform in Automotive Products
Methyl chloroform is used in automotive products for metal degreasing
and carburator cleaning. Based upon the number of automotive aerosol
products sold in 1975 relative to household products and coatings and
furnishing, JRB estimates that 10 percent of the methyl chloroform in CPSC
registered products was used in automotive products (Kirk-Othmer, 1971).
Based upon this estimate, the quantity of methyl chloroform in aerosol
automotive products is estimated as follows:
Total Methyl Chloroform Percent which are = Quantity of
in Methyl CPSC Registered Automotive Products Chloroform in
Products Automotive Aerosol
Products
(5000 kkg) (0.1) = 500 kkg
This estimate is considered accurate to ±36% considering the
uncertainties related to total methyl chloroform used in aerosol products
(±20%) and the uncertainty for the percent used in automotive products
(±30%).
Methyl chloroform has been listed as an ingredient in the following
automotive products (Battelle, 1979):
-Engine degreaser and cleaner
-Brake cleaner
-Belt dressings
-Lubricants.
3-35
-------
A list of chemical ingredient formulations of the automotive aerosol
products is itemized in the Appendix D.
3.2.4.1 Emissions to the Air During the Formulation Phase
Assumptions similar to those established in Section 3.2.3.1 also
apply here. We estimate that from 2 percent to 3 percent of the total
consumption of methyl chloroform for aerosol uses is emitted to the air
during the production phase. The emission to the air during the production
of automotive aerosol products can then be calculated by multiplying the
quantity of methyl chloroform available for the production of automotive
products by the emission factor of 2.5 percent:
Quantity of Methyl Percent Released = Quantity Released
Chloroform in During Formulation During Formulation
Automotive Products
(500 kkg) (0.025) - 12.5 kkg
The uncertainty of this estimate is ±41%. This range accounts for
uncertainties related to quantities of methyl chloroform in aerosol
products, the percent used in automotive products and the quantity
released during formulation.
3.2.4.2 Emissions to the Environment Due to the Use of Automotive Products
The use of automotive aerosol products is not unlike that of household
products. Thus, we can assume that 90 percent of the contents of an
aerosol package is released by spraying and the remaining 10 percent is
landfilled as residue in used containers.
The emission to air from the use of automotive products is estimated
as follows:
Quantity Methyl Releases to Air Percent Emitted = Quantity
Chloroform in - During x to Air Emitted to Air
Automotive Formulation
Products
(500 kkg - 12.5 kkg) x (0.9) = 439 kkg
3-36
-------
The quantity landfilled is estimated as follows:
Quantity of Methyl - Releases to Air Percent = Quantity
Chloroform in During x Landfilled Landfilled
Automotive Formulation
Products
(500 kkg - 12.5 kkg) x (0.1) - 48.8 kkg
The overall uncertainty estimates for the quantity of methyl
chloroform emitted to air and landfilled are ±41% and ±99% respectively.
These ranges account for uncertainties related to the total quantity of
methyl chloroform used in aerosols, the percent used in automotive
products and the percent released to air or landfilled.
3.2.5 Use and Emissions of Methyl Chloroform in Coatings and Finishes
Methyl chloroform has also found use in the production of lacquer
stains, fixative and protective coatings, racing bottom treatment reagent,
and polyurethane coatings. The list of chemical ingredients of these
products is shown in the Appendix D.
We assume that the remaining 30 percent of the total consumption of
methyl chloroform for the production of aerosols registered with the CPSC
is consumed in the coating and finishing products business. Again, this
estimate is based solely on the number of aerosol containers sold in 1975
in this product category, relative to household and automotive products.
The consumption of methyl chloroform in coating and finishing can be
calculated from the following equation:
Total Methyl Percent Used in = Quantity Used
Chloroform in Coatings and in Coatings and
CPSC Registered Finishes Finishes
Products
(5000 kkg) (0.3) = 1500 kkg
3-37
-------
The uncertainty of this estimate is ±36%, based on the uncertainty
of the total methyl chloroform used in aerosol products (±20%) and the
uncertainty of the quantity used in coatings and finishes (±30%).
3.2.5.1 Emissions During the Production Phase
It is estimated that air emissions account for all methyl chloroform
releases during the production phase. The emission factor is assumed to
be 2.5 percent (see Section 3.2.3.1) with an uncertainty value of ±20%.
Based on these conditions, the atmospheric emission of methyl chloroform
from the production of coating and finishing products can be estimated
as follows:
Methyl Chloroform
in Coating and
Finishing Products
(1500 kkg)
Percent Emitted
to Air During
Formulation
(0.025)
Quantity Emitted
to Air
37.5 kkg
The overall uncertainty for this estimate is ±41%.
3.2.5.2 Emissions from the Uses of Coating and Finishes
The emission to the air from the use of coating and finishing products
are again estimated to be 90 percent of the total emissions.
Quantity of Quantity Emitted Percent Emitted
Methyl Chloroform - to Air During x to Air from Use
in Coating and Formulation
and Finishing
Products
(1500 kkg
- 37.5 kkg)
x
(0.9)
Quantity
Emitted to
Air
1320 kkg
3-38
-------
The remaining 10 percent is landfilled as residual in discarded
containers.
Quantity of Methyl Quantity Emitted Percent Quantity
Chloroform in - to Air During x Landfilled = Landfilled
Coating and Formulation
Finishing Products
(1500 kkg - 37.5 kkg) x (0.1) = 146 kkg
The uncertainty of the estimates for the quantity released to air and
landfilled are ±41% and ±99% respectively.
3.2.6 Use and Emissions of Methyl Chloroform in Personal Care Products
and Pesticides Products
As mentioned in Section 3.2.1, it is estimated that 15,000 kkg of
methyl chloroform was consumed in the process of manufacturing personal
care and pesticide products. The use of methyl chloroform in personal
care products is regulated by the Food and Drug Administration (FDA).
Pesticide products are under the jurisdiction of the Environmental Pro-
tection Agency (EPA). There is little information on the use of methyl
chloroform for the production of these aerosols. We assume that it is
used as a solvent and as a vapor pressure depressing agent. A list of
methyl chloroform containing pesticide aerosol products is shown in
Appendix D.
3.2.6.1 Emission to the Air During the Production Phase
Again, since the manufacturing processes are similar to those of the
household product industry, we assume from 2 percent to 3 percent methyl
chloroform is released to the air during the production of these aerosol
products. Therefore, we estimate that the emission factor is 2.5 percent
of the total consumption for the production process with a deviation of
±20%. The emission to the air from the production of the personal care
and pesticide aerosol products are then estimated as follows:
3-39
-------
Total Methyl Chloroform Percent Emitted = Quantity Emitted
in Personal Care and During Formulation During Formulation
Pesticide Products
(15,000 kkg) (0.025) = 375 kkg
The overall uncertainty of this estimate is ±41% to account for
uncertainties related to total methyl chloroform used in aerosols (±20%),
quantity used in personal care and pesticide products (±30%) and the
percent emitted to air during formulation (±20%).
3.2.6.2 Emissions to the Environment Due to the Use of Personal Care
and Pesticide Products
It is estimated that 90 percent of the contents in an aerosol package
is consumed and 10 percent remains intact in the package and is disposed
of in landfills (see Section 3.2.3.2). These are only estimates and
should be verified by later studies.
The total release of methyl chloroform to the air due to the use of
personal care and pesticide products can then be calculated from the
following equation:
Methyl Chloroform Quantity Lost Percent Emitted = Quantity
in Personal Care - During x to Air Emitted
and Pesticide Formulation to Air
Products
(15,000 kkg - 375 kkg) x (0.9) - 13,200 kkg
The amount of methyl chloroform that is considered to be disposed in
landfills can be estimated as follows:
(Total Quantity) - (Air Emissions) = Quantity landfilled
(14,600 kkg) - (13,200 kkg) - 1,400 kkg
3-40
-------
The uncertainties of these figures are ±41% for the quantity emitted
to air and ±99% for the quantity landfilled.
3.2.7 Multimedia Environmental Losses
Figure 3.2-2 summarizes the environmental releases of methyl chloroform
from the production and use of aerosol products.
3-41
-------
U)
i.
10
Mr
Air
20
,000 kkg .
/*
(+ 20%)
500 kkg '
(+ 36%)
V
Formulation
of
aerosols
19,500 kkg
17,600 kkg
(+ 36%)
End uses
I
of
aerosols
J,
1890 kkg
(+ 62 %)
Landfilled
Figure 3.2-2 Multimedia Environmental Losses of Methyl
Chloroform from the Production and Use of Aerosols
* Numbers may not add due to rounding
-------
3.3 ADHESIVES
Approximately 20 percent of all adhesives produced annually are
solvent based (Effluent Guidelines, 1979). Solvent based adhesives have
an advantage over water based types because they are generally more
tacky and provide high early bond strength. Chlorinated solvents are
used in.specific applications to increase the solvency of an adhesive
and where non-flammable solvents are required. They are also used
selectively in making resin emulsions or elastomers for water based
adhesives.
3.3.1 Quantification of Methyl Chloroform Used in Adhesives
Although raw materials used in the production of adhesives have
been quantified in the 1977 Census of Manufacturers (Adhesives Age,
1979), solvents were not included in this inventory. A rough estimate
of the total chlorinated solvents used in the adhesives industry has
been made by researchers at Skeist Laboratories. It was estimated that
27,000 kkg of chlorinated solvents (±20%) were used in adhesives, and
methyl chloroform was by far the major chlorinated solvent used (Miron,
J., Skeist Labs, 1979). Chemical Marketing Reporter estimated that
19,800 kkg of methyl chloroform are used in the production of adhesives
(Chemical Marketing Reporter, 1977). This estimate is 73 percent of the
estimate made by Skeist Labs for total chlorinated solvents and thus
seems reasonable when one considers that methyl chloroform is the major
chlorinated solvent used. For purposes of the materials balance calculations,
19,800 kkg of methyl chloroform (±20%) will be used.
Contacts with the adhesives industry, however suggest that the
status of methyl chloroform as a solvent for adhesives is changing.
Hercules, which sells resins for adhesives, indicated that many of their
clients are phasing out solvent based adhesives and substituting "hot
melts" and water based types (Hercules, 1979). Contacts at National
Starch, UPACO and Mobay Chemicals also indicated that solvent based
adhesives were being phased out, wherever possible. These changes are a
result of existing or potential regulations imposed by State Implementation
3-43
-------
Plans, the Clean Air Act Amendments, and OSHA requirements (Reich, J.,
1979; Sweeny, 1., 1979; and Witzman, C., 1979) (see Appendix B).
Industry contacts did not distinguish between currently exempt and non-
exempt solvents when discussing their programs for phasing out the use
of solvents, since manufacturers felt that currently exempt solvents
would also be regulated.
3.3.2 Use of Methyl Chloroform in the Adhesives Industry
Table 3.3-1 lists the 15 product subcategories for adhesives, 1977
production data for each subcategory, and the percentage of plants using
methyl chloroform (Effluent Guidelines, 1979).
Since adhesive plants often produce many formulations within several
subcategories, plants using methyl chloroform for production of adhesives
in one subcategory may be "double counted" in another subcategory. For
example, many plants producing solvent based resin adhesives also produce
solvent based .elastomer adhesives. Although methyl chloroform may only
be used in one subcategory, it would appear, in Table 3.3-1, in the other
as well. The geographic distribution of plants using methyl chloroform
was not available for this study. However, Figure 3.3-1 shows that the
adhesives industries in general are concentrated in the northeast, and
to a lesser extent in the Great Lakes area and Texas. The results of
the effluent guidelines survey, summarized in Table 3.3.1, indicated the
following with respect to methyl chloroform:
o Methyl chloroform is used in the production of water based
adhesives as well as solvent based types.
o Further analysis of the survey results indicated that 50
plants within subcategories 1-7 used methyl chloroform (a
total of 70 plants, shown for subcategories in Table 3.3-1 ,
indicates that many plants are making adhesives in more than
one subcategory and are therefore "double counted").
o Among the plants producing water based adhesives, methyl
chloroform is most widely used in production of synthetic
resin-based adhesives.
3-44
-------
Table 3.3-1 Adhesive Subcategories
Subcategory
Number of
Plants
Annual
Production
kkg
Nuaber of
Plants
Using
He thy 1
Chloroform
. Percent of
Plants
Using
Methyl
Chloroform
Solution of protein
material In water
87
90,350
Solution of carbo-
hydrates In water
110
129,400
7Z
Solution of inorganic
materials in water
31
518,000
31
Dispersion of
natural elastomer
In water
74
15.000
31
Solutions or dis-
persions of other
natural organlcs
in water
46
23.000
91
Solutions or disper-
sions of synthetic
elastomers in water
113
532,000
61
Solutions, emulsions,
dispersions of syn-
thetic resins in water
208
606.600
48
231
Solutions of natural
organic compound in
water
Solutions, dispersions
of natural elastomer
in solvent
Solutions of synthetic
resin in solvent
Solution of synthetic
elastomer in solvent
IOOZ sythetlc or
natural resin, "hot
melt" products
Chemically reactive
Dry blends
Others
54
48
139
116
79
73
45
14
44,500 5 9Z
29.500 8 171
210 x 10°!.
91,300 21 151
164,000 39 341
180,100 0 0
52.700 1 It
78,500 0 0
33,200 6 43Z
3-45
-------
mlMnnctuRL moitcnoH flOLicr
STORET SYSTEM
MISCELLflNEOUS CHEMICflLS
S-I.C.2891 FROM
g rtISC CHEn DUN & BRADSTREET AUC/77
KBLf-1 TO ZOOOSCOO OK 31S.C6 nll.fS/INCH
* Figure 3.3-1 Georgraphic Distribution of Adhesive Industries
-------
o Forty-nine producers of solvent based adhesives use methyl
chloroform. Only the solvent toluene was used by more plants
producing solvent based adhesives. The chlorinated solvents
methylene chloride and trichloroethylene were used much less
frequently; 34 percent fewer plant-subcategories reported
using methylene chloride and 71 percent fewer used trichloro-
ethylene (Effluent Guidelines, 1979).
o Among producers of solvent based adhesives, methyl chloroform
was used most widely among producers of synthetic elastomers
and synthetic resins in solvent.
o The survey further indicated that although half the plants
using methyl chloroform produced water based adhesives,
these plants, as expected, use less solvent.
Based on calculations presented in Sections 3.3.3 and 3.3.4, JRB
estimated that approximately 20 percent of the methy chloroform used in
the adhesives industry is used for production of solvent based adhesives.
This estimate seemed "reasonable" to one industrial contact with whom
several of JRB's assumptions were reviewed (industrial contact, 1979).
3.3.3 Use and Emissions of Methyl Chloroform in Solvent Based Adhesives
Solvents have three uses in the production of solvent based
adhesives:
1) Dissolution of Natural and Synthetic Rubber and Synthetic Resins
Solvent based adhesives are prepared by dissolving the milled
elastomer or resin in solvent within enclosed churns or mixers. The
volume of methyl chloroform can vary from 5 percent where other solvents
are also used to 90 percent where methyl chloroform is the only solvent
(Hall, J., 1979). Solvent losses during formulation are low since dissolution
is carriedout in enclosed vessels (Hall, J., 1979; Wilholdt Cement,
1979). Vapor recovery systems have been included in many solvent based
adhesive operations to recover solvent losses (Effluent Guidelines,
1979).
3-47
-------
2) Solution Polymerization
A monomer or monomer mixture is dissolved in solvents and
polymerization is effected at elevated temperatures in the presence of
an initiator. Solvents used in this process must be inert to free
radicals (Skeist, 1977) and consequently chlorinated solvents would
not be used.
3) Cleaning of Vessels or Reactor
Chlorinated solvents are used in cleaning up spills in vessels
and reactors. It is likely that methyl chloroform would be used more
widely among plants using this solvent in their formulations. Spent
solvent is often given to outside contractors (Effluent Guidelines, 1979)
Figure 3.3-2 shows estimated losses of methyl chloroform from
solvent based adhesives. These estimates were based largely on
engineering judgements although assumptions were verified with indus-
trial contacts where possible. Although several industrial contacts
were made, JRB could not generalize for the industry as a whole;
typically an adhesive plant produces adhesives in several subcategories
and changes formulations frequently. A more accurate estimate of
methyl chloroform losses would require a survey of the industry.
3.3.3.1 Vessel Cleaning
This section estimates the amount of methyl chloroform used to
clean vessels and quantifies environmental releases through various
media. Based on the Effluent Guidelines profile of the industry, about
one-third of all plants surveyed use solvent cleaning, although many
use caustic wash and dry wash as well. (Effluent Guidelines, 1979)
About 50 percent of the plants produced some solvent based adhesives
(Effluent Guidelines, 1979).
3-48
-------
Therefore:
Number of Plants Percent Using = No. of Plants
Surveyed Solvent Cleaning Using Solvent
Cleaning
(322) ,' (0.33) = 106 plants
Number of Plants Percent Producing = No. of Plants
Plants Surveyed Solvent Based Producing Solvent
Adhesives Based Adhesives
(322) (0.5) = 161 plants
If we assume that plants using solvent for cleaning are also those
plants which produce solvent based adhesives, then the percentage using
solvent for cleaning is:
106 plants ,,-„, . , ,
T-T;—i——- = 65% using some solvent cleaning
161 plants & °
Vessels used for adhesives formulation can range in size from 400
liters to 18,750 liters (Effluent Guidelines, 1979); an average vessel
was assumed to be 7,500 liters. JRB also assumed that an average wash
would require a volume of solvent 1/10 the vessel size (1 kkg solvent)
and that methyl chloroform is used in 1/3 of the solvent washings.
Other solvents may include methylene chloroide and toluene. Changes in
formulation may be very frequent in some industries but cleaning
frequency could be reduced by switching to a similar formulation. It
was assumed that a typical plant would operate about 5 vessels and
that cleaning would be required biweekly. Then, the total quantity of
methyl chloroform used for solvent vessel cleaning is estimated using
the following equation:
3-49
-------
Quantity of Number of Percent Using Number of Percent
Methyl Vessels Solvent Cleaning Plants Using of Solvent
Chloroform Per Plant Methyl which is
Per Vessel Chloroform Methyl
Chloroform
Number of = Total Methyl
Cleaning /Year Chloroform used
for Cleaning
1 kkg/vessel x 5 vessels x 0.65 x 50 plants x 0.3 x 26/yr = 1270 kkg
plant
If another 10 percent is used for cleanup of spills, then:
1270 kkg (0.1) - 127 kkg solvent for spills
The estimate of 1400 kkg methyl chloroform used for vessel
cleaning is considered accurate to +30% and -50% to account for un-
certainties related to solvent cleaning practices, and "typical" plant
conditions which effect the quantity of solvent needed.
Environmental Releases from Vessel Cleaning
JRB assumes that about 15 percent of the solvent is emitted to
air during cleaning of vessels or spills. No information is available
on this topic and this estimate is based on engineering judgment. Therefore:
Total Solvent Percent Emitted = Total Lost to
Used for Cleaning Air from Cleaning
(1400 kkg) (0.15) = 210 kkg
The Effluent Guidelines Survey indicated that many plants using
solvents for cleaning contract their waste solvent for reclamation.
However, no quantitative estimates were made for solvent reclamation.
JRB assumed that 65 percent of the plants contract their waste solvent
for solvent recovery, which is assumed to operate at 95 percent effi-
ciency (Effluent Guidelines, 1979; EPA, 1979e). This reclaimed solvent
is assumed to be sold for use outside the industry. Larger plants may
be equipped with their own solvent reclamation equipment which would
probably operate at slightly lower efficiency. It is assumed that
3-50
-------
15 percent of the plants reclaim the solvent in-house at 90 percent
efficiency and that this solvent is reused. It is probable that solvent
recovery services incinerate the remaining still bottoms (5 percent) at
95 percent efficiency (±4%) and that still bottoms resulting from in-
house reclamation are landfilled. Finally, the remaining 35 percent of
the waste solvent is assumed to be discharged. The following series of
calculations estimates releases of waste solvent from reclamation and
disposal:
Total Atmospheric
Solvent - Losses from
Used Cleaning
for
Cleaning
(1400 kkg - 210 kkg)
Percent of Plants
Using Outside
Solvent Reclama-
tion
Services
(0.65)
Efficiency
of
Reclamation
(0.95)
Methyl
Chloroform
Reclaimed
735 kkg
This reclaimed solvent is sold to users outside the adhesive
industry.
Total Atmospheric
Solvent - Losses from
Used for Cleaning
Cleaning
(1400 kkg - 210 kkg)
Percent of Plants
Using Outside
Recovery
Services
(0.65)
Percent
Incinerated
(0.05)
Quantity of
Methyl
Chloroform
Incinerated
45.5 kkg
Quantity of
Methyl Chloroform
Incinerated
(45.5 kkg)
Quantity of
Methyl Chloroform
Incinerated
(45.5 kkg)
1-Incineration
Efficiency
(1- 0.95)
Incineration
Efficiency
(0.95)
Air Emisions of
Methyl Chloroform from
Incineration
2.28 kkg
Quantity of Methyl
Chloroform
Destroyed
43.2 kkg
3-51
-------
Total Atmospheric
Solvent - Losses from
Used for Cleaning
Cleaning
(1400 kkg - 210 kkg)
Percent Recovered
In-house
(0.15)
Percent
Efficiency
(0.9)
Methyl
Chloroform
Reclaimed
In-house
161 kkg
Total Atmospheric
Solvent - Losses from
Used for Cleaning
Cleaning
(1400 kkg - 210 kkg)
Percent Recovered
In-house
(0.15)
Percent
Landfilled
(0.10)
Quantity
Methyl
Chloroform
Landfilled
17.9 kkg
Total
Solvent -
Used for
Cleaning
Atmospheric
Losses From
Cleaning
Percent
Discharged
= Quantity
Discharged
(1400 kkg - 210 kkg)
(0.20)
238 kkg
It is assumed that 95 percent of this quantity or 226 kkg are volatilized
before stream discharge and the remaining 12 kkg remain in water.
JRB's uncertainty estimates for the percent releases to various
media are tabulated below. The individual uncertainties account for
uncertainties related to solvent cleaning practices, the extent to
which reclamation is practiced and waste solvent disposal practices.
Table 3.3-2 also shows overall uncertainties which account for an uncertainty
of +30% and -50% for total methyl chloroform used in vessel cleaning.
3-52
-------
Table 3.3-2 - Summary of Uncertainties for Environmental Releases from
Vessel Cleaning
Source
Percentage of Percentage of
Quantity Individual Overall
(kkg) Uncertainty Uncertainty
Solvent emitted to air
Solvent reclaimed by outside services
Still Bottoms Incinerated
Air Emissions Incinerator
Methyl Chloroform Destination
(Incineration)
Solvent Reclaimed In-house
Still Bottoms Landfilled
Solvent Discharged
210
565
45.5
2.28
43.2
161
17.9
238
±25
+10/-30
-HO/-30
±80
±4
±25
±25
+30 /-I 0
+39/-S6
+40/-64
+40 /-64
+89, -100
+40, -6 4
+46/-61
+46/-61
+49 /-5 7
3.3.3.2 Methyl Chloroform Losses from Solvent Based Cement Products
Several industry contacts indicated that rubber based cements,
especially neoprenes, are the largest single user of methyl chloroform
in the adhesive industry. However, no contacts would venture to
estimate what percentage of methyl chloroform used in solvent based
adhesives is used in rubber based cements.
Because we were unable to identify any large users of methyl
chloroform for other subcategories of adhesives, it is assumed that
rubber based cements (synthetic elastomers) used 85 percent of the
methyl chloroform used in solvent based adhesives. Solvent based
adhesives are typically 20 percent solids (Skeist, 1977; Effluent
Guidelines, 1979) and approximately 10 percent of the solvent based
cements contain methyl chloroform as compared to other solvents (based
3-53
-------
on contact with Wilholdt Glues only, 1979). Using 1977 production
data for synthetic elastomers in solvent (including neoprene cements,
SBR, NBR, Butyl and polyiso-butyl cements) we can estimate total
methyl chloroform used in this subcategory. 1977 production is estimated
•j
at 164 x 10 kkg for this subcategory. (Effluent Guidelines, 1979)
Total Production Percent Solvent Percent Solvent Methyl
of Synthetic in Solvent-based Based Cements = Chloroform
Elastomers Cements with Methyl in Solvent
in Solvent Chloroform Based Cements
(164 x 103 kkg) (0.1) (0.8) = 13,100 kkg
If this quantity represents 85 percent of all methyl chloroform
used in solvent based adhesives, then total methyl chloroform in
solvent based adhesives is estimated as follows:
Methyl Chloroform in Rubber Cements = Total methyl chloroform
Percent of Methyl Chloroform in in solvent based adhesives
Rubber Based Cements
13,100 kkg/0.85 - 15,400 kkg
This estimate is considered accurate to ±15% to account for uncertainties
related to the quantity of solvent in solvent based adhesives products.
Contacts with industry (Hall, J., 1979; Wilholdt Cement, 1979)
indicated that very small amounts of solvent are lost in production,
and may account for only 0.5 percent of the solvent. JRB considers
this estimate to be accurate to +50% and -22%.
(15,400 kkg) (0.005) = 77.0 kkg lost in the process.
Accounting for an uncertainty of ±15% for the total methyl chloroform
in products, the overall uncertainty is +52% and -25%.
It was assumed that 95 percent of the methyl chloroform in end
products is lost to the air and 5 percent is landfilled when used
adhesives containers are disposed of.
3-54
-------
These quantities are estimated using the following expression:
Total Methyl
Chloroform in
Solvent Based
Adhesives
(15,400 kkg
Total Methyl
Chloroform in
Solvent Based
Adhesives
(15,400 kkg
Quantity
Released
During
Production
77.0 kkg)
Quantity
Released
During
Production
77.0 kkg)
Percent
Released
to Air
Percent
Released
to Land
(0.05)
Quantity Emitted
to Air from End
Use of Products
(0.95) = 14,600 kkg
Quantity Emitted
to Land from End
Use of Products
766 kkg
The quantity of methyl chloroform emitted to air from use of
solvent based adhesives is accurate to ±5% and the quantity landfilled
is accurate to ±75%.
Accounting for an uncertainty estimate of ±15% for the total methyl
chloroform in solvent based adhesive products, the overall uncertainty
is ±16% for releases to air and ±76% for releases to land.
Figure 3.3-2 indicates that 96 percent of the solvent used in
solvent based adhesives is lost to the environment or destroyed and 4
percent is recycled. Solvent losses from end products account for 97
percent of the total solvent lost. Less than 1 percent of the solvent
is emitted directly to the atmosphere from vessel cleaning or from
product formulation. Another two percent is discharged to wastewater
treatment and about 0.2 percent is landfilled. The remaining waste
solvent, amounting to 0.2 percent, is destroyed by incineration.
Since most solvent losses are from product end use, several
industries were contacted to determine the major end uses of their
solvent based adhesives. It was learned that solvent based cements
are used widely in construction related activities, and in consumer
contact cements. They are also used in the automotive industry, the
shoe and textile industries and in preparation of pressure sensitive
tapes. (Miron, J., 1979; Witzman, C., 1979; Hall, J., 1979).
3-55
-------
Ul
16,700 kkg
t ,
i i
1
<- -L-
735 kkg
(+40%, -645
Sold
43.2 kkg
(+40%, -64%)
Incinerated
(destroyed)
16,900 kkg
Recycled
L6 kkg
(+46%, -61%)
Solvent
recovery
°)
\
s
2.28 kkg
A(+89%,- 1
100%)
Air
emission
Solvent
based
adhesives
1
1
896 kkg
^ 289 kkg
(+65%, -61%) '. .... ,.
Process air U-6™* k«
emissions A -
1 Air
15, 400 kkg ^^ ^ 7fift Vlrg (+ lfi%)
(+ 15%) ' products ' Land
\
' 238 kkg (+49%, -57%)
Water
^ i;.9 kkg (+46%, -61%)
Land
Figure 3.3-2 .Multimedia Environmental Losses of Methyl Chloroform
from Solvent Based Adhesives
-------
No quantitative breakdown of losses from end uses could be
obtained within the scope of the study.
3.3.4 Use and Emissions of Methyl Chloroform in Water Based Adhesives
Solvent losses from water based adhesives result from the use of
solvents in emulsions and from cleaning vessels and reactors. Solvent
washing of vessels and reactors is not common among plants formulating
only water based adhesives. Furthermore, even in plants that produce
both water based and solvent based adhesives, solvent cleaning is
probably less frequent during formulation of water based adhesives.
Most of the compounds used in formulation of water based adhesives are
water soluble and might not require expensive chlorinated solvents for
cleaning. In formulating emulsions, chlorinated solvents can be used
to facilitate adhesion. As with solvent based adhesives, solvent
use can be highly variable. Again, process losses are expected to
be small because of the use of vapor recovery systems and enclosed
mixers.
Figure 3.3-3 shows estimated losses of methyl chloroform from
the formulation and use of water based adhesives.
3.3.4.1 Vessel Cleaning
It was assumed that only 25 percent of plants making water based
adhesives used solvent cleaning. All other assumptions were the same
as those made for solvent based adhesives. Using these assumptions,
the following estimates were made:
3-57
-------
U)
01
CO
(H
. 3040 kkg
/
j _ _ _ _
282 kkg
/ _i /. n
-------
Quantity of
Solvent per
Vessel for
Cleaning
Number of
Vessels
Per Plant
Percent of
Plants which
Use Solvent
Cleaning
Number of Plants
Using Methyl
Chloroform
Percent Methyl
Chloroform
Used in Solvent
Number of
Cleanings
Per Year
Total Methyl
Chloroform Used
for Vessel Cleaning
(1 kkg/vessel) x (5 vessels) (0.25) (50 plants) (0.3) (26) = 488 kkg
plant
Assuming another 10 percent is used to clean up spills, the total
quantity used for cleaning is then equal to the quantity used to clean
vessels plus the quantity used to clean spills.
(488 kkg) + (48.8 kkg)
537 kkg
This estimate for methyl chloroform used in vessel cleaning is
not considered more accurate than +30% and -50%.
Emissions from Cleaning Vessels from Water Based Adhesives
Using assumptions discussed in Section 3.3.3.1, for solvent based
adhesives the following estimates are made.
Total Solvent
Used for
Cleaning
Percent Emitted
to Air
Quanity Released
(537 kkg) (0.15)
Quantity of Quantity Percent
Solvent - Emitted Reclaimed
Used in to Air by Outside
Cleaning Contractor
(537 kkg - 80.6 kkg) (0.65)
80.6 kkg
Efficiency
of Solvent
Recovery
(0.95)
Quantity
Reclaimed by
Outside
Contractor
282 kkg
3-59
-------
Quantity of
Solvent
Used in
Cleaning
Quantity
Emitted
to Air
Percent
Reclaimed
by Contractor
(537 kkg - 80.6 kkg)
(0.65)
Percent
Incinerated
(0.05)
Quantity
Incinerated
14.8 kkg
Quantity of
Methyl
Chloroform
Incinerated
1-Incineration
Efficiency
Air Emissions of Methyl
Chloroform from Incineration
(14.8 kkg) (1-0.95)
Quantity of
Methyl
Chloroform
Incinerated
(14.8 kkg)
Incineration
Efficiency
(0.95)
0.740 kkg
Quantity of Methyl
Chloroform
Destroyed
14.1 kkg
Quantity of
Solvent
Used in
Cleaning
Quantity
Emitted
to Air
Percent
Reclaimed
In-house
Efficiency
of Solvent
Recovery
Quantity
= Reclaimed
In-house
(537 kkg
80.6 kkg)
(0.15)
(0.9)
61.6 kkg
Quantity of
Solvent
Used in
Cleaning
Quantity
Emitted
to Air
Percent
Reclaimed
In-house
Percent
Landfilled
(537 kkg - 80.6 kkg)
Quantity of
Solvent
Used in
Cleaning
Quantity
Emitted
to Air
(537 kkg - 80.6 kkg)
(0.15)
Percent
Discharged
(0.20)
(0.1)
Quantity
Landfilled
6.85 kkg
Quantity
Discharged
91.3 kkg
It is assumed that 95% of the quantity discharged (86.7 kkg) will
evaporate and the remaining 4.27 kkg will remain in water.
3-60
-------
The percents of methyl chloroform released or reclaimed are
estimated to have the uncertainties shown in Table 3.3-3 also shows
overall uncertainties which have accounted for an uncertainty estimate
of +30% and -50% for the total methyl chloroform used to clean vessels
from water based adhesive formulations.
Table 3.3-3 Summary of Uncertainties for Environmental Releases from
Vessel Cleaning
Percentage Percentage
of of
Source Quantity Individual Overall
(kkg) Uncertainty Uncertainty
Quantity Emitted to Air
Quantity Reclaimed by Outside Contractor
Quantity of Still Bottoms Incinerated
Incinerator Air Emissions
Methyl Chloroform Destinction
(Incineration)
Quantity Reclaimed In-house
Quantity of Still Bottoms Landfilled
Quantity Discharged
80.6
282
14.8
0.740
14.1
61.6
6.85
91.3
±25
+10/-30
+10/-30
±80
±4
±25
±25
+30/-10
+39/-S6
+40 /-64
+40 /-64
+89/-100
+40/-64
+46/-61
+46/-61
+497-57
3.3.4.2 Solvents for Emulsions
It is assumed that all other losses of methyl chloroform occur
in the formulation and end use of emulsion adhesives.
These losses can be estimated using the following equation.
3-61
-------
Total Methyl Quantity Quantity Used Total Solvent
Chloroform Used - Used for + For Cleaning = Used for
in Adhesives Solvent Vessels for Water-Based
Industry Based Water-based Emulsions
Adhesives Adhesives
(19,800 kkg) - (16,700 kkg + 537 kkg) = 2,560 kkg
Since this estimate is the difference between total solvent used in the
adhesives industry and the losses from solvent based adhesives plus
water based adhesives vessel cleaning there is a large uncertainty
associated with this value. JRB estimates the uncertainty to be ±75%.
Of the total methyl chloroform lost from water based emulsions,
an estimated 0.5 percent is lost during production (Hall, J., 1979;
Wilholdt Cement, 1979). JRB considers this estimate to be accurate to
+50% and -20%.
Methyl Chloroform Percent Lost Quantity Lost
Emissions from During = During Production
Water-based Production
Emulsions
(2.560 kkg) (0.005) = 12.8 kkg
Considering the uncertainty estimate of ±75 percent for total solvent
releases from end products, the overall uncertainty is estimated at +90%
and -78%.
The remaining 2,550 kkg are lost during end-use of emulsion based
adhesives. Assuming that 95 percent is emitted to air from the use of
these adhesives and 5 percent is landfilled as residue in containers,
releases to air and land are estimated as follows:
3-62
-------
(Releases from Use of Water (Percent Emitted _ Quantity Emitted
Based Adhesives) to Air) ~ to Air
(2,550 kkg) (0.95) = 2,420 kkg
(Releases from Use of Water (Percent Landfilled) = Quantity
Based Adhesives) Landfilled
(2.550 kkg) (0.05) = 128 kkg
JRB's estimate for the percent released to air and land are
considered accurate to ±15% and ±75% respectively. Accounting for the
uncertainty estimate of ± 75% for the quantity used in solvent based
adhesives, the overall uncertainties are estimated to be ±76% for releases
to air and +106% and -99% percent for releases to land.
The results of this analysis, shown in Figure 3.3-2 suggest that 91
;
percent of the total solvent losses are from end uses. Three percent is
reclaimed by contractors and sold for other uses. Only one percent of
the solvent is emitted directly to the atmosphere from the process and 3
percent is discharged to wastewater treatment systems. Less than one
percent of the solvent is lost by landfilling or destroyed by incineration.
3.3.5 Multimedia Environmental Losses
Figure 3.3-4 summarizes the environmental releases of methyl chloroform
from the production and use of adhesives.
3-63
-------
U)
57.3 kkg t
(+57%, -91%)
Incinerated
(destroyed)
19,800 kkg 20,000 kkg ^
' Recycled
^ i
3.02 kkg .
(+126%, -100%)
Air
emissions
Adhesives
I 223 kkg 1
1 (+65%, -86%)
1 1-
i I
V 383 kkg
(+92%, -86%)
Process air
emissions
17,900 kkg
\. oon 1.1
W<
., - X
17 OOQ
, ' ,,
Av+ loA)
1* - , .
I Air
kk
8
End
894 kkg
—>(+131%,-99%)
Land
<_ --- J_
1017 kkg
(+57%, -91%)
Sold
Solvent
recovery
J
\t240 kkg
,-81%)
^24.8 kkg (+65%,-86%)
Land
Figure 3.3-4 Total Multimedia Environmental Losses from the
Formulation and Use of Adhesives
-------
3.4 TEXTILES
3.4.1 Use and Quantification of Methyl Chloroform in Textiles
Methyl chloroform is used in the textile industry as a cleaning
and scouring solvent, and as a dye carrier. There is little information
on the quantity of methyl chloroform used in these applications. Contact
with various textile trade associations and dye carrier manufacturers
did not yield a significant amount of information detailing the use of
methyl chloroform by the textile industry.
Millions of pounds of methyl chlorofprm are used in the textile
industry as a scouring solvent for wool and knit material, but the
quantity used in the dye carrier business is negligible (Perkins, 1979).
Contacts with various dye carrier producers indicated that methyl
chloroform is not used extensively as a dye carrier. They also suggested
that the quantity of methyl chloroform used in the production of dye
carrier in 1978 could have been as high as 10 kkg (Piedmont, 1979;
Tanatex, 1979). Thus, it is assumed that the use of methyl chloroform
in the textile industry is primarily as a scouring and cleaning solvent.
A flow diagram of the quantity of methyl chloroform used in the
textile industry is shown in Figure 3.4-1.
3.4.2 Emissions of Methyl Chloroform from the Production of Textiles
A total of 1973 establishments that perform dyeing and/or finishing
operations were identified as potential sources of hazardous pollutant
releases (EPA, 1976; EPA, 1979d). These textile establishments were
divided into the subcategories presented in Table 3.4-1.
Of these subcategories, methyl chloroform has been identified in
the effluent of subcategories 1, 4, and 5 where much of the scouring
work is performed (EPA, 1979d). Monitoring data obtained for the textile
mills in subcategories 1, 4, and 5 revealed that methyl chloroform was
present at an average level of 7mg/l, with a maximum level of use of
17mg/l (EPA, 1979).
3-65
-------
1940 kkg
Scouring
Air
Recycle
Waste water
treatment
Water
I
Land
Air
2940 kkg
987 kkg
U)
a,
Cleaning textile
and machinery
tools
Air
10 kkg
Dye
carrier
Figure 3.4-1 Flow Diagram of Methyl Chloroform Used in Textiles
* Numbers may not add due to rounding
-------
Table 3.4-1 Subcategories of the Textile Industry
Subcategories Number of Plants
1. Wool Scouring 17
2. Wool Finishing 37
3. Low Water Use Processing 808
4. Woven Fabric Finishing 336
5. Knit Fabric Finishing 282
6. Hosiery Finishing 160
7. Carpet Finishing 58
8. Stock and Yarn Finishing 217
9. Non-woven Manufacturing 38
10. Felted Fabric Processing 20
Total 1,973
Source, EPA, 1979d
3-67
-------
According to a survey done by the Institute of Textile Technology,
a textile plant uses approximately 100 Ibs/month, or 0.54 kkg per year,
of methyl chloroform (Barhorsky, 1979). An uncertainty of +50%, -30%,
was attached to this estimate, due to the degree of error inherent in
surveys, the varying size and production capacities of scouring plants,
the different methods of scouring employed, and the substitution of
other scouring solvents (perchloroethylene, trichloroethylene). Because
this survey was performed by an organization primarily concerned with
the production process of textiles, it is assumed that this quantity is
used for cleaning textile machinery and tools. Survey information
provided by an industry official described the annual use of 720 gallons
(3.6 kkg) of methyl chloroform in textile establishment (Owenbey,
1979). An uncertainty of ±30% is assigned to this estimate, due to the
error inherent in surveys. Based on the fact that this amount of use
covers all operations of a typical textile plant, it is assumed that
this quantity of methyl chloroform is consumed for both scouring and
cleaning.
In accordance with the above assumptions, the amount of methyl
chloroform used for scouring in a textile plant can be calculated as
follows:
Amount of Methyl Amount of Methyl Amount of Methyl
Chloroform Used - Chloroform Used = Chloroform Used
Scouring and For Cleaning For Scouring
Cleaning
3.6 kkg - 0.54 kkg = 3.06 kkg
The uncertainty of the amount of methyl chloroform used for scouring is
+58%, -42%, because of the uncertainty of the amount of methyl chloroform
used for scouring and cleaning (±30%) and the uncertainty of the amount
of methyl chloroform used for cleaning (±50, -30%).
The total number of plants involved in scouring operations, as
indicated by subcategories 1, 4, and 5 in Table 3.4-1, is 635. The
uncertainty of this total is ±10%, because data documenting the type of
3-68
-------
operations performed in textile plants is available. Accordingly, the
total amount of methyl chloroform used for scouring in the textile
industry can be calculated as follows:
Total Number of Annual Amount of Methyl Total Number of
Plants Involved Chloroform Used for = Methyl Chloroform
in Scouring Scouring Per Plent Used for Scouring
Operation
(635) (3.06 kkg) = 1,940 kkg
The uncertainty of the annual amount of methyl chloroform used for
scouring is +59%, -43%, due to the uncertainty of the total number of
plants involved in scouring operations (±10%) and the uncertainty of the
annual amount of methyl chloroform used for scouring (+58%, -42%).
3.4.2.1 Emissions Due to Textile Scouring
Based on the analysis of available data, it was determined that a
majority of the textile plants recycle their solvents. The recycle effi-
ciency has been estimated at 95 percent (±2%) (Bahorsky, 1979). A
simplified diagram of the scouring system is as follows:
38,800 kkg Scouring 1,940 kkg
(wastewater)
Recycle
36,900 kkg
Due to the high efficiency of the solvent recovery system, it was assumed
that there were no air emissions of methyl chloroform during the scouring
process (Bahorsky, 1979). An uncertainty of +71%, -59% for the quantity
of solvent used for scouring and the amount of methyl chloroform recycled
due to the reliability of recycle efficiencies.
3-69
-------
3.4.2.1.1 Emissions to Air from Wastewater Treatment
As stated above, 1,940 kkg of methyl chloroform is assumed to be
discharged to the wastewater of textile plants. During wastewater treat-
ment, the following steps occur: a) preliminary wastewater treatment,
b) aeration and/or activation of sludge, and c) secondary wastewater
treatment. Based on the high volatility of methyl chloroform, it is
assummed that 99 percent of the total amount present in the wastewater is
evaporated during the aeration/activation of the sludge. An uncertainty of
+0.75%, -1%, was assigned to this assumption, due to the empirical nature of
methyl chloroform's volatility and the high degree of agitation obtained
during.aeration/activation of sludge. The amount of mehtyl chloroform
volatilized during aeration can be calculated as follows:
Amount of Methyl Percent of Methyl Amount of Methyl
Chloroform in Chloroform = Chloroform
Wastewater Volatilized Volatilized
(1,940 kkg) (0.99) = 1,920
The uncertainty of the amount of methyl chloroform volatilized is +59%,
-43%, due to the uncertainty of the amount of methyl chloroform discharged
to the wastewater (+59%, -43%), and the uncertainty of the percent of methyl
chloroform volatilized (+0.75%, -1%).
3.4.2.1.2 Emission to Water after Wastewater Treatment
Of the remaining 1 percent, it is assumed that 10 percent and
90 percent are dissolved in the effluent and absorbed in the sludge,
respectively. These assumptions are based on the solubility of mehtyl
chloroform in water (1,300 ppm) and the low degree of methyl chloroform
biodegradation by microorganisms (Section 2.6). An uncertainty of ±20%
is assigned to these percentages, which reflects the empirical nature of
both of these assumptions.
3-70
-------
The amount of methyl chloroform dissolved in the wastewater
effluent can be calculated as follows:
Amount of Methyl Percent of Methyl Amount of Methyl
Chloroform Discharged Chloroform = Chloroform in
to Wastewater Dissolved Wastewater
(1,940 kkg) (0.001) = 1.94 kkg
The uncertainty of the amount of methyl chloroform dissolved in wastewater
effluent is +62%, -47%, because the uncertainty of the amount of methyl
chloroform discharged to the wastewater is +59%, -43%, and the uncertainty
of the percent of methyl chloroform dissolved is ±20%.
The average concentration of methyl chloroform in the aqueous ef-
fluent of a textile scouring plant can be calculated based on the following
assumptions:
o Total annual amount of methyl chloroform discharged in
effluent: 1.94 kkg;
o Total number of textile scouring plants: 635;
o Average rate of water discharge from a textile scouring
plant: 1.56 x 108 liters/yr (EPA, 1979d).
As discussed earlier, the uncertainty of the amount of methyl
chloroform discharged in the effluent is +62%, -47%, while the uncertainty
of the total number of textile scouring plants is ±10%. The uncertainty of
the average rate of water discharge from a textile scouring plant is ±25%,
due to the error inherent in averaging calculations. Accordingly, the
average concentration of methyl chloroform in the effluent can be calculated
as follows:
3-71
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Annual Amount of Methyl Chloroform
Discharged in Effluent
Number of Textile Scouring Plants
1.94 kkg
635
Average Quantity of Methyl
Chloroform Discharged by
One Textile Scouring Plant
0.00306 kkg/plant/year
3.06 x 103 g/plant/year
Average Annual Quantity of Methyl
Chloroform by One Textile
Scouring Plant
Average Rate of Water Discharged From
a Textile Scouring Plant
3.06 x 10 g/plant/yr
Q
1.56 x 10 liters/plant/yr
Average Concentration
of Methyl Chloroform in
Aqueous Effluent of a
Textile Scouring Plant
19.5 ywg/liter
The uncertainty of the average concentration of methyl chloroform in the
aqueous effluent is +66%, -52%, due to the uncertainties of the assumptions
stated earlier.
3.4.2.1.3 Emission to Land from Wastewater Sludge
As stated earlier, 90 percent of the methyl chloroform not volatilized
during wastewater treatment is absorbed by the wastewater sludge. Therefore,
the amount of methyl chloroform absorbed in the wastewater sludge can be
calculated as follows:
Amount of Methyl
Chloroform Discharged
in Wastewater
(1,940 kkg)
Percent of Methyl
Chloroform Absorbed
in Sludge
(0.009)
Amount of Methyl
Chloroform Absorbed
in Wastewater Sludge
17.5 kkg
The uncertainty of the amount of methyl chloroform absorbed in the wastewater
sludge is +62%, -47%, due to the amount of methyl chloroform discharged
to the wastewater (+59%, -43%) and the uncertainty of the percent of methyl
chloroform absorbed in the sludge (±20%).
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3.4.2.2 Emission Due to Cleaning Textile Machinery and Tools
According to Bahorsky, methyl chloroform and other chlorinated solvents
are also used as cleaning solvents for textile machinery and tools, such as
fiber spools (Bahorsky, 1979). However, quantitative information to
substantiate this statement was not available. Therefore, it was assumed
that 0.5 kkg of methyl chloroform is consumed per year by a typical textile
plant. Because this assumption is not based on any corroborating data an
uncertainty of ± 95% was assumed. These assumptions should be verified
in later studies.
As stated earlier, 1,973 textile plants were identified as solvent
users by EPA (EPA, 1979d). An uncertainty of ±10% was assigned to this
number, for reasons stated earlier with regard to the number of textile
scouring plants in this country. The amount of methyl chloroform used for
cleaning can be calculated as follows:
Number of Textile Annual Amount of Total Amount of Methyl
Textile Plants Methyl Chloroform = Chloroform Used for
Using Solvents Used per Plant Cleaning by Textile
Industry
(1,973) (0.5 kkg) = 987 kkg
The uncertainty of the amount of methyl chloroform used by the textile
industry is ±96%, due to the uncertainty of the number of textile
plants (±10%) and the uncertainty of the annual amount of methyl chloroform
used per plant (±95%).
Investigations conducted by JRB did not reveal the use of air and
water emission controls during cleaning operations. Therefore, it was
assumed that 100 percent (+0%, -5%) of the methyl chloroform used for
cleaning was volatilized. This estimate is based on the empirical
nature of methyl chloroform's volatility. The possibility that some
methyl chloroform volatilized during cleaning operations can be
calculated as follows:
3-73
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Amount of Methyl Percent of Methyl Amount of Methyl
Chloroform Used Chloroform Volatilized = Chloroform Volatilized
for Cleaning During Cleaning During Cleaning
Operations
(987 kkg) (1.0) = 987 kkg
The uncertainty of the amount of methyl chloroform volatilized during
cleaning is ±96% due to the uncertainty of the amount of methyl chloro-
form used for cleaning (±96%) and the uncertainty of the percent of
methyl chloroform volatilized during cleaning (+0%, -5%).
3.4.2.3 Emission Due to Use as a Dye Carrier
As stated earlier in Section 3.4.1, an estimate of 10 kkg was obtained
for the use of methyl chloroform as a dye carrier. An uncertainty of
±50% is assigned to this estimate, due to its reliance on verbal communications.
In conversations with industry officials, it was established that
measures are not used to control the air emission of solvents during
their use in textile material dyeing operations (Owenbey, 1979). Therefore,
it was assumed that 100 percent of all methyl chloroform used as a dye
carrier is volatilized, discounting the minimal amount that is absorbed
on the dyed material (Owenbey, 1979; Tanatey, 1979; Bahorsky, 1980).
This assumption is based on the volatility of methyl chloroform and the
nature of its use during dyeing operations. An uncertainty of ±25% was
assigned to this assumption, based on the measured value of methyl
chloroform's volatility. The amount of methyl chloroform volatilized
during dyeing operations can be calculated as follows:
Amount of Methyl Percent of Methyl Amount of Methyl
Chloroform Used in Chloroform Volitilized = Chloroform Volatilizei
Dyeing Operations During Dyeing Operations During Dyeing
Operations
(10 kkg) (1.0) = 10 kkg
The uncertainty of the amount of methyl chloroform volatilized during
dyeing operations is ±56% due to the uncertainty of the amount of
3-74
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methyl chloroform used in dyeing operations (±50%) and the uncertainty of
the percent of methyl chloroform volatilized (±25%).
3.4.3 Multimedia Environmental Losses
Figure 3.4-2 summarizes the environmental release of methyl
chloroform from the production of textiles.
3-75
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1940 kkg
(+59%, -43%)
38,800
kkg
/ft s
Scouring
1 1
. Recycle I
1_ _ _ _ — I
36,900 kkg
(+71%, -59%)
ATT-
:, 1920 kkg
1940 kkg /I f+SQ2.-4^
(+59%, -43%)
Waste water
treatment
Water v
/
1.94 kkg
(+62%, -47%)
1 17.5 kkg
xj, (+62%, -47%)
Air
to
i,
2940 kkg
/K 987 kkg
(+ 96%)
Cleaning textile
987 kkg machinery
(+ 96%)
10 kkg
\
(+ 50%)
^r
l\ 10 kkg
(+ 56%)
Dye
carrier
Figure 3.4-2
Multimedia Environmental Losses of Methyl Chloroform
from Textiles
-------
3.5 DRAIN CLEANERS AND SEPTIC TANK CLEANERS
3.5.1 Use of Methyl Chloroform in Drain and Septic Tank Cleaners
Organic solvent based drain cleaners and septic tank cleaners are
intended to alleviate drains and pipes clogged by grease. These products
usually contain petroleum distillates, namely methylene chloride,
methyl chloroform and/or orthodichlorobenzenes. (Chem. Week, 4/79;
Nassau County Health Dept., 1979). Concern over the use of these
products arose when high concentrations of methyl chloroform were found
in the groundwater of Nassau County, NY. A Nassau County Consumer
Product Survey identified 12 solvent based cleaners, 4 of which con-
tained methyl chloroform. The survey determined that in 1977 there were
100 kkg of methyl chloroform sold in Nassau County alone in septic tank
cleaners and drain cleaner products. Two septic tank cleaners manufactured
by one company accounted for 80 percent of the sales (Nassau County
Health Dept. , 1979).
Following the identification of high levels of methyl chloroform in
Nassau County groundwater in 1977, those drain cleaning products making
up 20 percent of methyl chloroform sold in drain cleaners and septic
tank cleaners combined were removed from the market (Chem. Week, 4/79;
Nassau County Health Dept., 1979). It is not known if these products
were removed from markets in other geographic areas as well. However,
the septic tank cleaners, representing 80 percent of the methyl chloro-
form sales in this product category, remained on the market throughout
1978. The manufacturers of these products claim to have changed their
formulation recently, but no analysis is yet available (P. Skinner,
1979).
An accurate estimate of the nationwide sales of these products
would require that a consumer product survey be conducted nationwide or
that proprietary sales data be released. Neither method was feasible
within the scope or time-frame of this study.
It is known however that sales of these products in Nassau County,
Long Island are not representative of sales nationwide. The following
information suggests that these products were not so widely used
nationwide in 1978 as they were in Nassau County.
3-77
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o Municipal Environmental Research Labs (MERL) was not aware of
these products being used extensively outside the east coast,
with the possible exception of commercial establishments
(by phone J. Kreissel, MERL, 1979).
o The N.Y. State Attorney General's Office found, that although
septic tank cleaners were sold in upstate N.Y., sales volume
was considerably lower than in Nassau County (P. Skinner,
1979). These products were known to be used in Cape Cod,
Connecticut and Florida although the quantities used are not
known (P. Skinner, 1979).
o Several septic tank cleaning services in the Washington
Metropolitan area were contacted about the use of solvent
based cleaners. While some indicated that the solvent based
cleaners were probably sold, caustic type cleaners were far
more frequently used (Americana, Great Falls, and Fairfax
Septic Tank Services, 1979; Suburban Sanitary Engineers,
1979).
3.5.2 Quantification of Methyl Chloroform Used in Drain and
Septic Tank Cleaners
Total methyl chloroform used in solvent based drain cleaners and
septic tank cleaners in 1978 was estimated at 1,500 kkg or 0.5 percent
of total methyl chloroform produced. This estimate was made by assuming
a "reasonable use" of these products among homeowners in eastern states.
Since this estimate is not based on actual end use data, it is not
expected to be more accurate than +75 and -50%. The estimate for
septic tank cleaners assumed that in 1978, 30 percent of homeowners with
septic tanks experienced drainage problems or took precautionary measures
to avoid these problems. This is based on health department and septic
tank services recommendations that septic tanks at homes with garbage
disposals should be pumped annually and those without garbage disposal
should be pumped every 3-5 years (Fairfax County Health Dept., 1979;
Great Falls and Fairfax Septic Tank Services, 1979). Since a majority
of homeowners do not have their tank pumped until they have problems, it
seems reasonable to estimate drainage problems at 30 percent for an upper
limit. Such problems almost invariably occur every 1-1.5 years where a
garbage disposal is used (Great Falls and Fairfax Septic Tank Services,
1979), although homeowners without a garbage disposal may go 10 years without
3-78
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problems. It was also assumed that only 10 percent of the homeowners
with drainage problems used solvent based cleaners, and that 90 percent
used caustic cleaners or immediately called for the services of a plumber
or septic tank cleaner.
It was assumed that these products were sold to an estimated population
of 90 x 10 in the eastern states of: New York, New Jersey, Pennsylvania,
Connecticut, Rhode Island, Massachusetts, Delaware, Maryland, Florida,
Georgia, Virginia, and Ohio. About twenty-five percent of the homes are
estimated to have septic tanks (based on a national average) (Hammer, 1975).
If we estimate an average household size of 3.0 for homes served by
sewers and 4.0 for homes without sewers, then, the number of homes with
septic tanks is estimated as follows:
Population = Residents Percent No. of Residents Percent No. of
of Eastern per x with x House- + per x with x House-
States Household Sewers holds Household Septic holds
in Sewered with with Septic Tanks on Septic
Homes Sewers Tanks Tanks
(90 x 10 residents) - (3 residents (.75 x)) + (4 residents (.25 x))
homes homes
0.75x = 20.5 x 10 homes on sewers
0.25x = 6.9 x 10 homes with septic tanks
We assumed that 30 percent of home owners with septic tanks experienced
drainage problems in 1978. Ten percent of these tried to "unclog" the
system with solvent based cleaners or took precautionary measures to avoid
these problems by using solvent cleaners and 90 percent used caustic cleaners
or immediately called for services of a plumber or a septic tank service. It
was also estimated that 30 percent of total solvent used was methyl chloroform
(based on Nassau County Consumer Product Survey, 1978) and that homeowners
used two applications of a full 7.5 liter (2.0 gal.) dose. Total methyl
chloroform used by homes with septic tanks was then estimated as follows:
3-79
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No. of Homes Percent with Percent Using Percent Methyl
with Septic Drainage Solvent Chloroform in
Tanks Problems Cleaners Cleaners
(6.9 x 106 homes) (.3) (.1) (.3)
Volume of •» Volume of
Cleaner Methyl Chloroform Used
(15 liters/home) = 93 x 104 liters
Since the density of methyl chloroform is 1.32 g/ml, then the quantity
of methyl chloroform used equals
93 x 104 liters x 1.32 kg/liter = 1200 kkg
This estimate corresponds to an annual average household use of 0.2 kg.
Average household use of methyl chloroform in septic tank cleaning products
in Nassau County was 0.7 kkg/household or a full 2 gallon "dose" used by 22
percent of the homes with septic tanks. Estimates of methyl chloroform used
in drain cleaners alone were made by assuming that they represent 25 percent
of the quantity of methyl chloroform used in septic tank cleaners (based on
Nassau County Survey).
Quantity Used Percent of This = Total Methyl
in Septic Tank Quantity Used in Chloroform in Drain
Cleaners Drain Cleaners Cleaners
(1200 kkg) (.25) = 300 kkg
The total quantity used in drain cleaners is then estimated as follows:
Quantity Used in Quantity Used in = Total Methyl
Septic Tank + Drain Cleaners Chloroform Used
Cleaners
(1200 kkg) + (300 kkg) = 1500 kkg
3.5.3 Multimedia Environmental Losses
Figure 3.5-1 shows multimedia environmental losses of methyl chloroform
from drain cleaners and septic tank cleaners assuming that 1978 losses amounted
to 1,500 kkg or 0.5 percent of the total methyl chloroform.
3-80
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75 kkg
(+90%, -71%)
A Air
1500 kkg
Septic tank
and
drain cleaners
214
QOft
(+78%
t
kkg N Waste
treat
kkg " Ground
,-64%)
203 kkg
k(+75%,-50%)
Air
water j 10.7 kkg
ment Water
water
303 kkg ' Sludge
(+92%,-100%)
Figure 3.5-1 Multimedia Environmental Losses of Methyl
Chloroform from Septic Tank Cleaners and
Drain Cleaners
-------
3.5.3.1 Multimedia Environmental Releases from Septic Tank Cleaners
Since methyl chloroform Is denser than water, it sinks to the bottom
of the septic tank. The solvent then acts by dissolving the sludge. The
dissolved or semi-dissolved sludge containing methyl chloroform can then
pass into the leachfield with the water, thereby contaminating the ground-
water. Often the chemically treated sludge gets stuck in the pipe leading
to the leachfield and a plumber's services are required (Suburban Sanitary
Engineers, 1979; Fairfax County Health Dept., 1979).
To determine multimedia environmental losses from septic tank cleaners,
it was assumed the 5 percent of the solvent is lost by evaporation. Of the
solvent discharged to the septic tank, it was assumed that 25 percent
remains in the sludge and is lost by evaporation when the septic tank is
pumped. The other 75 percent is discharged to the groundwater. Methyl
chloroform does not degrade in the groundwater and will be lost from this
media only when the water is pumped for consumptive or non-consumptive
uses. These assumptions need to be confirmed by further study. The
distribution of methyl chloroform between air, sludge and groundwater is
estimated as follows:
Total Methyl Chloroform Percent
in Septic Tank Cleaners Evaporated
(1200 kkg) (0.05)
Quantity of Methyl
Chloroform Evaporated
60 kkg
Releases to sludge and groundwater are similarly estimated by multiplying
the total methyl chloroform in septic tank cleaners by the percent released
to groundwater or sludge.
Methyl Chloroform
in Septic Tank
Cleaners
(1200 kkg
Quantity of Methyl
Chloroform
Evaporated
60 kkg)
Percent
Retained
in Sludge
(0.25)
Quantity of
Methyl
Chloroform
Retained in
Sludge
285 kkg
3-82
-------
Methyl Chloroform Quantity of Percent Quantity of
in Septic Tank - Methyl Chloroform Released = Methyl
Cleaners Evaporated to Chloroform
Groundwater in Ground-
water
(1200 kkg - 60 kkg) (0.75) = 855 kkg
These estimates are not based on actual data and should be verified in
later studies. Our estimate for the percent released to air is probably
accurate to ±50%. The estimate for percent released to groundwater
is considered accurate to +20% and -40% and releases to sludge have an
uncertainty of +60% and -100%. Accounting for the uncertainty of +75%
and -50% for the quantity of methyl chloroform used in drain cleaners
and septic tank cleaners our overall uncertainties are:
o +90% and -71% for releases to air
o +92% and -100% for releases to sludge
o +78% and -64% for releases to groundwater
3.5.3.2 Multimedia Environmental Releases from Drain Cleaners
Drain cleaning products are used in sewered and unsewered areas alike.
It is assumed that 75 percent of the drain cleaners are used by homeowners
served by sewers (based on national percentage of homes with sewers), that
5 percent (±80%) of the solvent losses are due to evaporation and 95 (±4%)
percent is discharged to municipal treatment systems, where the solvent
is largely evaporated prior to stream discharge.
For homeowners with septic tanks, the quantity of methyl chloroform
lost to groundwater and the quantity retained in sludge is assumed to be
similar to those estimates for septic tank cleaners. Based on these
assumptions, releases of methyl chloroform from the use of drain cleaners
are estimated as follows:
Releases from Homes with Sewers
Quantity of Methyl Percent Used by = Quantity of Methyl
Chloroform in Sewered Homes Chloroform Used by
Drain Cleaners Sewered Homes
(300 kkg) (0.75) = 225 kkg
3-83
-------
Quantity Evaporated;
(225 kkg)(0.05) = 11.3 kkg
Quantity Discharged;
(225 kkg)(0.95)
214 kkg
Accounting for uncertainties related to total methyl chloroform
used in drain cleaners (+75% and -50%) and the quantities evaporated and
discharged, overall uncertainty estimates are +75% and -53% for the
quantity discharged and +110% and -94% for releases to air. It is
assumed that about 95 percent of the quantity discharged (203 kkg) will
volatilize before stream discharge and the remaining 10.7 kkg will remain
in the water.
Releases from Homes with Septic Tanks
The remaining 25 percent of the methyl chloroform released from
drain cleaners was used by homes with septic tanks.
Quantity of Methyl
Chloroform in Drain
Cleaners
(300 kkg)
Percent of Homes
with Septic Tanks
(0.25)
Quantity of Methyl
Chloroform used by Homes
with Septic Tanks
75 kkg
Assuming the solvent is released similarly to the release pattern
for septic tank cleaners, then:
Quantity Evaporated;
(75 kkg)(0.05) = 3.75 kkg
Quantity Released to Sludge;
(75 kkg - 3.75 kkg)(.25) = 18 kkg
3-84
-------
Quantity Released to Groundwater:
(75 kkg - 3.75 kkg)(.75) = 53 kkg
Overall uncertainties for these estimates are:
o +90% and -71% for releases to air;
o +96% and -100% for releases to sludge;
o +78% and -64% for releases to groundwater.
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3.6 PAINTS
The use of methyl choroform in the paints industry was investigated.
It has been identified as a solvent raw material for the formulation of
paints (EPA, 1979e). However, additional quantitative date regarding the
amount of use was unavailable. Conversations with industry officials
revealed that it is used as a solvent in traffic paint formulations
(Moen, 1979; Nolt, 1979). In a conversation with a trade association
official, it was determined that methyl chloroform comprised no more
than 1 percent of the total amount of aliphatic hydrocarbons used by the
paint industry. This official estimated the total amount of aliphatic
hydrocarbons used by the paint industry at 500,000 kkg (Benedict, 1979).
Due to the gross nature of these estimates, and lack of any additional
substantive data, an uncertainty of ±75% was estimated for these assumptions.
The amount of methyl chloroform used in the paints industry can be
calculated as follows:
Amount of Aliphatic Methyl Chloroform Amount of Methyl
Hydrocarbons Used in Percentage of = Chloroform Used in
Paints Industry Total Amount of Paints Industry
Aliphatic Hydrocarbons
(500,000 kkg) (0.01) - 5,000 kkg
The uncertainty of the amount of methyl chloroform used by the paints
industry is +106%, -99%, due to the ±75% uncertainties of the total
amount of aliphatic hydrocarbons used and methyl chloroform percentage
of that total amount.
3.6.1 Emissions to Air
Traffic paints containing methyl chloroform are used for various
road applications (lane lines, turn arrows, etc.). Because the primary
mode of application is by spray equipment, it is assumed that no emis-
sion controls are used. Accordingly, it is assumed that 98 percent of the
3-86
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methyl chloroform used is emitted to the atmosphere as evaporative
losses and the remaining 2 percent (unused amounts in containers,
machinery cleaning residues) is disposed of in landfills. Uncertainties
of ±2% and ±99% are assigned to the above assumptions, respectively,
based on the relative confidence in the lack of emission controls used
for spray application. The amount of methyl chloroform emissions to air
can be calculated as follows:
Amount of Methyl Percent Emitted Amount Emitted
Chloroform Used to Air During = to Air During
in Paints Industry Use Use
(5,000 kkg) (0.99) = 4,950 kkg
The uncertainty of the amount of methyl chloroform emitted to air is
+106%, -99%, due to the uncertainty of +106%, -99%, for the amount of
methyl chloroform used in the paints industry and the uncertainty of ±2%
of the percent emitted to air.
3.6.2 Emissions to Water
Sampling programs have documented the presence of methyl chloroform
in the wastewater effluent of paint manufacturing facilities. A recent
study found methyl chloroform, at a mean concentration of 141 ^g/liter, in
approximately 50 percent of all paint facilities sampled (EPA, 1977e).
The range of measured values for this study was lO^g/liter to gSO^g/liter.
Therefore, an uncertainty of ±50% was assigned to the mean concentration.
The same study estimated the total amount of wastewater discharged to be
28,500,000 liters/yr. An uncertainty of ±25% was assigned to this estimate,
as the survey did not contact all paint manufacturing facilities.
The amount of traffic paint produced in 1974 was estimated to be
95,000,000 liters, or 2.69 percent, of the total paint production in 1974
3-87
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(EPA, 1979e). An uncertainty of ±10% was assigned to this estimate, due
to the availability of information to document this estimate. It was
assumed that the 1978 production level of traffic paints was equal to the
1974 figure, due to lack of data concerning 1978 production amounts.
Based on the above assumptions, the annual amount of methyl chloro-
form emissions to water can be calculated as follows:
Amount of Traffic Paint Mean Amount Amount of
Wastewater Percentage of of Methyl = Methyl Chloroform
Discharged by Total Paint Chloroform Discharged to
Paint Industry Production Per Liter Wastewater
(28.,500,000 liters) (0.0269) (1.41 x 10~10 kkg) = 1.08 x 10~4 kkg
As shown above, the amount of methyl chloroform emissions to water are
very small. Because traffic paints are solvent base paints, very
little wastewater is generated from their formulation. Hence, the
assumption that approximately 2.69 percent of the amount of wastewater
discharged from the industry is due to traffic paint formulation processes
is probably excessive. However, if the amount of wastewater was decreased,
this would lower the amount of methyl chloroform discharged to wastewater,
which is already at a minimum.
The uncertainty of the amount of methyl chloroform discharged to
wastewater is ±57% because of the uncertainty of the amount of
wastewater discharged by the paints industry (±25%), the uncertainty of
the traffic paint percentage of total industrial production (±10%), and
the uncertainty of the mean concentration of methyl chloroform in waste-
water (±50%).
3.6.3 Emissions to Land
As stated earlier in Section 3.6.1, 2 percent (±99%) of the methyl
chloroform used by the paint industry is emitted to land. The amount
emitted to land can be calculated as follows:
3-88
-------
Amount of Methyl
Chloroform Used by
Paints Industry
Percent of Methyl
Chloroform Emitted
to Land
Amount of
Methyl Chloroform
Emitted to Land
(5,000 kkg)
(0.02)
100 kkg
The uncertainty of the amount of methyl chloroform emitted to land is
+145%, -99%, due to the uncertainty of the amount of methyl chloroform
used by the paint industry (+106%, -99%) and the uncertainty of the
percent emitted to land (±99%).
3.6.4 Multimedia Environmental Losses
Figure 3.6-1 summarizes the multimedia emissions of methyl chloro-
form from the paints industry.
3-89
-------
4,950 kkg
(+106%,-99%)
Air
5,000 kkg (+106%,-99%)
Traffic paint
usage
1.08xlO
~4
(+ 57%)
UJ
i
vK
100 kkg
+145%,-99%)
Land
Water
Figure 3.6-1 Multimedia Environmental Losses of Methyl Chloroform
from Traffic Paints
-------
3.7 INKS
Methyl chloroform is used in the ink industry as a grease cutter
and as a cleaner for typewriter keys (MacGregor, H., 1979; Miller, W. ,
1979). Annual usage information was not available. However, methyl
chloroform usage in the ink industry is assumed to be limited, as is the
case for the paint industry. It is also worth noting that the metal
cleaning aerosols industry and the adhesives industries comprise approxi-
mately 86 percent of the total United States methyl chloroform consump-
tion and therefore only a small percentage of the methyl chloroform
remains unaccountable. Because the ink industry uses only small quanti-
ties of methyl chloroform, it is assumed that 1 percent of the total
production of methyl chloroform was used in 1978. This estimate has an
uncertainty of ±75%, due to the lack of quantitative data. The uncer-
tainty of the total production of methyl chloroform is +7%, -5%, due to
its basis in International Trade Commission data. The amount of methyl
chloroform used by the inks industry can be calculated as follows:
Amount of Percent of Total Amount of Methyl
Methyl Chloroform Production Used = Chloroform Used
Produced in 1978 by Ink Industry by Ink Industry
(284,000 kkg) (0.01) = 2,840 kkg
The uncertainty of the amount of methyl chloroform used by the ink indus-
try is ±75%, due to the uncertainty of the total amount of methyl chloroform
produced (+7%, -5%) and the uncertainty of the percent of total production
used by the ink industry (±75%).
3.7.1 Emissions to Air
No emission controls were identified in the application of methyl
chloroform as a grease cutter and a typewriter key cleaner. This seems
reasonable because the cleaning of typewriter keys and machinery is done
3-91
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predominantly by hand application. It is assumed that 98 percent of the
methyl chloroform used is emitted to the atmosphere as evaporative losses
and the remaining 2 percent is disposed of in landfills due to quantities
remaining in containers and industrial machinery cleaning residues. Un-
certainties of ±2% and ±99% were assigned to these estimates, due to the
confidence in the lack of emission controls. The amount of methyl chloro-
form released to air can be calculated as follows:
Amount of Methyl Percent Emitted Amount of
Chloroform Used to Air = Methyl Chloroform
by Ink Industry During Use Emitted to Air
(2,840 kkg) (0.98) = 2780 kkg
The uncertainty of the amount emitted to the air is ±75%, due to
the uncertainty of the amount used by the ink industry (±75%) and
the uncertainty of the percent emitted to air (±2%).
3.7.2 Emissions to Water and Land
Data detailing emissions of methyl chloroform to water was not
available. Based on the manner of its use, it was assumed that insigni-
ficant amounts were emitted to water.
As stated in Section 3.7.1, 2 percent (±99%) of the total amount of
methyl chloroform used by the ink industry is emitted to land via land-
fill disposal. The amount emitted to land can be calculated as follows:
Amount of Methyl Percent Amount of
Chloroform Used Emitted = Methyl Chloroform
by Ink Industry to Land Emitted to Land
(2,840 kkg) (0.02) = 56.8 kkg
3-92
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The uncertainty of the amount of methyl chloroform emitted to land is
+124%, -99%, due to the uncertainty of the amount used by the ink indus-
try (±75%) and the uncertainty of the percent emitted to land (±99%).
3.7.3 Multimedia Environmental Losses
Figure 3.7-1 summarizes the multimedia emissions of methyl chloro-
form from the ink industry.
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Air
/K 2,780 kkg
Ink industry
2,840 kkg
OJ
.1.
Land
57 kkg
Figure 3.7-1 Multimedia Environmental Losses of Methyl Chloroform
from the Ink Industry
-------
3.8 Miscellaneous Minor Uses of Methyl Chloroform
Methyl chloroform is used in small quantities in a variety of
industries as a solvent or degreaser.
Hydrophobic material-based catalyst preparations are formulated using
organic compounds (such as methyl chloroform) as a solvent. In pharmaceuticals,
methyl chloroform is used to extract active drug ingredients when non-polar
solvents are required. Methyl chloroform provides the high gloss and weather-
proofing properties required by the leather industry.
Other miscellaneous uses of emthyl chloroform are identified in
Appendix D. Some of these products are included in other categories
(for example: aerosol applied pesticides). Those products not included
elsewhere represent approximately 2.5 percent (or 7,780 kkg) of the total
methyl chloroform production. The environmental releases from these
products were assumed to be similar to the losses from all other uses.
Therefore, environmental emissions from other miscellaneous uses are
the following:
o Destroyed 145 kkg ( 2%)
o Air 6730 kkg (87%)
o Water 76 kkg ( 1%)
o Land 829 kkg (11%)
3-95
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3.8.1 Catalyst Preparation
Information on the use of methyl chloroform for the preparation of
catalysts is not readily available. According to Bartholomew, organic
chemicals, such as ethanol and chloroform, have sometimes been used as
solvents in the preparation of hydrophobic material-based catalysts
(Bartholomew, 1979). The quantity of methyl chloroform consumed in this
category is not mentioned anywhere in the literature, and we suspect that
this amount is very small «0.01 percent) compared to other uses. An
uncertainty of ±100% is assigned to this estimate, due to the lack of
quantitative data. Furthermore, based on general application techniques
of volatile solvents in catalyst preparation, 100 percent is assumed to
be emitted to the air. The uncertainty of this estimate is ±10 percent,
because the high volatility of methyl chloroform and the nature of its
use ensures a high degree of volatilization.
Total consumption of methyl chloroform in catalyst preparations
can be estimated as follows:
Total 1978 Methyl Percent of Methyl = Methyl Chloroform
Chloroform Production Chloroform Used in Used in Catalyst
Catalyst Production Production
(284,000 kkg) (0.001) = 28.4 kkg
The uncertainty of this value is ±100% due to the uncertainty for methyl
chloroform production (+7%, -5%) and the uncertainty for the percent of
total production consumed in catalysts (±100%). Since 100 percent is assumed
to be emitted to the air, total air emissions from catalyst preparation is
28.4 kkg (±100%).
3-96
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3.8.2 Film Cleaning
Methyl chloroform is used as a film cleaner because it is both non-
flammable and an excellent degreaser (A. Knapp, Edwal Sci Products, 1979;
M. Green, Polaroid, 1979; B. Klanderman, Eastman Kodak Co., 1979). How-
ever, methyl chloroform, because of its relatively high cost as compared
with alcohol based cleaners, is limited to special applications, such as
movie film cleaners.
Major users and distributors of film cleaners containing methyl
chloroform were contacted (Edwal, 1979; Eastman-Kodak, 1979; Polaroid).
As a result of these conversations, the amounts of methyl chloroform
used by each were estimated at 15 kkg, 50 kkg, and 45 kkg, respectively.
An uncertainty of ±50% was assigned to these estimates because they are
based on verbal communications; and lack any quantitative data to validate
the assumptions. During the course of these conversations, other users
and distributors, besides the three contacted, could not be identified.
Therefore, it was assumed that 50 percent of all the methyl chloroform
used in the film cleaning industry was used by the three major users
identified above. An uncertainty of ±30% was assigned to this estimate,
since other industries which are dominated by a few companies have
roughly similar market percentage ratios of 50:50 (split between large
and small companies). Based on the above assumptions, the amount of
methyl chloroform used by the film cleaning industry can be calculated
as follows:
Amount of Methyl Chloroform Used by
Three Largest Companies
Percentage of Total Methyl Chloroform
Used by Three Largest Companies
(15 kkg + 50 kkg + 45 kkg)
0.5
Amount of Methyl Chloroform
Used by Film
Cleaning Industry
220 kkg
3-97
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The uncertainty of the amount of methyl chloroform used by the film
cleaning industry is ±58%, due to the uncertainty of the amount of
methyl chloroform used by the three largest companies (±50%) and the
uncertainty of the percentage of the total methyl chloroform used by the
three largest companies (±30%).
3.8.2.1 Emissions to Air
Typically, cleaning film with methyl chloroform is done by hand
application with a soft cloth (Knapp, A. W., Edwal Scientific Products,
1979). Because of this type of application, no emission control techno-
logy is assumed to be employed. As a film cleaner, methyl chloroform
usually is packaged in small bottles (4 oz. to 16 oz.)(Knapp, A. W.,
1979). Therefore, it was assumed that 99 percent of the methyl chloro-
form used is volatilized during use. An uncertainty of ±1% was assigned
to this estimate, based on the confidence in the assumption that no
emission control is used. The remaining 1 percent was assumed to be
disposed of in landfills (accounting for unused amounts remaining in
bottles). An uncertainty of ±98% was,assigned to this estimate, also
due to confidence in the assumption of no emission control. Accordingly,
the amount of methyl chloroform emitted to the air can be calculated as
follows:
Amount of Methyl
Chloroform Used by
Film Cleaning Industry
Percent Emitted
to Air
During Use
Amount of Methyl
Chloroform Emitted
to Air from
Film Cleaning
(220 kkg)
(0.99)
218 kkg
The uncertainty of the amount emitted to air is ±58%, due to the uncertainty
of the amount used by the film cleaning industry (±58%) and the uncertainty
of the percent emitted to air (±1%).
3-98
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3.8.2.2 Emissions to Water and Land
Data detailing the amount of methyl chloroform discharged to waste-
water from film cleaning was not available. : It is assumed that wastewater
discharges were insignificant, and are not calculated in this materials
balance.
As stated in Section 3.8.2.1, 1 percent (±98%) of the total amount
of methyl chloroform used by the film cleaning industry was disposed of
in landfills. The amount of methyl chloroform emitted to the land can
be calculated as follows:
Amount of Methyl Percent Emitted Amount of Methyl
Chloroform Used by to Land = Chloroform Emitted
Film Cleaning Industry During Use to Land from
Film Cleaning
(220 kkg) (0.01) = 2.2 kkg
The uncertainty of the amount emitted to land is +114%, -99%, due to
the uncertainty of the amount used by the film cleaning industry
(±58%) and the uncertainty of the percent emitted to land (±98%).
3.8.2.3 Multimedia Environmental Losses
Figure 3.8-1 summarizes the multimedia emissions of methyl chloroform
from the film cleaning industry.
3-99
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220 kkg (+ 58%)
Air
1
218 kkg
(+ 58%)
Film cleaners
2.23 kkg (+114%,-99%)
Land
CO
i
o
o
Figure 3.8-1 Multimedia Environmental Losses of Methyl Chloroform
from Film Cleaning
-------
3.8.3 Pharmaceuticals
3.8.3.1 Use of Methyl Chloroform
Since chlorinated solvents are used for extraction of active drug
ingredients when non-polar solvents are required, the use of methyl chloro-
form in such applications was investigated. Contacts at the Bureau of
Drugs indicated that methyl chloroform is not an active ingredient in any
pharmaceutical, but that it may possibly be used in extraction procedures
(Fehnel, P., 1979; Dr. Casola, 1979; Dr. Kukumian, 1979).
Methyl chloroform was found in the wastewater of several pharmaceu-
tical companies during the Effluent Guidelines Survey of this industry
(Neptune, D., 1978). Unfortunately, this data was not available for
this study.
Several pharmaceutical companies were contacted regarding the use of
methyl chloroform. Contacts at Upjohn, Bristol-Myers, Wyeth, Schering-
Plough and Smith-Kline were not aware of any pharmaceutical procedures
which use methyl chloroform, although they generally indicated that it
could be used. Chlorinated solvents that were reportedly used in extraction
procedures include chloroform and methylene chloride. (Street, E., 1979;
Shrock, R., 1979; Wyeth, R+D Division, 1979; Henley, 1979; Bast, B.,
1979).
Other possible uses of methyl chloroform in the pharmaceutical in-
dustries were also investigated. Based on industry contacts it does not
seem likely that this solvent is used in drug capsule production (Henley,
1979), but may be used in small quantities for cleaning vessels and
equipment (Street, E., 1979).
Although the pharmaceutical industries contacted are among the largest
in the nation (these five companies are responsible for over 40 percent of
all antibiotic sales) (Kirk-Ottomer, 1978), it is possible that some medicinal
chemical processes do use methyl chloroform. The calculations which follow
were made to determine methyl chloroform losses, assuming that a very small
percentage of all chlorinated solvents used are methyl chloroform.
3-101
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3.8.3.2 Multimedia Environmental Losses
Figure 3.8-2 shows a representative flow diagram of a process for
production of medicinal compounds using chlorinated solvents.
Halogenated solvents are used in the extraction of active ingredients
for medicinal chemicals and botanicals. Halogenated waste solvent generated
in 1977 was estimated at 3,800 kkg and 70 kkg for these two processes,
respectively, and were projected to increase at a rate of 7 percent per year
(EPA, 1976). Based on conversations with pharmaceutical houses it seems
reasonable to assume that not more than 5 percent of chlorinated waste
solvent is methyl chloroform. Based on these assumptions we estimate the
quantity of methyl chloroform in waste solvent as follows:
Quantity of Total Quantity of Halogenated
Halogenated Waste Growth Rate = Waste Solvent Generated
Solvent Generated in 1978
(3800 kkg + 70 kkg) (1.07) = 4140 kkg
Quantity of Percent which Methyl Chloroform
Halogenated is Methyl = Waste Solvent
Waste Solvent Chloroform Generated in 1978
Generated in 1978
(4140 kkg) (0.05) = 207 kkg
This estimate is not considered more accurate than +25 and -100%.
An uncertainty of -100% accounts for the possibility (although unlikely)
that no methyl chloroform is used by the pharmaceutical industry.
JRB assumes that all waste solvent was unreclaimed solvent from
solvent recovery systems. These systems operate, on an average, at 95
percent efficiency (±4%). Then, the total methyl chloroform used by the
industry is estimated as follows:
3-102
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o
CO
Air
Purification
4
Biological
treatment
JLandfilled
Figure 3.8-2
Typical Process for Extraction of Medicinal
Chemicals
-------
Quantity of Waste T-
Generated
Percent of Solvent
which is Waste
Solvent
(207 kkg)
0.05
4140 kkg
Total Methyl Solvent
Chloroform Used
It is also assumed that 3 percent (±50%) of the total solvent is
emitted to air during production. This low percent release assumes that
enclosed vessels are regularly used for extractions.
Total Methyl
Chloroform Used
in Pharmaceuticals
(4140 kkg)
Percent Emitted
to Air
(0.03)
Quantity Emitted
to Air
124 kkg
This estimate is not considered more accurate than +98% and -100%.
The range accounts for uncertainties related to the qquantity of methyl
chloroform used (4140, +84%, -100%) and the percent released to air
(0.03, ±50%).
Based on a survey conducted by the EPA, about 50 percent of large
pharmaceutical companies have on-site incineration and many other companies
contract waste to be incinerated off site. Only small companies and R&D
installations landfill waste solvent (EPA, 1976). We assume 90 percent
(±5%) of the waste is incinerated at 95 percent efficiency (±4%) and 10
percent (±50%) is landfilled.
Methyl Chloroform
Solvent
(207 kkg)
Methyl Chloroform
Waste Solvent
(207 kkg)
Percent
Incinerated
(0.9)
Percent
Incinerated
(0.9)
Efficiency
(0.95)
1-Efficiency
(1-0.95)
Quantity Waste
Incinerated
(Destroyed)
177 kkg
Quantity Emitted
to Air
9.32 kkg
3-104
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Methyl Chloroform Percent = Quantity
Waste Solvent Landfilled Landfilled
(207 kkg) (0.1) = 20.7 kkg
Uncertainties for these estimates are: -$4%, -100% foe the quantity
incinerated; +116%, -100% for releases to air from incineration and
+98%, -100% for the quantity landfilled.
Figure 3.8-3 shows multimedia losses of methyl chloroform from
production of medicinal chemicals, based on assumptions discussed above.
Based on these estimates, 41 percent of the methyl chloroform
losses from the pharmaceutical industry is emitted to air, 53 percent is
incinerated and the remaining 6 percent is landfilled.
Use of methyl chloroform as a solvent in pharmaceutical processes
could be confirmed by reviewing new drug applications on record with the
Bureau of Drugs. However, clearance to review these records could not
be obtained for this study.
3-105
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CO
I
177 kkg
(+84%, -100%) ,
Incinerated
330 kkg 4140 kkg ^
T
^ 9.32 kkg /
(+116%, -100%)
V
Air emissions x
Pharmaceutical
industry
i
i 3810 kkg
I
1 J Solvent
j recovery
124 kkg
^ (+98%, -100%)
Air emissions
20.7 kkg
v (+^R7,1-tr\(\7.
/ Landfilled
Figure 3.8-3 Multimedia Environmental Losses of Methyl
Chloroform from Pharmaceutical Processes
-------
3.8.4 Leather Tanning and Finishing
Investigations were conducted to determine the amounts of use and the
magnitude of multimedia emissions of methyl chloroform from its use in the
leather tanning and finishing industry. Quantitative data could not be
obtained detailing the amount of methyl chloroform used by the industry.
However, it was determined that it is used by various segments of the
industry, and that air and water emissions occur. Figure 3.8-4 details a
typical complete chrome tannery.
3.8.4.1 Emissions to Air
It was determined that solvents are used in the tanning finishing
process, although their use is being curtailed due to handling difficulties
and their inherent fire hazard (EPA, 1979b). During this process, a water
or solvent based finish is applied to give the leather the required pattern
gloss or waterproof qualities. Methyl chloroform is used in the finishing
process as a carrier for water and stain repellant (EPA, 1979b).
Application of the finish is typically done in a spray booth, which is
equipped with an exhaust air water wash system to remove fumes and parti-
culates from the spray booth working environment (SCS Engineers, Inc.,
1976). The particulates are collected by the wash system, while the fumes
are vented to the atomosphere. A flow diagram of a typical leather finishing
process is presented in Figure 3.8-5.
Volatile organic compound (VOC) air emissions from these operations
have been estimated to be 0.45 kkg per 1000 equivalent hides, where an
equivalent hide has an area of 40 ft2 (Department of Commerce, 1976) and
a weight of 0.023 kkg (Rapp, 1980). An uncertainty of ±25% is assigned
to the amount of volatile organic compound emissions, due to the volatility
of methyl chloroform and VOC's and their use as a carrier agent. No
significant chemical absorption of methyl chloroform (or other VOC's)
by the finish occurs. There is no uncertainty relative to the area of
an equivalent hide, as this is an established unit of measurement. An
uncertainty of ±20% is assigned to the stated weight of an equivalent
hide, due to the range of the verbal estimate obtained (0.018 kkg to
0.028 kkg).
3-107
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Figure 3.8-4 — Flow Diagram for the Chrome Tanning Process
(all units are kg/1000 equivalent hides on a dry weight basis
except solid wastes which are given on a wet/dry basis)
Materials Added
Cured Cattle Hides
(12,300)
Bactericides (2) — ) 1
Lime (900) / Side
Na2S/NaHS (230) \ » Soak
Soda Ash (450) \ Flesh
_J
CrOHSO. (ISOOT^
/
(NH. ), SO. (700) /
4 2 4
NaCl (450) V , Bate
NaCOOH (360) / Pickle
H2S04 (260) Tan
Misc. (250) ) 1
Wring
Split
Shave
|
Syntans (730)) Retan
Fatliquors (500)1 .Color
Dyes & Pigments (300) ( Fatliq
Misc. (2bO)J
Dry
Water & Solvent "I Trim
Base Finishes (1000) }— • Condition
Misc. (100) J Buff
Finish
Trim
1
1 1
^-^ Fleshings (800) ,
1
1
1
Misc.
Solid
' (5
1
^Trim
•' 1
1
1
1
1
Process
Wastes ^T^ ii
50/450)
1 1
(325/140) ^-.
x-K Shavings (930/400) xK
x — NSplits f7600/14001 X^N J
I
uor
X"j~^ *
+
By-Products i
1
/olatiles To
Atmosphere (450) i
^-vLeather Trim (114/100) J
s-^ Buffing Dust (27/25) '
xKFinishing Residues (150/45) J
s — N-Finished Leather Trim
J 1 (220/200) '|
Finished Leather Wastewater
(5000) Jf |
| Screening | Screenings (390/90) .
|
Sewer
Sump
Sludge (2700/300) J
; i
Wastewater
to Sewer '
(Solids - 9200)
* An equivalent hide has an area of 40 ft.2
Process Solid Wastes
to Sanitary Landfill
(5,410/1,750)
3-108
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Figure 3.8-5 —Flow Diagram for a Typical Leather Finishing Process
(All units are kg/1000 equivalent hides on a dry weight basis
except solid wastes which are given on a wet/dry basis)
Crust Leather
(5000)
Materials Added
Pigments
Water Base Finish
Solvent Base
Finish (1100)
Misc.
Spray
Finishing
Finished Leather
(5000)
Buffing Dust (11/10)
•(Finishing Residue (150/45)
Solvents & Volatiles
To Air (450)
kWastewater to Sewer
Solids (600)
Misc. Process Solid
Wastes (85/75)
Process Solid Waste
To Sanitary Landfill
(245/130)
* An equivalent hide has an area of 40 ft.'
3-109
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Data could not be found which detailed the constituents of the VOC
emissions occurring from leather tanning and finishing processes.
Eighteen volatile organic compounds (VOC's) have been identified in
leather tanning facility wastewater effluents (EPA, 1979b). Of these
18, benzene, dichloromethane, ethylbenzene, toulene, and trichloromethane
appeared in 17, 17, 23, 22, and 11 of the 24 facilities analyzed, respec-
tively. Because methyl chloroform appeared in only 6 of the facilities
studied, and due to the lack of other pertinent information, it is
assumed that methyl chloroform constitutes only 1 percent of the total
'volatile organic compound (VOC) emissions resulting from leather finishing.
An uncertainty of ±95% is assumed for this estimate due to the lack of
corroborating information.
It was determined that an estimated 23,000,000 equivalent hides
were processed in 1976 (EPA, 1979b). The industry experienced a decline
in since the mid-1960's, and began to increase in 1974 (EPA, 1979b).
Therefore, it was assumed that the 1978 level of production will remain
at the 1976 level of 23,000,000 equivalent hides. An uncertainty of
±10% is assigned to this estimate due to the error inherent in production
estimates, although the estimate is based on substantial data.
Based on the above assumptions, the amount of methyl chloroform air
emissions from the finishing process can be calculated as follows:
Amount VOC
per
Equivalent
Hides
.00045
kkg/hide
Percent Methyl
Chloroform in
VOC
0.1
Amount of
Equivalent
Hides
Processed
1978
23,000,000
hides
Amount of Methyl
Chloroform Volatilized
from Finishing
Process
104 kkg
The uncertainty of the amount of methyl chloroform volatilized from the
finishing process is ±99%, due to the uncertainty of the amount of VOC
per hide (±25%), the uncertainty of the percent of methyl chloroform in
the VOC (±95%), and the uncertainty of the amount of equivalent hides
processed in 1978 (±10%).
3-110
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3.8.4.2 Emissions to Water
Seven subcategories have been developed which depict the manufacturing
process of the leather industry from the handling of raw materials through
the finished product (EPA, 1979b). Methyl chloroform was identified in
three of these subcatogories during a wastewater sampling and analysis
program involving 22 of the estimated 188 leather tanning and finishing
plants in the United States.
Subcateogry 1, "Hair Pulp/Chrome Tan/Retan-Wet Finish," consists of
facilities which primarily process raw or cured cattle or cattle-like hides
into finished leather products by chemically dissolving the hair, tanning
with chrome,and retanning and wet finishing. Methyl chloroform has been
detected in the wastewater effluent from 1 out of 3 such facilities tested,
at a mean concentration of "present;" that is, detectable but below the
quantifiable level. Methyl choloroform is presumably used as a solvent
and degreasing agent, as a solvent carrier for water and stain repellant
compounds, as a solvent for organics (oil, greases, waxes, fats, tars),
as a flammability retardant, and to add solvent properties.
Subcategory 2, "Hair Save, Chrome Tan, Retan-Wet Finish," consists
of facilities which employ the same processes as Subcategory 1 facilities,
but which chemically loosen and mechanically remove the tar. Methyl chloro-
form has also been detected in the wastewater effluent of 1 of 2 facilities
tested, at a mean concentration of 10 /xg/liter. Methyl chloroform is presumably
used in the same applications stated earlier for Subcategory 1 facilities.
Subcategory 6, "Through-the-Blue," consists of facilities which
process raw or cured cattle or cattle-like hides into the blue tanned state
only by chemically dissolving the hair and tanning with chrome, with no
retanning or wet finishing. As with Subcategory 1, methyl chloroform was
detected at a. mean concentration of "present" in the wastewater effluent of
only facility tested. Methyl chloroform is presumably used in the same
applications as for Subcategory 1. However, because there is no retan
or wet finish, it is not used as a solvent carrier for water and stain
repellants.
3-111
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A number of assumptions were made to calculate water emissions from
Subcategories 1, 2, and 6. Water consumptions for Subcatoegories 1, 2,
and 6 were determined to be 38,000, 46,000, and 23,000 liters/kkg,
respectively (EPA, 1979b). Data was not available concerning the number
of hides processed per subcategory, which would have enabled calculation
of methyl chloroform emissions from each subcategory. Therefore, an
average of the three flow rates was calculated (35,600 liters/kkg of equivalent
hide). An uncertainty of ±35% was estimated for this average flow rate,
as a result of the incompleteness of the survey (22 out of 188 tanneries
sampled). Also, approximately 50 percent of the plants in these three
subcategories reported flows below the average mean.
As stated earlier, the amount of methyl chloroform in the effluent
of subcategories 1, 2, and 6 ranged from "present" to lOug/liter.
Accordingly, it is estimated that the amount of methyl chloroform in the
effluent is 10 yug/liter, assuming worst case. An uncertainty of ±95%
is assigned to this estimate, based on the restricted number of tanneries
sampled and the number of samples taken.
The weight of a liter of methyl chloroform was calculated. Based
on a density of 1.3390 (Weast, 1972), it was determined that one liter
of methyl chloroform had a mass of 0.00134 kkg. A low uncertainty of
±5% was assigned to this calculation, due to the empirical nature of
densities.
As stated earlier in Section 3.8.4.1, one equivalent hide has a mass
of 0.23 kkg, ±20%.
Based on the above assumptions, the amount of methyl chloroform
discharged to water can be calculated as follows:
Number of
Equivalent
Hides
Processed
per Year
(23,000,000)
hides
Mass of an
Equivalent
Hide
(0.23)
kkg /hide
Amount of H20
Used per kkg
of Equivalent
Hide
(35,600)
liters/kkg
Amount of
Methyl
Chloroform
per Liter
of Water
(1 x 10"11)
kkg/liter
Amount of
Methyl
= Chloroform
Discharged
to Water
= 1.88 kkg
3-112
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The uncertainty of the amount of methyl chloroform discharged to waste-
water is ±42%, due to the uncertainties, stated earlier, of each factor
in the equation.
3.8.4.3 Multimedia Environmental Losses
Figure 3.8-6 summarizes the multimedia emissions of methyl chloroform
from the leather tanning and finishing.
3-113
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Air
104 kkg
(+ 99%)
106 kke
Leather
tanning and
finishing
1.88 kke
Water
(+ 42%)
OJ
i
Figure 3.8-6
Multimedia Environmental Losses of Methyl
Chloroform in the Tanning Industry
-------
3.9 EXPORTS
3.9.1 Export of Methyl Chloroform - 1978
The total U.S. export of methyl chloroform in 1978 was 18,000 kkg (+ 10%)
or 6.4 percent of the total production (Schedule B, U.S. ITC, 1979).
Table 3.9-1 shows the distribution of exports to various countries and the
percentage of total methyl chloroform exports imported by each country.
TABLE 3.9-1 - U.S. Export of Methyl Chloroform
Methyl Chloroform Percent of
Exported Total Export
Country kkg
Algeria 7 4
Argentina 192 1
Australia 4,983 28
Bahamas 34 1
Barbados 5 1
Belgium 10 1
Bolivia 1 1
Brazil 3,570 20
Canada 439 2
Chile 22 1
China 20 1
Columbia 45 1
Costa Rica 3 1
Dominican Republic 20 1
Ecuador 3 1
France 304 2
Germany-West 503 3
Guatamala 11 1
Haiti 34 1
Honduras 1 1
Hong Kong 0.5 1
Indonesia 3 1
Iran 10 1
Israel 42 1
Jamaica 10 1
Japan 1,810 10
Jordan 9 1
Korea 29 1
Lebanon 0.4 - 1
Mexico 452 3
3-115
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TABLE 3.9-1 - U.S. Export of Methyl Chloroform (cont.)
Methyl Chloroform Percent of
Exported Total Export
Country kkg
Netherlands 1 1
Nigeria . 0.4 1
Philippines 11 1
Rep. S. Africa 14 1
Salvadore 5 1
Singapore 4,895 27
South Arabia 4 1
Spain 0.3 1
Sudan . 1 1
Surinam 0.2 1
Switzerland 1 1
Trinidad 9 1
T. Pac I 11 1
United Kingdom 300 2
Uruguay 3 1
Venezuela 193 1
Zaire 1 1
Source: U.S. ITC, 1979
Eighty-five percent of the 1978 exports went to Japan, Brazil, Australia, and
Singapore; all other countries imported 3 percent or less.
3.9.2 Method of Export
Methyl chloroform is exported to approximately 50 countries in
annual quantities varying from 1 - 20,000 barrels (1 kkg = 4 barrels).
All importing countries require marine transport except for Mexico and
Canada where road or rail transport is possible. Mexico and Canada will
not be considered separate from the remaining importing countries,
because their combined annual import is only 5 percent of the total U.S.
export of methyl chloroform (see Table 3.9-1).
3-116
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Methyl chloroform is transported abroad in 54 gallon barrels via
container ships.
Due to its volatile nature and the absence of vapor recovery
systems at marine terminals, significant methyl chloroform losses could
occur during the loading and offloading of cargo unless the cargo is
packaged in a closed container such as a barrel.
For example, one percent of the cargo transferred during the
loading of crude oil is lost via evaporation with even greater losses
probable for volatile methyl chloroform (DOE, 1978). The quantities
exported are quite small in comparison to the cargo capacity of a
relatively small tanker. An 18,000 deadweight ton tanker has a cargo
capacity of 120,000 barrels with an individual tank typically holding
7,000 barrels. Therefore, shipments would require containers on the
order of a barrel as opposed to the tanks of a tanker. The filling of
barrels with methyl chloroform is assumed to take place at the pro-
duction site. Losses of methyl chloroform from this operation has been
included in evaporation emissions at the production site. Emissions of
methyl chloroform do not usually occur during the transport of a sealed
barrel.
3.9.3 Trends in the Export of Methyl Chloroform
U.S. exports of methyl chloroform in 1968 and from 1973-1978 are
presented in Table 3.9-2 (EPA, 1979a). Export amounts for the years
1973-1975 reflect an increased usage of methyl chloroform abroad. A
decrease in exports in the subsequent years can be attributed to increased
foreign production capacity. Therefore, future export quantities of
methyl chloroform should remain steady, as exhibited by the 1976-78
export quantities. It is not likely that methyl chloroform exports will
return to the large quantities of 1973-75. Thus, we expect that the
export of methyl chloroform should remain on the order of 20,000 kkg
during the next few years.
3-117
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Table 3.9-2 — U.S. Exports of Methyl Chloroform
Year Exports (kkg)
1968 18,000
1973 35,000
1974 37,000
1975 21,000
1976 14,000
1977 N/A
1978 18,000
Source: EPA, 1979a.
Bureau of Census, 1979.
3-118
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4.0 DISPOSAL AND DESTRUCTION OF END PRODUCTS
^'1 Contamination of End Products
The presence of methyl chloroform in other products as an impurity
has been carefully analyzed since little information exists on this
subject. According to a typical analysis of vinylidene chloride monomer,
methyl chloroform has been reported at 150 ppm by weight (Mark, Gaylord,
1971). Unfortunately, the source of this figure is not discussed in the
report. The same report also details a typical analysis of vinyl
chloride monomer. The results of the analysis does not identify any
traces of methyl chloroform among the reported impurities. Methyl chloroform
was not identified as a contaminant of other chemical products although
several references on this subject were consulted. (EPA, 1979a; TRW, 1975;
EPA, 1977; EPA 1972)
4.1.1 Emission of Methyl Chloroform as a Contaminant of Vinylidene Chloride
Products
The quantity of vinylidene chloride monomer produced in 1978 was
estimated at 77,000 kkg (SRI, 1975). Based on this assumption, the
amount of methyl chloroform introduced to the environment as an impurity
of vinylidene chloride monomer can be calculated by multiplying the
following factors:
1) the quantity of vinylidene chloride produced in 1978
2) the contaminated level of methyl chloroform in vinylidene
chloride monomer
Therefore:
(77,000 kkg) (150 x 10~6) = 12 kkg.
This quantity is eventually destroyed during the consumption of
vinylidene chloride monomer in the production of its polymer and other
end-products. Therefore, the net release of methyl chloroform to the
environment from the production and use of vinylidene chloride monomer
is neither measurable nor quantifiable (^0 kkg).
4-1
-------
4.2 Summary of Disposal and Destruction of End Products
This chapter summarizes the information pertaining to the quantities
of methyl chloroform landfilled and the quantities destroyed. Incineration
was the only significant method used to destroy methyl chloroform wastes in
1978. Biological degradation undoubtedly plays a very minor role.
Table 4.2-1 shows that 76 percent of the methyl chloroform produced is
lost directly to air and water within one year. Only about 2 percent is
destroyed by incineration. Of the methyl chloroform produced, 9.2 percent
was landfilled in 1978 as waste solvent in sludge or still bottoms or as
residue in cans. Because of the volatile nature of methyl chloroform,
improperly landfilled methyl chloroform wastes would be readily evaporated.
Table 4.2-1 shows estimates for the percentage of landfilled wastes that
could typically be expected to be lost by evaporation within one year. The
losses depend upon the type of container used and their resistance to crushing
or impaction. The rationale for our estimates of percent evaporation is
discussed in Table 4.2-1. By multiplying the percent evaporation from each
end use times the quantity landfilled from each end use, and taking the
average of the total emissions, it was determined that 31 percent
of the methyl chloroform landfilled will evaporate per year (see Table 4.2-1).
In order to estimate the cumulative load of methyl chloroform in landfills
since production startup in 1951, emission controls, waste disposal practices
and quantities of methyl chloroform used for each particular end use are
required. Acquisition of this data was not within the scope of this study.
The cumulative load was estimated for the 5 year period from 1974-1978 by
assuming that waste disposal practices (total of 9.2 percent landfilled
annually) and the percent of methyl chloroform used for each particular
end use were constatn over this five year period. We estimated an annual
release rate from landfill's of 29 percent. Table 4.2-2 shows quantities
landfilled and cumulative load in landfills over the 5 year period (1974
through 1978). The quantity of methyl chloroform accumulated in landfills
is 49,700 kkg.
4-2
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TABLE 4.2-1 — Disposal and Destruction of End Products
Z
Process
Cold Cleaning
Open Top Vapor
Degree s ing
Conveyorlzed
Vapor
De.gr easing
Conveyorlzed
Non-Boiling
Degreasers
Adhesives
Aerosols .
Paints
Inks
Drain Cleaners
Textiles
Film Cleaners
Pharmaceuticals
Miscellaneous
TOTAL
PERCENT TOTAL
Air
Plus
Water
37.100
79,100
35.200
9.490
17.700
18,100
4,950
2,780
289
908*
2,920
218
124
6.940
215,800
Lost By
Incineration
870
2,190
905
236
57
-
-
-
-
-
177
145
4.580
1.6
Landfllled
(kkg)
7,600
10,500
3,270
863
919
1,890
100
57
303
18
2
21
829
26,400
9.3
Released
from Landfill
In One Year
25
25
25
25
25
75
75
100
10
25
100
25
-
Amount In
•Landfill
(kkg) Rationale for Estimate of Percent Release
5,700
7,880
2,450
647
689
473
25
0
273
14
0
16
622
18,800
71Z
It was assumed that 75Z of the ua t
Is adequately containerized and will not
leach within 1 year period.
Methyl chloroform will leach when containers
are crushed and compacted. Slow release due
to improperly tightened cans.
Small containers are probably not tightened
sufficiently to prevent losses.
Lost from the sludge only when the septic
tank is pumped .
See metal cleaning
Small containers are probably not tightened
sufficiently to prevent losses.
It was assumed that 75Z of the waste is
properly containerized and will not leach
within 1 year period.
See metal cleaning
(Percent of Total Landfllled)
* - Ground water Discharge
-------
SUMMARY OF METHYL CHLOROFORM LANDFILLED
TABLE 4.2-2 OVER 5 YEAR PERIOD (kkg)
Year
1974
1975
1976
1977
1978
U.S.
Production
268,000
208,000
261,000
287,000
284,000
Quantity to
Landfill (1)
24,700
19,100
24,000
26,400
26,100
Quantity
Released from
Landfill
7,200
5,500
7,000
7,700
7,600
Quantity in
Landfill
( cumulat ive)
17,500
26,000
35,500
43,900
49,700
(1) Assumes 9.2% landfilled annually
Although not an end product, stockpiles represent a significant
quantity of methyl chloroform not released to the environment. Using the
data found in Section 2.7.1, we estimate the quantity of methyl chloroform
in stockpiles is approximately 120,000 kkg. If the three producers stopped
production, at the present rate of methyl chloroform use, existing
stockpiles would be consumed within 5 months.
4-4
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5.0 SUMMARY OF ENVIRONMENTAL RELEASES OF METHYL CHLOROFORM
The discussion of this section will help pinpointing locations
where large emissions of methyl chloroform can potentially occur.
The largest quantity of methyl chloroform emitted to the environment
is due to the use of this chemical as a solvent in cold cleaning and
vapor degreasing. Cold cleaning and vapor degreasing establishments are
dispersed throughout the United States, but are more heavily concentrated
in the northeast.
Other potential "hot spots" where large emission of methyl chloroform
can occur are industrial users of solvent based adhesives and the production
sites of this chemical. As previously discussed, the location of methyl
chloroform production facilities are situated in the Gulf Coast of the
United States, particularly in Freeport, Texas and in Geismar and Lake
Charles, Louisiana. These locations are probably most heavily exposed
to methyl chloroform.
-------
6.0 SUMMARY OF UNCERTAINTIES
Table 6.0-1 lists the estimates for environmental releases of methyl
chloroform by process and by media of release. The uncertainty of each
number is included in the table to give the reader easy access to the
uncertainty of each estimate. The rationale for assigning a specific
uncertainty of each number is discussed in detail in Chapters 2 and 3.
Our recommendations for "fine tuning" the material balance to reduce the
uncertainty of these estimates is discussed in Chapter 7.
The uncertainties were calculated by taking the square root of the
sum-of-the-squares of individual uncertainties unless otherwise specified,
An example from the text is presented below:
Section 2.2.2.2 - Air Emissions from Intermediate Storage
Air Emissions = 179 x 103 kkg (+6%, -7%) x 0.05 kkg/103 kkg
(±25%) x (4% x 1%}(±24%) x 1-85% (±5%) * =
0.000537 kkg (±49%)
Upper Bound -
\(.06)2 + (.25)2 + (.25)2 + (.33)2 = .49 or 49%
Lower Bound -
""\|(.07)2 + (.25)2+ (.25)2 + (.33)2 = .49 or 49%
*Note: 1 - 85% (±5%) is equivalent to 15% (±33%)
6-1
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TABLE 6-1
SUMMARY OF UNCERTAINTIES
Process/Operation
Waste
Quantity
(kkg)
Uncertainty
Total U.S. Production
284,000
+7/-5
Production -
Vinyl Chloride
Total methyl chloroform 179,000
produced
o Direct emissisons to air 6.62
o Emissions to air from air
pollution controls 74.1
o Quantity landfilled 3.58 x 10
o Quantity emitted to air
from incineration 1.79 x 10
o Quantity retained in
water 0.133
o Quantity volatilized
from water 13.9
-5
-6
+6/-7
±50
+171/-57
+103/-100
+131/-100
±35
+107/-62
Production -
Ethane
Total methyl chloroform 25,500
produced
o Direct emissions to air 2.89
o Emissions to air from air
pollution controls 6.31
o Quantity landfilled 0.00383
o Quantity emitted to air
from incineration 0.000191
o Quantity retained in
water 0.430
o Quantity volatilized
from water 4.48
+101-2
+60/-59
+61/-52
+112/-100
-H38/-100
±41
+109/-66
6-2
-------
Process /Operation
Production -
Vinylidene
Chloride
Metal Cleaning
Waste
Total methyl chloroform
produced
o Direct emissions to air
o Emission to air from air
pollution controls
o Quantity landfilled
o Quantity emitted to air
from incineration
o Quantity retained in water
o Quantity volatilized
from water
Total methyl chloroform used
in metal cleaning
Total in vapor degreasing
Total in cold cleaning
Total used for non-
conveyorized cold cleaning
o Releases to water
o Releases to land
o Quantity incinerated
o Air emissions
Quantity
(kkg)
79,500
2.94
48.5
~0
3.98
0.115
12.0
187,700
131,400
56,300
45,700
8,530
7,600
623
28,600
Uncertainty
(%)
+0/-14
+54 /-56
+3657-99
-
+80/-81
±31
+106/-60
+11 f-2
+11/-21
+39/-2
+39/-2
+43 /-33
+46 /-29
+7 7/-8S
+587-29
Total used for open top
vapor degreasing
o Releases to water
o Releases to land
o Quantity incinerated
91,700
8,470
10,500
1,580
+357-39
+20/-21
+3S/-74
+37/-76
6-3
-------
Process/Operation Waste
Metal Cleaning o Air emissions
(cont. )
Total used for conveyorized
vapor degreasers
o Releases to water
o Releases to land
o Quantity incinerated
o Air emissions
Total used for conveyorized
non-boiling degreasers
o Releases to water
o Releases to land
o Quantity incinerated
o Air emissions
Aerosols Total methyl chloroform
in adhesive products
Methyl chloroform in
household products
o Emissions to air during
production
o Releases to air from use
o Quantity landfilled
Total methyl chlorform used
in aerosol products
o Emissions to air during
production
o Emissions to air from
end-use
o Quantity landfilled
Quantity
(kkg)
70,600
39,300
2,000
3,270
619
33,200
10,600
546
863
159
8,940
20,000
3,000
75.0
2,640
293
500
12.5
439
48.8
Uncertainty
(%)
+42/-41
+3S/-39
+60/-61
+69/-93
+687-95
+357-39
+347-32
±35
+527-47
+51/-52
+477-46
±20
±36
±41
±41
±99
+567-44
±41
±41
±99
6-4
-------
Process/Operation Waste Quantity Uncertainty
(kkg) (%)
Aerosols (cont.) Total methyl chloroform 1,500 ±36
used in coating and
finishing products
o Emissions to air during
production 37.5 ±41
o Emissions to air from
end-use 1,320 ±41
o Quantity landfilled 146 ±99
Total methyl chloroform in 15,000 ±36
personal care and pesticide
products
o Emission to air during
formulation 375 ±41
o Emission to air from
end-use 13,200 ±41
o Quantity landfilled 1,400 ±99
Adhesives Total solvent used in 19,800 ±20
adhesives
Methyl chloroform used to 1,430 +30/-50
clean vessels from solvent
based adhesives
o Solvent to air from
vessel cleaning 210 +39/-S6
o Solvent reclaimed by
outside services 735 +40/-64
o Still bottom incinerated 45.5 +40/-64
o Incinerator air emissions 2.28 +89/-100
o Methyl chloroform destroyed 43.2 +40/-64
6-5
-------
Process/Operation Waste Quantity Uncertainty
(kkg) (%)
Adhesives (cont.)
o Solvent reclaimed in-house 161 +46/-61
o Still bottoms landfilled 17.9 +46/-61
o Solvent discharged 238 +49/-S7
Methyl chloroform in solvent- 15,400 ±15
based adhesive products
o Releases to air from
production 77.0 +52/-25
o Releases to air from
end-use 14,600 ±16
o Releases to land 766 ±76
Methyl chloroform used to 537 +30/-50
clean vessels from water-
based adhesives
o Quantity emitted to air 80.6 +39/-S6
o Quantity reclaimed by
outside contractor 282 +40/-64
o Quantity of still
bottoms incinerated 14.8 +40/-64
o Incinerator air emissions 0.740 +89/-100
o Methyl chloroform destroyed 14.1 +40/-64
o Quantity reclaimed in-house 61.6 +46/-61
o Quantity of still
bottoms landfilled 6.85 +46/-61
o Quantity discharged 91.3 +497-57
Methyl chloroform in water- 2,560 ±75
based adhesive products
o Emissions to air from
production 13 +90/-78
6-6
-------
Process/Operation
Waste
Quantity
(kkg)
Uncertainty
Adhesives (cont.)
Textiles
Drain Cleaners/
Septic Tank
Cleaners
o Emissions to air from
end-use
o Emissions to land
Average use of methyl
chlorofirm for scouring
per plant
Total methyl chloroform
used for scouring
o Quantity evaporated
to air
o Quantity remaining
in water
o Quantity absorbed
in sludge
Total methyl chloroform
used for cleaning
o Quantity evaporated
to air
2,440
129
3.06
1,940
1,920
1.94
17.5
987
987
Methyl chloroform volatilized 10
during dyeing operations
Methyl chloroform used in 1,500
drain and septic tank cleaners
Total methyl chloroform in 1,200
septic tank cleaners
o Releases to air from
evaporation 60
o Quantity retained in
sludge 285
±76
+106/-99
+5S/-42
+S9/-43
+S9/-43
+62/-47
+62/-47
±96
±96
±56
+75/-50
+75/-50
+90/-71
+92/-100
6-7
-------
Process/Operation
Waste
Quantity
(kkg)
Uncertainty
Septic Tank o Quantity released
Cleaners (cont.) to groundwater
Total methyl chloroform
in drain cleaners
o Quantity evaporated/
sewered homes
o Quantity discharged/
sewered homes
o Quantity evaporated/
homes with septic tanks
o Quantity retained in
sludge/homes with
septic tanks
o Quantity released to
groundwater
Paints
Inks
Methyl chloroform used in
paint industry
o Quantity emitted to air
o Quantity emitted to
wastewater
o Quantity emitted
to land
Methyl chloroform used
in inks
o Quantity emitted to air
o Quantity emitted
to land
855
300
11.3
214
3.75
18
53
5,000
4,950
1.08 x 10
100
2,840
2,780
56.8
-4
+78/-64
+75/-50
+110/-94
+75/-50
+90/-71
+96/-100
+7S/-64
+106/-99
+106/-99
±57
+106/-99
±75
±75
+124/-99
6-8
-------
Process/Operation
Waste
Quantity
(kkg)
Uncertainty
Film Cleaning
Total methyl chloroform
used in film cleaning
o Quantity emitted to air
o Quantity emitted to land
220
218
2.2
±58
±58
+114/-99
Pharmaceuticals
Methyl chloroform emitted 124
to air from extractions
o Quantity landfilled 20.7
o Quantity incinerated/
destroyed 177
o Incinerator air emissions 9.32
+98/-100
+98/-100
+84/-I00
+116/-100
Leather Tanning
Methyl chlorofrom volatil-
ized from finishing process
o Quantity discharged to
wastewater
104
1.88
±99
±42
6-9
-------
7.0 DATA GAPS AND RECOMMENDATIONS
This section presents a brief description of the types of data needed
to "fine tune" the materials balance for methyl chloroform. Further
data acquisition should emphasize the major uses of methyl chloroform.
Because methyl chloroform used in cleaning, adhesives and aerosols
accounts for over 80 percent of the total U. S. production, and 86
percent of the total actually used in the United States in 1978 (6 percent
was stockpiled and 6 percent was exported), accurate data on these end
uses is important.
For minor end uses such as the leather tanning industry, the
pharmaceutical industry, film cleaning and catalyst preparation, where
cumulatively less than one percent of the methyl chloroform is used,
the overall materials balance would not be significantly improved by
obtaining additional information on these end.uses.
In the discussion which follows, major data gaps and uncertainties are
discussed for each end use and recommendations are made as to how this
data could be be obtained.
7.1 Methyl Chloroform Production With the Vinylidene Chloride Method
There are few data gaps in the production process of methyl chloroform
from vinylidene chloride.
The actual flow diagram of the vinylidene chloride-based production
process was not obtained and thus an accurate evaluation potential emission
source was not possible. This information can be obtained if the
producer is willing to provide a simplified flow diagram of the process.
Emissions of methyl chloroform from this process were estimated
based on a derived flow diagram of the process. If a simplified flow
7-1
-------
diagram of the actual process and emission factors from appropriate
sources were provided, these revised estimates could be evaluated and
the materials balance corrected as necessary.
For future considerations, the vinylidene chloride method does not
warrant more in-depth studies since Pittsburgh Plate Glass (PPG) placed
this process on standby in late 1978. The newly developed production
process for methyl chloroform in 1979 (see Section 2.4) probably uses
vinyl chloride as the raw material. Thus, it will be worthwhile to study
this new production process in future tasks. Information confirming the
production process and estimating emission quantities from this new process
should be gathered for further studies. If the new process is vinyl chloride-
based, emissions factors from the Dow facilities (Section 2.2) could
be used as an interim method for a 1979 materials balance.
The quantity of methyl chloroform produced in 1978 via this process
was not known, and was estimated using the percentage obtained for 1976.
This presents an uncertainty which could affect the entire materials
balance of methyl chloroform produced by the vinylidene chloride method.
Since relatively small quantities of methyl chloroform are released
by this process (i.,02 percent of total production) , the importance of
monitoring plant releases is minimal. For example, previous monitoring
efforts have shown water emissions to be in ppb.
7.2 Vinyl Chloride Process
The vinyl chloride process has been described by both Dow Chemical
Company and Hydroscience, Inc. (Dow, 1979, Hydroscience, 1979). Since
the process is known and emission factors have been provided in the
literature, there are no data gaps.
To improve the uncertainty of the emission values, proprietary data
must be obtained and air and solid waste monitoring must be performed.
Production data is reported to the Department of Commerce annually. This
information should be obtained from Dow or the Department of Commerce to
7-2
-------
provide a better estimate of the total methyl chloroform production and,
subsequently, better emission estimates.
Emissions to the environment were calculated using emission factors
provided by Hydroscience, Inc. and through various other indirect
methods. Except for emissions from product storage and handling, the
request for information from Dow's proprietary records or the monitoring
of their facility would have relatively little value. The emissions from
these sources within the Dow plant are insignificant (0.01%) when compared
to other emission sources. For example, previous water effluent monitoring
has resulted in quantities measuring in the ppb.
Emission factors from product storage and handling should be
verified. Either information from Dow's monitoring records or EPA monitoring
would be necessary to improve the accuracy of these values. An alternative
method would be to review the filling and emptying processes and the
quantities transferred for both storage and handling of methyl chloroform.
Also, the quantities stored and the length of time in storage, would permit
the calculation of more accurate emission factors (see Appendix F).
7.3 Ethane Process
Ethane process has been described by Hydroscience, Inc. (Hydroscience,
1979). Since the process for a model plant is known and emission factors
have been provided in the literature, there are no data gaps.
To improve the uncertainty of the emission values, proprietary data
must be obtained and monitoring must be performed. Production data is
reported to the Department of Commerce annually. This information should
be obtained from Vulcan or the Department of Commerce to provide a better
estimate of the total methyl chloroform production and, subsequently,
better emissions estimates.
7-3
-------
Emissions to the environment were calculated using emission factors
provided by Hydroscience, Inc. and through various indirect methods. Except
for emissions from product storage and handling, the request for information
from Vulcan's proprietary records or the monitoring of their facility would
have relatively little value. The emissions from these sources within
the Vulcan plant are insignificant (<0.001%) when compared to other
emission sources.
Emission factors from product storage and handling should be
verified. Either information from Vulcan's monitoring records or EPA
monitoring would be necessary to improve the accuracy of these values.
An alternative method would be to review the filling and emptying processes
and the quantities transferred for both storage and handling of methyl
chloroform. Also, the quantities stored and the length of time in
storage, would permit the calculation of more accurate emission factors
(see Appendix F).
7.4 Metal Cleaning
Our estimate for the total methyl chloroform losses from the metal
cleaning industry, are probably as accurate as one could hope to obtain;
this estimate was based on survey results and industrial contacts, and
has accounted for solvent substitution for trichloroethylene.
We are somewhat less confident, however, of our estimates for the
various methods of environmental release. Our highest degree of
uncertainty is for the estimates made for total waste solvent, especially
from cold cleaning, and for the ultimate disposal of waste solvent
(whether landfilled or discharged). Because air emissions were calculated
by subtracting the difference between total emissions and waste solvent,
this uncertainty is transferred to our estimates for air emissions, as well.
These uncertainties are due to varying data on the extent to which solvent
recovery is practiced, the extent to which good housekeeping practices
are enforced(i.e., use of covers) and the variable nature of solvent
degreasing operations. Similar uncertainties were also expressed by
7-4
-------
OAQPS (1977) which had several support studies available to them, including
the Dow survey results. This suggests that these uncertainties probably
cannot be resolved. A higher degree of confidence in our estimates, could
be obtained, however, if manufacturers of solvent degreasers could review
the estimates and assumptions used in calculating environment losses.
Small operations are the biggest problem in assessing emissions from
the metal cleaning industry. There are thousands of small metal cleaners
throughout the United States. These operations may account for as much
as 50 percent of the total methyl chloroform used in metal cleaning. Without
a detailed survey of all operations, the emission estimates presented
in this report can only be considered as accurate as the large uncertainties
placed upon them.
7.5 Aerosols
The quantity of methyl chloroform consumed in the production of
aerosol products is estimated by many information sources; such as SRI
and Chemical Marketing Reports. Thus, the uncertainty assigned to this
figure is very small.
The estimated emissions of methyl chloroform from the consumption
of aerosol products was less certain since it depends greatly on the
general usage and habits of consumers. Emissions from the production
phase were estimated based on the information obtained from experts in
the aerosol production field. Therefore, the uncertainty of this figure
is correspondingly small.
We are confident that emissions estimates of methyl chloroform
from the production and consumption of aerosol products are accurate to
within the given uncertainties. These estimates assume the consumption
of methyl chloroform in aerosol products does not deviate from that reported
herein.
7-5
-------
A study should be undertaken to identify the average quantity of
aerosol products remaining in a can which has been disposed. The
percentage of methyl chloroform remaining in landfilled containers could
be more accurately defined.
7.6 Adhesives
There are few data gaps on the use of methyl chloroform in the
adhesives industry, but there are several areas where the uncertainty
of our estimate is significant. The estimate of total methyl chloroform
used by the adhesives industry is considered to be reasonably accurate,
since this was verified by industry. Percentage distribution of methyl
chloroform losses betewen solvent based and water based adhesives is also
considered accurate. However, a more accurate estimate of the amount of
solvent used in cleaning vessels is considered important. Although the
amount of solvent used for this purpose is less than 5 percent, these
losses can be easily controlled with solvent recovery practices. Further-
more, in geographic areas where adhesive industries are highly concentrated
(the Northeast, Texas, and the Great Lakes area) good housekeeping practices
would eliminate these areas as possible "Hot Spots". Although we have
assumed that solvent recovery is widely practiced, quantitative information
is needed.
Since more than 95 percent of all solvent losses are from product
use, we need to specify the quantities of methyl chloroform used in
various types of adhesives and their specific end uses. In certain end
uses, such as the manufacture of pressure sensitive tapes, solvent
recovery is practiced. Conversely, solvent losses from household use of
solvent based adhesives are uncontrolled. These end use emissions may
vary widely.
Ideally, an industry-wide survey could be made to determine solvent
cleaning practices and to quantify the methyl chloroform used in solvent
7-6
-------
based adhesives. An industry review of the assumptions used in arriving
at the estimates included herein might be adequate to "fine tune" the
materials balance.
7.7 Textiles
Emission and consumption quantities of methyl chloroform used for
textile were not obtained during the preparation of this report. The
quantities presented in this report were all estimated based on very
scattered data provided by textile trade associations.
The following recommendations are suggested in order to gather more
information on this category: a) a survey should be done on the amount
of methyl chloroform used by many major textile plants and/or the quantity
of methyl chloroform sold to all the textile establishments in the
United States; the latter can be obtained if the major producers are
willing to provide the information; b) the information on the process in
which the chemical is used and the waste treatment facilities of
representative textile establishments should be made available.
7.8 Paints
Methyl chloroform use in the paint industry is limited to traffic
paints (verified by references and verbal communication with major
paint manufacturers). The total quantity used is known to be extremely
small. Exact quantification might be obtained by contacting or surveying
a representative sample from among the 1,500 paint manufacturers, but
this effort does not seem justified for such a small use.
The assumption that 98 percent of the methyl chloroform used in
paints is emitted directly to the atmosphere is considered reliable due to
the method of application of traffic paints.
7-7
-------
7.9 Inks
Although industrial contacts were made to identify the amount of
methyl chloroform used in inks and ink cleaning products, JRB was not
able to obtain quantitative data. Written requests for quantitative
information should be made to manufacturers of those products (see
Appendix D). Also, efforts should be made to quantify the amount used
in this industry as a grease cutter. Considering the small quantity of
methyl chloroform estimated to be used in inks and related products, a
study to quantify methyl chloroform used in presently unidentified
products would not contribute significantly to the overall methyl chloroform
materials balance.
7.10 Septic Tank Cleaners and Drain Cleaners
There is a total lack of quantitative data on the use of septic
tank cleaners and drain cleaners containing methyl chloroform. Estimates
made for this material balance were determined by assuming a "reasonable
use" of these products among home owners. Quantitative information on
the use of these products is important because once methyl chloroform is
discharged into the groundwater, there is no opportunity for it to degrade.
The information needed to quantify methyl chloroform used in these
products in 1978 could be obtained by doing a nationwide consumer product
survey. Also, since some of these products have been taken off the
market in recent years, an estimate of the methyl chloroform which has
accumulated in groundwater would require all previous sales figures.
7.11 Methyl Chloroform Used in the Preparation of Catalysts
The information on the quantity of methyl chloroform used in this
category does not exist anywhere in the literature. We expect that the
quantity of methyl chloroform used for the preparation of catalysts
does not contribute significantly to the total consumption of this
chemical, thus any further investigations on this subject are not worthwhile.
7-8
-------
7.12 Film Cleaning
The major users of methyl chloroform as a film cleaner have been
identified. Although an estimate was required to account for minor
users, JRB is confident that the total use of methyl chloroform in this
application is very small and that the estimate made is reasonably
accurate. The information that would be gained by tracking down all
other users would not be worth the time invested since only about 0.1
percent of all methyl chloroform produced is used in film cleaning.
Because of the small amount of methyl chloroform used and the method of
application, the assumption that 99 percent of the solvent is lost to
the air is considered accurate.
7.13 Leather Tanning
Although no quantitative data was available on the amount of methyl
chloroform used in leather tanning, use in this industry is known to be
very small. The estimate made for this materials balance was based on
information from contacts and our knowledge of the use of solvent
in this industry. Although these estimates are not expected to be more
accurate than ±50 percent, an industry survey would be required to
quantify end uses more accurately. The information that would be obtained
by such a survey would not contribute significantly to the overall
materials balance since the quantity of methyl chloroform used by this
industry is so small.
7-9
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8.0 DISCUSSION OF NATIONAL ACADEMY OF SCIENCE STUDY OF OZONE DEPLETION
BY HALOCARBONS
The objective of this chapter is to discuss the results of the
recently published National Academy of Science study on Stratospheric
Ozone Depletion by Halocarbons, as it relates to methyl chloroform (NAS,
1979). The impact of methyl chloroform on ozone depletion was not the
major emphasis in the NAS study and consequently methyl chloroform is
only discussed generally.
8.1 Comparison of Production Estimates
Global production estimates for 1977-1982 were derived from 1976
data obtained by Detrex Corporation, a major manufacturer of metal cleaning
equipment. At that time, it was projected that 1977 production would
approximate 587,000 kkg and that growth would average 10 percent from 1977
to 1979 and 5 percent from 1979 to 1982. At this rate, 1982 production would
approximate 853,000 kkg (McConnell and Schiff, 1978). Detrex was contacted
to determine how these estimates were made. Dr. McCracken of Detrex indicated
that this estimate was made in 1976 and was based on global production
capacity and on projections for a "booming" market for methyl chloroform in
the coatings industry (McCracken, 1979). Dr. Harold Schiff, Chairman of
the NAS committee on Impacts of Stratospheric Change also indicated that the
estimates used in the NAS study were based on capacity and not on actual
production. (Schiff, 1978).
In 1976, it was anticipated that methyl chloroform would capture the
United States market loss by trichloroethylene and perchloroethylene as a
result of Los Angeles' Rule 66 and similar regulations enacted in other states
concerning photochemical oxidation. However, both Dr. McCracken (McCracken,
1979) and a recently published article in Chemical and Engineering News
indicated that the market has not "taken off" as was expected. However,
8-1
-------
NIOSH regulations and potential regulations under Section III of the Clean
Air Act Amendments have encouraged industries to phase out use of methyl
chloroform. Several industrial contacts which were made during the Level II
materials balance for methyl chloroform, supported the contention that the market
has not grown as expected. Hercules, which sells resins to adhesive manufacturers
indicated that their clients are phasing out solvents-based adhesives and
substituting with "hot-melts" and water based adhesives (Hercules, 1979). Con-
tacts with UPACO and Mobay Chemicals, which formulate adhesives indicated
that they are anticipating regulations on all chlorinated solvents (UPACO, 1979;
Mobay, 1979). They are not interested in substituting methyl chloroform for
trichloroethylene because they feel that it will eventually be regulated as
well. HIOSH regulations and data on the carcinogenicity of methyl chloroform
have also been influential in encouraging the adhesives industry to phase out
the use of methyl chloroform. Similar sentiment was expressed by contacts
in the textile industry. Contacts of the Wool Bureau and the Institute of
Textile Technology indicated that they are also phasing out chlorinated solvents
in anticipation that they will be regulated.
In this materials balance study, JRB had used a 1977 global production
estimate of 427,000 kkg or 73 percent of the NAS estimate. This figure was
approximated by the Dow Corporate Product Development (Neely and Agin, 1978).
Dr. McCracken indicated the the 1976 projections made by Detrex have not been
realized and that the production estimates made by the DOW Corporated Product
Department are probably correct (McCracken, 1979). In a recently held conference
on methyl chloroform (EPA, 1979d), DOW speculated an average annual increase
in methyl chloroform production of 6 percent (Farber, 1979c). DOW indicated that
they expect peaks and valleys in production and the uncertainty of their 6
percent estimate is ± 100 percent. • It does not seem likely that the growth
rate would exceed DOW's estimates for the following reason. In 1978, the
United States produced nearly 60 percent of the methyl chloroform produced
globally. Between 1976 and 1977, U. S. production increased by only 1 percent.
Between 1978 and 1979, the growth rate declined by 2 percent. To attain a
growth rate of 6 percent annually, production outside the United States would
need to increase at about 15 percent/year. Therefore, this growth rate is
8-2
-------
consistent with the growth rate projected in the NAS study (NAS, 1979).
If the 1977 global production estimate of 427, 000 kkg was more accurate
than the NAS estimate of 587,000 kkg then production in 1982 may be sub-
stantially lower than NAS predicted. Assuming two unique scenarios, where
average production increases by 6 percent and 10 percent respectively,
Table 8.8-1 shows that 1982 production would be in the range of 572 - 689
x 103 kkg or 67 - 81 percent of the NAS estimate.
Table 8.1-1 Estimated Global Production of
Methyl Chloroform From 1977-1982 Using
Three Possible Scenarios (kkg x 10^)
JRB Estimate JRB Estimate
Year 6% Growth 10% Growth NAS Estimate
1977
1978
1979
1980
1981
1982
427
453
480
509
540
572
427
470
517
569
626
689
587
-
707
-
-
853
SOURCE: NAS, 1979 (Taken from McConnell and Schiff).
JRB, based on estimate from Dow Corp. Product Dept. and Dow
estimate for growth.
8.2 Discussion of Estimates for Ozone Depletion
The NAS study also compared the impact of methyl chloroform on
stratospheric ozone depletion to that of F-ll and F-12. The study predicted
that, based on 1976 production figures, methyl chloroform destroys 8 to 15
percent of the ozone destroyed by F-ll and F-12. Using the half-lifes of
of these halocarbon estimated in the study and 1976 production data, this
estimate is accurate.
8-3
-------
NAS also predicted that in 1982, destruction of ozone by methyl
chloroform will be 20 percent greater than the amount destroyed by F-ll
and F-12. This estimate is unreasonably high and there is some question
about the accuracy and clarity of this statement. We have clarified
this error with NAS Chairman, Dr. Harold Schiff. It seems that an incorrect
estimate of 1982 production was used for this calculation. It was assumed
that 1982 production was 16 x 10^ kkg, nearly twice the production estimated
earlier in the document (853 x 103 kkg) .
JRB has made an independent estimate of the percentage of ozone
destroyed by methyl chloroform in comparison to F-ll and F-12, 1982.
Global production estimates for methyl chloroform of 852 x 10^ kkg and
572 x 103 kkg were considered.
A half-life of 8-12 years, 70 years, and 110 years was used for
methyl chloroform, F-ll and F-12, respectively (NAS, 1979). Based on
these half-lives, it was estimated that between 10 and 20 percent of the
methyl chloroform molecules reach the stratosphere, and 80 percent of the
F-ll molecules and 90 to 100 percent of the F-12 molecules reach the
stratosphere. It was also assumed that production of F-ll and F-12
would remain constant until 1982, at 331 kkg and 424 kkg, respectively.
Then the ratio of ozone destroyed by F-ll and F-12 as compared to methyl
chloroform is calculated by multiplying the ratio of half-lives times
the ratio of production estimates times the ratio of chlorine atoms.
Assuming 852 x 103 kkg is an accurate estimate of 1982 global production
For F-ll
0.8/0.15 x 331 x 103 kkg/852 x 103 kkg x 3 Cl/3 Cl = 2.1:1
For F-12
1.0/0.15 x 424 x 103 kkg/852 x 103 kkg x 2 Cl/3 Cl = 2.2:1
TOTAL 4.3:1
8-4
-------
The estimated percentage of ozone destroyed by methyl chloroform
as compared to F-ll plus F-12 is 23 percent, if 1982 methyl chloroform
production approximates 852 x 10 kkg.
Assuming 527 x 103 kkg is more representative of 1982 production
figures, then:
For F-ll
0.8/0.15 x 331 x 103 kkg/527 x 103 kkg x 3 Cl/3 Cl = 3.3:1
For F-12
1.0/0.15 x 424 x 103 kkg/527 x 103 kkg x 2 Cl/3 Cl = 3.6:1
TOTAL 6.9:1
Then, assuming 1982 global production of 527 x 103 kkg, methyl
chloroform would destroy about 14 percent as much ozone as F-ll and F-12.
Based on JRB's calculations, ozone depletion by methyl chloroform
in 1982 will be 14-23 percent of that destroyed by F-ll and F-12.
8-5
-------
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R-3
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R-4
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R-7
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APPENDIX A
PROCESS DESCRIPTIONS
(Sources: Hydroscience, 1979 and EPA 1979a)
A.I Introduction
The processes for producing methyl chloroform from vinyl chlor-
ide, from ethane and from vinylidene chloride are described.
In 1978, most of the methyl chloroform produced domestically is
made by the vinyl chloride process, with lesser amounts made by the
vinylidene chloride and ethane processes. Vinyl chloride, which is
produced from ethylene dichloride, is first .hydrochlorinated with
hydrogen chloride to 1,1-dichloroethane, which is then thermally chlori-
nated to produce methyl chloroform. The yields from vinyl chloride
are over 95%.
With ethane and chlorine as raw materials, methyl chloroform is
produced by the noncatalytic chlorination of ethane. Ethyl chloride,
vinyl chloride, vinylidene chloride, and 1,1-dichloethane are also pro-
duced, with the relative quantities of the various product fractions
being somewhat dependent on operating conditions. When methyl chloro-
form is the only desired product, vinyl chloride and vinylidene chloride
are hydrochlorinated to 1,1-dichloroethane and methyl chloroform respect-
ively, and ethyl chloride and 1,1-dichloroethane are recycled to the
chlorination step.
Methyl chloroform is produced directly from vinylide chloride by
hydrochlorination and distillation. Yields from vinylidene chloride
are approximately 98%.
A-l
-------
A. 2 Vinyl Chloride Process
Starting with vinyl chloride the following reactions are re-
quired to produce methyl chloroform: the hydrochlorination of vinyl
chloride to 1,1-dichloroethane and the chlorination of 1,1-dichloro-
ethane to methyl chloroform. The hydrochlorination of vinyl chloride
to 1,1-dichloroethane takes place according to the following reaction:
CH =CHC1 + HO. Fed CH--CHC1
2 J N •> 2
(vinyl chloride) (hydrogen chloride) (1,1-dichloroethane)
The chlorination of 1,1-dichloroethane to methyl chloroform takes place
according to the following reaction:
CH3-CHC12 + C12 > CH3-CC13 + HC1
(1,1-dichloroethane) (chlorine) (methyl chloroform) (hydrogen chloride)
Figure A-l represents a flow diagram for a process in which methyl chloro-
form is produced from vinyl chloride. Vinyl chloride (stream 1) from
storage, hydrogen chloride (stream 2), and the recycled overhead stream
(7) from the light-ends column are fed to the hydrochlorination reactor.
The reaction is exothermic and takes placi
of a catalytic amount of ferric chloride.
The reaction is exothermic and takes place at 35 to 40 C in the presence
Ammonia (stream 4) is added to the reactor effluent (stream 3),
forming a solid complex with the residual hydrogen chloride and the
ferric chloride catalyst. The complex is removed by the spent catalyst
filter as a semisolid waste stream (source G). The filtered hydrocarbon
stream (stream 5) passes to the heavy-ends column, where high-boiling
chlorinated organics (tars) are removed as a waste stream (source H)
from the bottom.
The overhead (stream 6) passes to the light-ends column, where a
separation is made between 1,1-dichloroethane and the lighter components,
A-2
-------
MCI
>
u>
FUGITIVE.
HVDOO-
CHCORlVJ
BEACT08.
C.O.UMU
T
n
CJ4H1
CUD6
CCX-UUU
NHj
MCI
COLUMU
1
^L^
V
I.I.
TCI
CO*.
xv
1-
CHLOK)
1 .
ML
1
9-
So
^J)
ffr*6u-'te"
t>
•
*
,© p
U~J 1 V.XVTIVM
| >C)W«.UKt
TOCA$C OLOA3IU«1 j) (f)
Fig. A-l. Flow Diagram for Methyl Chloroform from Vinyl Chloride
-------
primarily unreacted vinyl chloride. The overhead stream (7) is
recycled to the hydrochlorination reactor. The 1,1-dichloroethane
product is removed as the bottom stream (8) and transferred to inter-
mediate storage.
1,1-Dichloroethane from intermediate storage and chlorine (stream
9) are combined and fed to the chlorination reactor, where the 1,1-
dichloroethane is converted to methyl chloroform. The reaction is
exothermic and noncatalytic, occurring at a temperature of about 400 C.
The reactor effluent (stream 10) passes to the hydrogen chloride column,
where the hydrogen chloride formed in the reaction and some low-boiling
organic compounds are removed overhead (stream 11). This stream may be
used to supply the hydrogen chloride requirements of other chlorinated
organic processes directly (e.g., the ethylene dichloride process) or
it may be purified to remove the contained organics before it is used.
The bottom stream (12) from the hydrogen chloride column passes to
the methyl chloroform column. The purified product is removed overhead
(stream 13) and, after the addition of a stabilizer, is transferred to
storage. The bottom stream (14) from the methyl chloroform column,
composed primarily of 1,1,2-trichloroethane, is transferred as feed to
other chlorinated organic processes (e.g., perchloroethylene-trichloro-
ethylene).
The distillation column vents (A), which release primarily noncon-
densable gases, are sources of process emissions. Storage emissions
(vents B and C) include emissions from intermediate storage of 1,1-
dichloroethane and from methyl chloroform product storage. Handling
emissions (source D) result from the loading of methyl chloroform into
tank trucks or tank cars for shipment.
Fugitive emissions (B) occur when leaks develop in valves or
compressor seals. When process pressures are higher than the cooling-
A-4
-------
water pressure, VOC can leak into the cooling water and escape as a
fugitive emission from the cooling towers.
Secondary emissions can occur when wastewater from miscellaneous
process sources (source F) is sent to a wastewater treatment system and
the contained VOC are desorbed. Other sources of secondary emissions
are from the disposal of catalyst residue (source G) in landfill and
from the combustion of organic wastes (source H) . (Secondary emissions
occur when VOC are emitted with the combustion flue gas.)
A. 3 Ethane Process
When chlorine is reacted with ethane, the main sequence of re-
actions occurring can be summarized as follows :
+C1 +C1 +C1
(ethane) (ethyl chloride) .... , ,. . , / „, , ,, ,. N
7 (1,1-dichloro- (methyl chloroform)
ethane)
-HC1 -HC1 -HC1
CH2=CH2 CH2=CHC1 CH2=CC12
(ethylene) (vinyl chloride) (vinylidene chloride)
Minor quantities of 1,2-dichloroethane and 1,1,2-trichloroethane are also
produced. The product mix attained can be varied somewhat through changes
in operating conditions. When methyl chloroform is the only desired product,
the ethyl chloride and 1,1-dichloroethane produced are recycled to the
chlorination reactor, and the vinyl chloride and vinylidene chloride are
catalytically hydrochlorinated to 1,1-dichloroethane and methyl chloroform
respectively, as represented by the following reactions:
A-5
-------
Fed
CH2=CHC1 + HC1 - ^— > CH3-CHC12
(vinyl chloride) (1,1-dichloroethane)
Fed
CH2-CC12 + Hd - — > CH
(vinylidene chloride) (methyl chloroform)
Figure A-2 represents a flow diagram for an ethane chlorination process.
For startup, ethane is circulated through the chlorination reactor and
through a fuel-fired furnace (not shown) to bring the reactor temperature
to about 350 C before normal feed flows are established. Chlorine
(stream 1) and ethane (stream 2) supplied by pipeline are then fed to
the reactor. The approximate chlorination reaction conditions are a
temperature of 400 C and a pressure of 600 kPa. The reactor is operated
adiabatically with a residence time of about 15 sec. A catalyst is not
required for the chlorination reaction. When recycle flows are established,
the 1,1-dichloroethane and ethyl chloride formed in the process (12 and 19)
are also introduced as chlorination reactor feed.
The exit stream (3) from the reactor contains ethane, ethylene,
vinyl chloride, ethyl chloride, vinylidene chloride, 1,1-dichloroethane,
1,2-dichloroethane, 1,1,2-trichloroethane, methyl chloroform, a small
amount of other chlorinated hydrocarbons, and hydrogen chloride.
The reactor effluent gas (stream 3) enters the quench column, where
it is cooled and a residue stream consisting primarily of tetrachloroethane
and hexachloroethane is removed (source H).
The overhead stream (4) from the quench column enters the hydrogen
chloride column for separation of ethane, ethylene, and hydrogen chloride
from the chlorinated hydrocarbons. A part of the hydrogen chloride
column overhead stream (5) supplies the hydrogen chloride requirements
A-6
-------
•TO HCI
CJHAUC
FttCM
OICHI-CXO- RtCOvtlV
Figure A-2. Flow Diagram for Methyl Chloroform from Ethane
-------
of the hydrochlorination reactor. The excess hydrogen chloride and
the contained ethane and ethylene (stream 6) pass to a hydrogen chloride
purification step (not shown), eventually providing hydrogen chloride
for other processes.
The hydrogen chloride-free chlorinated hydrocarbons (stream 7) from
the hydrogen chloride column pass to the heavy-ends column, where the
higher boiling components (primarily 1,2-dichloroethane and 1,1,2-tri-
chloroethane) are removed as a bottoms stream (8) and are transferred
as feed to other chlorinated hydrocarbon processes (e.g., perchloroethylene)
The overhead stream (9), composed primarily of methyl chloroform vinyl
chloride, vinylidene chloride, ethyl chloride, and 1,1-dichloroethane,
is combined with the bottoms stream (18) from the product recovery
column and fed to the methyl chloroform column. Refined methyl chloro-
form is transferred to product storage.
The overhead stream (11) from the methyl chloroform column is fed
to the 1,1-dichloroethane column, where 1,1-dichloroethane is separated
as the bottoms stream (12) and is recycled as feed to the chlorination
reactor. The overhead stream (13), composed of vinyl chloride, vinyli-
dene chloride, and ethyl chloride, is fed to the hydrochlorination reactor,
where vinyl chloride is converted to 1,1-dichloroethane and vinylidene
chloride is converted to methyl chloroform. Hydrogen chloride require-
ments are supplied by a part of the hydrogen chloride column overhead
stream (stream 5). Hydrochlorination reactor conditions include a
temperature of 65 C, a pressure 450 kPa, and a catalytic amount of
ferric chloride (stream 14).
Ammonia (stream 16) is added to the reactor effluent stream (stream
15) and reacts with the residual hydrogen chloride and ferric chloride
to form a solid ammonium chloride—ferric chloride—ammonia complex.
The solid complex is removed by the spent catalyst filter as a semisolid
waste stream (source G). The filtered hydrocarbon stream (17) passes to
the product recovery column, where a rough separation of methyl chloroform
A-8
-------
from the 1,1-dichloroethane—ethyl chloride fraction is made. The
bottoms fraction (stream 18), composed primarily of methyl chloro-
form, is recycled to the methyl chloroform column. The overhead
stream (19), consisting primarily of ethyl chloride and 1,1-dichloro-
ethane, is recycled to the chlorination reactor.
The distillation column vents (A), which release primarily non-
condensable gases, are the only significant source of process emissions.
Storage emission sources (vents B and C) include intermediate storage
and product storage. Handling emissions (vent D) result from the
loading of methyl chloroform into tank cars and tank trucks.
Fugitive emissions (E) occur when leaks develop in valves or in
pump seals. When process pressures are higher than the cooling-water
pressure, VOC can leak into the cooling water and escape as a fugitive
emission from the cooling towers.
Secondary emissions can occur when wastewater from miscellaneous
process sources (source F) is sent to a wastewater treatment system
and the contained VOC are desorbed. Other sources of secondary emissions
are from the disposal of catalyst residue (source G) and from the combustion
of liquid wastes (source H). (Secondary emissions occur when VOC are
emitted withi the combustion flue gas.)
A.4 Vinylidene Chloride Process
Methyl chloroform is produced by reacting vinylidene chloride
and hydrogen chloride in the presence of a catalyst (FeCl,). This
hydrochlorination of vinylidene chloride to methyl chloroform takes
place according to the following reaction:
FeCl
CH =CC1, + HC1 -—> CH.CC1
£- £~ - j J
Vinylidene Hydrogen Methyl
chloride chloride chloroform
A-9
-------
The vinylidene chloride used as raw material is obtained by:
(a) chlorination of ethylene or 1,2-dichloroethane with chlorine to
form 1,1,2-trichloroethane and by-product hydrogen chloride; and (b)
dehydrochlorination of the 1,1,2-trichloroethane to form vinylidene
chloride.. The reaction of vinylidene chloride with the hydrogen chlor-
ide evolved in step (a) yields methyl chloroform (Lowenheim and Mbran,
1975).
Presently, the vinylidene chloride process is used to produce
methyl chloroform only when the demand exceeds PPG's new plant capacity
(Section 2.4.1). The new plant uses vinyl chloride as the primary raw
material. Since the vinylidene chloride process is effectively on standby,
there was little information given in the Hydroscience report (Hydroscience,
1979) and only a cursory overview of the process presented in the MRI
report (EPA, 1979a).
Figure A-3 represents a "derived" flow diagram for the vinylidene
chloride process.
Vinylidene chloride and hydrogen chloride from storage and recycled
gases from the first distillation column (primarily methyl chloroform,
vinylidene chloride and hydrogen chloride) are fed to the hydrochlorination
reactor. The reaction of vinylidene chloride with hydrogen chloride is
ideally conducted in the liquid phase with ferric chloride as a catalyst.
The chemical reaction is conducted at 25 to 35° C under slightly super-
atmospheric pressure.
Ammonia is added to the hydrochlorination reactor effluent, forming
a solid complex with the residual hydrogen chloride and the ferric chlor-
ide catalyst. The complex is removed by the spent catalyst filter as
a semisolid waste stream (source G) . The filtered hydrocarbon stream
passes to the distillation column where lower boiling point compounds;
mostly unreacted hydrogen chloride and vinylidene chloride; are removed
overhead for recycle.
A-10
-------
Hydrochlorination
reactor vent
Vinylidene
Chloride
HC1
FeCl-
3 \
catalyst
Hydrochlorinator
reactor
V|MRU ;
/
/ •
.
Recycle"
r
x_^
_i
Catalyst
„„
-------
Crude methyl chloroform is removed as a bottom stream for further
purification in the second distillation column. The second column removes
high-boiling point chlorinated organics (tars) as a waste stream (source H)
from the bottom. The overhead stream, composed of methyl chloroform, is
condensed by a mechanical refrigeration unit (MRU). Liquid methyl chloro-
form is transferred from the MRU to product storage.
The hydrochlorination reactor distillation column vents (A^ and A?),
which release primarily noncondensable gases, are sources of process
emissions. Storage emissions (vent C) include emissions from methyl
chloroform product storage. Handling emissions (source D) result from
the loading of methyl chloroform into tank trucks or tank cars for
shipment.
Fugitive emissions (E) occur when leaks develop in valves or com-
pressor seals. When process pressures are higher than the cooling-water
pressure, volatile organic compounds (VOC) can leak into the cooling
water and escape as a fugitive emission from the cooling towers.
Secondary emissions can occur when wastewater from miscellaneous
process sources (source F) is sent to a wastewater treatment system and
the contained VOC are desorbed. Other sources of secondary emissions
are from the combustion of catalyst residue (source G) and organic wastes
(source H). These emissions occur when VOC are emitted with the combustion
flue gas.
A-12
-------
APPENDIX B
Legislation Effecting the Use of Methyl Chloroform
Methyl chloroform is used in several non-consumptive applications
which favor the use of chlorinated solvents. The status of methyl
chloroform as a solvent for various end-uses is changing as a result of
OSHA regulations and existing or potential regulations concerning ozone
formation in the troposphere and ozone depletion in the stratosphere.
Rule 66, the well known Los Angeles Ordinance that was designed to
reduce photochemical oxidation, has led to widespread solvent substitution
in the metal cleaning industry. Methyl chloroform, an exempt solvent,
has been widely substituted for trichloroethylene, a non-exempt solvent.
Rule 66 was originated in 1966 and many other locations subsequently
enacted similar ordinances. Regulations under Rule 66 are stringent
controlling emissions to 18 kg/day. Given the alternative of trying to
meet the regulations or substituting with an exempt solvent, the decision
in the metal cleaning industry has invariably been to substitute.
In other industrial applications however, where chlorinated solvents
can be substituted by water, or other solvents, the trend has been to
phase out the use of cholorinated solvents.
Under the Clean Air Act Amendment, EPA is given the authority to
pass legislation to regulate depletion of ozone in the stratosphere as
well as formation of ozone in the troposhere. The primary strategy
used to attain ozone standards in the troposphere is to control emissions
of volatile organic chemicals under the State Implementation Plans
(SIP's). Many SIP's currently being prepared exempt methyl chloroform
while requiring RACT (Reasonable Available Control Technology) for
trichloroethylene. Methyl chloroform was originally exempt because it
is resistant to tropospheric hydrolysis and does not lead to ozone
B-l
-------
formation in the troposphere. However, evidence that the long half-life
of methyl chloroform permits diffusion of this compound into the stratosphere
and subsequent destruction of stratospheric ozone, has led EPA to consider
regulating methyl chloroform under Section III of the Clean Air Act.
Under this section, methyl chloroform could be regulated as a solvent in
the metal cleaning industry under standards of performance for New
Stationary Sources. Although, EPA is considering the deletion of methyl
chloroform from the list of exempt solvents, they are not necessarily
going to disapprove SIP's that have exempted this solvent, since many
states have nearly completed preparation of their regulatory package
(Kellum, EPA, 1979c).
In the uncertainty surrounding regulations of methyl chloroform,
certain industries have begun to phase out the use of this solvent as
well as other chlorinated solvents. For instance, researchers in the
adhesives industry are concentrating their efforts on developing water
based adhesives and hot metals, rather than investigating new applications
for exempt solvents. Many of the adhesives industries indicated that
they are phasing out use of chlorinated solvents (UPACO, 1979; Mobay, 1979;
Hercules, 1979), although they are still very important in rubber based
cements.
Similar sentiment was expressed by contacts in the leather tanning
and textile industries. Existing and future OSHA regulations
under the Clean Air Act Amendments have encouraged these industries bo
phase out the use of chlorinated solvents.
B-2
-------
APPENDIX C-l
BACKGROUND
Solvent degreasing describes those processes which use non-aqueous
solvents to clean and remove soils from metals. Based on a 1972 Census of
Manufacturers the metal working industry includes the eight SIC categories
listed in Table C-l.
TABLE C-l USE OF SOLVENT DEGREASING AMONG METAL WORKING SIC CATEGORIES
Metal Furniture
Primary Metals
Fabricated Products
Men-Electric Mach.
Electric Equipment
Transportation Equip.
Instruments/C.1 ocks
Misc.
TOTAL
(Source: Dow. 1976)
SIC
Category
25
33
34
35
36
37
38
_
Percent Using
Solvent Degreasing
29
17
23
33
33
22
42
30
28
Percent Using Solvent
Degreasing & Alkaline
Wash
17
19
19
19
22
28
23
8
20
There are anproximately 184,000 plants within these industrial categories
(D&B, 1977 and Census Manufacturers, 1979). The percentage of metal working
operations using solvent degreasing has been estimated by two independent
surveys at 24 percent and 29 percent (Dresser, K., 1979; Dow 1976; respectively).
The number of metal cleaning operations was calculated as follows:
24% + 29%
184,000 plants x-
49,000 plants.
The uncertainty of this number is ±9%.
C-l
-------
It is assumed that the plants which practice solvent degreasing are
geographically distributed in a pattern that is similar to entire metal
working industry. Figure 3.1-1 in the text, shows the geographic distribution
of metal working operations.
For purposes of quantifying emissions from solvent degreasing, the
following operations are distinquished:
o Wiping - Solvent dampened clothes are used to clean metal parts.
Chlorinated solvents are rarely used in these applications.
o Cold Cleaning - Metal parts are cleaned in a tank of solvent
maintained at a temperature below the solvent boiling point.
There were an estimated 1.35 million cold cleaning operations
nationwide in 1978 (CEH, 1978). This represents an increase of
3 percent per year since 1974 when 1.22 million units were reported
(EPA, 1977b).
o Open Top Vapor Degreasing - A batch load operation using heated
solvent in which the units are loaded continuously by means of a
conveyor. The solvent is heated to the boiling point thus
creating a zone of solvent vapor contained by a set of cooling
coils.
At the close of 1978 there were 32,000 open top vapor degreasers
(CEH, 1978). A separate report estimated 22,000 units in 1974
(EPA, 1977b) suggesting a 10 percent growth rate per year.
o Conveyorized Vapor Degreasing - Parts are loaded continuously by
means of a conveyor. These units can operate in either the cold
cleaning or vapor degreasing mode. 5,000 conveyorized degreasers
were reported in 1978 (CEH, 1978).
C-2
-------
APPENDIX C-2 — CALCULATION TO DETERMINED PERCENTAGE OF METHYL CHLOROFORM
USED IN COLD CLEANING AND VAPOR DECREASING
Estimate of Quantities of Methyl Chloroform Reported by Metal Cleaners
Survey by Dow in 1974
(Representative of segment surveyed only)
Source
1) Total methyl chloroform accounted for in survey:
30,600 kkg (cold cleaning) + 53,900 kkg (vapor
degr easing) = 84,500 kkg used metal cleaning Dow, 1976
2) Percent used in cold cleaning:
30,600 kkg/84,500 kkg = 36 percent Dow, 1976
3) Percent used in solvent degreasing :
53,900 kkg/84,500 kkg = 64 percent Dow,. 1976
Solvent Substitution
4) Solvent substitution of trichloroethylene in cold cleaning since 1974
is estimated by multiplying the total used in cold cleaning in 1974
times total 1978 production divided by total 1974 production, and
subtracting this quantity from the amount of trichloroethylene used in
cold cleaning in 1974.
• 15'500
19,600 kkg - 15,500 kkg trichloroethylene = 4,100 kkg substituted by
methyl chloroform
5) Solvent substitution of trichloroethylene in vapor degreasing.
50,700 kkg x °° Prodded 1974 = ^^ kkg trichloroethylene stlll used
50,700 kkg - 40,000 kkg = 10,700 kkg substituted by methyl chloroform
C-3
-------
6) Accounting for solvent substitution in cold cleaning.
30,600 kkg + 4,100 kkg = 34,700 kkg
7) Accounting for solvent substitution in vapor degreasing.
53,900 kkg + 10,700 kkg = 64,600 kkg
Annual Growth Rate
Source
8) 3 percent growth rate was estimated for cold EPA 1977b
cleaning operations based on number of SRI, 1978
units reported in 1974 (1.22 x 106) and
number reported in 1978 (1.35 x 106)
.'. 34,700 kkg in 1974 x (1.03)4 = 39,055 kkg in 1978
9) 10 percent annual growth rate was estimated
for vapor degreasing operations based on
number of units reported in 1974 (22,000)
and the number reported in 1978 (32,000)
64,600 kkg in 1974 x (1.10)4 = 95,200 kkg in 1978
10) Total quantity of methyl chloroform = 134,200 kkg = 40,200 kkg + 94,000 kkg
Total Percent of Methyl Chloroform for Industry Segment Surveyed in 1978
11) Percent used in cold cleaning = Total quantity used divided by quantity
used in cold cleaning
40,200 kkg/134,200 kkg = 30 percent
12) Percent used in vapor degreasing = Total quantity used divided by
quantity used in vapor degreasing.
94,000 kkg/134,200 kkg = 70 percent
C-4
-------
APPENDIX C-3
METHYL CHLOROFORM RELEASES FROM COLD CLEANING
Total Cold Cleaners Using Methyl Chloroform
The following assumptions are used to estimate the number of cold
cleaners using methyl chloroform:
Source
1) 1.35 x 10 cold cleaning units (SRI, 1978)
2) 30 percent of total are manufacturing
units which are more likely to use (EPA, 1977b)
chlorinated solvents
3) 18 percent of manufacturing units Based on Dow Survey
use methyl chloroform (1976) and corrected
to account for
solvent substitution
Total Cold Percent Using Percent Using Cold Cleaners
Cleaning are Manufacturing Methyl Chloroform = Using Methyl
Units Units Chloroform
(1.35 x 106) (0.3) (0.18) = 72,900 units
The estimated uncertainty for the number of cold cleaning operations using
methyl chloroform is ±20%.
Losses from Non-Boiling Conveyorized Degreasers
Losses of methyl chloroform from non-boiling conveyorized degreasers
are considered in section 3.1.2.4. Losses from these units are subtracted
from the total cold cleaning units.
It is estimated that there are 5000 conveyorized degreasers (±10%),
15 percent (±27%) of which are non-boiling conveyorized degreasers
(SRI, 1978; EPA, 1977b). Using the results of the Dow Survey and accounting
for solvent substitution for trichloroethylene, it is estimated that
about 18 percent (±30%) of the cold cleaners use methyl chloroform. The
number of conveyorized non-boiling degreasers using methyl chloroform is
estimated as follows:
C-5
-------
Number of Percent which Percent Using Total Number
Conveyorized .are Non-boiling . Methyl = of Non-boiling
Units Conveyorized Chloroform Conveyorized
Degreasers Degreasers
Using Methyl
Chloroform
(5,000) (0.15) (0.30) = 225 units
The accuracy of the number of non-boiling Conveyorized degreasers
is ±42%.
Average loss for a non-boiling Conveyorized degreaser has been
estimated at 47 kkg/yr (±10%) (EPA, 1977b) and total methyl chloroform
losses from these units are estimated using the following equation:
Methyl Chloroform Number of Total Methyl Chloroform
Losses per Unit Units = Losses from Non-boiling
Conveyorized Degreasers
(47 kkg/unit) (225) = 10,600 kkg/yr
Total methyl chloroform losses from non-boiling Conveyorized
degreasers has an uncertainty of ±43%.
The losses from non-boiling Conveyorized degreasers are subtracted
from total cold cleaning losses (56,300 kkg, +39%, -2%) to estimate the
losses from non-conveyorized cold cleaners.
56,300 kkg - 10,600 kkg = 45,700 kkg
The estimated uncertainty is +39%, -2%.
The average loss per non-conveyorized unit can then be estimated as follow
Total Methyl Chloroform Losses
from Non Conveyorized Cleaners = Methyl Chloroform Losses per
Total No. of Cold Cleaning Units Non-conveyorized Cold Cleaner
(45.700 kkg) - 0.63 kkg/unit
(72,900 units)
The uncertainty is estimated to be +44%, -20%.
C-6
-------
APPENDIX C-4 CALCULATIONS FOR ENVIRONMENTAL LOSSES OF METHYL
CHLOROFORM FROM COLD CLEANING
This appendix estimates multimedia environmental releases of
methyl chloroform from the use of non-conveyorized cold cleaners.
Waste Solvent
OAQPS estimated that 40-60 percent of the virgin solvent becomes
waste solvent in a typical manufacturing cold cleaner (EPA, 1977b).
However, most cold cleaners did not recycle at that time and it was
assumed that about 50 percent of losses are waste solvent in operations
which are not reclaiming solvent.
An estimate for the number of cold cleaners which are currently
recycling methyl chloroform is difficult to obtain. JRB estimates that
about 30 percent (±33%) of the cold cleaners are recycling the waste
solvent. This estimate is based on conversations with Dow and the
National Solid Waste Management Association (NSWMA); it was estimated
that at the time of the Dow Survey about 20 percent of the operations
were reclaiming methyl chloroform but there is a trend towards increased
recycling (Richards, D., 1979; Dow, 1976; NSWMA, 1979).
An Effluent Guidelines survey conducted for the Mechanical Products
Industries found that 73 percent of solvents were either reclaimed or
contract hauled for reclamation in 1978. However, this survey did not
distinguish between cold cleaners and vapor degreasers (Dresser, K.,
1979).
OAQPS estimated that 45 percent of all metal cleaning solvents were
recycled in 1974 and that most of the recycled solvents were halogenated
(EPA, 1977b).
C-7
-------
Assuming that waste solvent was 50 percent (+10%, -25%) of the
solvent is lost, the average waste solvent per unit can be estimated as
follows:
Total Methyl Chloroform
Losses per Unit per Year
(0.63 kkg/unit)
Percent Waste
Solvent
(0.5)
Average Unit Losses
of Waste Solvent
0.315 kkg/unit
For cold cleaning units with solvent recovery at 90 percent efficiency
(+7%, -2%), the average waste solvent losses are estimated as follows:
Average Losses of
Waste Solvent per
Unit
(0.315 kkg/unit)
1-Efficiency
of Solvent
Recovery
(1.0-0.9)
Average Waste
Solvent Losses
from Solvent
Recovery
0.0315 kkg/ unit
Total annual losses from waste solvent are estimated by multiplying
the average loss per unit by the number of units.
Average Waste
Solvent per
Unit Without
Solvent
Recovery
Total Number
of Cold Cleaning
Units
(0.315 kkg/unit) (72,900 units)
Percent
Which do
not Recover
Solvent
(0.7)
Total Waste
Solvent from
Units Without
Solvent Recovery
16,100 kkg
Average Waste
Solvent per Unit
After Solvent
Recovery
Total Number
of Cold Cleaning
Units
(0.0315 kkg/unit) (72,900 units)
Percent Which
Recover Waste
Solvent
(0.3)
Total Waste
Solvent Where
Recovery is
Practiced
689 kkg
Because of the uncertainty related to waste reclamation practices,
our estimate for the quantities of still bottoms generated is not
considered more accurate than +56%, -73%. Our estimate for the quantity
of waste solvent generated from units without solvent recovery is probably
accurate to +43%, -29%.
C-8
-------
Waste Solvent Disposal
The results of the 1974 Dow Survey suggested that unreclaimed waste
was handled as follows:
o 3 percent (±5%) was incinerated at 95 percent efficiency (±4%)
o 44 percent (+15%, -5%) was landfilled
o 53 percent (+5%, -15%) was flushed.
More recent information was sought to update the trends on the
final disposal of waste solvent, but information on current practices
was not consistent with regards to landfilling and flushing. A major
manufacturer of solvent degreasing equipment indicated that most of
their clients disposed of waste solvent by landfilling, but that flushing
was also common. Incineration was not widely practiced. (Personal
Communication, 1979).
An Effluent Guidelines survey (1979) found that a large majority of
waste solvent was flushed; 79 percent of plants did not reclaim and
discharged to municipal sewers; 21 percent discharged to land; and none
incinerated (only 14 plants reporting). Based on these contacts, it was
decided to use the results of the Dow Survey and to use an estimated
uncertainty of +5%, -15% and +15%, -5% for waste disposal to water and
land and ±5% for the quantity incinerated. The quantities disposed of
to various media can be estimated as follows:
Total Waste Percent Disposed Quantity Released to
Solvent of to Land, or Water, = Land, or Water, or by
Generated or by Incineration Incineration
(0.44) = 7080 kkg landfilled
(0.53) = 8530 kkg flushed
Assumed 95 percent efficiency for incineration (±4%).
C-9
-------
(16,100 kkg) (0.03) (0.95) = 459 kkg incinerated
(16,100 kkg) (0.03) (1-.95) = 24.2 kkg released to air from incineration
Table C-2 summarizes the individual and overall uncertainties
for the above derived values.
Table C-2 - Summary of Uncertainties for Waste Solvent
Waste
Waste Solvent
Releasted to Water
Landfilled
Incinerated
Released to Air
from Incineration
Quantity
(kkg)
16,100
8,530
7,080
459
24.2
Individual
Uncertainty
(%)
—
+5/-15
+15/-5
±5/±4
±80
Overall
Uncertainty
(%)
+43 /-29
+43 /-33
+46/-29
+43/-30
+91/-85
Disposal of Still Bottoms;
It was estimated that 689 kkg (+56%, -73%) of methyl chloroform
waste solvent is generated from solvent recovery. Little information
was available on the final disposal of the waste solvent. Some solvent
reclamation services incinerate the waste solvent (Solvent Recovery
Service of the Northeast, 1979) although there are still few approved
incinerators in the country (NSWMA, 1979). JRB assumed that 25 percent
(±30%) of these still bottoms are incinerated at 95 percent efficiency
(±4%) and the remaining 75 percent (±9%) are landfilled. The quantities
incinerated, emitted to air from incineration or landfilled are estimated
as follows:
C-10
-------
Incinerated
(689 kkg) (0.25) (0.95) = 164 kkg
Emitted to air from incineration
(689 kkg) (0.25) (1-0.95) = 8.61 kkg
Landfilled
(689 kkg) (0.75) = 517 kkg
The uncertainties of these estimates are +57% and -74% for the
quantity landfilled and +102%, -100% from incineration. These uncertainties
account for an uncertainty of +56%, -73% for the total still bottoms
generated (689 kkg) and ±30% for the percent incinerated as well as an
uncertainty of +39 and -2% for the total solvent used in cold cleaning.
Atmospheric Losses;
Atmospheric losses of methyl chloroform are estimated by subtracting
the waste solvent losses from the total solvent losses due to cold
cleaning.
Total Methyl Waste Solvent Total Solvent
Chloroform Losses - Losses = Emitted to Air
from Non-conveyorized
Cold Cleaning
(45,700 kkg) - (16,100 + 689) = 28,900 kkg
The uncertainty of the methyl chloroform emitted to the air from
non-conveyorized cold cleaning is +58%, -29%.
Only about 1.5 percent (±50%) of the cold cleaners use carbon
adsorption for recovery of atmospheric emissions (Dow, 1976; Raquat, D.,
1979). The efficiency for carbon adsorption is about 60 percent (±10%)
(Dow, 1976). The remaining solvent is emitted directly into the air.
To estimate the quantities of methyl chloroform emitted to the air, the
following expressions are used:
C-ll
-------
Total Solvent Percent of Percent Total Quantity
Emitted to Air Operations Efficiency = Adsorbed by
Using Carbon of Carbon Carbon
Adsorption Adsorption
(28,900 kkg) (0.015) (0.6) = 260 kkg
Assumimg that carbon regeneration is 95 percent effective (±4%) and
95 percent (±4%) of the total methyl chloroform adsorbed will be destroyed
during regeneration, the quantities of methyl chloroform destroyed and
emitted are calculated as follows:
Total Methyl Percent Methyl Chloroform
Chloroform Absorbed Regeneration = Destroyed During
Efficency Regeneration
(260 kkg) (0.95) = 247 kkg
Total Methyl 1-Percent Methyl Chloroform
Chloroform Destroyed = Emitted to Air from
Adsorbed Regeneration
(260 kkg) (1-0.95) = 13.0 kkg
The overall uncertainties for the quantities adsorbed during carbon
adsorption and for the quantity emitted to air from generation are +77%,
-59% and +111%, -99% respectively.
The total chloroform emitted directly to the air is determined by
subtracting the quantity of methyl chloroform adsorbed to carbon from
the total methyl chloroform emitted to air.
(28,900 kkg) - (260 kkg) = 28,600 kkg
Direct air emissions are thought to be accurate to +58% and -29%.
Since atmospheric losses were estimated to be the difference between
total solvent losses and waste solvent, the uncertainty factor accounts
for variations in waste solvent control practices, which in turn would
affect atmospheric losses.
C-12
-------
APPENDIX C-5 CALCULATIONS FOR ANNUAL LOSSES OF METHYL CHLOROFORM
FROM OPEN TOP VAPOR DEGREASERS (OTVD)
Average Annual Emissions
It has been estimated that there were about 32,000 (±10%) open top
vapor degreasers in operation during 1978 (SRI, 1978). Using the Dow
Survey and accounting for solvent substitution, an estimated 30 percent
(+15%, -10%) of these units use methyl chloroform (Dow, 1976). The
total annual losses from open top vapor degreasers is estimated by
subtracting losses from conveyorized vapor degreasers (see Appendix C-6)
from the total vapor degreasing losses estimated in Section 3.1.1.
Total Vapor Losses from Total Losses from
Degreasing - Conveyorized = Open Top Vapor
Losses Vapor Degreasers Degreasers (OTVD)
131,000 kkg - 39,300 kkg = 91,700 kkg
The average annual emissions per unit are estimated by dividing the
total methyl chloroform released by the number of open top vapor degreasers
using methyl chloroform.
Total Methyl Chloroform Average Annual
Released from OTVD _ = Emissions
OTVD Using Methyl Per Unit
Chloroform
(91.700 kkg) =
(32,000 units x 0.30) '
This estimate agress closely ( < 0.5% error) with an estimate of
9.5 kkg made by OAQPS for average unit losses from uncontrolled OTVD
(EPA, 1977b). Although the calculated uncertainty for this emission rate
is +39%, -42%, we are assuming the square of this uncertainty (+15%,
-17%) to account for the similarity between the JRB estimate and the
OAQPS estimate.
Waste Solvent Losses
It has been estimated that 20-25 percent (or 22.5 percent, ±11%) of
the total virgin solvent becomes waste solvent (EPA, 1977b). We assume
C-13
-------
that 75 percent of all OTVD are equipped with stills. This estimate is
based on a conversation with Phillips Corporation, a manufacturer of
metal cleaning equipment, (Raquat, D., 1979). Similarly, an Effluent
Guidelines survey found that 73 percent of the respondents reclaimed
solvent (Effluent Guidelines, 1979). Total waste solvent generated is
estimated using the following equation:
Total Methyl
Chloroform Losses
(91,700 kkg)
Percent of Losses
Which are Waste
Solvent
(0.225)
Total Waste
Solvent Generated
from OTVD
20,600 kkg
Assuming that 75 percent (±10%) of the operations practice solvent
recovery at 90 percent efficiency (+7%, -2%), the quantities of still
bottoms and unreclaimed waste solvent are estimated using the following
series of equations:
Total Number
of OTVD
(9,600 units)*
Total Number
of OTVD
(9,600 units)
Percent Which
Recover Solvent
(0.75)
Percent Which
do not Recover
Solvent
(0.25)
Total Number of
OTVD Practicing
Solvent Recovery
7,200 units
Total Number of
OTVD Which do not
Recover Solvent
2,400 units
At those operations which reclaim solvent, only 10 percent
(+20%, -70%) of the solvent becomes waste solvent. The average unit
losses can be estimated as follows:
No. of
OTVD
Which
Reclaim
Solvent
Percent of
Solvent in
Still
Bottoms
Quantity of
Waste +
Solvent
Generated/
Unit
No. of OTVD
Which do
not Reclaim
Solvent
(7,200 units) (0.1)
Total Waste
Solvent Losses
20,600 kkg
* 32,000 units x 30 percent
00
(2,400)
Quantity of
Waste Solvent
Generated/Unit
(x)
C-14
-------
x = 6.60 kkg Unreclaimed Waste Solvent/Unit
.Ix = 0.660 kkg Still Bottoms/Unit
The total unreclaimed waste solvent is equivalent to the average
unit loss times the number of units which do not reclaim solvent.
2,400 units x 6.60 kkg/unit = 15,800 kkg unreclaimed waste solvent.
The total still bottoms are similarly estimated by multiplying the
total number of units which reclaim solvent by the average quantity of
still bottoms per unit.
7,200 units x 0.660 kkg/unit = 4750 kkg still bottoms
Because of the uncertainty related to solvent recovery practices, our
estimate for the quantity of still bottoms generated is only accurate to
+29%, -72%. The estimate of 15,800 kkg waste solvent is considered accurate
to +36%, -33%.
Disposal of Still Bottoms
As was the case for cold cleaning operations, we assume that 75
percent (+7%, -3%) of the solvent is landfilled and 25 percent (+10%,
-20%) is incinerated at 95 percent efficiency (±4%).
Landfilled:
(4750 kkg) (0.75) = 3560 kkg
Incinerated:
(4750 kkg) (0.25) (0.95) = 1130 kkg
Emitted to air from incineration:
(4750 kkg) (0.25) (1-0.95) = 59.4 kkg
The uncertainties of the quantity of methyl chloroform disposed in
landfills, destroyed by incineration, and emitted to the air from
incineration are +30%, -72%; +31%, -75%; and +86%, -100% respectively.
C-15
-------
Waste Solvent Disposal
It Is assumed that unreclaimed waste solvent is disposed of as
follows:
o 3 percent (±5%) is incinerated at 95 percent efficiency (±4%)
o 44 percent (+15%, -5%) is landfilled
o 53 percent (+5%, -15%) is flushed
These estimates are based on the results of the Dow Survey (Dow, 1976),
Other information pertaining to the final disposal of waste solvent was
discussed in Appendix C-4. The total quantities of unreclaimed solvent
disposed of to various media are estimated using the expression:
Total Waste
Solvent
Incinerated:
Percent Disposed
of to Land, Water
or Incinerated
(15,800 kkg) (0.03) (0.95)
Emitted to Air from Incineration
(15,800 kkg)
Landfilled;
(15,800 kkg)
Flushed;
(15,800 kkg)
(0.03) (1-0.95)
(0.44)
(0.53)
Total Solvent to
Land, Water or
Incinerated
450 kkg
23.7 kkg
6950 kkg
8470 kkg
Table C-4 summarizes the uncertainties of quantities of waste
solvent.
C-16
-------
Table C-3 Summary of Uncertainties for Waste Solvent from Vapor Degreasing
(OTVD)
Waste
Total waste solvent
Released to water
Landfilled
Incinerated
Emitted to air
from incineration
Quantity
15,800
8,470
6,950
450
23.7
Individual
Uncertainty
%
—
+5/-15
+15/-5
±5/ ±4
±80
Overall
Uncertainty
%
+19/-14
+20/-21
+24/-15
+20/-15
+82/-81
Direct Atmospheric Losses
Direct atmospheric losses of methyl chloroform are those emissions
resulting from diffusion and convection, roof vent emissions and carry out.
These losses are equivalent to the total methyl chloroform losses minus
losses from waste solvent.
Total Methyl Waste Solvent = Total Direct Atmospheric
Chloroform Losses - Losses Emissions
(91,700 kkg) - (15,800 kkg + 4750 kkg) = 71,200 kkg
Approximately 1.5 percent (±50%) of the OTVD use carbon adsorption
systems which operate at about 60 percent (±10%) efficiency (Dow, 1979;
Raquat, D., 1979). The quantity of chloroform adsorbed is estimated by
multiplying total atmospheric losses by the percent of units using
carbon adsorption by the efficiency of recovery.
(71,200 kkg) (0.015) (0.6) = 641 kkg
It is further assumed that carbon is regenerated at 95 percent efficiency
(±4%) and 95 percent (±4%) of the methyl chloroform is destroyed.
Methyl Chloroform Efficiency of Quantity of Methyl
Adsorbed by Regeneration = Chloroform Destroyed
Carbon in Regeneration
(641 kkg) (0.95) » 609 kkg
C-17
-------
Total Methyl 1-Efficiency Methyl Chloroform
Chloroform of Regeneration = Emitted to Air from
Adsorbed by Carbon Regeneration
Carbon
(641 kkg) (0.05) = 32.1 kkg
Direct atmospheric losses are equal to the total atmospheric
emissions minus the quantity adsorbed by carbon.
(71,200 kkg) - (641 kkg) = 70,500 kkg
Direct atmospheric emissions are considered accurate to +42%,
-41%. Since atmospheric losses were estimated as the difference between
total solvent losses and waste solvent, the uncertainty factor accounts
for uncertainties related to waste solvent control practices and the
uncertainty related to total solvent used in vapor degreasing.
The quantities of methyl chloroform destroyed during carbon
regeneration and the quantity emitted to air from carbon regeneration
are considered accurate to +66%, -65% and +104%, -100%, respectively.
C-18
-------
APPENDIX C-6
ANNUAL METHYL CHLOROFORM LOSSES FROM CONVEYORIZED VAPOR DEGREASERS
Of an estimated 5,000 conveyorized degreasers (±10%), approximately
85 percent (±5%) of are vaporized degreasers (EPA, 1977b). The percent
of conveyorized vapor degreasers (CVD) using methyl chloroform is estimated
to be about 30 percent (+15%, -10%) (Dow, 1976). Using these estimates,
the total number of CVD using methyl chloroform is determined as follows:
Total Number of Percent CVD Percent Using Total No. of
Conveyorized Methyl = CVD Using Methyl
Degreasers Chloroform Chloroform
(5000 units) (0.85) (0.3) = 1280 units
OAQPS estimates that 30 percent (±33%) of all solvent losses from
vapor degreasers are from CVD. Then, total methyl chloroform losses
from these units are estimated as follows:
Total Methyl Chloroform Percent Due to CVD Total Losses
Losses from Vapor = from CVD
Degreasing
(131,400 kkg) (0.3) = 39,300 kkg
This corresponds to an annual average loss of 30.7 kkg/unit (+40%,
-42%), which is nearly 30 percent higher than an estimate (23.7 kkg/unit)
made by OAQPS for average losses of all solvents (EPA, 1977b). The OAQPS
estimate is within the uncertainty given for the calculated average
annual loss.
Waste Solvent
It has been estimated that 10 to 20 percent of the virgin solvent
becomes waste solvent from the operation of a CVD (EPA, 1977b). Assuming
an average of 15 percent waste solvent (±33%), the quantity of waste
solvent generated is determined as follows:
(39,300 kkg) (0.15) - 5900 kkg
C-19
-------
Solvent recovery is widely practiced among CVD users with an
estimated 85 percent (±10%) of the operations recovering solvents (EPA,
1977b). In order to estimate the quantity of waste solvent in still
bottoms and the quantity in unreclaimed waste solvent the following
approach is used:
Total No. of CVD
(1280 units)
Total No. of CVD
(1280 units)
Percent Using
Solvent Recovery
(0.85)
Percent Which Do
Not Use Solvent
Recovery
(0.15)
Number of Units
Using Solvent Recovery
1090 units
Number of Units Not
Using Solvent Recovery
192 units
Assuming that solvent recovery is 90 percent efficient (+7%, -2%),
the waste solvent losses per unit can be estimated from the following
expression:
No. of Units 1-Solvent Waste
Which Practice Recovery Solvent
Solvent Efficiency Generated
Recovery Per Unit
(1,090 units) (0.1) (x)
• Total Waste
Solvent
5,900 kkg
No. of Waste
Units Solvent
Which Do Generated
Not Reclaim Per Unit
Solvent
(192 units)
x
O.lx
19.6 kkg
1.96 kkg
unreclaimed waste solvent per unit
still bottoms per unit
(x)
Total waste solvent in still bottoms is equal to the 'number of
units with solvent recovery times the unit waste solvent losses.
1,090 units x 1.96 kkg/unit
2,150 kkg
C-20
-------
Total unreclaimed waste solvent is similarly estimated by multiplying
the number of units which do not recover solvent by the average waste
solvent generated per unit.
192 units x 19.7 kkg/unit = 3780 kkg
Due to the uncertainty related to waste solvent control practices
and to quantity of solvent which is waste solvent, we estimate the
uncertainty of these estimates at +29%, -72% for the quantity of still
bottoms and +60%, -59% for the quantity of unreclaimed waste solvent.
Disposal of Waste Solvent
Unreclaimed waste solvent is assumed to be disposed in a pattern
similar to that found by Dow for all solvents (Dow, 1976).
o 3 percent (±5%) is incinerated at 95% efficiency (±4%)
o 44 percent (+15%, -5%) is landfilled
o 53 percent (+5%, -15%) is flushed
The quantities of methyl chloroform disposed of to land, water
or incinerated are estimated as follows:
Incinerated;
(3780 kkg) (0.03) (0.95) = 108 kkg
Emitted to air from incineration;
(3780 kkg) (0.03) (1-0.95) = 5.67 kkg
Landfilled;
(3780 kkg) (0.44) - 1660 kkg
Flushed;
(3860 kkg) (0.53) = 2000 kkg
C-21
-------
Table C-4 summarizes the uncertainties which have been estimated
for releases of waste solvent.
Table C-4 Summary of Uncertainty for Waste Solvent from Conveyorized
Vapor Degreasers (CVD)
Waste
Total Waste Solvent
Released to Water
Landfilled
Incinerated
Emitted to Air
From Incineration
Quantity
3780
2000
1660
108
5.67
Individual
Uncertainty
(%)
—
+5/-15
+15 1-5
±51 ±4
±80
Overall
Uncertainty
(%)
+60/-59
+60/-61
+62 /-59
+60/-59
+100/-99
Disposal of Still Bottoms;
It is assumed that 25 percent (+10%, -20%) of the still bottoms are
incinerated at 95 percent efficiency (±4%) and the remaining 75 percent
(+7%, -3%) are landfilled.
Incinerated;
(2150 kkg) (0.25) (0.95) = 511 kkg
Emitted to Air from Incineration;
(2150 kkg) (0.25) (1-0.95) = 26.9 kkg
Landfilled;
(2150 kkg) (0.75) = 1610 kkg
C-22
-------
The estimate for the percent emitted to land is considered accurate
to +7%, -3%. Accounting for an uncertainty of +29%, -72% for the total
still bottoms generated, as well as the uncertainty related to total
solvent used in CVD (39,300 kkg; +35%, -39%) these estimates are considered
accurate to +31%, -75% for methyl chloroform incinerated, +86%, -100%
for air emissions, and +30%, -72% for still bottoms landfilled.
Atmospheric Losses;
Total atmospheric emissions are equivalent to the total methyl
chloroform losses from CVD minus the waste solvent losses.
Total Methyl Chloroform -
Losses From CVD
Waste Solvent
Losses
Direct Atmospheric
Emissions
(39,300 kkg)
- (2150 kkg + 3780 kkg) « 33,400 kkg
Roughly 1.5 percent (±50%) of the operations use carbon adsorption
to recover solvents and the efficiency of this operation is about 60
percent (±10%) (Dow, 1976; Raquat, D., 1979).
Direct
Atmospheric
Emissions
(33,400)
Percent Using
Carbon
Adsorption
(0.015)
Percent
Efficiency
(0.6)
Methyl Chloroform
Adsorbed in Carbon
Adsorption
301 kkg
It is further assumed that carbon is regenerated at 95 percent
efficiency (±4%) and 95 percent (±4%) of the methyl chloroform is destroyed
during regeneration. The remaining 5 percent is emitted to air during
regeneration.
Total Methyl
Chloroform
Adsorbed
(301 kkg)
Total Methyl
Chloroform
Adsorbed
(301 kkg)
Percent Efficiency
for Regeneration
(0.95)
Percent Emitted
During Regeneration
(0.05)
Quantity Destroyed
During Regeneration
286 kkg
Quantity Emitted to
Air During
Regeneration
15.1 kkg
C-23
-------
Direct atmospheric losses are equal to the total atmospheric emissions
minus the quantity adsorped by carbon adsorption.
(33,400 kkg) - (301 kkg) = 33,100 kkg
This estimate for air emissions is considered accurate to +35%,
-39%. Since atmospheric releases were determined by subtracting waste
solvent losses from total solvent losses. This uncertainty accounts for
uncertainties related to waste solvent and total solvent.
The uncertanties for the quantity destroyed during regeneration
and for the quantity emitted to air during regeneration are +62%, -64%
and +101%, -100%.
C-24
-------
APPENDIX C-7
LOSSES OF METHYL CHLOROFORM FROM NON-BOILING CONVEYORIZED DEGREASERS
The OAQPS has estimated that there are 5000 conveyorized degreasers
(±10%), 15 percent (±27%) of which are Conveyorized Non-Boiling Degreasers
(CND). Using the Dow Survey, JRB estimates that 30 percent (+15%, -10%)
of the CND use methyl chloroform (Dow, 1976). The total number of
CND using methyl chloroform is estimated as follows:
Total Number
of Conveyorized
Degreasers
(5000)
Percent Which
Are CND
(0.15)
Percent
Using =
Methyl
Chloroform
(0.30) =
Total Number
of CND Using
Methyl Chloroform
225 units
Total methyl chloroform losses from CND were estimated by assuming
an average unit loss of 47 kkg/unit (±10%). This is an estimate made by
OAQPS for all solvents and the actual losses of methyl chloroform
undoubtedly vary from other solvents (EPA, 1977b).
Total Number
of CND
(225 units)
Waste Solvent
Average Loss Per
Unit
(47 kkg/unit)
Total Methyl Chloroform
Losses From CND
10,600 kkg
It has been estimated that 10-20 percent of the virgin solvent
becomes waste solvent during the operation of a CND (OAQPS, 1977).
Assuming an average of 15 percent (±33%) of the solvent becomes waste
solvent, the total waste solvent can be estimated using the following
expression:
Total methyl
Chloroform Losses
(10,600 kkg)
Percent of Waste
Solvent
(0.15)
Total Waste
Solvent
1590 kkg
C-25
-------
This estimate includes losses from unreclaimed waste solvent as
well as from still bottoms and is considered accurate to +47%, -46%.
Assuming, as we did for CVD, that solvent recovery is practiced by
85 percent (±10%) of the operations at 90 percent efficiency (+7%, -2%),
we can estimate the quantities which are still bottoms and unreclaimed
waste solvent using the following expressions:
Number of CND
(225 units)
Percent Which Reclaim
Solvent
(0.85)
Number Which
Reclaim Solvent
191 units
The remaining 35 CND's do not practice solvent recovery. The waste
solvent losses for each of these units can be estimated as follows:
No. of Units
With Solvent
Recovery
1- Solvent
Recovery
Efficiency
(191 units) (0.1)
= Total Waste Solvent
1590 kkg
Waste No. of Units
Solvent + Without
Per Unit Solvent
Recovery
(X)
(34)
Waste
Solvent
Per Unit
(X)
x = 29.4 kkg unreclaimed waste solvent
O.lx - 2.94 kkg still bottoms
No. of Units
With Solvent
Recovery
(191)
No. of Units
Without Solvents
(34)
Quantity Still
Bottoms Per Unit
(2.94 kkg)
Quantity of
Unreclaimed
Solvent
(29.4 kkg)
Total Quantity
Still Bottoms
562 kkg
Total Unreclaimed
Wasted Solvent
1030 kkg
C-26
-------
Our estimate for the quantity of unreclaimed waste solvent is
considered accurate to +35%, -32% and the estimate for still bottoms is
accurate to +39%, -77%.
Disposal of Waste Solvent
Unreclaimed waste solvent is assumed to be disposed of as follows:
o
o
o
Total Methyl
Chloroform
Unreclaimed
Waste Solvent
Incinerated:
(1030 kkg)
3 percent (±5%) is incinerated at 95 percent efficiency (±4%)
44 percent (+15%, -5%) is landfilled
53 percent (+5%, -15%) is flushed
Percent Incinerated,
Landfilled and
Flushed
(0.03) (0.95)
Emitted to Air from Incineration:
(1030 kkg)
Landfilled;
(1030 kkg)
Flushed;
(1030 kkg)
(0.03) (1 -0.95)
(0.44)
(0.53)
Total Quantity
Incinerated,
Landfilled or
Flushed
29.4 kkg
1.55 kkg
453 kkg
546 kkg
Table C-5 summarizes the uncertainties related to release from
waste solvent.
C-27
-------
Table C-5 Summary of Uncertainties for Solvent from Conveyorized
Vapor Degreasers (CND)
Waste
Total Waste Solvent
Releases to Water
Landfilled
Incinerated
Released to Air
fron Incineration
Quantity
1030
546
453
29.4
1.55
Individual
Uncertainty
(%)
—
+5/-15
+15/-5
±5/ ±4
±80
Overall
Uncertainty
(%)
+3S/-32
±35
+3S/-32
+36/-33
+877-86
Disposal of Still Bottoms:
JRB estimates that 75 percent (+7%, -3%) of the still bottoms are
landfilled and 25 percent (+10%, -20%) are incinerated at 95 percent
efficiency (±4%).
Methyl Chloroform
in Still Bottoms
(546 kkg)
Methyl Chloroform
in Still Bottoms
(546 kkg)
Methyl Chloroform
in Still Bottoms
(546 kkg)
Percent Landfilled =
Total Still
Bottoms Landfilled
(0.75)
Percent
Incinerated
(0.25)
Percent
Incinerated
(0.25)
410 kkg
Efficiency
(0.95)
1-Efficiency
(1-0.95)
Total Still
Bottoms
Incinerated
130 kkg
Total Emitted
to Air from
Incineration
6.83 kkg
These still bottoms estimates are considered accurate to the
following:
o Landfilled +36%, -35%
o Incinerated +36%, -40%
o Incinerator Air Emission +88%, -90%.
C-28
-------
Direct Atmospheric Emissions
Direct atmospheric emissions are estimated by subtracting the total
waste solvent generated from the total methyl chloroform losses from
CND.
(10,600 kkg) - (1590kkg) = 9010 kkg
The quantity actually emitted to air is adjusted to account for an
estimated 1.5 percent (±50%) of the operations which use carbon adsorption
systems operating at about 60 percent efficiency (±10%).
Total Air Percent Units Percent Total Methyl
Emissions Using Activated Efficiency = Chloroform
Carbon Adsorbed By
Activated
Carbon
(9010 kkg) (0.015) (0.6) - 81.1 kkg
Activated carbon regeneration is assumed to be 95 percent efficient
(±4%). 95 percent (±4%) of the methyl chloroform is assumed to be
destroyed during regeneration and the remaining 5 percent (±80%) is
assumed to be emitted to air.
Methyl Chloroform . Efficiency of = Quantity Destroyed
Adsorbed Regeneration During Regeneration
(81.1 kkg) (0.95) = 77.0 kkg
Methyl Chloroform 1-Efficiency Quantity Emitted
Adsorbed of = To Air from
Regeneration Regeneration
(81.1 kkg) (1-0.95) = 4.06 kkg emitted to air
The quantities destroyed and emitted to the air during regeneration
are accurate to ±69% and +106%, -100%, respectively.
C-29
-------
The total actual direct atmospheric losses are estimated to be the
difference between the total atmospheric releases and the quantity
adsorbed by carbon adsorption.
(9010 kkg) - (81.1 kkg) = 8930 kkg lost to air
Air emissions are considered accurate to +47%, -46%.
C-30
-------
APPENDIX C-8
GEOGRAPHIC BREAKDOWN FOR >ETAL CLEANING REGIONS PRESENTED
IN SECTION 3.1
In section 3.1, data on metal cleaning is presented with
reference to geographic locations. The following lists the
states within each location.
NORTHEAST
SOUTHEAST
CONNECTICUT
DELAWARE
MAINE
MARYLAND
MASSACHUSETTS
NEW HAMPSHIRE
NEW JERSEY
NEW YORK
PENNSYLVANIA
RHODE ISLAND
VERMONT
ALABAMA
FLORIDA
GEORGIA
No, CAROLINA
So, CAROLINA
TENNESSEE
VIRGINIA
ARKANSAS
WASHINGTON/ D,C,
PUERTO Rico
MID-WEST
ILLINOIS
INDIANA
KENTUCKY
MICHIGAN
OHIO
WEST VIRGINIA
WISCONSIN
FAR WEST
ARIZONA
CALIFORNIA
HAWAII
IDAHO
NEVADA
OREGON
WASHINGTON
UTAH
NORTH CENTRAL
COLORADO
IOWA
KANSAS
MINNESOTA
MISSOURI
MONTANA
NEBRASKA
NORTH DAKOTA
SOUTH DAKOTA
WYOMING
SOUTHWEST
LOUISIANA
MISSISSIPPI
OKLAHOMA
TEXAS
NEW MEXICO
C-31
-------
APPENDIX D-l
List of Products Containing Methyl Chloroform
Name of Products
Producers
% of Methyl
Chloroform in
the Formulation
Purpose of
Use
Amway Drain
Mate
Amway Dri-Fab
Amway Oven'N'Grill
Amway Remove
Amway Wonder Mist
Anchor-Weld 0911
Anchor-Weld 2000
Balkampchoke
Cleaner
Barton's Spot Remover
Carbo-Cholor
Carbona No. 10
Special Spot
Remover
Carbona Spray Spot
Remover
Carter's Type Cleaner
Difficult Stains
Dowclene
Dressup
Edwal Color Film
Cleaner
Glamorene Spot Clean
Gripdust
IBM Adhesive
IBM Cleaning Fluid
IBM-SMS Card Contact
Cleaner
IBM Stain Remover
IBM Tape Developer
Cleaner
Amway Corp.
Amway Corp.
Amway Corp.
Amway Corp.
Amway Corp.
Roberts Consolidated
Ind.
Roberts Consolidated
Ind.
Balkamp, Inc.
Dyanshine Products
Division
Sunnyside Products
Inc.
Carbona Products Co.
Carbona Products Co.
Carter's Ink
Albatross Chemical
Dow Chem., U.S.A.
Dolge C.B. Co.
Edwal Scientific
Products Corp.
Glamorene Products
Corp.
Dolge C.B. Co.
IBM
IBM
IBM
IBM
IBM
u.k.
u.k.
u.k.
u.k.
u.k.
23%
25%
Approx 100%
Solvent based
Drain Cleaner
Water Repellant
Spray
Aerosol Over
Protectorant
Spot Remover
Aerosol Lubricant
Safety Solvent
Safety Brushage
Contact Cement
Choke Cleaner
Spot Remover
Metal Cleaner,
Spot Remover,
Grease and tar
Remover
Spot Remover
Aerosol Spot
Remover
Ink Cleaner
Cleaning Fluid
Spot Remover
Aerosol
Furniture Polish
Photographic
Supply
Aerosol Powder-
Spot Cleaner
D-l
-------
APPENDIX D-l (cont.)
List of Products Containing Methyl Chloroform
Name of Products
Kitchen Drano
(Liquid)
Mildew stop Spray
Producer
Drackett
Cardinal Products
% of Methyl
Chloroform in Purpose of
the Formulation Use
Approx. 75% Drain Cleaner
by wt.
25% Mold-Mildew and
Moxie 50 W.P.
Muffi Spot Remover
OAB 37
One Time Rug Frost
P-3576
Pow Liquid Drain
Cleaner
Quik'n Easy Spot
Lifter
Roberts 41-0911
Roberts 41-4001
Roberts 41-4015
Sila-Slide
Corp.
Ansul
Plough
Kentile
One Time Package
Prod.
Calgon Corp.
Penn Champ
Penn Champ
Roberts Consolidated
Ind.
Roberts Consolidated
Ind.
Roberts Consolidated
Ind.
Scientific Inter-
national Research Inc.
Musty Odor
Preventative
6 % Insecticide
- Spot Remover
- On and Below
Grade Adhesive
Spot Remover
- Solvent
99 % Drain Cleaner
70 % Spot Remover
Universal Cuslieon
Back Seam Solvent
Carpet Pad Adhesive
- Cushion Back Seam
Adhesive
Multi-Purpose
- Silicone Lubricant;
Industrial Use
Source: Chemcial Toxicology of Commercial Products, 1976
D-2
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Appendix D-2 — Registered Pesticide Containing Methyl Chloroform (cont.)
Product Use Company Methyl
Chloroform
Moorehead 10% DD-VPspray Tobacco warehouses Moorehead Ind., Inc. 20%
Hopkinton, MA
Moorehead 50% - WE cone. Tobacco warehouses Moorehead Ind., Inc. 30%
Hopkinton, MA
Swit - wasp & hornet
spray Insecticide Dymon, Inc.
Kansas City, KA
Anti Shield Anti-shield, Inc.
Louisville, KY
Source: Chemical Toxicology of Commercial Products, 1976
D-4
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Appendix D-2 — Registered Pesticide Containing Methyl Chloroform
Product Use Company
Methyl
Chloroform
Dog Shield - Dog Personal protection
Repellant from dog
Prentox - 50% DDVP cone.
Prentox - DDVP - aerosol
cone. #G-1553
Prentox - DDVP aerosol For manufacturing
cone. purposes only
Capitol DDVP cone.
aerosol
Fumo - aero-spray
Bruce Terminex
Clipper Mate
Stephenson Chem. -
DDVAP 14%
Stephenson Chem. -
DD-VP-20%
Carmel Chem. - non-
flammable vapona
fogging insecticide
Industrial use only
Professional
insecticide
Lubricates, sanitizers
cools
Insecticide
Carmel Chem. - non-
flammable tobacco -
pyrethrum spray form F-13
Tobacco insecticide
Pybutox - aerosol -
F-201 D
Insecticide/miticide
Gabriel DD-VP-90% cone. Insecticide/miticide
Moorehead 5% DD-VP spray
Chase Products -
Broadview, IL
Prentice Drug & Chem. 30%
N.Y., NY
Prentice Drug & Chem. 64%
N.Y., NY
Prentice Drug & Chem. 67%
N.Y., NY
Capitol Chem. Co.
Washington, DC
Fumol Corp. -
L.I., NY
Terminex Div. of Cook 8%
Industries
Memphis, TN
Carson Chem., Inc. -
New Castle, IN
Stephenson Chem. Co. -
New Castle, IN
Stephenson Chem Co. -
New Castle, IN
Carmel Chem. Corp. 60%
Westfield, IL
Carmel Chem. Corp. 60%
Westfield, IL
Gabriel Chemical
Paterson, NJ
Gabriel Chemical 10%
Paterson, NJ
Moorehead Ind., Inc. 20%
Hopkinton, MA
D-3
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APPENDIX E
PHYSICAL PROPERTIES
OF
METHYL CHLOROFORM
Methyl
:hlorofoi
Chemical Abstracts Service
registry number
Molecular formula
Structure
Molecular weight
Composition (% by wt)
Boiling point, °C
Freezing point, °C
Flash point
Fire point
Vapor density
Specific gravity
Density, Ib/gal
Specific heat, Btu/(lb)(°F)
Heat of vaporization, Btu/lb
Viscosity, cP at 25°C
71-55-6
ooo
Cl H
Cl-C—C-H
Cl H
133.42
C 18.007o
H 2.27%
Cl 79.72%
74
-37
None
None
4.55
1.320
10.99
0.25
102
0.79
E-l
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PHYSICAL PROPERTIES OF METHYL CHLOROFORM INFLUENCING EVAPORATIVE LOSSES
Solubility in water (ppm)a 1,300
Vapor Pressure no Hq(25°)a 123
Partition Coefficient b 0.68
Evaporation half-life, min c 20±3
a - Kirk-Otmer Encyclopedia of Chemical Technology, 2nd edition, Interscience
Publishers, N.Y.
b - c air/c water
c - Dilling, et.al. 1975.
Calculated at room temperature, with constant mixing.
E-2
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APPENDIX F
BREATHING AND WORKING LOSSES
Breathing and working loss rates calculated in the following section
for vented fixed roof tanks are based on equations found in AP-42 (EPA,
1977c) and assumptions used by Hydroscience (Hydroscience, 1979). These
assumptions are presented in Table F-l.
The breathing loss equation is:
BL = 2.21 x ID'4 M [ T1-fIF-] °'68 D1'73 H °'51 T0'5° C
BL = Fixed roof breathing loss (lb/day)*
M = Molecular weight of vapor in storage tank (Ib/lb mole)
P = True vapor pressure at bulk liquid conditions (psia)
D = Tank diameter (ft)
H = Average vapor space height
T = Average ambient temperature cahnge from day to night (°F)
C = Adjustment factor for small diameter tanks (dimensionless)
The working loss equation is:
WL = 2.40 x 10~2 MPN
3
WL = Fixed roof working loss (lb/10 gal throughput)
M = Molecular weight of vapor in storage tank (Ib/lb mole)
* This loss is neglected if non-vented tanks are employed.
F-l
-------
Table F-l Assumptions Used in Breathing and Working Loss Rate Calculations
HJ
Tank Number Tank Tank Tank
Type of Volume Height Diameter
Tanks (M3) (ft) (ft)
Vinyl Chloride. 4 598 30 30
Process -
Refined Product
Tank
Vinyl Chloride 2 98 16 16
Process -
Crude Product
Tank
Ethane Process 4 174 20 20
Refined Product
Tank
Ethane Process 2 29 11 11
Crude Product
Tank
Vapor Average
at 27°C Vapor
(psia) Space
Height
(ft)
2.6 15
2.6 8
2.6 10
2.6 5.5
Temper- Molecular Turnover
ature Weight Factor
Change Vapor
(±F) Ib/lb mole
20 133 0.9
20 133 1
20 133 1
20 133 1
Small
Diameter
Adjustment
Factor
1
.8
.9
.55
Source: Hydroscience, 1979; EPA, 1977c.
-------
P = True vapor pressure at bulk liquid conditions (psia)
N = Turnover factor (dimensionless)
1) Total loss rate for vinyl chloride (VC) process for
refined product storage (based on 136,000 kkg/year
of refined product)
a) Breathing Loss for on tank:
BL = 2.21 x 10-4(133)( T^276)°-68(30)1-73(15)°-51(20)-50(l)
= 64.3 Ibs/day
=29.2 kg/day
For the process on an annual basis:
Total Breathing Loss = 0.31 kg/kkg
b) Working Loss:
WL = 2.40 x 10"2 (133) (2.6) (.9)
= 7.4 lb/103 gal.
= .88 kg/kkg
Total Emission Rate = .31 + .88 = 1.19 kg/kkg
2) Total loss rate for VC process for crude product storage
(based on 136,000 kkg/year of refined product and 6,625
kkg of crude product throughout)
F-3
-------
a) Breathing Loss for one tank:
BL - 2.21 x ID'4 (133)(14j:^6)°-68(10)1-73(8)0-51(20)-50(.8)
= 12.6 Ibs/day
= 5.8 kg/day
For the process of an annual basis:
Total Breathing Loss = .03 kg/kkg
b) Working Loss
WL = 2.40 x 10~2 (133) (2.6) (1)
= 8.3 lb/103 gal
= .98 kg/kkg oc crude product throughput
For the process on an annual basis:
Total Working Loss = .98 x (6,625 kkg of crude throughput)/
(136,000 kkg of production)
= .05 kg/kkg of production
Total Emission Rate - .03 + .05 = .08 kg/kkg
3) Total loss rate for the Ethane process for refined product
storage (based on 29,500 kkg/year of refined product)
a) Breathing Loss (for fixed roof tanks only) for one tank:
BL = 2.21 x 10'4 (133)(14^:^6)0'68 (20)1 '73(10) '51(20) '5°(.9)
=23.3 Ibs/day
= 10.6 kg/day
F-4
-------
For the process on an annual basis:
Total Breathing Loss = .52 kg/kkg
b) Working Loss
WL = 2.40 x 10~2(133)(2.6)(1)
= 8.3 lbs/103 gal
= .98 kg/kkg
Total Emission Rate = .52 - .98 = 1.50 kg/kkg
4) Total loss rate for the Ethane process for crude product storage
(based on 29,500 kkg/year of refined product and 1,660 kkg of
crude product throughput)
a) Breathing Loss (for fixed roof tanks only) for one tank:
BL = 2.21 x 10"4 (133) (^'^ 6)°-68(ll)1-73(5.5)°-51 (20)'5° (.55)
=3.7 Ibs/day
-1.7 kg/kkg
For the process on an annual basis:
Total Breathing Loss = .04 kg/kkg
b) Working Loss
WL = 2.40 x 10~2 (133) (2.6) (1)
= 8.3 lbs/103 gal
= .98 kg/kkg of crude product throughput
For the process on an annual basis:
F-5
-------
Total Working Loss = .98 x (1,660 kkg of crude throughput)/
(29,550 kkg of production)
= .06 kg/kkg
Total Emission Rate = .04 + .06 = .10 kg/kkg
F-6
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