United States
Environmental Protection
Agency
Office of
Toxic Substances
Washington DC 20460
January 1980
EPA-560/13-80-002
Toxic Substances
xvEPA
Materials Balance Review
1,2- Dichloroethane Copy
Level I — Preliminary
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FINAL DRAFT
LEVEL I MATERIALS BALANCE:
1,2-DICHLOROETHANE
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF PESTICIDES AND TOXIC SUBSTANCES
SURVEY AND ANALYSIS DIVISION
Task No. 11
Contract No. 68-01-5793
Michael Callahan - Project Officer
C. Richard Cothern - Task Manager
Prepared by:
JRB ASSOCIATES, INC.
8400 Westpark Drive
McLean, Virginia 22102
Project Manager: Karen Slimak
Task Leaders: Kathleen Durrell
• Karen Slimak
Contributing Writers: Hal Bryson
Eliot Harrison
Virginia Hodge
Le-Tan Phuoc
Sidney Paige
Submitted: February 8, 1980
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THE FINAL REPORT PRESENTED HEREIN RESULTED FROM A LEVEL I
MATERIALS BALANCE STUDY ON 1,2-DICHLOROETHANE. THE RESULTS
WERE BASED ON AN ANALYSIS OF LITERATURE SUPPLIED BY EPA.
ALTHOUGH SUPPLEMENTARY INFORMATION UNDOUBTEDLY EXISTS,
OBTAINING IT WAS OUTSIDE THE SCOPE OF THIS TASK. THE LEVEL
REPORT IS INTENDED TO SERVE AS A FOCUS OF DISCUSSION AND AS
A BASIS FOR FUTURE MATERIALS BALANCE STUDIES: IT IS NOT
MEANT TO BE A DEFINITIVE STUDY.
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LEVELS OF ENVIRONMENTAL MATERIALS BALANCES
Materials balance studies are performed at three levels or
depths of study and effort. In general the study of a chemical
proceeds sequentially through these three levels. Particular
chemicals are assigned 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 (CID) to provide readily
available information. The first draft of most Level I Materials
Balances is completed within a three to six week period; CID
literature searches are generally completed within two weeks. Thus
the total time required for preparation of the initial draft of a
Level I materials balance ranges from five to eight 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 MATERIALS BALANCE generally involves the assimilation
of new data obtained. It buildb on the Level II literature searches
and reviews of industrial production data by filling in data gaps
through site visits and monitoring. The data generated for a Level III
Materials Balance are intended to be statistically valid and have known
confidence values. Level III Materials Balances are also intended to
provide a basis for regulations or legal proceedings.
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TABLE OF CONTENTS
Page
Executive Summary i
1.0 Introduction 1-1
2.0 Environmental Releases Associated with the Production
of 1,2-Dichloroethane 2-1
2.1 Environmental Releases of EDC Associated with
Direct Production Processes 2-1
2.1.1 Releases of EDC Associated with the Direct
Chlorination Process 2-3
2.1.2 Releases of EDC Associated with the
Oxychlorination Process 2-17
2.2 Environmental Releases of EDC Associated with
Indirect Production Processes 2-31
2.2.1 Releases of EDC Associated with the
Chlorination of Public Water Supplies 2-31
2.2.2 Releases of EDC Associated with the
Chlorination of Industrial Wastewaters 2-34
2.2.3 Releases of EDC Associated with the
Incineration of Chlorinated Organics 2-34
2.2.4 Other Possible Inadvertent Sources of
EDC Releases 2-36
2.2.5 Releases of EDC Associated with Other
Manufacturing Processes 2-37
2.2.6 Releases of EDC Associated with
Laboratory Use 2-38
2.3 Stockpiles 2-38
2.4 Imports 2-40
3.0 Environmental Releases During the Use of EDC 3-1
3.1 Releases Associated with the Major Uses of EDC 3-1
3.1.1 Releases of EDC Associated with the
Production and Use of Vinyl Chloride
Monomer 3-1
-------
3.1.2 Releases of EDC Associated with the
Production and Use of Trichloroethylene 3-8
3.1.3 Releases of EDC Associated with the
Production and Ijse of Perchloroethylene 3-12
3.1.4 Releases of EDC Associated with the
Production and Use of Vinylidene Chloride 3-18
3.1.5 Releases of EDC Associated with the
Production and Use of Methyl Chloroform 3-23
3.1.6 Releases of EDC Associated with the
Production and Use of Ethyleneamines 3-30
3.1.7 Releases of EDC Associated with Its Use
as a Leaded Gasoline Additive 3-35
3.2 Releases Associated with the Minor Uses of EDC 3-40
3.2.1 Releases from EDC Use in the Manufacture
of Paints, Coatings, and Adhesives 3-43
3.2.2 Releases from EDC Use as an Extraction
Solvent 3-44
3.2.3 Releases from EDC Use in Cleaning
Solvents 3-46
3.2.4 Releases of EDC Associated with Manu-
facture and Use of Polysulfides 3-47
3.2.5 Releases from EDC Use in Grain Fumigation 3-49
3.2.6 Releases from Other Uses , 3-51
4.0 Summary of Points of Environmental Release 4-1
5.0 Summary of Disposal and Destruction of EDC End-
Products 5-1
6.0 Summary of Uncertainties 6-1
7.0 Data Gaps 7-1
7.1 Data Necessary to Increase the Validity of
Emissions Estimates for Various Production
Processes 7-1
7.2 Estimates of the Occurrence and Releases of
EDC as a By-Product of Manufacturing Processes
for Which EDC is not a Feedstock 7-1
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7.3 Determining Emission Levels of EDC Associated
with Certain Major Uses 7-2
7.4 Data Caps Relating to Minor Uses of EDC 7-3
7.5 EDC Production during the Chlorination of Water
and Wastewater 7-3
7.6 EDC Production from the Incineration of Chlorinated
Organic Compounds 7-4
8.0 References 8-1
APPENDIX A Physical Properties of EDC A-l
APPENDIX B Excerpted Descriptions of Major Processes Which
Produce or Use EDC B-l
APPENDIX C Occurrence of EDC in Raw and Finished Water . C-l
APPENDIX D Flow Diagram for EDC D-l
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OF FIGURES
Figure Page
1.0 • Environmental Materials Balance
for EDC (1977) v
2.1 Locations of Plants Manufacturing
EDC 2-2
2.2 Production Trends for EDC 2-4
2.3 Production of EDC Via the Direct
Chlorination Process 2-6
2.4 Environmental Releases of EDC
from the Direct Chlorination
Process 2-18
2.5 Production of EDC Via the
Oxychlorination Process 2-20
2.6 Environmental Releases of EDC
from the Oxychlorination Process 2-32
3.1 Location of Vinyl Chloride
Manufacturing Facilities 3-3
3.2 Production of Vinyl Chloride
from EDC 3-4
3.3 Location of Trichloroethylene
Manufacturing Facilities 3-9
3.4 Production of Trichloroethylene
from EDC ' 3-10
3.5 Location of Perchloroethylene
Manufacturing Facilities 3-13
3.6 General Process for Production
of Perchloroethylene from EDC 3-14
3.7 Production of Perchloroethylene
Via the Acetylene Method 3-17
3.8 Location of Vinylidene Chloride
Manufacturing Facilities 3-19
-------
LIST OF FIGURES (cont'd.)
Figure Page
3.9 Production of Vinylidene Chloride 3-20
3.10 Location of Methyl Chloroform
Manufacturing Facilities 3-24
3.11 Production of Methyl Chloroform
from Vinyl Chloride 3-26
3.12 Production of Methyl Chloroform
from Vinylidene Chloride 3-28
3.13 Production of Ethyleneamines from
EDC 3-31
3.14 Location of Ethyleneamines
Manufacturing Facilities 3-38
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LIST OF TABLES
Table Page
1.0 Summary of Uses.of EDC iv
2.1 Producers of EDC (1977) 2-5
2.2 Summary of Potential Releases of EDC
from Production Processes Which Do
Not Involve EDC as a Starting Material
or as an End-Product 2-39
3.1 Products Manufactured from EDC-
derived VCM 3.7
3.2 Minor Uses of EDC 3-42
3.3 'Composition of Selected Fumigants 3-50
5.1 Solid and Liquid EDC-Containing
Wastes: Quantities, Disposal,
Environmental Releases 5-2
6.1 Summary of Uncertainties for Estimates
of Environmental Release from Produc-
tion and Use of EDC 6-2
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EXECUTIVE SUMMARY
General Description of 1,2-Dichloroethane
1,2-Dichloroethane is a synthetic organic compound with the
following chemical structure:
H
1
H
H
1
1
H
CL C C CL
The common name for t his compound is ethylene dichloride (EDC). It
is a colorless, oily liquid with a sweet taste and an odor similar to
that of chloroform. EDC has a density of 1.2351 and is very volatile
(vp=62.5 mm Hg at 20 C). It is a powerful solvent: for unvulcanized
rubber, fats, greases, waxes, resins and many other organic compounds.
EDC is only slightly soluble in water, but is completely miscible
with most of the usual organic solvents. Vapors from EDC burn
readily in air, but the liquid burns poorly with a smoke flame. Bulk
quantities of the compound are stable when kept dry at room temperature,
but the material undergoes slow decomposition when exposed to air,
moisture and light.
Unlike some other chlorinated hydrocarbons (namely, DDT and PCB),
EDC does not appear to accumulate in the environment. The material
evaporates rapidly from water into the atmosphere, where photo-oxidation
appears to be the main destructive mechanism. Hox/ever, EDC is toxic
to humans following oral, respiratory or skin and mucous membrane absorp-
tion.
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Production and Primary Uses
Of all the chlorinated organic compounds manufactured in the
United States, EDC is produced in the greatest quantity. The U.S.
prod i iff ion figure for 1977 Is 4.99 million metric tons. Figures nro
not yet available for 1978 but are expected to have escalated by about
4%. The major use of EDC is as a raw material for the production of
vinyl chloride monomer and other chlorinated hydrocarbons. The break-
down statistics for the use of EDC in these production processes is
shown in Table 1.0.
Summary of Materials Balance of EDC
Of the 5.05 million kkg of EDC actually produced in the U.S. in
1977, a total of 6.7 x 10 kkg or about 1.4% of that produced) is
estimated to have been released to the environment. Of this total,
4
5.4 x 10 kkg (88%) is estimated to have been released to the air;
190 kkg (0.3%) to water; an insignificant amount to land; and
4
1.3 x 10 kkg was destroyed by incineration. This estimate is based on
little available information and should be verified in later studies.
The remaining 4.99 million kkg is either exported, destroyed via
combustion processes, or chemically bound in the products made from
EDC, including other chemicals. Figure 1.0 shows the flow of EDC from
the production to the use phase, the environmenta.. releases associated
with each phase, and the materials balance. The Materials balance is .
based on the 1977 data, since production figures were not yet avail-
able for 1978. Most of EDC releases occur during production processes.
The releases associated with the manufacture of EDC are close to
4.12 kkg, or 61% of the tot; 1 release of EDC to the environment.
The third most important group of releases occur during the manu-
facturing processes which utilize EDC as a feedstock (e.g., the
production of vinyl chloride monomer, trichloroethylene, polysulfide
rubber, etc.). For these manufacturing processes, most of the emissions
are released directly to the atmosphere (60%), but some EDC is associated
with various.sludges that are generated. Total emissions from this
source are estimated at 5600 kkg. From the total amount of EDC used as
ii
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lead scavenger (9.7 x 10 kkg), EDC emission to the environment was
estimated at 1200 kkg (or 18% of the total EDC emission). The
2
remaining quantity (9.6% x 10 kkg) \
destroyed by the combustion process.
2
remaining quantity (9.6% x 10 kkg) was estimated to have been
iii
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TABLE 1.0 SUMMARY OF USES OF EDC
USE
VINYL CHLORIDE MONOMER PRODUCTION
METHYL CHLOROFORM PRODUCTION
ETHYLENEAMINE PRODUCTION
PERCHLOROETHYLENE PRODUCTION
TRICHLOROETHYLENE PRODUCTION
ADDITIVE TO GASOLINE
VINYLIDENE CHLORIDE PRODUCTION
TOTAL OF MAJOR USES
rFQRMULATION OF PAINTS, COATINGS, AND ADHESIVES
EXTRACTION SOLVENT
CLEANING SOLVENT
POLYSULFIDES MANUFACTURE
GRAIN FUMIGATION
MISCELLANEOUS
TOTAL OF MINOR USES
EXPORTS
GRAND TOTAL (MAJOR USES + MINOR USES + EXPORTS) =
AMOUNT OF
EDC USED (KKG)
fi
4.1 x 10
2.2 x 105
5
1.5 x 10
5
1.2 x 10
1.0 x 105
4
9.6 x 10
4
5.3 x 10
6
4.8 x 10
1.4 x 103
3
1.1 x 10
2
9.1 x 10
2
5.2 x 10
2
4.6 x 10
4.6 x 102
3
4.8 x 10
5
1.8 x 10
6
5.0 x 10
PERCENT
OF TOTAL
82%
4'%
3%
2%
2%
2%
: 1%
96%
< 1%
< 1%
< 1%
< 1%
< 1%
< 1%
< 1%
3.6%
100%
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PAGE NOT
LABLE
DIGITALLY
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1.0 INTRODUCTION
This report presents the results of a Level I Enviror nental
Materials Balance for 1,2-dichloroethane (EDC). The study was con-
ducted for the Survey and Analysis Division of the U.S. EPA Office of
Pesticides and Toxic Substances (OPTS). The primary objective of the
study was to estimate within the constraints of time and information
availability, the quantity of EDC released to the environment annually,
the sources and locations of these emissions, and the form in which
EDC is released.
By definition, a Level I materials balance involves a survey of
readily available information supplied mostly by the Chemical Information
Division of OTS. In a Level I study many assumptions and estimations
must be made in accounting for all releases of the chemical to the
environment. The results are based on all the assumptions presented and
represent the best analysis of the currently available data.
The following pages present the findings of this study. Section 2.0
explains the production of EDC and examines all releases of EDC to the
environment during these processes. Section 3.0 describes the releases
related to all end products and uses of EDC following its production.
A summary of all the environmental releases of EDC is presented in
Section 4.0. Section 5.0 is a detailed review of the disposal and
destruction of EDC. The uncertainties of the estimates presented ir
the report are summarized in Section 6.0. The final section of the
report, Section 7.0, identifies the gaps in the available data. The
appendix provides supplementary information which substantiates some
of the conclusions drawn in this report.
1-1
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2.0 ENVIRONMENTAL RELEASE ASSOCIATED WITH THE PRODUCTION OF
EDC
The sources of EDC in the United States are (1) direct
production for either captive or dispersive uses, (2) indirect or
inadvertent production via other processes, and (3) stockpiles of
EDC produced in previous years. There are no imports of EDC to the
United States.
2.1 ENVIRONMENTAL RELEASE OF EDC ASSOCIATED WITH DIRECT
PRODUCTION PROCESSES
Direct production of EDC is accomplished in industry primarily
through the direct chlorination of ethylene or oxychlorination of
ethylene. In the United States, 11 manufacturers in 17 production
facilities produce EDC. Figure 2.1 shows the locations of the
plants.
In 1977, 4.99 million kkg of EDC was produced in the United
States (USITC, 1978). This quantity represents only that amount
reported to the USITC by the manufacturers. Because of reporting
problems in earlier years, there were discrepancies in quantities
reported to have been manufactured and quantities reported to have
been used. Therefore, an independent method was used to check the
accuracy of the USITC data for 1977.
This method is based on the following equation:
Total EDC Produced = (Total EDC Used in Major Uses) + (Total
EDC Used in Minor Uses) + (EDC Exports)
+ (Stockpiles)
The first step, determining the amount of EDC necessary to produce
the major chemicals, can be found in Section 3.0. By adding all
the quantities calculated, 4.82 x 10 kkg is obtained. By adding
the total of minor uses and exports to this quantity, the total
production figure is calculated as follows:
2-1
-------
(1) Allied Chemical Co., Baton louge, Louisiana
(2) Conoco Chemicals, Lake CharLes, Louisiana
.(3) Diamond Shamrock Corp., Deer Park, Texas
(A) Dow Chemical Co., Freeport, Texas
(5) Dow Chemical Co., Oyster Creek, Texas
(6) Dow Chemical Co., Plaquemine, Louisiana
(7) Ethyl Corp., Baton Rouge, Louisiana
(8) Ethyl Corp., Houston, Texas
(9) B.F. Goodrich Co., Calvert City, Kansas
(10) PPG Industries, Inc., Lake Charles, Louisiana
(11) PPG Industries, Inc., Guayanilla, P.R.
(12) Shell Chemical Co., Deer Park, Texas
(13) Shell Chemical Co., Norco, Louisiana
(14) Stauffer Chemical Co., Long Beach, California
(15) Union Carbide Corp., Taft, Louisiana
(16) Union Carbide Corp., Texas City, Texas
(17) Vulcan Materials Co., Geismar, Louisiana
FIGURE 2-1. LOCATIONS OF PLANTS MANUFACTURING KDC
2-2
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100% of total production = Exports (3.7% of total production)
•f Minor Uses (0.1% of total
production) + Major Uses (4.82 x
106 kkg) + Stockpiles (0)
Total Production = 4.82 x 10 kkg
96.2%
= 5.01 x, 106 kkg
Since no significant variation exists between the two figures
obtained, the quantity reported to, the US1TC, 4.99 x 10 kkg, is
used throughout this report.
Table 2.1 lists the producers, plant locations, annual
capacity, estimated production, and respective production methods
for EDC. Based on current and projected markets for EDC, it has
been established that annual production will rise between 4% and 5%
each year through 1981; production in 1981 is expected to be
approximately 6.06 million kkg (Chemical Marketing Reporter, 1977b).
The production trends since 1974 are shown in Figure 2.2.
2.1.1 Release of EDC Associated With the. Direct Chlorination
Process
Approximately 59%, or 2.94 x 10 kkp, of EDC manufactured by
industry in 1977 was produced by the direct chlorination of ethylene
in the presence of an FeCl_ catalyst (EPA, 1979a). The chemical
reaction involved in this process is presented below (McPherson,
1979):
FeCl3
C12 + CH2 = CH2 **" C1CH2CH2C1
A detailed discussion of the direct chlorination process is
shown in Appendix B. The production is represented diagrammatically
in Figure 2.3.
2-3
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-O
6-
MII.UON
KKC 5-
4-
3-
2-
1-
4.16
3.62
4.98
4.99
-
5.2-
5.25
5.4-
5.5
5.6-
5.8
1979***
I960**
*llased upon data from USITC, 1974-1977.
**Based on
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TABLE 2.1
PRODUCERS OF EDC (1977)
ro
01
Producer
Allied Chemical Corp. C
Continental Oil Corp.
Diamond Shamrock Chem. Co.
Dow Chemical Co., U.S.A.
Ethyl Corp.
S.I. Goodrich Chemical Co.
PPG Industries, Inc.0
Shell Chemical Co.
Stauffer Chemical Co.
I'nion Carbide Corp.
Vulcan Material Co.
TOTAL
Locat ion
Baton Rouge, 'LA
Lake Charles, LA
Deer Park, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Baton Rouge, LA
Houston, TX
Calvert City, KY
Lake. Charles, LA
Cuayanllla, PR
Deer Park, TX
Norco, LA
Long Beach, CA
Taft, LA
Texas City, TX
Ceismar, '.A
Annual
Capacity
(million kkg)
0.272
0.544
0.145
0.726
0.499
0.590
0.318
0.144
0.454
0.585
0.485
0.635
0.544
0.141
0.068
0.068
0.159
6.35
Estimated*
1977
Production
(million kkg)
0.214
0.428
0.114
0.571
0.392
0.464
0.250
0.113
0.357
0.460
0.381
0.499
0.428
0.111
0.053
0.053
0.125
4.99
Production
nirect Chlorl-
nation (X)
66.7
49.2
35.8
57.1
51.7
52.7
100.0
33.3
77.2
66.2
69.2
100.0
100.0
0.0
Method1"
Oxychlorl-
nation (I)
33.3
50.8
64.2
42.9
48.3
47.3
0.0
66.7
22.8
33.8
30.8
0.0
0.0
100.0
"Based upon 4.99 million kkg total production (78.6Z of annual capacity in 1977). the production for 'each facility was
estimated by applying 78.6X to each plant's capacity.
Based on 1974 data (Pervier et al., 1974)
In July 1978, Allied Chemical disclosed, plans to sell its Baton Rouge vinyl chloride complex, including production faculties
for 1,2-dichloroethane, to ICI Americas. '
Goodrich Chemical Co. has announced plans to construct a 1.2-dlchloroethane plant in Convent, Louisiana, that will have an
annual capacity of 0.36 million metric tons.
A planned expansion of vlny1. -»•-"- -iant at uke Charles was announced In July 1978 by PPG Industries, Inc.
Source: US EPA, 1979a
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Cl.
F.thvlune
—©
(LI
Separa-
tor
l^ 2 -d i b r om_oc!t hj^ne
recvcle
d D
f. E
4J 3
O ^H
o o
To Waste
Water
0.0025 kg/kg
\0.0012 kg/kg
Heavy Ends
1 , 2-dir.1iloro.-th.-im
Pioduct
Siorage
Fugitive
Emissions
Source: Adapted from ORNL(EPA 1979a)
FIGURE 2.3 PRODUCTION OF EDC VIA THE DIRECT CHLOKINATION PROCESS
2-6
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2.1.1.1 Emission to Air
According to the flow diagram of the direct chlorination process
(Figure 2.3), EDC emissions to air can occur at the following
sources: (a) the chlorinator vent (Stream A of Figure 2.3), (b)
the light-end column vent (Stream B of Figure 2.3), (c) the EDC
distillation column vent (Stream C of Figure 2.3), (d) product
storage tanks (Stream D of Figure 2.3) and (e) miscellaneous
fugitive emissions.
The emission factors of EDC to air from Streams A, B, and C
are, respectively, 1.6 kg, 1.7 kg and 1.7 kg, based on 1.6 kkg of
EDC produced (EPA, 1979a), or 1.0 kg, 1.0 kg and 1.0 kg, based on
1 kkg of EDC produced . The combined emission factor obtained from
Bellamy & Schwartz is 3.0 kg/kkg of EDC produced (EPA, 1979a).
Comparing this emission factor to that of Medley el; al. (1975),
(7.5 kg/kkg), we arrive at a +150% deviation. We also assume that
some emission of EDC to air must exist in this process, therefore,
the lower bound of the uncertainty of the combined emission factor
is estimated at -95%.
t~
a. Emission of EDC to Air From The Chlorinator Vent (Stream A)
A 1.6 kg/1.64 kkg of EDC produced is released uncontrolled to the
atmosphere in the direct chlorination process (EPA, 1979a). According
to Section 2.1.1.1, we assume that the uncertainty of this emission
factor is also +150%, and -95%.
The quantity of EDC emitted uncontrolled to the air from the
.chlorinator vent can be calculated as follows:
(2.94 x 106 kkg) (1.6 x 10~3 kkg/1.64 kkg) = 2.9 x 103 kkg
2.94 x 10 kkg = quantity of EDC produced by the direc ;
where;
106 kkg =
chlorination process
_3
1.6 x 10 kkg/1.64 kkg = emission factor obtained frou EPA,
1979a
3
2.9 x 10 kkg = amount of EDC released uncontrolled to the air
from the chlorinator vent
2-7
-------
If we assume that the uncertainty of the emission factor is
+150% and -95%, and that of the production figure is + 1%, then the
uncertainty of tlie uncontrolled emission quantity ifi +150% and -96%.
The information on the method of emission control of this
source does not exist in the literature.
Assuming that this emission source is equipped with an
incinerator (typical in many processes) which serves as an emission
control device, and also assuming that a 98% control efficiency can
be achieved, then the controlled emission from the chlorinator vent
can be calculated as follows:
(2.9 x 103 kkg) (0.02) = 58 kkg
where;
3
2.9 x 10 kkg = the uncontrolled emission quantity
0.02 = the inefficiency factor nf the incinerator
58 kkg = the controllf-d emissioi quantity from the chlorinator
vent
The uncertainty tif this figure is +530% and -100% because of
the following factors: (a) the uncontrolled emission quantity has
an uncertainty of +150%,, and -96%, and (b) the typical observed range
of the destruction efficie?icy of an incinerator is from 95% to 100%,or
the inefficiency factor range of 0% to 5% (or +150% and -100%).
b. Emission of EDC to Air From The Light-End Column (Vent B)
The estimated emission factor of EDC to air from this source is
1.7 kkg/1.64 kkg of EDC produced (EPA, 1979a). The uncertainty of
this figure is also +150% and -95%, as discussed in Section 2.1.1.1.
The uncontrolled emission of EDC from the light-end column vent
can be calculated by multiplying the quantity of EDC produced via
the direct chlorination process by the obtained emission factor.
In that case,
(2.94 x 106 kkg) (1.7 x 10~3. kkg/1.64 kkg) = 3.0 x 103 kkg
2-8
-------
The uncertainty of this figure is +150% and -96% because of
the uncertainty of the production figure of + 1% and the
uncertainly of the omission factor of +1507, and -95%.
Assuming that this emission source is controlled by using a
scrubber of 90% removal efficiency (typical scrubber efficiency
ranges from 85% to 92%), then £he controlled emission of EDC to
air from the light-end column:,yent can be calculated as follows:
(3.0 x 103 kkg) (0.1) = 3.0 x 1()2 kkg
where:" '
3
3.0 x 10 kkg = uncontrolled emission of EDC from
Vent Bl
0.1 = the inefficiency factor of the scrubber
?
3.0 x 10. kkg = quantity of EDC released from this
source
This figure has an uncertainty of +280% and -97% because of the
uncertainty of the uncontrolled emission (+150%, and -96%), and the
uncertainty of the inefficiency factor of the scrubber (+50% and -20%).
c. Emission of EDC .to Air,From The EDC Distillation Column Vent
(Stream C)=
There is no information available on the emission to the air
from the EDC distillation column vent. We assume that the
emission factor obtained for the light-end column vent (Stream B)
can also be used in calculating the emission of EDC from the EDC
distillation column vent. In that case, the emission factor of
EDC to air from this source is also 1.7 kg/1.64 kkg of EDC
produced. The uncertainty of this figure is +200% and -95%, since
we expect that more EDC can be emitted from this source because in
this column, EDC is drawn out as a head stream.
The uncontrolled quantity of EDC released from the distillation
column vent can then be calculated as follows:
2-9
-------
(2.94 x 106 kkg) (1.7 x 10 3 kkg/1.64 kkg) = 3.0 x 103 kkg
where:
2.94 x 10 kkg = quantity of EDC produced via the direct
chlorination process
1.7 x 10~ kkg/1.64 kkg = emission factor of EDC to air
3
3.0 x 10 kkg = quantity of EDC released from this source
The uncertainty of this figure is +200% and -96% because of
the uncertainty of the production quantity (+ 1%) and the
uncertainty of the emission, factor (+200% and -95%).
Assuming that the emission from this source is also controlled
by a scrubber which has a 90% removal efficiency (+2%, -6%), then
the controlled emission from this source can be calculated as
follows:
(3.0 x 103 kkg) (0.1) = 3.0 x 102 kkg
The associated uncertainty of this figure is +350% and -97%
because of the uncertainty of the uncontrolled emission quantity
(+200%, -96%) and the uncertainty of the inefficiency factor of
the scrubber (+50%, -20%).
d. Total Quantity of EDC Released Directly to the ALr From
Vents A, B and C of Figure 2*3'
The total quantity of EDC released directly to the air from
Vents A, B and C can be calculated by taking the sum of all
uncontrolled emissions from these sources. In that case,
(2.9 x 103 kkg) + (3.0 x 103 kkg) + (3.0 x 103 kkg) =
8.9 x 103 kkg
The uncertainty of this figure is +170% and -96%.
The total controlled quantity of EDC emitted to the air from
these sources can also be calculated as follows:
2-10
-------
(58 kkg) + (3.0 x 102 kkg) + (3.0 x 102 kkg) =
6.6 x 102 kkg
where:
58 kkg = controlled emission from Vent A (+530%, -100%)
3.0 x 102 kkg = controlled emission from Vent B (+280%, -97%)
3.0 x 102 kkg = controlled emission from Vent C (+350%, -97%)
The calculated uncertainty of the above combined controlled
emissions quantity is +330% and -97%.
e. Emission of EDC to Air From Product Storage Tanks (Stream D)
There are two kinds of emission from storage tanks: (a) loss
due to tank breathing and (b) working loss or loss due to tank
cleaning and tank filling.
According to the AP-42 report (EPA, 1977g), emission factors of
EDC to air from "old" fixed roof tanks are 0.012 kg/day-103 liters
because of breathing loss and 0.28 kg/10 liters because of working
loss.
(1) Emission of EDC to Air Because of Tank Breathing
Tank breathing losses are defined by the AP-42 report as the
losses resulting from the vapor expelled from a tank because of the
thermal expansion of existing vapors, vapor expansion as a result
of barometric pressure changes, and/or an increase in the amount of
vapor because of added vaporization in the absence of a liquid-level
change (EPA, 1977g).
To calculate the amount of EDC lost to the air because of tank
breathing, we make the following assumptions:
• EDC is stored in fixed roof tanks, and the tank condition
is old;
• All EDC produced is stored for at least one day before it
is distributed for other uses; and
2-11
-------
• There are 360 days in a working year, based on a typical
three turnovers per year (for cleaning purposes).
Based on the above assumptions, the annual emission factor
because of breathing loss can be calculated by multiplying the
daily emission factor by the number of estimated working days in a
year. In that case,
(0.012 kg/day-10 liters) (360 days/year) = 4.3 kg/year-10 liters
The estimated quantity of EDC lost directly to the air because
of tank breathing can then be calculated as follows:
(4.3 kg/year-103 liters) (2.94 x 106 kkg) (103 liters/1.24 kkg) =
1.0 x 10 kg or 1.0 x 10 kkg/year
where:
3
4.3 kg/year-10 liters = emission factor because of tank
breathing
/ of EDC pi
chlorination process
the reciprocal c
(1.24 kg/1 @20°C)
2.94 x 10 kkg = quantity of EDC produced via the direct
10 liters/1.24 kkg = the reciprocal of EDC density
The uncertainty of this figure is +_50% because of the
uncertainty of the production figure (+10%), the uncertainty of
the emission factor (+20%), and the uncertainty of the number of
fixed roof tanks still in use as EDC storage tanks (+29%).
Assuming that the emission to air due to tank breathing can be
controlled by a refrigerated vapor recovery system which has a 95%
recovery efficiency (typical range of vapor recovery systeir; is 90% to
98% efficient) EPA, 1979g, we can calculate the controlled
emission to air because of tank breathing as follows:
(1.0 x 104 kkg) (0.05) = 5.0 x 102 kkg)
where:
4
1.0 x 10 kkg = uncontrolled emission because of tank
breathing
2-12
-------
0.05 = the inefficiency factor of the recovery system
2
5.0 x 10 kkg = quantity of EDC emitted to the air aJlter
control
The uncertainty of this figure is +200% and -80% as a result
of the following factors: (a) the uncertainty of the uncontrolled
emission quantity is +50%; (b) the uncertainty of the recovery
system efficiency is (+3%, -5%), or the uncertainty of the
percentage lost through the recovery system of +100% and -60%.
(2) Emission of EDC to Air Because of Working Loss
Emission of EDC resulting from handling and tank filling is
called working loss.
According to the AP-42 report (EPA, 1977g), the emission
factor of EDC to air because of tank filling and handling is 0.28
2
kg/10 liters. -Based on essential knowledge of typical handling and
tank filling methods, we can assign an uncertainty value of +_30% to
this emission factor.
The estimated quantity of EDC released uncor trolled to the air
during tank filling and handling can be calculated by multiplying the
volume of EDC produced via the direct chlorination process by the
emission factor obtained from the AP-42 report. In that case,
(0.28 kg/103 liters of EDC throughput) (2.94 x 106 kkg) (103 liters,
1.24 kkg) = 6.(i x 102 kkg
where:
2.94 x 10 kkg = production of EDC via the direct
chlorination process
emiss:
from AP-42
0.28 kg/10 liters throughput = emission factor obtained
3
10 liters/1.24 kkg = the reciprocal of the EDC density
The uncertainty of this figure is +31%, based on a +30%
uncertainty of the emission factor and a +1% uncertainty of the
production quantity.
2-13
-------
Assuming that the emission from this sourr.e can also be
controlled by installing a refrigerated vapor recovery system in
the source, and also assuming that the recovery system has a 95%
(+3%, -5%) efficiency (See Section 2.1.1.1, paragraph e (1)), then
the controlled emission of EDC from this source can be
calculated as follows:
(6.6 x 102 kkg) (0.05) = 33 kkg
The uncertainty of this figure is +160% and -72%, based on a
+31% uncertainty of the uncontrolled emission quantity and the
uncertainty of the percentage lost through the recovery system of
+100% and -60%.
f. Emission to Air From Miscellaneous Fugitive Emission Sources
Sources of fugitive.emissions within the production plant
include process pump, compressors, process valves, and pressure-
relief devices. According to Bellamy and Schwartz (EPA, 1979a),
these fugitive emissions amount to 0.1 kg/1.64 kkg of produced.
We also assign a +150%, --95% uncertainty to the figure for the
same reasons stated in Section 2.1.1.1.
The quantity of EDC emitted to the air because of fugitive
emissions can then be calculated by multiplying the quantity produced
by the direct chlorination process by the emission factors.
Therefore:
(2.94 x 106 kkg) (0.1 kg/1.64 kkg) = 1.8 x 102 kkg
The uncertainty of this figure +_150%, -96%, results from the
uncertainty of the emission factor (+150%, -95%), and a +1%
uncertainty of the production quantity.
2-14
-------
Assuming that 90% (±10%) of the fugitive emissions can be
controlled by regular maintenance procedure, quick response and
repair of leaks, then the contcolled emission of EDC from fugitive
emission sources can be calculated as follows:
(1.8 x 102 kkg) (0.1) = 18 kkg
The uncertainty of this figure.is +340% and -100%, as a result
of the uncertainty of the uncontrolled emission (+150%, -96%) and
the uncertainty of the uncontrolled percentage (+110%, -90%).
2.1.1.2 Emission to Water (Stream E)
We assume that the same percentage of the total emission from
the direct chlorination process given by the ORNL report (EPA, 1979a)
can also be applied in this report. According to the ORNL report,
the percentages of emission to air, land and water are, respectively,
57%, 14%, and 29%. ;
-------
The waterborne emission factor can them be calculated by multi-
plying the ai r omi.ssi.on factor by the ratio of 29% to 57%. In that
case,
(3.0 kg/kkg) (29%/57%) = 1.5 kg/kkg
Then, the uncontrolled waterborne emission discharged by the direct
chlorination process can be calculated as follows:
(2.94 x 106 kkg) (1.5 kg/kkg) = 4.4 x 103 kkg
The uncertainty of this figure, +150% and -96%, results from the un-
certainty of the production quantity (+1%) and the uncertainty of the
emission factor (+150%, -95%).
a. Emission to Air Because of Wastewater Treatment
Due to the high volatility of EDC, we assume that 100% of EDC dis-
charged by the production process to water is re-released to the air
from the wastewater treatment system (particularly during the secondary
treatment phase, which consists of aerated sludge treatment process).
Therefore, the quantity of EDC re-released to the air because of the
wastewater .treatment is 4.4 x 10 kkg, +150%, -96%.
2.1.1.3 Emission to Land (Stream F)
As it was suggested b' Bellamy and Schwartz (EPA, 1979a), the quantity
of EDC released to land as heavy-end waste is estimated at 1.2 kg/1.64 kkg
of product. The uncertainty of this figure is also +150%, -95% (for the
same reason stated in Section 2.1.1.1).
The uncontrolled emission of EDC to land as heavy-end waste can then
be calculated by multiplying the quantity of EDC by the direct chlorina-
tion process by the emission factor. Therefore,
(2.94 x 106 kkg) (1.2 kg/1.64 kkg) = 2.2 x 103 kkg
2-16
-------
The uncertainty of this figure is +150%, -96% because of a +1%
uncertainty of the production figure and +150%, -95% uncertainty of the
emission factor.
a. Emission of Air Because of Incineration of Heavy-End Waste
Most of the EDC production plants incinerate their heavy-end waste.
The typical efficiency of the incinerator is 95%, +2%; therefore, we
assume that 5% of the heavy-end waste escapes intact to the air from the
incinerator. The uncertainty of this percentage is +38%.
The quantity of EDC released to the air as a result of the incinera-
tion of solid waste can be calculated by multiplying the quantity of
EDC discharged as solid waste by 5%. Then,
(2.2 x 103 kkg) (0.05) = 1.1 x 102 kkg
The uncertainty of this figure is +250%, -98% because of the un-
certainty of the uncontrolled heavy-end waste (+150%, and -96%) and the
uncertainty of the undestroyed percentage (+38%).
b. Emission to Land Because of Incineration of Heavy-End Waste
We assume that the amount of EDC remaining in the ash after the
incineration of heavy-end wastes is negligible.
2.1.1.4 Multimedia Environmental Losses
Figure 2.4 shows environmental losses of EDC from the direct chlor-
ination production process.
2.1.2 Releases of EDC Associated With the Oxychlor:.nation Process
The remainder of the EDC manufactured industrially, 2.05 million kkg
in 1977 (EPA, 1979a) , was produced by the oxychlorination of ethylene
with hydrogen chloride and oxygfn in the presence of a catalyst (probably
CuCl_). All EDC produced via. tl>is process is an intermediate in the pro-
duction of vinyl chloride moncmer (SRI, 1975, EPA, 1978a) . The main
2-17
-------
AIR (uncontrolled)
AIR (controlled)
Process Vents
8.9 x 103 kkg (+ 170%, -96%)
Storage
1.1 x KT kkg (+ 44%)
Fugitive Emissions
1.8 x 102 kkg (+ 150%, -96%)
CONSUMPTION
2,94 x 10 kkg (+
N5
•+—'
00
AIR
1.1 x 10 kkg (+ 250%, -98%)
Production of EDC
from the direct chlorina-
tion process
2.97 x 106 kkg (+ U)
LAND
2.2 x 10 kkg (+ 150X, -961)
• Process Vents
6.6 x 102 kkg (+ 330X, -97%)
• Storage
5.3 x 102 kkg (+ 200%. -99%)
• Fugitive emissions
18 kkg (+ 340%. -100%)
WATER
4.4 x 10 kkg (+ 150%. -96%)
^
Uastevater
Treatment
System
^ AIR
4.4 x 103 kkg
(+ 150X. -96Z)
FIGURE 2.4 ENVIRONMENTAL RELEASES OF EDC FROM THE DIRECT CHLORINATION PROCESS
-------
reaction involved in this process is as follows:
Catalyst
CH = CH + 2HC1 + %0
A detailed description of this production process is given in Ap-
pendix B. Figure 2.5 is a simplified flow diagram of the oxychlorina-
tion process.
2.1.2.1 Emission to Air
According to the flow diagram of the oxychlorination process (Figure
2-5), EDC emissions to air can occur at the following sources: (a) the
absorber vent (Stream A), (b) the EDC stripper vent (Stream B), (c) the
light-end column vent (Stream C), (d) the EDC distillation column vent
(Stream D), (e) product storage t.inks (Stream E), and (f) miscellaneous
fugitive emissions. The obtained emission factors of Streams A, B, C,
and D are, respectively, 1.7 kg, 4.5 kg, 1.7 kg and 1.7 kg, based on 1.64
kkg of EDC produced (EPA, 1979a). The combined emission factor of these
sources amounts to 9.6 kg/1.64 kkg of EDC produced (or 5.9 kg/kkg). Com-
paring this emission factor to that of ORNL (EPA, 1979a) (11.4 kg/kkg),
we arrive at a +93% upper-bound deviation. We also expect that some
emission of EDC to air must exist in the oxychlorination process; there-
fore, the lower bound of the uncertainty of the emission factor must be
greater than -100%. Thus for the simplicity of .the calculation, we as-
sume that an uncertainty of +95% can be assigned to the combined emission
factor.
a. Emission of EDC to Air from the Absorber Vent (Stream A)
According to Bellamy and Schwartz (1975), a 1.7 kg/kkg of EDC pro-
duced is released uncontrolled to the air in the oxychlorination process
(EPA, 1979a). As it is stated in the above section, the same bounds of
uncertainty can also be assigned to this emission factor (+_95%).
The uncontrolled quantity of EDC emitted to the air can be calculated
as follows:
(2.05 x 106 kkg) (1.7 x 10~3 kkg/1.64 kkg) = 2.1 x 103 kkg
2-19
-------
t©
°T
OR AIR J
tHYLKNE
— 1
(
CAUSTIC
SODA
HC1
— »
"
Kr.ACl'OF.
— -v
*" t£.
U
g
(_
•
l/J
CAUSTIC
^ —
->
— *-SPEN'T
(
1
fSr.o
i
icc.v:-
. '1 KR
o
1
h
"~,~h
i
WASTE«ATER ,
^
CAUSTIC
CRUDE
'SURGE
TA.VK
D
3
j
<
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O
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^
o
^-_^_,
•«
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I U
Y
Fugitive Emission
•—
^
f "] 1 ^-^
_
o «
1= 5
t:
-------
Where:
2.05 x 10 kkg = quantity of EDC produced by the oxychlorina-
tion process
1.7 kg/1.64 kkg = emission factor obtained from EPA, 1979a.
3
2.1 x 10 kkg = uncontrolled emission of EDC from the absorber
vent
The uncertainty of this figure is estimated at +96%, based on the un-
certainty of the production quantity (+1%) and the uncertainty of the
emission factor (+95%).
Assuming that this emission source is controlled by a scrubber of 90%
efficiency (+2%, -6%) (see Section 2.3 .l.'l.b.c), then the controlled emis-
sion from the absorber vent can be calculated by multiplying the uncon-
trolled emission quantity by the percentage of gas escaped intact from the
scru bber.
Therefore:
(2.1 x 103 kkg) (0.1) = 2.1 x 102 kkg
The uncertainty of this figure is +190% and -97% because of the un-
certainty of the uncontrolled emission quantity (+_96%) and the uncertainty
of the inefficiency factor of the scrubber (+50%, -20%).
b. Emission of EDC to Air from the EDC Stripper Vent (Stream B)
The estimated uncontrolled emission factor is 4.5 kg/1.64 kkg of EDC
produced (EPA, 1979a). The uncertainty of this figure is also +95% (see
Section 2.1.2.1).
The uncontrolled emission of EDC from the EDC stripper vent can be
calculated as follows:
(2.05 x 106 kkg) (4.5 x 10~3 kkg/1.64 kkg) = 5.6 x 103 kkg
2-21
-------
where:
2.05 x 10 kkg = quantity pf EDC produced via the oxychlorination
process
-3
4.5 x 10 kkg/1.64 kkg = emission factor obtained from (EPA, 1979a)
and,
5.6 x 10 kkg = quantity of EDC released uncontrolled to the air
from the EDC stripper vent
The uncertainty of this figure is jf96% because of a +1% uncertainty
of the production figure and a +95% uncertainty of the emission factor.
We also assume that there is an incinerator of 98% (+2%, -4%) ef-
ficiency used as emission control equipment on this source; then the con-
trolled emission of EDC to air from the EDC stripper vent can be.calculated
by multiplying the uncontrolled emission quantity by the inefficiency
factor of the incinerator. In that case,
(5.6 x 103 kkg) (0.02) = 1.1 x 102 kkg
The uncertainty of this figure is calculated at +500%, and -100%,
based on the following factors: (a) the uncertainty of the uncontrolled
emission quantity is +96%, (b) the uncertainty of the inefficiency
factor of the incinerator is +200% and -100%.
c. Emission of EDC to Air from the Light-End Column Vent (Stream C)
There is no information available on the emission of EDC to the air
from the light-end column vent. Assuming that the emission factor ob-
tained from the light-end column vent of the direct chlorinatnon process
can also be applied for this process, then the emission factor of EDC to
air from this source is estimated at 1.7 kg/1.64 kkg of EDC produced (see
Section 2.1.1.1, paragraph b). The assigned uncertainty value of this
figure is also +95% (see Section 2.1.2.1 for reasons).
The uncontrolled emission of EDC from the light-end column can be
estimated by multiplying the quantity of EDC produced via the oxychlori-
2-22
-------
nation process by the emission factor obtained. Therefore,
(2.05 x 103 kkg) (1.7 x 10~3 kkg/1.64 kkg) = 2.1 x 103 kkg
The uncertainty of this fijure is 96%. The rationale for this un-
certainty is the same as stated in Section 2.1.2.1, paragraph a.
Assuming that there exists an emission control device on this source
such as a scrubber of 90% (+2%, -6%) efficiency, then the controlled
emission from this source can be calculated as follows:
(2.1 x 103 kkg) (0.1) = 2.1 x 102 kkg
where:
3
2.1 x 10 kkg = uncontrolled emission of EDC to air from
the light-end column vent
0.1 = the inefficiency factor of the scrubber
2
2.1 x 10 kkg = quantity of EDC released after control from
this source
The uncertainty of this figure is also +190%, and -97% because of
the uncertainty of the uncontrolled emission quantity (+_96%) and the un-
certainty of the inefficiency factor of the scrubber (+50%, -20%).
d. Emission of EDC to Air from the EDC Distillation Column Vent (Stream D)
The information on the emission of EDC from this source does not
exist in the literature. We assume that the emission factor obtained for
the EDC distillation column vent in the direct chlorination process is
also applicable for the oxychlorination process; thus the estimated emis-
sion factor from this source is 1.7 kg/1.64 kkg (See Section 2.1.1.1,
paragraph c). The uncertainty of this figure is also +_95%.
The uncontrolled emission of EDC to the air from the EDC distillat ion
column vent can then be calculated by multiplying the quantity of EDC
produced by the oxychlorination process by the emission factor. Therefore:
(2.05 x 106 kkg) (1.7 x 10~3 kkg/1.64 kkg) = 2.1 x 103 kkg
2-23
-------
The uncertainty of this figure is +95%. This value was obtained
.based on an uncertainty of +1% of the production quantity and an uncer-
tainty of +95% of the emission factor.
We also assume that this emission source is controlled by a scrubber
of 90% (+2% and -6%) efficiency; then the controlled emission from this
source can be calculated as follows:
(2.1 x 103 kkg) (0.1) = 2.1 x 102 kkg
where:
3
2.1 x 10 kkg = uncontrolled emission of EDC to air
0.1 = the inefficiency factor of the scrubber
2
2.1 x 10 kkg = quantity of EDC released after control from
this source
The uncertainty of this figure is also +190% and -9^% (see reasons
in Section Z.1.2.1, paragraph e).
e. Total Emission of EDC i:o Air from Streams A, B, C and D of Figure 2.5
The total uncontrolled quantity of EDC emitted to the air from
Streams A, B, C and D can be calculated by taking the sum of the emis-
sions from these streams. Therefore:
(2.1 x 103 kkg),+ (5.6 x 103 kkg) + (2.1 x 103 kkg) + (2.1 x 103 kkg)
= 1.2 x 10 kkg
The uncertainty of this figure is +96%.
The total controlled quantity of EDC released to the air from these
sources can also be calculated as follows:
(2.1 x 102 kkg) + (1.1 x 102 kkg) + (2.1 x 102 kkg) + (2.1 x 10' kkg)
= 7.4 x 10 kkg
2-24
-------
where:
2
2.1 x 10 kkg = the controlled emission of EDC to air from
Stream A (+190%, -97%)
le controlled emission ol
Stream B (+500%, -100%)
le controlled emission oj
Stream C (+190%, -97%)
2 • '•
1.1 x 10 kkg = the controlled emission of EDC to air from
2
2.1 x 10 kkg = the controlled emission of EDC to air from
2
2.1 x 10 kkg = the controlled emission of EDC to air from
Stream D (+190%, -97%)
The resulting uncertainty of the combined control quantity is +240%
and -97%.
f. Emission of EDC to Air from Product Storage Tanks
As is pointed out in Section 2.1.1.1, paragraph e, there are two
kinds of loss from product storage tanks: (a) tank breathing loss and
(b) working loss.
We assume that the same emission factors obtained in Section 2.1.1.1,
paragraph e are applicable to the calculation of EDC emission from storage
3 3
tanks in this process: (a) 0.012 kg/day-10 liters or 4.3 kg/year-10
3
liters for tank breathing loss, and (b) 0.28 kg/10 liters for working
loss (EPA, 1977g).
(1) Emission of EDC to Air from Tank Breathing Less
The quantity of EDC released uncontrolled as a result of breathing
loss can be calculated by multiplying the quantity of EDC produced by the
oxychlorination process by the emission factor.
In that case,
(2.05 x 106 kkg) (4.3 x 10~3 kkg/yr-103 liters) (103 liters/1.24 kkg)
= 7.1 x 103 kkg
2-25
-------
where:
2.05 x 10 kkg = quantity of EDC produced via the oxy-
chlorination process
-33
4.3 x 10 kkg/yr-10 liters = emission factor
o
10 liters/1.24 kkg = the reciprocal of EDC density
(1.24 kg/1 <320°C)
7.1 x 10 kkg = quantity of EDC released uncontrolled
to the air from this source
i
The uncertainty of this figure is +50% because of the follow-
ing factors: (a) the uncertainty of the production figure is 1%;
(b) the uncertainty of the emission factor is +20%; and (c) the un-
certainty of the number of fixed roof tanks still in use by the in-
dustry is +29%.
Assuming that the emission to air because of tank breathing can
be controlled by a refrigerated vapor recovery system which has a
95% (+3%, -5%) recovery efficiency (EPA, 1977g), the controlled
emission can then be calculated as follows:
(7.1 x 103 kkg) (0.05) = 3.6 x 102 kkg
where: '
3
7.1 x 10 kkg = uncontrolled EDC emission because of tank
breathing
0.05 = the inefficiency factor of the vapor recovery
system
2
3.6 x 10 kkg = quantity of EDC released after control
The uncertainty of this figure is +200% and -80% [see Section
2.1.1.1, paragraph e (1)].
2-26
-------
(2) Emission of EDC to Air Because of Working Loss
According to Section 2.1.2.1, paragraph f, the emission factor be-
cause of working loss is 0.28 kg/10 liters. Using this emission factor,
we can then calculate the release of EDC to the air as a result of tank
filling. In this case:
(2.05 x 106 kkg) (0.28 kg/103 liters) (103 liters/1.24 kkg)
= 4.6 x 102 kkg
The uncertainty of this figure is +31% because of the uncertainty of
the emission factor (+30%) [ see Section 2.1.1.1, paragraph e (2) ] and the
uncertainty of the production quantity (+1%).
We also assume that the emission from this source can be controlled
by a vapor recovery system of 95% efficiency (+3%, -5%) [ see Section
2.1.1.1, paragraph e (1)1; then the controlled emission of EDC to the air
from this source can be calculated as follows:
(4.6 x 102 kkg) (0.05) =2.3 kkg
The uncertainty of this figure is also +160% and -72% [ see Section
2.1.1.1, paragraph e (2)].
g. Emission of EDC to Air from Miscellaneous Sources
As is mentioned in Section 2.1.1.1, paragraph f, the emission factor
of EDC to air from fugitive emission sources is 0.1 kg/1.64 kkg of EDC
produced (see Section 2.1.1.1, paragraph f). The uncontrolled emission
of EDC to air from these miscellaneous sources can then be calculated
as follows:
(2.05 x 106 kkg) (0.1 kg/1.64 kkg) = 1.3 x 102 kkg
The uncertainty of this figure is +96% because of the following
factors: (a) the uncertainty of the production quantity is +1%; (b)
the uncertainty of the emission factor is +95% (see Section 2.1.2.1).
2-27
-------
Assuming that 90% (+_10%) of the fugitive emissions can be controlled
by proper maintenance procedures, then the controlled emission from these
sources can be calculated as follows:
(1,3.x 102 kkg) (0.1) = 13 kkg
where:
2
1.3 x 10 kkg = the uncontrolled emission of EDC from fugutive
sources
0.1 = the inefficiency factor
13 kkg = the controlled emission of EDC from this sourr.e
The uncertainty of this figure is +310% and -100% because of the un-
certainty of the uncontrolled emission (+96?) and the uncertainty of the
inefficiency factor (+110%, -90%).
2.1.2.2 Emission to Water (Stream G)
The information on the quantity of EDC emitted from this stream does
not exist in the Hedley report (Medley et al., 1975); therefore, by as-
suming the same percentage of the total emission from the oxychLorination
process given by ORNL (EPA, 1979a), the emission factor of EDC to water
can be calculated as follows:
[5.9 kg/kkg (to air)] [24.5% (to water/61% (to air)] = '2.4 kg/kkg
where:
5.9 kg/kkg = emission factor to air obtained in this report (see
Section 2.1.2.1)
24.5%/61% = the ratio of the percentage of the total emission to
water and the percentage of the total emission to
air (EPA, 1979a)
2.4 kg/kkg = emission factor to water
The uncontrolled emission of EDC to water can be calculated by multi-
plying the quantity of EDC produced via the oxychlorination process by
2-28
-------
the emission factor. In that case,
(2.05 x 106 kkg') (2.4 kg/kkg) = 4.9 x 103 kkg
The uncertainty of this figure is +96% because of the uncertainty
of the production quantity (+1%) and the uncertainty of the emission
factor (+95%).
a. Emissions to Air Because of Wastewater Treatment
As is mentioned in Section 2.1.1.2, paragraph a, the quantity of EDC
emitted to water is all re-released to the air as a result of evaporation
from the a.erated sludge treatment system. Thus we assume tliat this
3
quantity amounts to 4.9 x 10 kkg, +96%.
2.1.2.3 Emissions to Land
According to Figure 2.5, emissions of EDC to land can occur in the
following sources: (a) the heavy-end waste stream from the light-end
column (Stream H of Figure 2.5), and (b) the heavy-end waste stream from
the EDC distillation column (Stream I of Figure 2.5).
According to Bellamy & Schwartz (1975), the emission factor of EDC
released in the heavy-end waste stream from the EDC distillation column
(Stream I) is estimated at 1.2 kg/1.64 kkg of EDC produced (or 0.73 kg/kkg
of EDC) (EPA, 1979a). There is no information on the emission factor of
EDC released in Stream H. We then assume that the emission factor from
Stream H is also 1.2 kg/1.64 kkg of EDC. This assumption should be veri-
fied in later studies. The combined emission factor to land resulting
from these two sources can be calculated by taking the sum of the two
emission factors. Therefo :e:
(1.2 kg/1.64 kkg) (2) = 2.4 kg/1.64 kkg or 1.5 kg/kkg
Comparing this figure to that of ORNL (EPA, 1979a) (2.75 kg/kkg),
we arrive at a +83% deviation. Assuming that the lower bound of uncer-
tainty is -95% because some emissions of EDC must exist in these sources,
then the uncertainty of the combined emission factor is +83%, and -95%.
2-29
-------
Based on the above assumptions, the total quantity of EDC emitted
directly to land in heavy-end waste streams can be calculated by multi-
plying the quantity of EDC produced via the oxychlorination process by
the combined emission factor. In that case:
(2.05 x 106 kkg) (1.5 kg/kkg) = 3.1 x 103 kkg
The uncertainty of this uncontrolled emission quantity is +84%, -96%,
as a result of the following factors: (a) the uncertainty of the emission
factor is +83% and -95%; and (b) the uncertainty of the production quantity
is +1%.
a. Emission to Air Because of Incineration of Heavy-End Waste Streams
We assume that all heavy-end wastes discharged by the industry are
incinerated, and that the incinerator can achieve a 95% destruction ef-
ficiency (incinerator efficiency typically ranges from 93% to 97%); there-
fore, 5% of the heavy-end wastes can escape intact to the air. The uncer-
tainty of the inefficiency factor of the incinerator is estimated at +38%.
The quantity of EDC released uncontrolled to the air from incinera-
tion of heavy-end wastes can then be calculated as follows:
(3.1 x 103 kkg) (0.05) = 1.6 x 1Q2 kkg
where:
3.1 x 10 kkg = quantity of EDC discharged in heavy-end wastes
0.05 = the inefficiency factor of the incinerator
2
1.6 x 10 kkg = the quantity of EDC released to air after control
The uncertainty of this figure is +150%, -98%, because of a +38%
uncertainty of the inefficiency factor of the incinerator and a +84%
and -96% uncertainty of the quantity of EDC present in heavy-end wastes.
2-30
-------
b. Emission to Land After Incineration of Heavy-End Waste
We assume that the amount of EDC remaining in the ash after the in-
cineration phase is negligible.
2.1.2.4 Multimedia Environmental Losses
Figure 2.6 shows environmental losses of EDC in the oxychlorination
process.
2.2 ENVIRONMENTAL RELEASES OF EDC ASSOCIATED WITH INDIRECT PRODUCTION
PROCESSES
Indirect sources of EDC production include all other production of
EDC, even that which occurs inadvertently. There was no indication in
the literature that any natural sources of EDC exist. The sources
identified are:
• chlorination of public water supplies
• chlorination of wastewater
• incineration of chlorinated organics
• other industrial manufacturing processes
• laboratory preparations
• releases from stockpiles
2.2.1 Releases of EDC Associated With the Chlorination of Public Water
Supplies
In the chlorination of water at water treatment facilities, small
quantities of EDC are found to be produced. It is hypothesized the
chlorine reacts with organic impurities in the wattir to produce EDC
(Symons et al., 1975). In 1975 and 1976, the USEPA conducted the Na-
tional Organics Reconnaissance Survey (NORS) and the National Organic
Monitoring Survey (NOMS) to examine raw and finished water samples for
the presence of halogenated organic compounds in drinking water. The re-
sults of NORS indicated that EDC was not found in high concentr itions, or
even frequently, in public water supplies. The highest concent ration
in raw water was 3 jig/liter, while that in finished water was 6/ig/liter.
2-31
-------
AIR (uncontrolled)
AIR (controlled)
Process Vents
1.2 x 10 kkg (+ 962)
Product Storage Tanks
7.6 x 10 kkg (+ 44Z)
Fugitive-Emissions
1.3 x 10 kkg (+ 967.)
Process Vents
7.4 x 10 kkg (+ 2402, -977.)
Storage Tanks
3.8 x 10 kkg (+ 2002, -80*)
Fugitive Emissions
13 kkg (+ 310%, -1002)
NJ
OJ
CONSUMPTION ^-
2.05 x 10 kkg (+ 1Z)
AIR
1.6 x 10 kkg
(+ 1502. -982)
Production of EDC from
the Oxychlorination
Process
2.08 x 106 kkg (+ 1Z)
LAND
Incinerator
WATER
4.9 x 1Q kkg (+ 962)
—
3.1 x 10 kkg (+ 84Z. -962)
AIR
4.9 x 103
(+ 962)
kkg
FIGURE 2.6 ENVIRONMENTAL RELEASES OF EDC FROM THE OXYCHLORINATION PROCESS
-------
(Symons et al., 1975). The NOMS survey indicated that a median value
of 2 ^ig/liter was found in the potable water supplies (Mello, 1978).
To calculate the quantity of EDC produced as a result of the chlori-
nation of water, we make the following assumptions:
• Quantity in finished water minus quantity in raw water equals
the quantity of EDC as a result of the chlorination of public
water supplies
• U.S. population in 1977 approximated 225 x 10 persons (+5%)
• Water use is on the average of 100 gal./person/day in U.S. 0+20%)
(Hanmer, 1975).
Applying all the assumptions, an estimate of the quantity of EDC in
chlorinated public water supplies can be made. First, the total water
use per year is calculated by multiplying the total persons by the total
gallons used per day per person by total days per year:
(225 x 10 persons) x (100 gal./person/day) x (365 days/year)
= 8.2 x 1012 gal./year
The uncertainty of this figure is +25%, based on the following
factors: (a) the uncertainty of the U.S. population is +5%, and (b)
the uncertainty of the daily water use per capita is +_20%.
As presented in Table C-l of Appendix C, the difference between
the quantity of EDC in raw water and that in finished water averages
to 0.07 ^ig/liter (+100%). Using this concentration, we can then cal-
culate the average quantity of EDC produced as a result of chlorina-
tion of public water supplies by multiplying this concentration by the
total quantity of water used per year:
(0.07 jug/liter) (8.2 x 1012 gal./year) (3.781 liter/gal.)
12
= 2.2 x 10 jag/year or 2.2 kkg/year
The uncertainty of this figure is +150% and -100% because of the
uncertainty of the obtained concentration (+JLOO%). and the uncertainty
of the total quantity of water used per year (+25%).
2-33
-------
2.2.2 Releases of EDC Associated With the Chlorination of Industrial
Wastewaters
Documentation of the inadvertent production of EDC as a result of
the chlorination of wastewater was not found. However, since EDC is
produced in the chlorination of public water supplies, it is reasonable
to assume that EDC is also produced as chlorine reacts with the organic
constituents of wastewater during the chlorination of industrial waste-
water. The following assumptions must be made before calculation of
< ••
the production of EDC: r.
• Industrial wastewater discharge is (average) twice the amount
of water used per capita per year (Hammer, 1975)
12
• Residential water use in 1977 is estimated at 8.2 x 10 gal./year
(+25%) (see Section 2.2.1)
• The highest concentration found in the NORS survey (3 jag/1) is
the typical concentration of EDC formed after the chlorination
of industrial wastewater (since industrial wastewater probably
contains a higher quantity of substrates than the municipal
water supplies).
The quantity of EDC released to the water as a result of the chlori-
nation of wastewater can be calculated by multiplying the concentration
of EDC produced in wastewater by the total amount of chlorinated waste-
water in the U.S.
(3.*g/l) x (kkg/1012 jig) x (8.2 x 1012 gal./year x (2) x (3.781 1/gal.)
2
= 1.9 x 10 kkg/year
The uncertainty of this figure is +150% and -100% due to the fol-
lowing factors: (a) the uncertainty of industrial water use is +25%
and (b) the uncertainty of the concentration of EDC formed as a result
of chlorination of industrial wastewater is +100%.
2.2.3 Releases of EDC Associated With the Incineration of Chlorinated
Organics
EDC gas may be formed during the incineration of chlorinated organics
(Derby and Freedman, 1974). The EDC may be present as a contaminant Ln
the material or may be "manufactured" upon incineration. To estimate the
quantity of EDC released during incineration, we make the following
2-34
-------
assumptions and conditions:
• Chlorinated organics may be incinerated as wastes at industrial
facilities
• Production of chlorinated .organic compounds in 1977 was
1.03 x 10? kkg (USITC, 1978)
• 0.5% of production (as wastes) are incinerated
• 1.5 ppm of that quantity incinerated is released as EDC.
Therefore, the amount of EDC released is calculated by multiplying
the total quantity of chlorinated organic compounds produced in 1977
(1.03 x 10 kkg) by the percentage incinerated (0.5%) and by the concen-
tration of EDC in the off-gases (1-5 ppm}.
At 1 ppm:
(1.03 x 10 kkg chlorinated organict) x (0.005)
x (1 kkg EDC/10 kkg chlorinated organics) = 0.05 kkg EDC
At 5 ppm:
(1.03 x 10 kkg chlorinated organics) x (0.005)
x (5 kkg EDC/10 kkg chlorinated organics) =0.3 kkg EDC
In addition, chlorinated organics may be incinerated as a component
of municipal solid wastes. To estimate :his quantity, we make the fol-
lowing assumptions and conditions:
• Approximately 120 million kkg of municipal solid waste (MSW) is
produced annually in the U.S. (U.S. EPA, 1977f). (+10%)
• Approximately 1% of the total quantity of MSW is incinerated (+20%)
• Approximately 5% of the MSW is chlorinated organic waste (in-
cluding plastics)
• 1-5 ppm of the chlorinated organic waste incinerated is released
as EDC (EPA, 1977f) (+40%).
Therefore, by multiplying the total quantity of MSW (120 x 10 kkg)
by the percentage incinerated (1%), by the component, which is chlori-
nated organics (5%), and by the concentration of EDC in the off-gases
(1-5 ppm), the amount of EDC released is calculated.
2-35
-------
At 1 ppm:
I
=0.06 kkg EDC
(120 x 106 kkg MSW) x (0.01) x (0.05) x (1 kkg EDC/106 kkg MSW)
At 5 ppm:
(120 x 106 kkg MSW) x (0.01) x (0.05) x (5 kkg EDC/106 kkg MSW)
= 0.3 kkg EDC
Adding the amount of EDC released from industrial incineration to
the EDC released from the incineration, the total EDC released was be-
tween 0.1 kkg and 0.6 kkg in 1977.
The above figures have the uncertainty of +70% because of the fol-
lowing factors: (a) the uncertainty of: the quantity of chlorinated or-
ganics in MSW is +40%, (b) the uncertainty of the amount of MSW incin-
erated per year is +20%, and (c) the uncertainty of the quantity of MSW
released per year is +10%.
2.2.4 Other Possible Inadvertent Sources of EDC
Possible pathways for indirect production of EDC include
biological degradation, photochemical degradation and miscel-
laneous chemical reactions in rivers, soils, landfills, and the atmos-
phere.
The most likely source of EDC formation would be the conversion of
a number of EDC-related chemicals in the atmosphere. These chemicals
would include perchloroethylene, trichloroethylene, vinylidene chloride,
methyl chloroform, and vinyl chloride. A variety of reaction mechanisms
such as photo-oxidation, ozone attack, hydroxyl substitution and irradia-
tion could produce EDC from the compounds.
Other read ions in the atmosphe1e that ni;iy form EDC include chlorL-
nation of eth.-i.ne; however, chloride -adicals in the atmosphere are so
rare that negligible quantities of E>C would be expected to form.
2-36
-------
Vinylidene chloride (CH_ = CC1_) emissions to the atmosphere during
manufacture or subsequent polymerization are reported to react under cer-
tain conditions to form peroxide and epoxide compounds which tend to de-
compose spontaneously to form HC1, phosgene, various oxygenated organic
chlorides and EDC (USEPA, 1977c). It is estimated in this report that
total EDC emissions in 1977 from all sources amounted to approximately
600 kkg, all of which entered the atmosphere. Assuming a maximum con-
centration of atmospheric EDC reconversion at 1 ppm, indirect EDC pro-
duction from EDC emissions in 1977 is calculated:
(1 ppm EDC) x (.99) x (600 kkg EDC) = 5 x 10~4 kkg
The uncertainty of this figure is +200% and -100% because of the
very low possibility of occurrence of this kind of reaction.
EDC formation by biological degradation of EDC precursors is also
estimated to be slight. This is a result of the high volatility of these
EDC precursors.
2.2.5 Releases of EDC Associated With Other Manufacturing Processes
Another source of EDC release is chemical reactions which do not
involve EDC as a starting material or an end product but which can pro-
duce EDC as a by-product. A list of possible reactions which can form
EDC is presented below:
• Chlorination of methane to form CC1, (carbon tetrachloride)
Chlorination of ethane to form CC1, (carbon tetrachloride)
Chlorination of ethylene to form CH-CH Cl (ethyl chloride) in
the presence of Cu, Fe, Sb and Ca chlorides
• Chlorination of ethanol to form CH_CH.C1 (ethyl chloride)
• Chlorination of methane to produce methylene chloride (CH_C1_)
• Chlorination of acetylene in the production of perchloroethylene
• Chlorination of acetylene in the production of trichloroethylene
• Chlorination of 1,1-dichloroethane to produce 1,1,1-trichloro-
ethane
• Catalytic addition of HC1 to 1,1-dichloroethylene to produce
1,1,1-trichloroethane
• Chlorohydrin processes
2-37
-------
• Production of allyl chlorides from propene and Cl_
• Production of acid chlorides, especially chloroacetyl chloride
from carboxylic acids and thionyl chloride
• Chlorination of 1,2-dibromopropane to yield 1,2-dibromochloro-
proparie.
It can be estimated using USITC data that a total of 1.5 million kkg
of these other chemicals are produced in the United States. Table 2-2
presents the production data for these chemicals that are related to the
production of EDC as a by-product.
The yield of EDC in the above reactions is expected to be very
small; a crude estimate would quantify EDC by-product production be-
tween 0.5 and 100 ppm (Dow, 1979). Based on these estimates of yield
and production figures, the estimated values for the total amount of
EDC released as a'by-product is shown in Table 2.2.
2.2.6 Releases of EDC Associated With Laboratory Use
In industrial research laboratories, unidentified quantities of
EDC are produced as part of ongoing R&D efforts. In this practice, there
is potential for wastewater emissions routed to municipal wastewater treat-
ment facilities and air emissions from laboratory hood vents. This is
an area for which no data currently exists.
2.3 STOCKPILES
The quantity of EDC that is stockpiled for future use us estimated
to be negligible, since there was no data which indicated otherwise.
Based upon the available information, no appreciable quantities of EDC
are stockpiled for more than three days at a time, whereupon the chemical
undergoes further processing. Information on stockpiles of consumer
products containing EDC is contained in Section 3.0, Environmental Re-
leases During the Production and Use of Products Made from EDC. Emis-
sions of EDC from stockpiles stored are discussed in Sections 2.1.1
and 2.1.2.
2-38
-------
TABLE 2-2
SUMMARY OF RELEASES OF EDC FROM PRODUCTION PROCESSES "WHICH DO NOT. INVOLVE EDC AS A STARTING
MATERIAL OR AN END PRODUCT
CHEKICAL
TOTAL PRO-
DUCTION IN19770CKG)
ESTIMATED QUANTITY PRODUCEDc
WITH EDC AS BY-PRODUCT (KKG)
ESTIMATED RANGE OF
EDC RELEASE (KKG)
at 0.5 PPM at 100 PP»!
NJ
U)
VO
Carbon Tetrachloride
Ethyl Chloride
Methylene Chloride
Perchlorbethylene
Trichloroethylene
Methyl Chloroform
Others
3
2
2
2
1
2
1
.7xl058
.8 x 105
.2X10^
.8 x 105
.4 x 105
.9 x 105
.0 x 10*
2
2
2
8
13
2
1
.8
.8
.2
.2
.6
.7
.0
x 10
x 10
x 10
x 10
x 10
x 10
x 10
5
5
5
3
3
3
4
0.
P.
0.
0.
0.
0.
0.
1
1
1
004
003
001
005
20
20
20
0.
0.
0.
1.
8
6
2
0
TOTAL
1.6 x 10
8.1 x 10J
0.3
63
a) Sources: USITC, 1978
li) Based upon knowledge of production processes
-------
2.4 IMPORTS
According to the U.S. Department of Commerce statistics, no EDC
has been imported to the United States in the past five years. (U.S.
Department of Commerce, 1977).
2-40
-------
3.0 ENVIRONMENTAL RELEASES ASSOCIATED WITH THE
USE OF I5DC
Of the 4.99 million kkg of EDC produced in he United States in
1977, 4.81 million kkg was actually used. The re laining 0.18 million kkg
(3%) was exported for use outside the United States (U.S. Department: of
Commerce, 1977).
The uses of EDC are described in this report in two categories:
major uses and minor uses. The major uses account for 99.9% of the
annual production.
3.1 RELEASES ASSOCIATED WITH THE MAJOR USES OF EDC
Of the 4.99 million kkg of EDC produced and used in the United
States in 1977, 4.81 million kkg (97%) was used as an intermediate in
the production of other organic chemicals. These chemicals are: vinyl
chloride monomer (85% ), mechyl chloroform (4.6%), ethyleneamines (3.1%),
perchloroethylene (2.5%), trichloroethylene (2%), and vinylidene
chloride (1%). Two percent of this EDC was used as a gasoline additive
wholly as a lead scavenger. These percentages were determined from data
supplied by the USITC. According to the Chemical Economics Handbook
(SRI, 1975), annual growth rates for production of these chemicals has
been estimated at 9% for vinyl chloride, 6% for perchloroethylene,
9% for methyl chloroform, 7% for ethyleneamines, 7% for vinylidene
chloride and 7% for all others.
3.1.1 Releases of EDC Associated With the Manufacture and Use of
Vinyl Chloride Monomer
In 1977, vinyl chloride was produced by the following companies:
Allied Chemical, B.F. Goodrich, Borden, Continental Oil, Dow, Monochem,
PPG, Stauffer, Ethyl, and Uniroyal. Most of these production plants
are located in the Gulf Coast area, mainly in Texas and Louisiana
3-1
-------
(USITQ, 1978). Figure 3.1 shows the locations of vinyl chloride
production plants in the United States.
The total production of vinyl chloride reported in 1977 was
2.72 million kkg (USITC, 1978); of that, 91% (or 2.48 million kkg)
was produced by the EDC process (EPA, 1978) . This figure is based
only on the amount reported by the manufacturers. The uncertainty of
this number is - 1%.
Vinyl chloride monomer (VCM) is produced by the dehydrochlorina
tion of EDC at high-temperature conditions and in the presence of a
charcoal catalyst. The principal reaction in this process is:
C1CH0CH0C1 - »• CH0 = CHC1 + HC1
2. i catalyst L
More information about this process is shown in the appendix. The
overall yield of vinyl chloride in this process is from 96% to 98%
(Lowenheim, Moran, 1975). Figure 3.2 shows a typical vinyl chloride
production process via EDC.
As was mentioned above, the total production of vinyl chloride via
the EDC process was estimated at 2.48 million kkg in 1977. Assuming that
this process yields only 97% production (EPA, 1978c) , the quantity of
EDC needed to produce vinyl chloride in 1977 is calculated as follows:
quantity of VCM reciprocal of molecular
from EDC production x weight of VCM
x reciprocal rate of conversion molecular weight
from EDC to VCM x of EDC
_ amount of EDC necessary to produce quantity
of VCM reported
6 - kkm°le VCM 1 kkmole EDC
(2.48 x 10 kkg VCM) x (- m°e VCM 1 kkmole EDC
V.2.45 kkg VCM; x V0.97 kkmole VCM'
EDO
3-2
-------
Location
Annual Capacity.kkg Percent
Baton Rouge, La.
Celsmar, La
136.200
136,200
4.3
4.3
(1)Allied Chem. Corp.
Indust. Chema. Div.
(2)Borden Inc.*
. Borden Chert. Div.
Petrochems.
(3)Continental Oil Co.
Conoco Chens. Dlv.
(4)Dow Chemical,U.S.A.
(5)Dow Chemical,U.S.A.
(6)Ethyl Corp.
(7)Ethyl Corp.
(8)Ethyl Corp.
(9)The B.F. Goodrich Co.
B.F. Goodrich Chem.Co. Dlv.
(lOJtonochem, Inc.*
(ll)PPG Inudst.,Inc. Chem. Dlv.
Induct. Chem. Dlv.
(12)PPC Indus. (Carlbe)
(13)Shell Chemical Co.
(14)Shell Chemical Co.
(IS)Stauffer Chem. Co. Plastic Dlv.
Resins & Compounds West
*Using acetylene as feedstock.
Source: EPA, I979c
FIGURE 3.1 LOCATION OF VINYL CHLORIDE MANUFACTURING FACILITIES
Westlake, La.
Freeport, Tex.
Oyster Creek, Tex.
Plaquemlne, La.
Baton Rouge, La.
Pasadena, Tex.
Calvert City, Ky
Ce ismar , La .
Lake Charles, La
Guayanllla, P.R.
Deer Park, Tex.
Norco, La.
Carson, Calif.
TOTAL
317,800
90,800
317,800
204,300
149,820
68,100
454,000
136,200
181,600
227,000
381,360
317,800
79,450
3,198,430
9.9
2.8
9.9
6.4
4.7
2.1
14.2
4.3
5.7
7.1
11.9
9.9
J..5
1(10
3-3
-------
Ha SEPARATOR
PYROLYSIS
FURNACE
BASIS: 1 kj VINYL CHLORIDE MONOMER
ETHVLENE 0.50 kg
VINYL CHLORIDE
1.0kg
REFLUX
N.OH 4 CONDENSER
SOLUTION^
FILTER
CAUSTIC EFFLUENT
WASHAGE
CHLORINE 1.22 kg
CHLORINATION FEED FILTER LIGHT ENDS HEAVY ENDS
REACTOR NEUTRALIZATION REMOVAL REMOVAL
0 CAUSTIC WASHAGE (WATER)
OICHLOROETHANE
SODIUM HYDROXIDE
SODIUM CHLORIDE
VINYL CHLORIDE
METHYL CHLORIDE
ETHYL CHLORIDE
TO WATER
0.00435 kg
0.00098 kg
0.00033 kg
0.00098 kg
0.00085 kg
0.00085 kg
FILTER EFFLUENT (SOLID)
TARS TRACE
SOLIDS (AS CARBONS) 0.00008 kg
FILTER EFFLUENT (LIQUID)
OICHLOROETHANE 0.0005 kg
SODIUM HYDROXIDE TRACE
TO LAND
VENT ON REFLUX CONDENSER (CAS)
ETHANE
OICHLOROETHANE
METHANE
i
*
TCAIR
0.00*9 kg
0.012 kg
0.0049kg
HEAVY ENDS
OICHLOROETHANE
1. 1.2-THICHLOROETHANE
TETRACHLOROETHANE
TARS I
TO LAND
0.0024 kg
0.004 kg
0.004kg
TRACE
HEAVY ENDS
HEAVY ENDS
OICHLOROETHANE
TARS
SOLIOSASH
0.037 kg
0.0008 kg
0.00005 kg
0.0002 k«
TO LAND
Source: Gruber, 1975
FIGURE 3.2 VINYL CHLORIDE PRODUCTION PROCESS FROM EDC
3-4
-------
The uncertainty of this number is estimated to be - 2% because
of the uncertainty of the yield rate (- 1%) and the uncertainty of the
production figures (1%). The remaining 3% of EDC is recycled in the
process, emitted as waste, present as an impurity of vinyl chloride,
or converted to other chlorinated hydrocarbons during the production
process.
3.1.1.1 Emissions of EDC from VCM Production
In this process, major losses of EDC to the environment can
occur in the effluent of aqueous heavy ends from the vinyl chloride
separation unit. Stream 5 of Figure 3.2 illustrates where this release
occurs. According to Gruber, this stream typically contains about
-4 -4
8 x 10 kg of EDC per kg of vinyl chloride produced (or 8 x 10 kkg
EDC/kkg VCM) (Gruber, 1975). The uncertainty of this number is -50%
because the data is not sufficient to validate Gruber's estimate. The
calculated emission of EDC from the heavy-end waste stream of vinyl
chloride production is:
rate of EDC emission „„„ , . „„„ . . , ._,
,., .x VCM production = EDC emissions in solid wastes
in solid wastes r
(0.0008 kkg EDC/kkg VCM) x (2.-8 x 106 kkg VCM) = 2.0 x 103 kkg
The uncertainty of this figure is -51%, because of the uncertainty
of production figures (1% ); and 50% results from the uncertainty of the
rate of EDC emissions.
According to Gruber (1975), most of the solid wastes generated from
vinyl chloride manufacturing facilities were disposed of by incineration.
Assuming that all of the solid wastes are incinerated and a 95%, -2%
removal efficiency is achieved by incineration, 5% of EDC present in this
waste stream would then be released to the atmosphere intact.
3-5
-------
The uncertainty of this percentage is -40%. The total estimated
amount of EDC released to the atmosphere in 1977 from the incineration
of solid waste from vinyl chloride production was calculated as follows:
EDC emission in 5%-release to release of EDC to atmosphere
incineration atmosphere from incineration of solid wastes
(2 x 103 kkg) x (0.05) = 99 kkj;
The uncertainty of this number is +110%, -7C%, because of the
uncertainty of production figures (- 1%), the uncertainty of the rate of
EDC emissions in solid wastes (- 50%), and the uncertainty of the
incineration process (- 38%).
Emissions of EDC from other sources .(Streams 1, 2, 3, and 4 of
Figure 3.2) have been accounted for in the production phase of EDC.
3.1.1.2 Emissions of EDC from Vinyl Chloride Monomer Uses
Estimates were made concerning the amount ol: residual EDC found in
VCM production streams (after distillation to separate EDC from VCM).
Based on contacts with chemical producers and examination of the
physical and chemical properties of EDC and VCM, it is estimated that
1-10 ppm (parts per million by weight) residual EDC would exist in
VCM production streams. (Personal communication B.F. Goodrich, Borden,
1979; Mark and Gaylord, 1969). The total amount of EDC residue that
would be found in VCM may be calculated as follows:
annual VCM production jstimated residue _ total amount of EDC
derived from EDC X level of EDC ~ found in VCM product
(2.5 x 106 kkg) x 1-10 ppm (g/kk<>) =2.5 kkg EDC at 1 ppm
25 kkg EDC at 10 ppm
VCM is used in the production af a wide variety of consumer
products, as shown in Table 3.1. Assuming that 90% of residual EDC is
destroyed in the process 'of manufacturing these consumer products, it
is estimated that 8% of EDC is released to the environment .in the
production of consumer products arid that 25 would be present in products
3-6
-------
TABLE 3.1
PRODUCTS MANUFACTURED FROM EDC-DERIVED VCM
INDUSTRY
CONSUMER PRODUCT
Apparel
Building and Construction
Materials
Electrical
Home Furnishings
and Housewares
Packaging
Recreation
Transportation
Miscellaneous
Baby pants
Footwear
Outerwear
Extruded foam moldings
Flooring
Lighting
Panels and siding
Pipes and fittings
Rainwater systems
Soffits
Swimming pool liners
Weather stripping
Windows
Wire and cables
Appliances
Furniture
Garden hose
Housewares
Wall coverings and Wood surfacing
Blow molded bottles
Closure liners and gaskets
Coatings
Film
Sheet
Phonograph records
Sporting goods
Toys
Auto maps
Auto tops
Upholstery and seat covers
Agriculture (including pipe)
Credit cards
Laminates
Medical tubing
Novelties
Stationery supplies
Tool and hardware
Source: US EPA, 1979c
3-7
-------
derived From VCM. Therefore:
At. .1. ppm level of Impurity, KDC rele.-ised to air:
(0.08) x (2.5 kkg EDC) = 0.20 kkg of EDC
At 1 ppm level of impurity, EDC retained in VCM product:
(0.02) x (2.5 kkg EDC) = 0.05 keg of EDC
At 10 ppm level of impurity, EDC released to air:
(0.08) x (25 kkg EDC) = 2.0 kkg of EDC
At 10 ppm level of impurity, EDC retained in VCM products:
(0.02) x (25 kkg EDC) = 0.50 kkg EDC
At residue Jewels of 1 ppm, 0.20 kkg of F.I1C would be released to
environment during production of consumer products, and 0.05 kkg would
be present in consumer products; at 10 ppm, 2 kkg would be released to
the environment, and 0.50 kkg would be present in consumer products.
3.1.2 Releases of EDC Associated with the Production and Use of
Trichloroethylene
The total domestic production of trichloroethylene (TCE) in 1977
was estimated at 135 thousand kkg (USITC, 1978). This figure, obtained
by the U.S. International Trade Commission, is based only on the quan-
tities of trichloroethylene reported by manufacturing companies. The
uncertainty of this number is -1%. About 90% of trichloroethylene is
produced from EDC. The remaining .10% is manufactured via the
chlorination of acetylene. Trichloroethylene via EDC is made in
two steps: (2) chlorination of EDC to form tetrachloroethane and
(b) dehydrochlorination of the latter to produce TCE (EPA, 1979).
Thus the total production of trichloroethylene from the EDC process can
be calculated by multiplying the total production quantity by a factor
of 0.9:
(1.4 x 1Q~5 kkg of TCE) x (0.9) = 1.2 x 105 kkg TCE
The amount of EDC used to produce 1 kg of trichloroethylene is
estimated at 0.86 kg (or 0.86 kkg of EDC per kkg TCE) (EPA, 1979b).
This estimate is based on an estimated 85% conversion rate of EDC to
TCE. (EPA, 1979). The remaining 15% is recycled in the production
3-8
-------
(1) Diamond Shaorock Corp.
(2) Dou Chcm., U.S.A.
(3) Ethyl Corp. .
(4) Occidental Petroleum Corp.*
(5) PPC Indust.. Inc.;
Location
Deer Park, Tex.
Freeport, Tex.
Baton Rouge, La.
Taft, La.
Lake Charles, La.
TOTAL
Capacity.kkg Percent
40,860
68,100
18,160
22,700
127.120
276,940
14.8
24.6
6.5
8.2
45.9
100.0
»Dse acetylene as feedstock.
Source: US EPA, 1979c
FIGURE 3.3 LOCATION OF TRICHLOROETHYLENE
MANUFACTURING FACILITIES
3-9
-------
Co
H-•
o
Ethylen( —
OicMorid.
Cklor!n«
Oxygen
Steam
Reactor
Recycle
H2O
1
H2O
I
U
LJ
U
NHj H2O
u
i
•TCE
J
H2O
H2O
J
1
1
•)
a.
1
NH3 H2O
Recycle
™
J
s
a.
1
§
a
-5
o
u.
w
H
O
f
1
•PCE
Source: Lowenheim and Moran (1975)
FIGURE 3.4 PRODUCTION OF TRICHLOROETHYLENE FROM EDC
-------
process, emitted as waste, present as an imp irity in TCE, or converted
to other chlorinated hydrocarbons during production of TCE. The total
amount of EDC consumed by the trichloroethyl».ne production process
can then be calculated by multiplying the to :al production of tri-
chloroethylene via EDC process by a factor ol: 0.86 of EDC per 1 kkg
of trichloroethylene produced:
(1.2 x 105 kkg TCE) x (0.86 kkg EDC/kkg TCE) = 1.0 x 105 kkg EDC
The uncertainty of this figure is -2% due to the uncertainty of
the production quantity (-1%) and the uncertainty of the conversion rate
(-1%). Figure 3.3 shows the locations of the TCE production plants in
the United States.
A more elaborate discussion of the production process of
trichloroethylene is located in the appendix. Figure 3.4 illustrates
the process for the production of trichloroethylene from EDC.
3.1.2.1 Emissions of EDC from the Production Phase of Trichloroethylene
Atmospheric emissions of EDC from the trichloroethylene production
process were estimated at 600 kkg in 1976 (USEPA, 1979c); the basis
for this estimate was not discussed in the report. The uncertainty of
this number is -50% because of the lack of data to assess the above
estimate. Information on aqueous discharge and solid waste is not avail-
able in the above report.
.The estimated emission of EDC to the atmosphere in-1977 can be
calculated by multiplying the emission quantity in 1976 by a factor of
1.014. The factor of 1-.014 is a prorated value derived from an estimated
1.4% increase over the total consumption of EDC in 1976 (see Section 2.1).
This factor will be used later in other calculations.
(600 kkg) (1.014) = 610 kkg
The uncertainty of this number is estimated to be + 51% because of
the uncertainty of the estimate of atmospheric emissions (+50%) and the
uncertainty of the emission factor (+1%).
3-11
-------
Monitoring data is needed to properly assess the sources and
quantities of EDC emissions from. t:he trichloroethylene production process,
Potential sources of emissions that should be investigated include
wastewater and solid waste streams.
3.1.2.2 Emission of EDC from Trichloroethylene Uses
It is estimated that EDC is present at residual levels from
1-10 ppm (parts per million, by weight) in trichloroethylene streams
(personal communication, Dow Chemical, 1979). Assuming complete release
of EDC to the environment during the use of trichloroethylene-derived
products, the environmental release of EDC, as a result of usage of
trichloroethylene-derived products, can be calculated by multiplying the
total annual production of trichloroethylene (derived from EDC) by
the level of residual EDC in trichloroethylene streams:
annual production of residual level of EDC EDC release to
trichloroethylene x in trichloroethylene = environment
derived from EDC streams
1.2 x 10 kkg x 19/kkg =0.1 kkg at 1 ppm
1.2 x 105 kkg x 109 kkg = 1.2 kkg at 10 ppm
3.1.3 Releases of EDC Associated with the Production ; nd Use of
Perchloroethylene
Perchloroethylene (PCE) emerges as a co-product during the
production of trichloroethylene. The end use for perchloroethylene is
as a dry-cleaning solvent in metal cleaning and in textile finishing.
The total production of perchloroethylene in 1977 was 279,000 kkg
(USITC, 1978). The uncertainty of this figure is -1%. This production
volume is based on the quantities reported by the manufacturers.
Figure 3.5 shows the location of perchloroethylene production plants in
the United States. Figure 3.6 illustrates the production process for
perchloroethylene from EDC.
Stanford Research Institute has estinnted that 6.'>% of perchloro-
ethylene production uses EDC as a raw mateiial (CEH, 1975).
3-12
-------
(1) W—ood S>uwrock Corp.
(1) DDV O>cnl»l. O.S.t.
(}) Dou Chulul. n.S.A-
(4) Dov Chemical. D.S.L
(5) E.I. DuTont 4i llnouri t CD.
(t) tthyl Corp.
(7) Oeclt>l r.lrol.u, C
(8) PFC Induit.. Inc.
(1) Sl.udrt O>«.. CD.
(10) Vuleu Kjt.rl.l. Co.
OD Tulcu H»tcrUl» Co.
Location
D*«r Park, Tex.
Frccporl. Tu.
pitttbuti, aau.
Pl«qu«xla«, LA.
,Xoc. Corpti» Chrictl.Tu.
••toa Kouf*. La.
L*k< Ch«rl*«. L*.
loiilrvllli, «J. .
C«la»c, L».
Ulcblu, IL>ou«
TOUL
CapaeitT. 1
90,800
M.4SO
9,080
68,100
' 72,640
22,700
18,160
90.800
31,780
a.loo
22.700
i*».3«0
16.
9.
1.
12.
11.
«.
1.
16.
I.
12.
>.
•0«« MCtjrlco* •• f«*d«tock.
••D^rlBt** fro« 1OOX 4u€ to rou
Source: US EPA, 1979c
FIGURE 3.5 LOCATION OF PERCHLOROETHYLENE
MANUFACTURING FACILITIES
3-13
-------
CO
I
Dichloridt
Chlocin* -
Sttom
Reoclor
Rtcyclt
H2O
i
H2O
NHj HjO
U
•ICE
HjO
H2O
1
O
JC
_s
Pccchlor Slill
— vy-
1
|
Q
_0
u.
M
• PGf
Source: Lowenheim and Moran (1975)
FIGURE 3.6 GENERAL PROCESS FOR PRODUCTION OF PERCHLOROETHYLENE FROM EDC
-------
The principal reaction involved in the perchloroethylene pro-
duction process via EDC method is represented as follows:
C1CH2CH2C1 + 3C12 »8>C12C = CC12 + 4HC1
More details about the perchloroethylene process are discussed in the
appendix. It is estimated that 0.68 kg of EDC is needed to produce 1 kg
of perchloroethylene (EPA, 1979b). This estimate is based on the 90%
conversion rate from EDC to perchloroethylene. The remaining 10%.may
be recycled during the production process, emitted as waste, present in
perchloroethylene as an impurity, or converted to other chlorinated
hydrocarbons during production.
The amount of EDC consumed in the production of perchloroethylene
in 1977 can be estimated by multiplying the total production of per-
chloroethylene by 0.65 and by the ratio of 0.68 kkg of EDC consumed
per kkg PCE produced.
Therefore: .
(2.79 x 105 kkg PCE) (0.65) (0.68 kkg EDC/kkg PCE) = 1.2 x 105 kkg EDC
The uncertainty of this figure is also -2% (see Section 3.1.2).
3.1.3.1 Releases of EDC from the Production Process of Perchloroethylene
It is estimated that 894 kkg of EDC was released to the atmos-
phere from the perchloroethylene production process in 1976 (USEPA,
1979c) . -
The uncertainty of this number is -50% because of the lack of
data to support the above estimate.
Using the escalation factor of 1.014, the total emission of EDC
in 1977 from the above process can be calculated as follows:
(894 kkg) (1.014) - 910 kkg
The uncertainty of this figure is -51% because of the uncertainty
of emission during.the production process (-50% ) and the uncertainty of
the emission factor (-1%).
3-15
-------
The production process of p^rchloroethylene from acetylene has
also been studied (Gruber, 1975).
Figure 3.7 illustrates the product ion process of perchloroethylene
from acetylene. As pointed out by Gruber, EDC is emitted to the air
from the chlorinator reactor reflux condenser equipment of this process
(stream 3). The released quantity is estimated at 0.00245 kg of EDC
per kg of perchloroethylene produced. The uncertainty of this number Ls
-50% because of the lack of data to assess the above estimate.
Using this estimation, the emission of EDC from this source to
the air can be calculated by multiplying the total acetylene^based
production of perchloroethylene by 0.00024.
Therefore:
.(8.4 x 103 kkg of PCE) x (0.0024 kkg EDC/kkg PCE) = 20 kkg EDC
The uncertainty of this figure is -51% because of the uncertainty
of EDC emissions during the production process of perchloroethylene
from acetylene (-50%) and the uncertainty of the quantity of perchloro-
ethylene produced (-1%).
Traces of EDC can be found in the heavy ends from the perchloro-
ethylene column, but monitoring data is needed to estimate the quantity
of EDC present in the waste streams.
Although monitoring data from the acetylene-based and the EDC-
based production processes of perchloroethylene do not reveal EDC in
wastewater discharge (Gruber 1975, EPA 1979), it is suspected that air-
borne emission of EDC could occur during wastewater treatment because of
its high volatility. Therefore, air emission from aquatic discharge
should be investigated in further studies.
Solid wastes discharged by ooth mentioned production processes do
not contain EDC (EPA, 1979, Gruber 1975). Again, this source of
emission should be verified in further studies.
3-16
-------
KNT on REFIUI COnOCNSER (US)
[TXAHt O.OOIUS
ICTXANC 0.001135
TCIMCMIODOCTHMC O.OO0453
TML CAS ABSOWEI (CAS)
KIDROCCN CHLCWIK 0.0009
irtRACHlOBOTTKAflt 0.0004U
Tmon.oiiotTHn.tiic o.oooius
TCTKAOILOIIOtTHTlCHC 0.0009
UFIUI
COHOCNStR PURGE (CAS)
T«ICM.OAO[THn.CNt O.OOZB
rcuTAoaooocTHMc 0.0003
DIOtLOROtTHANC 0.00215
All
FKASf SCPARATOHS A.10 UASTt
IIQUOI S1RIPP[« ATTACMtO TO
OIHrOSOCKLORIMATOI (UOU10)
CMLOItlKATCO SOI.VUTS - TlAd
CALCIUM HTODOIIDt O.J40S
CALCIUM OllORllX O.JII5
HtAVT CUDS FRON PCRCHl.OROnim.tllt
AIIO TRICHlOROtTHtLtXt CO.VK1S (L1QU10-50L1D)
MttACHlOROBUTADItNt 0.23
CHlOROOtNZtXtS 0.02
CHLOROCTHAIICS 0.01
OaOROBVTADifHCS 0.01
TAXS AKO RtSIDUtS 0.02
i
LAM
Source: Gruber, 1975
FIGURE 3.7 PRODUCTION OF PERCHLOROETHYLENE
VIA THE ACETYLENE METHOD
3-17
-------
3.1.3.2 Emission of EDC from Perchloroethylene Uses
It is estimated that perchloroethylene streams contain impurities
of EDC from 1-10 ppm (part per million, by weight, personal communica-
tion, Dow Chemical, 1979). The uses of perchloroethylene include
textile cleaning, metal degreasing, fluorocarbon manufacture and solvent:
in textile processing. The use of products derived from perchloro-
ethylene can thus result in the environmental release of EDC. To
quantify the environmental release of EDC from perchloroethylene-
derived products, the total annual production of perchloroethylene
derived from EDC is multiplied by the level of EDC residue in
perchloroethylene streams. It is assumed that there is complete release
to the environment of EDC during usage of perchloroethylene-derived
products. Therefore:
total annual production residue levels of EDC environmental
of perchloroethylene x in perchloroethylene = release of EDC
derived from EDC streams
1.8 x 10 kkg x 1 g/kkg =0.2 kkg at 1 ppm
1.8 x 105 kkg x 10 g/kkg =1.8 kkg at 10 ppm
3.1.4 Releases of EDC Associated with the Production and Use of
Vinylidene Chloride
Vinylidene chloride (VDC) was produced in 1977 by Dow Chemical
Company and PPG, Inc. The plant locations are illustrated in Figure 3.8.
According to SRI (1975), the total production of vinylidene chloride in
1977 was estimated at 105,000 kkg. Of that, 62,500 kkg was used in the
production of methyl chloroform (see Section 3.1.5). It is difficult
to validate the total production figure of vinylidene chloride. The
production quantities of vinylidene chloride were reported to the U.S.
International Trade Commission. These figures could not be released to
the public, since the USITC policy prohibits such release when there are
three or fewer producers.
The production process of vinylidene chloride is shown in the
appendix. Figure 3.9 shows a typical production process of vinylidene
3-18
-------
Coopany
(1) Dou Chemical U.S.A.
(2) Dou Chemical U.S.A.
(3) PFC Indust., Inc.
location
Frecport, Tex.
Flaqucmlne, La.
Lake Charles, La.
Source: EPA. 1979c
FIGURE 3.8 LOCATION OF VINYLIDENE CHLORIDE
MANUFACTURING FACILITIES
3-19
-------
Inhibitor
NJ
O
Caustic Solution
Fresh Feed
1,1,2-
Trichloroetlinne
Purge
Condenser
JL
Water
Reactor
Separator
I
309
te
Heater
Waste
Finished Vlnylidene
Chloride to Storage
Drying
and
Lights
Column
Reboiler
Cooling
Water
Condenser
Steam
Finishing]
Column j|eavles
Was te
Recycle 1,1,2-Trichloroethane
Waste
• Purge
Source: US EPA, 1978c
FIGURE 3.9 PRODUCTION OF VINYLIDENE CHLORIDE
-------
chloride. The principal rcnction involved in the process. is:
CH2C1CHC12 + NaOH - - )» CH, = CC12 + NaCl + H20
Vinylidene chloride is formed in two steps: (a) chlorination
of EDC to produce 1 ,1 ,2-trichloroethane, and (b) dehydrochlorina-
tion of the latter to produce vinylidene chloride. For the
purpose of this materials balance, it is estimated that 1.18 kg of EDC
is needed to produce 1 kg of vinylidene chloride. This estimate is
based on a 96% conversion rate from EDC to 1 ,1 ,2-trichloroethane. The
uncertainty of this number is estimated to be -2% because of the lack
of information on yield rate.
The total amount of EDC consumed in vinylidene chloride production
in 1977 can be calculated by multiplying the production quantity by
the ratio of 1.18 kg of EDC consumed per kg of vinylidene chloride
produced :
1.05 x 105 kkg VDC (1.18 ffi ™^) = 1. I x 105 kkg EDC
The uncertainty of this number is -3% because of the uncertainty
of yield rates (2%) and the uncertainty of production figures (1%).
The quantity of EDC used in the production of methyl chloroform
using vinylidene chloride as intermediate is estimated at 74,000 kkg
in 1977 (see Section 3.1.5). Thus, the quantity of EDC used for the
total consumption in vinylidene chloride production can be calculated
by subtracting the amount of EDC cons imed in the production of the
vinylidene chloride used as an intermediate in the manufacture of
methyl chloroform from the amount of EDC used in the total production
of vinylidene chloride :
(1.2 x 105 kkg EDC) - (7.4 x 104 kkg EDC) = 4.6 x 104 kkg EDC
The uncertainty of this figure is estimated to be -3%.
3-21
-------
3.1.4.1 Emission of EDC from the Manufacturing Process of Vinylidene
''• Chloride
•».'
In a report obtained from EPA, an atmospheric emission of 594 kkg
of EDC was estimated in 1976 from the vinylidene chloride production
facilities (USEPA, 1979c). The uncertainty of this number is -50%
because of the lack of data to assess the above estimate. Using the
escalation factor of 1.014 for 1977, the estimated total emission of EDC
from this process is calculated by multiplying the 1976 emission figure
(594 kkg) by the escalation factor (1.014):
(594 kkg) x (1.014) = 600 kkg
The uncertainty of this figure is -51% because of the uncertainty
of EDC emissions during the manufacture of vinylidene chloride (-50%)
and the uncertainty of the emission factor (-1%).
For the purpose of this materials balance, it is also suggested
that the wastewater stream from the manufacturing process for vinylidene
chloride is a common source of airborne emission of EDC. Monitoring
data is needed to properly assess the quantity of EDC released by this
source.
According to Figure 3.9, heavy-ends waste or solid waste streams
are not.identified in the production process of vinylidene chloride.
Therefore, it is as.sumed that there are none.
3.1.4.2 Emission of EDC from Uses of Vinylidene Chloride
L{
It is estimated that EDC is present at residual levels from
1-10 ppm (parts per million, by weight, personal communication
Aldrich Chemical Company, 1979) in vinylidene chloride streams. The
uses of vinylidene chloride include VDC polymer, packaging film, coating
for packaging materials, flame-resistant fiber, and coating for textiles,
carpets, nonwovens and paper. Assuming complete release of; EDC to the
»3* •
environment during the use of vinylidene chloride-derived products,
the environmental release of EDC as a result of usage of products
derived from vinylidene chloride can be calculated by multiplying the
total annual production of vinylidene chloride (derived from EDC) by
3-22
-------
the level of residual EDC in vinylidene chloride itreams:
.•mniKil production of rcs.Ldiu I k-vcl of KDG I''.I)C, rc.l e;iKo to
viny.J Ldc'iie cliJ.orJ.de x .in tricliloroethyleni: = IMW i ronmc-.nt
derived from liDC . streams
.4.3 x 104 kkg x 1 g/kkg = 0.04 kkg at 1 ppm.
4.3 x 104 kkg x 10 g/kkg = 0.4 kkg at 10 ppm
3.1.5 Releases of EDC Associated with the Production and Use of
Methyl Chloroform
' 'v
It is estimated that 60% of the production of methyl chloroform '"
(MC) is derived from vinyl chloride and 30% is based on the use of
vinylidene chloride as raw material (EPA, 1979). The total production
of methyl chloroform in 1977 was estimated at 288,000 kkg (USITC, 1978).
The uncertainty of this number was estimated to be -1%. The remaining
10% of methyl chloroform is a derivation from ethane rather than a
product of EDC. There are no documented EDC emissions related to
this process. This production is based solely on the quantities of
methyl chloroform reported by the manufacturers. The total production
of methyl chloroform from the vinyl chloride method can be calculated by
multiplying the annual total production quantity by 60%.
(2.88 x 105 kkg) (0.60) = 1.7 x 105 kkg (1)
The uncertainty of this number was estimated to be -1%.
The amount of methyl chloroform produced from the vinylidene
chloride method can also be calculated by multiplying the total produc-
tion of methyl chloroform in 1977 by 30%.
(2.88 x 105 kkg) (0.30) = 8.6 x 104 kkg (2)
The uncertainty of this number was estimated to be -1%.
Production plants for methyl chloroform are located mainly
along the Gulf Coast of the United States (Figure 3.10).
3-23
-------
Company •
(1) Dow Chemical U.S.A.
(2) PPC Indust., Inc.
(3) Vulcan Materials Co.*
Location
Freeport, Tex.
Lake Charles, La.
Geismar, La.
TOTAL
Annual Capacity, kkg Percent
204,300 65.2
79.450 25.4
29.510 9.4
313,260
100.0
•Using ethane as feedstock
Source: US EPA, 1979c
FIGURE 3.10 LOCATION OF METHYL CHLOROFORM
MANUFACTURING FACILITIES
3-24
-------
A typical production process of methyl chloroform using vinyl
chloride as raw material is discussed. in greater detail in the appendix.
Figure 3.11 shows a typical methyl chloroform production process from
the vinyl chloride method.
CH0 = CHC1 + HC1 - •»> C«H,C10 . (3)
. . • i. 2. D 2
C2H2C12 + C12 - (4°° *fr CH3CC13 + HC1 (4)
It is estimated that 0.5 kg vinyl chloride is needed to produce
1 kg of methyl chloroform (Gruber, 1975). This estimate is based on
an estimated 95% conversion rate of vinyl chloride to methyl chloroform
(Lowenheim and Moran, 1975). The uncertainty of this number was
estimated to be -1%.
The total amount of vinyl chloride consumed to produce 173,000 kkg
of methyl chloroform can then be calculated by multiplying this amount
by a ratio of 0.5 kkg vinyl chloride per kkg of methyl chloroform:
(1.73 x 105 kkg MC) x (0.5 -) = 8t65 x 1Q kkg VCM
.The uncertainty of this number was estimated to be -2%.
**'.
The U.S. International Trade Commission does not report the amount
of vinyl chloride that is produced from EDC for the manufacture of
methyl chloroform. Therefore, it is necessary to calculate the quantity
of EDC used to produce 865,000 kkg of vinyl chloride as intermediates
in the manufacturing process of methyl chloroform. This quantity can be
calculated by (a) multiplying the quantity of vinyl chloride by the
molecular weight of EDC, .and (b) dividing by the molecular weight
of vinyl chloride and by the ratio of 0.96 riole of vinyl chloride
produced per mole of EDC consumed (See Section 3.1.1):
(8.6 x iq kkg VCM) x (98. 9
AS kkg VCM . ,0.98 kkmole VCM.
>'° kkmole VCM; X ( kkmole EDC'
The uncertainty of this figure was estimated to be -3%.
3-25
-------
h.ln I Kg M.lhrl CMo,»lo.«
Vii.,1
CMo.1*. •
0.5
CHIo.ld.
Sl..t-Up <
Hrdiochlorlnol<»
IICI «.«,cl. Sunn
Hyilrachlailnolot Vin
Cklorlnol
lUoclot
Chlorln. 0.3?5-
OUKIara-
lilchlo.
MC. 1.0 Kg
•*• Sl«o» Slllpfxt
Wol.i (lllu.nl
Hrdiachlo
-------
As mentioned above, methyl chloroform may also be produced by
the vinylidene process. The quantity of methyl chloroform produced
• »
by this process is estimated at 86,000 kkg in 1977. Figure 3.12 shows
a typical. process of methyl chloroform production via the vinylidrne
chloride method. The basic reaction in this procass is:
Fed-
CH2 = CC12 + HC1 - - - >JkCH3CCl3 (7)
Methyl chloroform is formed by the hydrochlorination of
vinylidene chloride in the presence of Fed catalyst. More informa-
tion pertaining to the vinylidene chloride-based methyl chloroform
production process is given in the appendix.
The amount of vinylidene chloride used to produce 86,000 kkg of
methyl chloroform in 1977 can be calculated by multiplying the quantitj
of methyl chloroform by a factor of 0.73 kg of vinylidene chloride used
per kg of methyl chloroform produced (EPA, ]979b):
(86 x 103 kkg MC) x (0.73 = 6-
A 99.5% yield from Reaction (7) is estimated from the ratio of
the amount of vinylidene chloride used (0.73 kg) per kg of methyl
chloroform produced. The theoretical yield of methyl chloroform from
Reaction (7) is over 98% (Lowenheim and Mora, 1975).
The amount of EDC consumed in the methyl chloroform production
process using vinylidene chloride as intermediate can thus be calculated
by multiplying the calculated vinylidene chloride needed for the methyl
chloroform production by the ratio of 1.26 kg of EDC consumed per kg of
•vinylidene produced (see Section 3.1.4):
(6.3 x 104 kkg VDC) x (1.18 ) = 7.4 x 104 kkg EDC
The total quantity of EDC consumed by both methyl chloroform
production processes in 1977 (the vinyl chloride-based and the vinylidene
chloride-based) can then be calculated by taking the sum of Equation (6)
and Equation (9) :
(1.4 x 105 kkg EDC) + (7.4 x 104 kkg EDC) = 2.1 x 105 kkg EDC
3-27
-------
LO
NJ
OO
Vinylidene— ^
Chloride
r o r r i c • ^>
Chloride
r
Hydrochlorinotor
t
-n
Fractionotor
Recycle
j — OMC
-
Fractionator
Heavy
.*•-. f \.
'" *~- cna»
Waste
Sourcet Lowenhein and Moran (1975).
FIGURE 3.12 PRODUCTION OF METHYL CHLOROFORM FROM VINYLIDENE CHLORIDE
-------
3.1.5.1 Emissions of KDC from the' Production Processes of Methyl
Chloroform
Figure 3.11 shows the gas and liquid waste stream for the methyl
chloroform production process from the vinyl chloride method. The two
major sources of EDC emission to the atmosphere from the vinyl chloride-
based production process of methy] chloroform arc.: (a) the hydro-
chlorinator vent, and (b) the ste;;m stripper gas effluent (Streams 1 and
2 of Figure 3.11). Based on 1 kg of methyl chloroform produced, the
quantities of EDC released from Stream 1 and Stream 2 of Figure 3.11
are, respectively, 0.0085 kg and (.0005 kg (Gruber, 1975). Thus the
amount of EDC emission to air fron the vinyl chloride-based process is
0.009 kg of EDC per kg of methyl chloroform produced. The uncertainty
of this number is estimated to be -50% because of the lack of data
necessary to assess EDC emissions.
The total amount of EDC emission to the air in 1977 from the raw
material can then be calculated by multiplying the methyl chloroform
production from vinyl chloride [Equation (1)] by the ratio of 0.009 kg
of EDC released per kg of methyl chloroform produced:
(173 x 103 kkg MC) (0.009 ° ) = 1.6 x 103 kkg
The uncertainty of this number is -51% because of the following
factors :
• the uncertainty of methyl chloroform production figures (-1%)
• the uncertainty of EDC emissions during production of methyl
chloroform (-50%).
Analysis of water samples from the vinyl chloride-based production
process of methyl chloroform does not show any trace of EDC (Gruber,
1975). Because of the high volatility of EDC, atmospheric emissions
from the aquatic discharge from the production facilities should be
t
investigated in later studies.
No land-destined solid wastes are discharged by the vinyl chloride-
based process (Gruber, 1975).
3-29
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Information on EDC emissions from the vinylidene chloride-based
production process of methyl chloroform is not available. It is
suspected that EDC could be present in the heavy-ends waste stream and
the aqueous effluent waste stream discharged by the vinylidene chloride-
based process. More information is needed to quantify the amount of EDC
released from these sources.
3.1.5.2 Emission of EDC from Methyl Chloroform Uses
It is estimated that methyl chloroform streams contain impurities
of EDC from 1-10 ppm (part per million, by weight, personal communi-
cation, J. T. Baker Company, 1979). Methyl chloroform is used as a
degreaser, aerosol depressant, solvent, coolant and lubricant in
cutting oil. The use of products derived from methyl chloroform can
result in the environmental release of EDC. To quantify the environmental
release of EDC from methyl chloroform-derived products, the total annual
production of methyl chloroform derived from EDC is multiplied by the
level of EDC residue in methyl chloroform streams. It is assumed that
there is complete release to the environment of EDC during use of methyl
chloroform-derived products. Therefore:
total annual production residue levels of EDC environmental
of methyl chloroform x in methyl chloroform = release of EDC
derived from EDC streams
260 x 10 kkg x 1 g/kkg =0.3 kkg at 1 ppm
260 x 103 kkg x 10 g/kkg =2.6 kkg at 10 ppm
3.1.6 Releases of EDC Associated with the Production and Use of
Ethyleneamines
Ethyleneamines (EA) are produced by reacting EDC with ammonia.
The basic reaction in this process is:
C1C2H4C1 = 2NH3 - *• NH2(CH2)2NH2 + 2HC1 + other ethyleneamines
Yield of this process depends heavily on the reaction conditions
(Lowenheim and Moran, 1975). Figure 3.13 shows a simplified production
process for ethyleneamines.
3-30
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RECYCLE AMMONIA
ETHYLENE D I BROMIDE
X
AMMONIA
/*
CAUSTIC SODA
}
>
^
REACTOR
s
FRACTIONING
TOWER
ETHYLENE
> DIAMENE
> Other
Ethylene
Anines
Source: Lowenheim and Moran (1975)
FIGURE 3.13 PRODUCTION OF ETHYLENEAMINES FORM EDC
-------
According to SRI (1975), 59,875 kkg of ethyleneamines were
estimated to have been produced in 1974. Based on an estimated 5%
increase per year in the production of ethyleneamines, the total increase
in the production of ethyleneamines in 1977 over that in 1974 will be:
First year: 5% of 1005? = 105%
Second year: 5% of 105% = 110.25%
Third year: 5% of 110.25% = 115.76%
The total production of ethyleneamines in 1977 can then be
calculated by multiplying the total production of ethyleneamines in
1974 by a factor of 1.158:
(59,875 kkg) x (1.158) = 6.9 x 104 kkg
The uncertainty of this number is estimated to be -5%.
Ethyleneamines are produced by Dow Company and Union Carbide plants
located in Texas and Louisiana. Figure 3.14 shows the locations of these
manufacturing plants.
It is estimated that 2.2 kg of EDC is needed to produce 1 kg of
ethyleneamines (SRI, 1975). The uncertainty of this number is estimated
to be -2% because the above estimate was not defined in the report. The
total amount of EDC can then be calculated by multiplying the estimated
total production of ethyleneamines in 1977 by the ratio of 2.2 kg of EDC
consumed per kg of ethyleneamines produced:
(2.2 ) x (6.9 x 10A kkg) = 1.5 x 105 kkg EDC
The uncertainty of this number is estimated to be -10% because of
the uncertainty of the production of ethyleneamines (-5%) and the
uncertainty of the amount of EDC needed to produce 1 kg of ethyleneamines
(-2%) .
3.1.6.1 Emissions of EDC from the Production Process of Ethyleueamines
The estimated emissions of EDC from tie ethyleneamine production
facilities was 600 kkg in 1976 (USEPA, 1979c). The uncertainty of this
number is estimated to be -50% because of the lack of data necessary
3-32
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Company
(1) Dou Chem., D.S.A.
(2) Union Carbide Corp.
(3) Union Carbide Corp.
location
Freeport, Tex.
Taft, la.
Texas City. Tex.
TOTAL
Capacity. WCR
13,620
17,706 '
10,896
42,222
Percent
32.3
41.9
25.8
100. 0
Source: US EPA, 1979c
FIGURE 3.14 LOCATION OF ETHYLENEAMINES
MANUFACTURING FACILITIES
3-33
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to assess the above estimate.
The estimated total emission of EDC to the air in 1977 from the
ethyleneamines production facilities is calculated by multiplying the
emission quantity in L976 (600 kkg) by the escalation factor of 0.014
for 1979 (see.Section 3.1):
(600 kkg) (1.014) = 610 kkg
The uncertainty of this number is -51% as a result of the
following factors:
• the uncertainty of the enission of EDC from ethyleneatnine
production (±50%)
• the uncertainty of the escalation factor (-1%).
Like the other chemical intermediate production processes, such
as the vinyl chloride-based methyl chloroform production process, it
is suspected that EDC emissions can occur in wastewater streams and
solid waste streams discharged by the production process of ethylene-
amines. More information is needed to determine properly the quantities
of EDC emitted from these sources.
3.1.6.2 Emissions of EDC from Ethyleneamine Uses
Ethyleneamines are used in producing carbamate fungicides,
chelating agents, dimethylethylene urea resins, and diaminoethyl-
ethanol. It is estimated that EDC is present at residual levels from
1-10 ppm (parts per million, by weight, personal communication, Dow,
1979) in ethyleneamine streams. Assuming complete release of EDC to the
environment during the use of ethyleneamine-derived products, the
environmental release of EDC, as a result of usage of ethyleneamine-
derived products, can be calculated by multiplying the total annual
3-34
-------
production of ethyleneamine (derived from EDC) by the level of residual
EDC in ethyleneamine streams:
annual production of residual level of EDC „„
,,.,., . ,, . EDC release to
ethyleneamine derived x in ethyleneamine =
,. „„„ environment
from EDC streams
6.9 x 104 kkg x 1 g/kkg =0.07 kkg at 1 ppm
6.9 x 104 kkg x 10 g/kkg - 0.07 kkg at 10 ppm
3.1.7 Releases of EDC Associated with Its Use as a Leaded Gasoline
Additive
EDC is used in conjunction with 1,2-dibromoethane as a lead
scavenger in leaded gasoline. EDC is added to leaded gasoline to provide
cleaner burning of the lead anti-knock compounds in the engine. It is
estimated that a typical gallon of leaded gasoline contains approximately
2.5 grams of lead per gallon'or 0.66 grams of lead (0.0032 moles) per
liter (EPA, 1979a), based on conclusions drawn from a report by Mara and
Lee (1978). Since two atoms of chlorine are available in EDC for each
atom of lead in the gasoline, 0.32 grams of EDC (0.0032 moles) are added
to each liter of leaded gasoline. In 1977, 1,899,166,000 barrels, or
3.015 x 10 liters, of leaded gasoline, were produced in the United
States (API personal communication, October 3, 1979). All leaded
gasoline is assumed to contain EDC as a lead scavenger.
The total EDC used as a lead scavenger in gasoline in 1977 is
calculated by multiplying the amount of leaded gasoline produced in
1977 (3.015 x 3.0 x 101'
gasoline (grams/liter):
1977 (3.015 x 3.0 x 1011 liters) by the amou it of EDC in a liter of
. . (3.015 x 1011) (0.32) = 9.7 x 1010 grams
or
9.7 x 104 kkg
Since there was no data to calculate EDC emissions from gasoline-
blending operations, for the purposes of this materials balance, JRB
estimates that the EDC emissions are 0.1% of EDC 5.n the processed
gasoline. These emissions are primarily air emissions:
(9.56 x 104) x (0.001) = 97 kkg EDC/year
3-35
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The uncertainty of this number is estimated to be -100% because
of the lack of data to estimate EDC emissions from gasoline.
3.1.7.1 Emissions of EDC from Gasoline
Releases of EDC from leaded gasoline to the environment occur
before and during combustion. No emissions of EDC occur after
combustion, since EDC is destroyed during the ignition and combustion
of the fuel. Emission of EDC occurs through four main vehicles:
• tank breathing
• vapor displacement (filling losses)
• spills, leaks and fugitive emissions
.• combustion.
a. Emissions from Tank Breathing
Gasoline and EDC are released from fixed roof or fixed volume
storage tanks even when there is not transfer activity. Temperature-
induced pressure differentials expel vapor and air as the temperature
increases and draw fresh air into the tank as the temperature decreases.
These releases of vapor and air are referred to as tank breathing or
breathing losses. Floating roof tanks and highly pressurized tanks
that are more common to refineries and very large storage sites do not
emit the breathing releases associated with fixed roof tanks and are
excluded from EDC emission considerations. The greatest number of fixed
roof gasoline tanks are found in bulk gasoline plants (EPA, December,
1977).
.The 1972 Census of Business indicates that there were 23,367
bulk plants in the U.S. The number of these bulk plants has been
decreasing in recent years, with an 1]% decrease from 1967 to 1972.
Therefore, for the purposes of this emission estimate, the number of
bulk plants in 1972 is reduced by 15% to account for the decrease.
through 1977, providing a base of 19,862 plants.
Additionally, 30% of these 19,862 facilities are underground
storage facilities, which further reduces the number of bulk plants
3-36
-------
under consideration to 13,903. The typical gasoline bulk plant
(EPA, 1977b) contains three tanks between 50,000 and 75,000 liters.
We assume each tank is estimated to lose 3 kg/day to breathing losses.
It is estimated that each bulk plant will have two tanks for leaded
gasoline.
The estimated breathing losses of EDC are calculated by
multiplying the daily hydrocarbon (gasoline) emissions per tank
(3 kg/day/tank) by the number of facilities with above-ground tanks
(13,903) by the number of tanks in a typical facility that contain
leaded gasoline (2) by the quantity (liters) of gasoline in a kg (1.5)
by the amount.of EDC (grams) in a liter of gasoline (0.32) by the
number of days in a year (365). The product is divided by 10 to
convert the answer to grams of EDC to kkg.
(3 kg/day/tank) x (13,903 facilities) x (2 tanks/facility) x
(1.15 liters gasoline/kg) < (0.32 grams EDC/liter gasoline) x
(365 days/year) ^ (1 kkg/13 grams) = 11.0 kkg/year
For this calculation, gasoline vapor and gasoline liquid composi-
tions were assumed to be the same. This assumption will increase the
EDC emission estimate slightly because gasoline is slightly, more
volatile than EDC.
b• Emissions of EDC from Vapor Displacement (Tank Filling .
Losses)
Emissions of EDC and miscellaneous hydrocarbons also occur
during the filling of fixed roof or fixed volume tanks. The hydro-
carbon vapor above the gasoline is forced into the atmosphere during
the filling of the tanks and is not usually drawn back in as the tank
is drawn down. These losses typically occur to some extent during all
transfer operations. EDC is discharged in small quantities with the
gasoline proper, thus providing a route for environmental vapor
emissions, principally to the air.
Filling operations emissions can be controlled by vapor balance
systems, hydrocarbon oxidation 'systems and refrigerated vent systems.
These emission control systems typically reduce tank filling losses and
3-37
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emissions by approximately 80%.
The following calculations estimate the EDC emissions from
gasoline tank filling operations in 1977.
The following conditions are assumed or are known for the EDC
emission calculations:
• In 1977, 1,899,166,000 barrels of leaded gasoline were produced
and distributed (API personal communication, October 3, 1979)
• The total volume of gasoline distributed is turned over three
times during shipment and storage (assumption)
• The raw emissions from 25% of the transfer operations are
reduced by 80% by emission control devices
• The displaced air and vapor leave the tanks saturated at 60°F
(15.6 C) (assumption)
• The EDC content of gasoline is 1.2 gram (9.01.2 mole) per gallon
or 1.04 mole % (EPA 1979)
• Vapor pressure of EDC @ 60°F is 48.7 mmHg or 0.06 atm (Perry
Chemical Engineering Handbook)
Vapor pressure of gasoline at I
Chemical Engineering Handbook).
Vapor pressure of gasoline at 60 F is 61.8 mmHg (Perry
The first step in calculating the EDC emissions from a gasoline
tank filling operation is to calculate the volume of gasoline vapor
3 • .
(ft ) needed per Ib-mole of EDC vapors. The vapor volume is calculated
3
by multiplying the molar volume of a gas (359 ft /Ib-mole) by a
temperature ratio (520/460) to convert the molar volume to 60 F, which
is the escaping vapor temperature. The product is then divided by the
molar ratio of EDC to gasoline (0.0004) and by the vapor pressure of
EDC in atmospheres at 60°F (0.064 atm).
(359 ft3 Ib/mole at STP) x
460°R
(0.0004 mole EDC/mole gasoline) (0.06 atm @ 60°F)
16,909,420 ft3 Ib-mole of EDC vapor in air
The next step is to calculate the volume of vapor and air emitted
during .tank filling operations in 1977. To calculate this volume, the
total supply of leaded gasoline (1,899,166,000 barrels/year) is
3-38
-------
3
multiplied by the number of cubic feet in a barrel (5.61 ft /barrel) and
by the number of times the total volume is assumed to be transferred
during distribution (3 turnovers):
(1,899,166,000 barrels/year) (5.61 ft3/barrel) (3 turnovers) =
10 3
3.2 x 10 ft vapor/year
The amount of uncontrolled EDC vapor emissions is then calculated
by dividing the total volume of vapor and air emitted during tank filling
10 3
operations in 1977 (3.196 x 10 ft year) by the cubic feet of vapor
needed for 1 Ib-mole of EDC (1.69 x 107 ft /lb-mole) and that product is
multiplied by the number of kg of EDC in a lh-mole (44.5 kg EDC/lb-mole).
No emission control: 3.2 x 10 ft vapor/year (44.5 kg EDC/lb-mole
1.69 x 107 ft3/lb-mole
84 kkg EDC/year
A more realistic estimate of tank filling losses is obtained when
the above 84,080 kg quantity of EDC emissions is reduced to reflect an
emission control of 25% of all transfer operations (0.75) (84,080 kg)
and an 80% reduction in emissions for those facilities that use emission
control .(0.25) (84,080) (.20).
With emission control:
[(0.75) x (84,260)] + [(0.25) x (84,260) x (.20)] = 67 kkg EDC/year
c. Emissions of EDC from Spills, Leaks, and Fugitive Emissions
of Gasoline
The impact of these miscellaneous emissions on the quantity of
environmental EDC is not believed to be significant. The overall
quantity of EDC. in gasoline is quite small, and the discharge of
gasoline is usually minimized as much as possible.
Emissions of EDC from gasoline will undoubtedly be reduced in the
future. In 1977, leaded gasoline accounted for 72.5% of all motor fuel.
In 1978, leaded gasoline accounted for 66.1% of all motor fuel, and
3-39
-------
during the first six months of 1979 leaded fuel accounted for 61.7% of
production (API personal communication, October 3, 1979). Recent
trends and future requirements for the use of unleaded fuels indicate
that the total demand for leaded fuels is diminishing. Therefore, the
use of EDC in leaded fuels is also decreasing. The estimates of EDC
emissions from gasoline could be refined, but the current trend of leaded
gasoline uses makes the presence of EDC from gasoline emissions short-
lived.
d. Emissions of EDC During Combustion
For the purposes of this materials balance, it is estimated that
1% of the EDC in gasoline is not destroyed during combustion and is
released to the atmosphere. This can be calculated as follows:
(0.01) x (9.56 x 104 kkg) = 9.6 x 102 kkg EDC
3.2 RELEASES ASSOCIATED WITH THE MINOR USES OF EDC
In Section 3.1, information is presented which describes the major
uses of EDC; these uses accounted for 99.9% of the chemical's annual
production. Also described are the environmental releases associated
with the listed uses. The purpose of this section is to briefly describe
the variety of uses which account for the remaining 0.1% of the annual
production of EDC. The emissions associated with these uses will also
be discussed.
The minor uses have been grouped as follows (Auerbach Associates,
1978):
• Manufacture of paints, coatings, and adhesives
• Solvent formulations for the extraction of foodstuffs
and pharmaceuticals
• Cleaning solvent formulations for PVC reactors and textiles
• Manufacture of polysulfide (rubber cements and elastomers)
• Grain fumigant formulations
• Miscellaneous uses including the manufacture of: color film,
the processing of copper ores and the formulation of various
pesticides and herbicides (used as diluent).
3-40
-------
According to the Stanford Research Institute, the minor uses of
EDC amounted to 7 kkg in 1974 (Stanford Research Institute, 1975,
as cited in U.S. Environmental Protection Agency, 1978a, and also
referenced in U.S. Environmental Protection Agency, 1978c). A more
recent estimate (for 1977), provided by Auerbach Associates, Inc.,
indicates that minor uses account for between 4.5 and 5.0 thousand kkg
per year (Auerbach Associates, Inc., 1978). The Auerbach Associates
estimate is purported to represent the results of a thorough review of
the sparse literature references on minor uses of EDC and also
numerous direct contacts with industrial facilities involved in the
production and use of this chemical. Auerbach Associates concluded
that certain solvent uses reported in the literature (and included in
the SRI estimates) are either "obsolete or represent an extremely small
volume." These uses are as follows: degreasing, fumigation of upholstery
and carpets, and additives to soaps and scouring compounds, and as
wetting and penetrating agents. The fact that Auerbach Associates did
not include the above in their estimate of the total minor uses, plus
the difference in base years (1974 vs. 1977), may account for the
differences in the estimates of Auerbach and SRI. In view of the fact
that the Auerbach Associates estimate represents quite recent direct
contacts with industrial concerns involved in the production and use of
EDC, it is considered to be the most credible source of available
information on minor uses. Table 3.2 is an adaptation from the Auerbach
.study and presents estimates of the amounts of EDC used in each of six
types of use. Based on estimates presented in Section 3.1 and the data
3
in Table 3.2, minor uses account for 0.1% (or 4.8 x 10 kkg) of the
annual production of EDC. Uncertainties were not calculated for the
above figures because of the insignificant amount of EDC consumed for
these uses.
The extent to which EDC emissions are generated as a result of
minor uses will vary greatly depending on the use and the manner in
which EDC is used within the process. In some processes virtually
all EDC used is apparently released to the environment (e.g., grain
fumigation). In other processes, the EDC is reacted with other
constituents and becomes a bound component of the resulting matrix
(e.g., manufacture of polysulfides). Therefore, to adequately assess
3-41
-------
TABLE 3.2 MINOR USES OF EDC
Amount (kkg) % of
Type of Use Range Mean Minor Uses
Paints, Coatings and
Adhesives 1364 28
Extraction Solvents 909-1364 1136 23
Cleaning Solvents 909 19
Polysulfides 455-591 523 11
Grain Fumigant 455 9
Miscellaneous Uses 455 9
Total 4842 99%*
*Deviates from 100% due to rounding
-------
the emission potential for the minor uses, it is necessary first to
obtain detailed information on how EDC is used in each of these
processes. Unfortunately, readily available information sources
generally do not provide the detailed descriptions required. Thus, in
those cases where there is a paucity of information, there will have
to be more reliance on assumptions. In the following paragraphs each
of the minor uses will be discussed, and the assumptions needed in
order to make emission estimates will be provided.
3.2.1 Releases from EDC Use in the Manufacture of Paints, Coatings,
and Adhesives
The uses of EDC in paints, coatings, and adhesives reportedly
accounts for over one-fourth of all minor uses. It is assumed that
the paints category consists of those paints which use various vinyl
polymers as resin. Polyvinyl chloride is one of the polymers used.
There are a variety of other protective coatings beside paints
(e.g., fabric finishes, leather finishes, and paper coatings) which
use vinyl polymers.as all or a major part of the coating binder
(Connolly, 1977). The use of EDC in adhesives is limited to the
acrylic type of compound.
Contact was made with the Paint, Varnish and Lacquer Association
in order to determine how EDC is used within this industry. The
technical representative contacted indicated he was not familiar with
the use of this compound for paints, but that it may be a component of
one of the adhesives which utilize "fast" solvents (Brown, 1979). In
the absence of data in the literature to the contrary, it is assumed
that EDC is used in paints, coatings, and adhesives as a solvent, and
that virtually all of the solvent contained in these materials is
eventually evaporated to the atmosphere during normal use of these
products. A similar assumption was made by the Oak Ridge National
Laboratory in a document prepared for EPA (U.S. Environmental
Protection Agency, 1978c). In addition to the emissions resulting
from the use of paints, coatings, and adhesives containing EDC, other
emissions of EDC to the air can be expected to occur during the initial
.forniu.Latioii processes at the manufacturing facilities. Based on this
assumption, it is estimated that the annual emissions of.EDC associated
3-43
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witli Che manufacture and use of paints, coatings, and adhesives amount
3
to 1.4 x 10 kkg, which is the total amount of EDC production ascribed
.to this use.
A Phase II investigation, which involves direct contacts with
major manufacturers, should ascertain how EDC is used in the formula-
tion of paints, coatings, and adhesives. If it is verified that
EDC becomes a bonded component of coatings of adhesives, it will be
necessary to reduce overall emissions estimates by the appropriate
amounts.
3.2.2 Releases from EDC Use as an Extraction Solvent
EDC is used in a number of solvent extraction applications.
These include the extraction of oil from seeds, the processing of
animal fats and the processing of pharmaceutical products. The
literature does not provide information on the composition of the
solvents used in these extraction procedures, nor are there details
describing the processes used. The solvent used in extraction
procedures is likely to be recovered via a distillation process
(probably involving reduced pressure). Because of the toxicity of
EDC, the residual amounts of this substance in the extracted material
should be quite small. In 1961, the Federal Food, Drug and Cosmetic
Act limited the concentration of EDC in spice oleoresins (for human
consumption) to 30 ppm or less, while the residual amounts in processed
animal feed in 1967 were limited to 300 ppm (USEPA, 1979a). Thus,
little of the EDC is expected to be transferred to the ultimate
product of the extraction procedure.
Solvent losses will likely occur during the extraction process.
Additional supplies of solvent will have to be added periodically to
make up the losses. It is generally assumed that the bulk of these
losses will be in evaporation (to the atmosphere) from valves, spills,
leaks and during material .transfer operations. For the purposes of
this materials balance, it is assumed that 95% of the EDC consumed
in solvent extraction processes will l>e lost in this manner. Thus
1.0 x 10 kkg of liDC will be emitted Lo the atmosphere via this method.
3-44
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The remaining 5% (60 kkg) is assumed to be associated with the sludge
expected to accumulate in the solvent during the extraction process.
The sludge will be either disposed of on land or incinerated. In
Section 2.1.1.3, it was assumed that 90% of the solid wastes generated
were incinerated and the remaining 10% were landfilled. It was further
assumed that in each of these processes 5% of the EDC was eventually
released to the atmosphere via an assortment of pathways including
fugitive emissions, losses during transportation, and incomplete
destruction of wastes in the incinerator. Using these same assumptions
for the sludges produced as a result of solvent extraction procedures,
the following estimates can be made:
.60 kkg = annual amount of EDC associated with
sludge generated during solvent
extraction procedures
The amount of EDC sent to the incinerator along with the sludge
can then be calculated by multiplying the total quantity of EDC
associated with the sludge by the estimated percentage designated to
be incinerated. In that case,
(60 kkg) (0.''0) = 54 kkg
The amount of EDC associated wit i the sludge sent to landfill
can also be estimated by multiplying the total amount of generated
sludge by the percentage designated to be landfilled. Therefore
(60 kkg) (0.1) = 6 kkg
The quantity of EDC released to the air from the incinerator
can also be calculated by multiplying the quantity of EDC associated
with the incinerated sludge by the inefficiency factor of the
incinerator. In that case,
(54 kkg) (0.05) = 2.7 kkg
More information needs to be obtained (most likely via direct
contacts with oil and pharmaceutical manufacturers and fat processors)
concerning extraction practices involving EDC. Such data could be
obtained during a Phase II investigation and would provide a basis upon
which to evaluate the validity of assumptions made.
3-45
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3.2.3 Releases from EDC Use in Cleaning Solvents
Solvents containing EDC are typically used for cleaning processes
within the PVC and textile manufacturing industries. The available
literature does not provide information on the composition of these
solvents, nor on the characteristics of the cleaning operations.
Based on the general nature of solvent-based cleaning processes, one
would expect virtually all the solvents used ultimately to be evapo-
rated from the surface of the substrate being cleaned (as opposed to
being chemically or otherwise permanently incorporated into the sub-
strate) . These evaporation losses represent releases to the atmo-
sphere. Lost solvent will be replaced with make-up, and it is assumed
that the EDC content of the make-up added accounts for most (95%) of
2
the 9.1 x 10 kkg of EDC consumed and assumed lost to the atmosphere
during solvent cleaning processes. Therefore, the quantity of EDC
released to the atmosphere during the solvent cleaning operations
can be calculated as follows:
(0.95) x (9.1 x 102 kkg) = 864 kkg = EDC
Solids and dense materials removed during the cleaning process will
accumulate in the solvent, and will thereby generate a sludge waste
stream. It is assumed the EDC associated with this sludge will account
for the remaining 5% of the EDC consumed during solvent cleaning oper-
ations. Therefore,
2
(0.05) x (9.1 x 10 kkg) = 46 kkg = Amount of EDC Associated with
the Sludge Generated During
Solvent Cleaning Operations
The sludge will likely be. removed during solvent racovery operations and
will be disposed of either by landfilling or incineration.
Using the same assumptions developed for the sludges produced from
3-46
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solvent extraction processes, the following estimates can be made:
The amount of EDC associated with the sludge sent to the
incinerator can be calculated by multiplying the total quantity of EDC
present in the sludge by a factor of 0.9. In this case,
(0.9) (46 kkg) = 41 kkg
The amount of EDC present in the sludge sent to landfill can
then be calculated by multiplying the total quantity of EDC in sludge
by the factor 0.1. Therefore:
(0.1) (46 kkg) = 4.6 kkg
The amount of EDC ultimately released to the atmosphere during
sludge incineration can also be calculated by multiplying the amount
of EDC in sludge sent to the incinerator by the inefficiency factor
of the incinerator. This amounts to:
(0.05) (41 kkg) = 2 kkg
3.2.4 Releases of EDC Associated with the Manufacture and Use of
Polysulfides
Polysulfides are a group of rubber-like polymers which are ob-
tained via the reaction between aliphatic dihalides and alkali poly-
sulfides (Hienisch, 1974; Considine, 1974). The basic formula for
the.reaction between EDC and Na-S, is given below (Considine, 1974):
n(EDC) + nNa2S, -* W » + 2nNaC1
After final processing, the resulting polymer has excellent resis-
tance to solvents (aliphatic and aromatic), oxidation, ozone, the effects
of weather, water and temperatures as low as -50 C (Hienisch, 1974).
Based on the chemistry of the reaction and the properties of
resulting polymer, it seems reasonable to assume that most of the EDC
used during the manufacturing of polysulfides ends up as a component of
the end product. For the purpose of this report, we are assuming this
amounts to 94%; this estimate is based on the typical industrial
chemical reactions and yields. . Since the portion of the total
3-47
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production of EUC consumed for the manufacture of polysulfides is
5.2 x 102 kkg, 4.9 x 102 kkj
in the polysulfide product.
2 2
5.2 x 10 kkg, 4.9 x 10 kkg is assumed to be chemically incorporated
(0.94) x (5.2 x 102 kkg) = 489 kkg = 4.9 x 102 kkg
It is generally assumed that an additional 5% (or 26 kkg) of
the EDC consumed in this process will be released to the atmosphere
via leaks, spills and fugitive emissions associated with the overall
polysulfide manufacturing process.
0.05 x 5.2 x 102 kkg = 26 kkg
The initial production reaction is typically performed in an
alkaline aqueous phase; therefore, some of tie unreacted EDO may dissolve
in the reaction mixture. Available data ind .cates that EDC is only
slightly soluble ( 1%) in distilled water (Weast, 1977; Windhbltz, 1976).
Thus, one would not expect more than 1% of the EDC to be dissolved, in
the mother liquor, as an unreacted species. It is possible that reaction
conditions (alkalinity, temperature, etc.) may induce hydrolysis of some
of the EDC present in the reaction mixture before it has had a chance to
react with the alkali polysulfide. It should be noted that if this were
to occur, it would still represent the chemical incorporation of EDC into
relatively stable compounds. But since the desired product of the
reaction is the polysulfide, it is reasonable to expect the reaction
conditipns to be adjusted to discourage the production of unwanted
by-products. In spite of the above, it seemed reasonable to assume that
1% of the EDC used for polysulfide manufacture remains as a dissolved
constituent in the mother liquor from which the polymer is produced.
Therefore, the amount of EDC remaining in the mother liquor can be
calculated by multiplying the total amount of EDC consumed for the
manufacturing of polysulfide by the estimated factor. In this case,
(0.01) (5.2 x 102 kkg) =.5.2 kkg
The fate of the mother liquor is not known, but for the purposes
of this materials balance, the mother liquor is assumed to be discharged
3-48
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as solid waste and stored in landfills.
3.2.5 Releases from EDC Use in Grain Fumigation
There are a variety of grain fumigant formulations for which EDC
is a constituent. The composition of some of the fumigants manufactured
by Dow are presented in Table 3.3 (Gosselin, et al., 1976). As shown
in Table 3.3, the grain fumigants manufactured by Dow are generally
various mixtures of EDC, dibromoethane and carbon tetrachloride. The
composition of fumigants produced by other manufacturers may differ, but
some of the formulations also contain EDC (Stanford Research Institute,
1976).
The process of grain fumigation involves exposing grain to fumigant
vapors under specified conditions of time, temperature, etc., and then
allowing for ventilation of the exposed grain. It is unlikely that
attempts will be made to collect the exhaust gases during ventilation;
therefore, it is reasonable to assume that all fumigant vapors which are
not retained by the grain will be released to the atmosphere. The
amount of fumigant retained by the grain depends on a variety of factors
including type of grain, extent of grinding, type and concentration of
fumigant applied, general exposure conditions, and length and nature of
subsequent ventilation (U.S. Environmental Protection Agency), 1978c).
It appears that the retention of EDC is due to both chemical and
physical processes, but investigators differ widely on the total
quantity of the chlorinated hydrocarbon which remains absorbed. Even
though some investigators have reported very high (84%) sorption
efficiencies for certain cereal substrates (Berck, 1965), the generally
accepted conclusions are that by the time the grain is processed and
ready to be consumed, essentially all of the retained EDC will have been
dissipated to the atmosphere (U.S. Environmental Protection Agency,
1978c). For this reason, it is assumed that 100% of the EDC used for
grain fumig;
atmosphere.
2
grain fumigation (totaling 4.6 x 10 kkg) is eventually released to the
3-49
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TABLE 3.3 COMPOSITION OF SELECTED FUMIGANTS*
Ul
I
Lfl
O
Trade Name ' Composition (%)
Dowfume 75
Dowfume EB-5
Dowfume EB-15
Inhibited
Dowfume EB-59
Dowfume J
Dowfume V
*Table represents
1,2 Dichloroethane
70
29
20
9
63.5
15
Carbon Tetrachloride
30
64
57
32
29.7
83
1 , 2 -Dibromo ethane
_
7
20
59
7.8
2
only those fumigants manufactured by Dow
Source: Adapted from SRI, 1975
-------
3.2.6 Releases from Other Uses
Three miscellaneous uses of EDC include (1) the manufacture of
color film, (2) a diluent for pesticides and herbicides, and (3) an amine
carrier during the leaching of copper ores. Here again, there is a
paucity of information in the readily available literature regarding the
details of the processes associated with these miscellaneous uses.
2
Therefore, it was assumed that the 4.6 x 10 kkg of EDC consumed for
this purpose was equally divided among the three identified uses. It
was further assumed that all of the EDC used in the color film and
pesticide/herbicide industry uas eventually released to the atmosphere,
but that used for copper processing was chemically incorporated with
amines and other materials involved in the copper leaching process. Thus,
2
66% of the 4.6 x 10 kkg of EDC used for miscellaneous purposes is
assumed to be released directly to the atmosphere, while the remaining
34% is assumed to be chemically incorporated into materials associated
with the copper leaching process.
The amount of EDC used for miscellaneous purposes can then be
calculated by multiplying the quantity of EDC used in this category
2
(4..6 x 10 kkg) by the estimated percentage. Therefore:
(4.6 x 102 kkg) (0.66) = 3.0 x 102 kkg
The remaining quantity of EDC used in copper leaching process can
also be calculated by multiplying the quantity used in this category by
the remaining percentage. In this case,
(4.6 x 102 kkg) (0.34) = 1.6 x 102 kkg
3-51
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4.0 SUMMARY OF POINTS OF ENVIRONMENTAL RELEASE
The environmental releases of EDC during its production, dis-
tribution, and use are estimated to have been 65,000 kkg in 1977.
This section highlights the releases that are of importance in
terms of quantity and location of release. Releases, the point-
sources of release and the geographic location of the producers and
users of EDC are shown in Section 2 and 3.
The two largest sources of release, each representing 30% of
the total quantity of EDC released, are the quantities of EDC re-
leased to the air during the direct chlorination and the oxychlor-
ination processes for producing EDC. The quantity of EDC released
from process vents and light-end streams of each production process
amounts to approximately twenty thousand kkg. Most of the plants
producing EDC use both of these processes. Therefore, a total of
seventeen plants producing EDC release close to 60% of the total
EDC released to the environment and this release is to the atmos-
phere. Most of these production facilities are located in the Gulf
Coast regions of Louisiana and Texas.
Monitor:! ng data have indicated that EDC is present in the
ambient air near production facilities. It has been theorized
from these data that the EUC emissions from a stack drop to the
ground level and, depending, on local cliinatologica.l. and topo-
graphic factors, they tend to follow valleys and.low-lying areas
(EPA, 1978d). This theory is dependent on and consistent with
the vapor density of EDC which is 3.42, given the density of air =
1. It is important to note here that, according to the American
Public Health Association statistics (1975), 1,379,000 people live
within 5 miles of an EDC manufacturing facility.
4-1
-------
The next two largest source?, of emissions are those in waste-
water streams from both production processes for EDC. These quan-
tities are 4,900 kkg (or 8% of the total) from the wastewater stream
of the oxychlorination process and 4,400 kkg (7% of the total) from
the wastewater stream of the direct chlorination process.
Other potentially important releases (each 1% of the total)
of EDC include the following:
• Methyl chloroform production process vents (2.3%)
• Paints, coatings, and adhesives formulation (2.0%)
• , Gasoline lead scavenger (1.6%)
• Extraction solvent (1.4%)
• Perchloroethylene production process vents (1.3%)
• Cleaning solvent (1.2%)
It is important to note that regulation promulgated by the
authority of the Occupational Safety and Health Act restricts the
quantities of EDC released in the workplace. The only workplace
environment where EDC releases are not fully regulated is the gas
station. It i.s not possible to adequately measure worker exposure
at gas stations since ambient air levels are not representative of
worker exposure.
4-2
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5.0 SUMMARY OF DISPOSAL AND DESTRUCTION OF SOLID AND
LIQUID EDC-CON^AINING WASTES ,
This chapter summarizes the information on the quantities of
EDC-containing solid and liquid wastes destroyed and disposed of
during the production and uses of EDC. According to Gruber (1975),
incineration was apparently the only method of disposing of EDC-
containing wastes.
As shown in Table 5.1, the amounts of EDC present in heavy-end
waste streams of the direct chlorination process, the oxychlorination
process and the vinyl chloride monomer production process are
2.2 x 103 kkg, 3.1 x 103 kkg, and 2.0 x 103 kkg respectively.
Assuming that the incinerator used in the destruction of heavy-end
waste achieves a 95% efficiency, the quantity of EDC destroyed from
3 3
the above heavy-end wastes is, respectively, 2.1 x 10 kkg, 2.9 x 10
3
kkg, and 1.9 x 10 kkg. The uncertainty of the.se figures is
unknown because of the lack of information.
The quantity of EDC present in the sludge generated from the
use of EDC as a solvent for paints, coating and cleaning purposes
is estimated at 100 kkg. The sludge is assumed to be incinerated
and the quantity of EDC destroyed amounts to 95 kkg. The
remaining 5 kkg is released intact to the air. The uncertainty of
this figure is not calculated.
5-1
-------
TABLE 5.1 - SOLID AND LIQUID EDC-CONTAINING WASTE
QUANTITIES, DISPOSAL, AND ENVIRONMENTAL RELEASE
en
to
AMOUNT OF EDC
PRESENT IN SLUDGE
TYPE OF GENERATED FROM
WASTE WASTEWATER
PRODUCED TREATMENT (kkg)
— Direct
chlorination
of ethylene
• Heavy-end
waste
— Oxychlorination
of ethylene
• Heavy- end
waste
QUANTITY
AMOUNT OF DESTROYED BY
SOLID WASTE INCINERATION
(kkg) (kkg)
2.2 x 103 2.1 x 103
3.1 x 103 2.9 x 103
QUANTITY
RELEASED TO
AIR FROM
INCINERATION
(kkg)
1.1 x 102
1.6 x 102
Vinyl chloride
monomer
production
process
• Heavy-end
waste
• Solvent for
paint and
coating 60
• Cleaning
solvent 46
2.0 x 103 1.9 x 103
54
41
1
6
5
1.0 x 102
-------
6.0 SUMMARY OF UNCERTAINTIES
Table 6.1 lists the estimates for environmental releases and
the associated uncertainties of EDC by process and by media of
release. The rationale for assigning a specific uncertainty to •
each number is discussed in Chapters 2 and 3. Our recommendations
for upgrading the material balance are presented in Chapter 7.
6-1
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TABLE 6.1 SUMMARY OF UNCERTAINTIES FOR
ESTIMATES OF ENVIRONMENTAL
RELEASE FROM PRODUCTION
AND USE OF EDC
Process/Operation
Method of Environmental
Release
Quantity (kkg)
Uncertainty
The direct chlorina-
tion process
TOTAL PRODUCTION
EMISSION TO AIR
- Chlorinator vent
a - uncontrolled
b - controlled 4
- Light-End column vent
a - uncontrolled
b - controlled
- EDC distillation column
vent
a - uncontrolled
b - controlled
- Product storage
a - uncontrolled
b - controlled
- Fugitive losses
a - uncontrolled
i> - controlled
- Wasteuater treatment
- Heavy-End waste
incineration
2.94 x 10
2.9 x 10
58
3.0 x 10^
3.0 x 10*
3.0 x 10,
3.0 x 10
1.1 x 10,
5.3 x 10
1.8 x 102
18 3
4.4 x 10J
1.1 x 10
+12
+1502, -952
+532, -1002
+1502, -962
+2802, -972
+2002, -962
+3502, -972
+442
+2002, -792 .
+1502, -962
+3402, -1002
+1502, -962
+2502, -982
The oxychlorination
process
TOTAL PRODUCTION
EMISSION TO AIR
- Absorber vent
a — uncontrolled
b — controlled
- EDC stripper vent
a — uncontrolled
b - controlled
- Light-End cclumn vent
a - uncontrolled
b - controlled
- EDC distillation
column vent
a - uncontrolled
b - controlled
- Product storage
a - uncontrolled
b - controlled
2.05 x 10
2.1
10
2.1 x 10
5.6 x 10*
1.1 x 10*
2.1 x 10*
2.1 x 10
2.1 x 10,
2.1 x 10
7.6 x 10*
3.8 x 10*
+12
+962
+1902, -972
+962
+5002. -1002
+962
+1902, -972
+962
+1902, -972
+442
+2002. -802
6-2
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TABLE 6.1 SUMMARY OF UNCERTAINTIES FOR ESTIMATES
OF ENVIRONMENTAL RELEASE FROM PRODUCTION
AND USE OF EDC (cont.)
Process/Operat Ion
Method of Environmental
Release
Quantity (kkg) Uncertainty
- Fugitive emission _
a - uncontrolled 1.3 x 10
b - controlled 13 ,
- Uastevater treatment 4.9 x 10
- Heavy-end waste Incin- -
eration 1.6 x 10
+96Z
+310Z. -100Z
+961
•1-1501, -981
Indirect Production
EMISSION TO WATER
- Quantity of POTW/year
- Amount of EDC released
- Quantity of industrial
uastevater treated/year
- Amount of EDC released
- Amount of EDC formed
by incinerating MSW
- Amount of EDC formed
from other inadvertent
sources
8.2 x 1012gal
2.2
1.6 x 10*3gal
1.9 x 10
0.06 - 0.3
5 x 10
.-4
+25X
+150Z..-100Z
+25Z
+1501. -1001
+70Z
+200Z, -100Z
Vinyl chloride monomer
production
TOTAL PRODUCTION (from EDC)
- Amount of .EDC used
- Emission of EDC to land
- Emission of EDC to air
(incineration)
2.48 x 10°
4.05 x 10
2.0 x 10
99
•HZ
+2Z
+51Z
+110Z, -70Z
Trichloroethylene
production
TOTAL PRODUCTION (from EDC)
- Amount of EDC used
- Emission of EDC to air
1.2 x 10
1 x 105
610
+1Z
-»-2Z
+51Z
Perchloroethylene
(from EDC)
TOTAL PRODUCTION (from EDC) 2.8 x 10^
- Amount oi EDC used 1.2 x 10
- Emission of EDC to air 910
+1X
±2*
+511
Perchloroethylene
(from acetylene)
- Emission of EDC to air
20
+51Z
Vinylidine chloride
production
TOTAL PRODUCTION (from EDC) 1 X 10 -
- Amount of EDC used 1.2 x 10
- Emission of EDC to air 600
+11
+3Z
+511
6-3
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TABLE 6.1 SUMMARY OF UNCERTAINTIES FOR ESTIMATES OF
ENVIRONMENTAL RELEASE FROM PRODUCTION AND
USE OF EDC (cont.)
Frocess/OperatIon
Method of Environmental
Release
Quantity (kkg) Uncertainty
Methyl chloroform
product Ion
Ethyl eneamines
TOTAt PRODUCTION (from EDC)
- Amount of EDC used
- Emission of EDC to air
TOTAL PRODUCTION (from EDC)
- Amount of EDC used
- Emission of EDC to air
2.6 x 10^
2.1 x 10,
1.6 x 10
6.9 x 10*
1.5 x 10
610
+1Z
+3Z
+51Z
+5Z
+10Z
+51Z
Lead scavenger
production
EDC USED 9.7 x 10 +100Z
- Emission of EDC to the air
during production of
leaded gasoline
- Emission of EDC to th< air
from tank breathing
- Emission of EDC to the air
from tank filling
a - uncontrolled
b - controlled
- Emission of EDC to thi air
from combustion 9.6 x 10 unknown
97
11
84
67
unknown
unknown
unknown
unknown
6-4
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7.0 DATA GAPS
During the preparation of this report, a series of significant
data gaps were identified. This section lists and discusses these
gaps in information. In. many cases, suggestions are made for
methods that could be utilized to obtain(the needed information.
Most important, this section pinpoints areas where-, additional re-
search is necessary.
7.1 DATA NECESSARY TO INCREASE THE VALIDITY OF EMISSIONS
ESTIMATED FOR VARIOUS PRODUCTION PROCESSES
The estimate of emissions for many of the major production
processes were based primarily on one reference (Hedley et al.,
1975). Review of this source indicates that no substantiating
information was provided. While the Hedley figures do not seem
unreasonable, it is clear that in its present unsubstantiated and
unexplained form, this report does introduce an element of un-
certainty. Additional supporting information should be obtained
by contacting Hedley or individuals in the manufacturing industry.
7.2 ESTIMATES OF THE OCCURRENCE AND RELEASE OF EDC AS A
BY-PRODUCT OF MANUFACTURING PROCESSES FOR WHICH EDC
IS NOT A FEEDSTOCK
Production processes which use synthetic organic chemical re-
act-ions could generate EDC as a by-product: along with the major de-
sired product. If produced, such a by-product stream could (1)
be recovered and sold, (2) become a contaminant of the major pro-
duct or (3) become a component of some waste stream. Since this
by-product generation could occur .in a manufacturing area unrelated
to those described in this report, any potential emissions of EDC
from such a source would not be accounted for in this analysis.
Therefore, any significant emissions of EDC which have been
7-1
-------
generated as a by-product could have a substantial effect on the
overall materials balance as represented in this report.
In Section 2 of this report, these possibilities are analyzed,
and very rough estimates are made. In addition, the Effluent
Guidelines Division of EPA has indicated that EDC as a priority
pollutant is present in the wastewater of many industries. This
area must be explored further. :
7.3 DETERMINING EMISSION LEVELS OF EDC ASSOCIATED WITH
CERTAIN MAJOR USES
As pointed out in Section 3.1 of this report, information on
EDC emissions to various segments of the environment is very limited
for production processes using EDC as a feedstock. These processes
include the following: production of vinyl chloride, trichloro-
ethylene, perchloroethylene, uthyleneamines and vinylidine chloride.
Thus, it is very difficult to properly assess the emission of EDC
during the production of the above chemicals. Further studies
should be conducted to expand the data base.
Analyses obtained from monitoring data on wastewater st.reams
discharged by the chemical producers mentioned above do not identify
EDC as a component of the. waste stream. It is suggested that EDC
contamination could occur in the wastewater stream and EDC could
rapidly evaporate to the air (due to its high volatility) before
the waste treatment cycle. Therefore, this potential source of EDC
release to the atmosphere should be investigated in further studies.
Likewise, information on EDC emission from solid waste such
as the heavy-end tars stream is iiot available for most of the pro-
duction processes (vinylidene chloride, trichloro -thylene, per-
chloroethylene, .and ethyleneamim s) . Possible release of EDC to
the environment from this source could be' significant; therefore,
it deserves more in-depth study in further investigations.
7-2
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7.4 DATA GAPS RELATING TO MINOR USES OF EDC
As described in Section 3.2, there is limited information
concerning minor uses of EDC and the associated emissions. Specif-
ic data gaps are presented below:
• Information on the nature of minor uses of EDC (e.g.,
whether EDC is used as a solvent or a bound constituent
in paints, coatings and adhesives; whether there are
vapor recovery systems for grain fumination; etc.)
• Composition of cleaning and extraction solvents which con-
tain EDC
• Accurate assessment.of the amount and nature of EDC use
(1) in the manufacture of color film; (2) as a herbicide
and pesticide diluent; and (3) in copper leaching processes.
Many of the data gaps concerning minor uses will have to be
closed via direct contacts with manufacturing concerns, since most
of the required information is not present in the available
literature.
7.5 EDC PRODUCTION DURING THE CHLORINATION OF WATER AND
WASTEWATER
The National Organic Monitoring Survey (NOMS) revealed the
presence of EDC at low levels (EPA, 1978) in both raw and finished
water. It was suggested that EDC .is formed by the reaction of
organic impurities present in water with chlorine added at the
water treatment plant. Another possible explanation for this oc-
currence of EDC in municipal water is that the raw water effluent
is taken near a point source of EDC emissions. The NOMS data for
these municipal systems should be examined to verify any conclusions;.
In addition, the formation of EDC as a result of wastewater chlori-
natiori requires further study.
7-3
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7.6 EUC PRODUCTION KKOM i NCINKKATTON OK CH1.OKJ NATK1) OKOANtC
COMPOUNDS
Although esti.mates were made for the release' of EUC as a re-
sulL of the incineration of chlorinated organic^, many assumptions
were used as the has;.is for the.su estimates. Vir .uully no hard data
was retrieved which indicated that EDC could in ,"act be produced
through the incineration of chlorinated organic compounds. Further
research in the behavior of these compounds must be conducted be-
fore accurate assessments can be made.
7-4
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8.0 LIST OF REFERENCES
Aldrich Chemical Co. Personal Communication in October 1979.
American Petroleum Institute. 1979. Personal Communication on
October 3, 1979.
American Public Health Association. 1975. Population Residing near
Plants Producing Vinyl Chloride. U.S. Env: ronment Protection
Agency, Washington, B.C. (unpublished).
Auerbach Associates, Inc. 1978. Miscellanerus and Small Volume
Consumption of Ethylene Bichloride. U.S. Environmental Protection
Agency, Washington, B. C. (unpublished). ' pp.
Barnhart, W. L., C. R. Toney, and J. B. Beviin. 1975 Environmental/
Industrial Hygiene Surveys of Vinyl Chloride Monomer Manufacturing
Operations and Operations Where Polyvinyl Chloride and Copo]ymers
of Polyvinyl Chloride Are Processed. U.S. Department of Health,
Education, and Welfare, Washington, B.C. (unpublished). 30 pp.
Bellamy, R. G., and W. A. Schwartz. 1975. Engineering and Cost Study
of Air Pollution Control for the Petrochemical Industry, Vol. 8,
Vinyl Chloride Manufacture by the Balanced Process. KPA-450/3-73-006-h.
U.S. Environmental Protection Agency, Research Triangle Par, N.C.
61 pp.
Berck, B. 1965. Sorption of Ethylene Bibromide, Ethylene Bichloride
and Carbon Tetrachloride by Cereal Products. J. Agric. Food Chem.
13 (3): 248-254.
Berck, B. 1974. Fumigant Residues of Carbon Tetrachloride, Ethylene
Bichloride, and Ethylene Bibromide in Wheat, Flour, Bran, Middlings,
and Bread. J. Agric. Food Chem. 22(6): 977-784.
B. F. Goodrich Co. Personal Communication in October 1979.
Borden Chemical Co. Personal Communication in October 1979.
Brown, Vice President of Technical Affairs, Paint, Varnish and Lacquer
Association, Personal Communication, September 1979.
Chemical Marketing Reporter. 1977a. Profile: !• thy.lene Bichloride.
212(3) :9.
Chemical Marketing Reporter. 1977b. Current Prices of Chemicals and
Related Materials. 212(3):62.
Chemical Marketing Reporter. 1978. Current Prices of Chemicals and
Related Matters. 214(3):42.
8-1
-------
Connolly, E.M., Chemical Economics Handbook Marketing Research Report
on Vinyl Surfnce Coatings, Stanford Research Institute, Menlo Park,
California. M;iy, 1977.
Considine, D. M. , Editor in Chief, Chemical and Process Technology
Encyclopedia, p. 284, 1974.
Dow Chemical Co. Personal Communication in October 1979.
Eimutis, E. C., and R. P. Quill. 1977. .Source Assessment: Noncriteria
Pollutant Emissions. EPA-600/2-77-107e. U.S. Environmental Protection
Agency, Research Triangle Park, N.C. 99pp.
Faith. W.L., D. B. Keyes, and R. L. Clark. 1965a. Ethylene Dichloride.
In: Industrial Chemicals, 3rd ed. John Wiley and Sons, New York.
pp. 368-371.
Faith, W. L., D. B. Keyes, and R. L. Clark. 1965a. Vinyl Chloride.
In: Industrial Chemicals, 3rd ed. John Wiley and Sons, New York.
pp. 805-810.
Gaylord, N. C., and Mark, H. F. 1971. Encyclopedia of Polymer Science
and Technology.
Gosselin, K. E., H. C. Hodge, R. P. Smith and M. N. Gleason, Clinical
Toxicology of Commercial Products: Acute Poisoning, Fourth Edition,
Section V, pp. 217-18, 1976
Gruber, G. I. 1975. Assessment of Industrial Hazardous Waste Practices,
Organic Chemicals, Pesticides and Explosive Industries. Report No.
25666-6010-TU-OO. TRW Systems and Energy, Redondo Beach, Calif, pp. 5-34
to 5-37.
Hardie, D. W. F. 1964. Vinyl Chloride. In: Kirk-Othmer Encyclopedia of
Chemical Technology, 2nd ed., Vol. 5. Interscience Publishers, New York.
pp. 171-178.
Hawley, G. G., ed. 1977. The Condensed Chemical Dictionary, 9th ed.
Van Nostrand Reinhold Co., New York. p. 358.
Hedley, W. H., S. M. Mehta, C. M. Moscowitz, R. B. Reznik, G. A. Richardson,
and D. L. Zanders. 1975. Potential Pollutants from Petrochemical Pro-
cesses. Technomic Publishing Co., Westport, Conn. pp. 193-195.
Hienisch, K. F., Dictionary of Rubber, pp. 475-478, 1974
Hobbs, F. D., J. A. Key, 1978, Emissions Control Options for the Synthetic
Organic Chemical Manufacturing Industry EPA Contract #68-02-2577.
Jacobs, M. B. 1941. The Analytical Chemistry of Industrial Poisons,
Hazards and Solvents. Interscience Publishers, New York. p. 459.
Johns, R. 1975. Air Pollution Assessment of Ethylene Dichloride.
MTR-7164. The MITRE Corporation, McLean, Va. 34 pp.
8-2
-------
Jones, J. H., and P. J. Bierbaum. 1974. Walk-Through Survey, Ethyl
Corporation, Pasadena, Texas, National Institute for Occupational
Safety and Health, Cincinnati, Ohio (unpublished). 22 pp.
J. T. Bnker Co. Personal Communication in October 1979.
.Keyes, and Clark's Industrial Chemicals, 4th ed. John Wiley and Sons,
New York. pp. 392-396. '
Mansville Chemical Products. April 1977. Chemical Products Synopsis-
Ethylene Bichloride. Mansville, New York.
Mara, S. J., and S. S. Lee. 1978. Atmospheric Ethylene Dibromide: A
Source-specific Assessment. Center for Research and Environmental
Systems Studies Report No. 39. SRI International, Menlo Park,
California. 78 pp.
McConnell, G., D. M. Ferguson, and C. R. Pearson. 1975. Chlorinated
Hydrocarbons and the Environment. Endeavour 34:13-18.
McPherson, R. W., C. M. Starks, G. J. Fryar, "Vinyl Chloride.Monomer"
Hydrocarbon Processing, 58, 3, 1979.
Mellow, W. 1978. National Organics Monitoring Survey March 1976
through January 1977. U.S. Environmental Protection Agency,
Washington, D.C. 126 pp.
National Institute for Occupational Safety and Health. 1976.
Occupational Exposure to Ethylene Bichloride (1,2-Bichloroethane).
U.S. Bepartment of Health, Education, and Welfare, Washington, B.C.
157 pp.
Patterson, R. M., M. I. Bornstein, R. R. Hall, and E. Garshick. 1975.
Assessment of Ethylene Bichloride as a Potential Air Pollution Problem,
Vol. III. Report No. GCA-TR-75-32-G(3). GCA Corp., Bedford, Mass.
25 pp.
Pervier, J. W., R. C. Barley, B. E. Field, B. M. Friedman, R. B. Morr::s,
and W. A. Schwartz. 1974. Survey Reports on Atmospheric Emissions from
the Petrochemical Industry, Vol. II. EPA-450/3-73-005-b. U.S. Environ-
mental Protection Agency, Research Triangle Park, N.C. 321 pp.
Polglase W., W. Kelly, 1977. Control of Hydrocarbons from Tank Truck
Gasoline Leading Terminals. EPA-450/2-77-026. Washington, B.C.
Radding, S. B., B. H. Liu, H. L. Johnson, and T. Mill. 1977. Review of
the Environmental Fate of Selected Chemicals. EPA-560/5-77-003. U.S.
Environmental Protection Agency, Washington, B.C. 147 pp.
Sax, N. I., ed. 1974. Industrial Pollution. Van Nostrand Reinhold Co.,
New York. p. 623.
Sax, N. I. 1975. Ethylene Bichloride. In: Bangerous Properties of
Industrial Materials, 4th ed. Van Nostrand Reinhold Co., New York.
p. 736.
8-3
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Schwartz, W. A., F. G. Higgins, Jr., J. A. Lee, R. Newirth, and J. W.
Pcrvier. .1.974. Engineering and Cost Study of Air Pollution Control
for tlic Petrochemical Industry, Vol. 3, Ktliylene. Dichl oridc Manufacture
by Oxychlorination. EPA-450/3-73-006-C. U.S. Environmental Protection
Agency, Research Triangle Park, N.C. 104 pp.
Shedd, S. A., N. Efird, 1977, Control of Volatile Organic Emissions from
Bulk Gasoline Plants, EPA-450/2-77-035, Washington, D.C.
Stanford Research Institute. 1975. Chemical Economics Handbook
Storck, W. J. 1978. Production Rises for Most Major Chemicals. Chem
Eng. News, 56(18):31-37.
Symons, J. M., T. A. Bellar, J. K. Carswell, J. DeMarco, K. L. Kropp,
G. Robeck, D. R. Seeger, C. J. Slocum, B. L. Smith, and A. A. Stevens.
1975. National Organics Reconnaissance Survey for Halogenated Organics.
J. Am. Water Works Association. 67:634-647.
U.S. Department of Labor. Selected General Industry Safety and Health
Standards - 29CFR 1910.1000. Table Z.2. 1977
U.S. Environmental Protection Agency. 1972. Air Pollution from Chlorination
Processes. PB 218.043.
U.S. Environmental Protection Agency. 1975. Standard Support .ind
Environmental Impact Statement: Emission Standard for Vinyl Chloride.
EPA-450/2-75-009. Research Triangle Park, N.C.
U.S. Environmental Protection Agency. 1977a. A Study of Industrial Data
on Candidate Chemicals for Testing. EPA-560/5-88-006. Washington, D.C.
592 pp.
U.S. Environmental Protection Agency. 1977b. Control of Volatile Organics-
from Bulk Gasoline Plants. EPA-450/2-77-035.
U.S. Environmental Protection Agency. 1977c. Market Input/Output Studies,
Task I, Vinylidene Chloride. EPA 560/6-77-033. 182 pp.
U.S. Environmental Protection Agency. 1977d. Multimedia Levels, Methyl
Chloroform. EPA 560/6-77-030.
U.S. Environmental Protection Agency. 1977e. Multimedia Levels, Trichloro-
ethylene. EPA 560/6-77-029.
U.S. Environmental Protection Agency. 1977f. Report to Congress: Resource
Recovery and Waste Reduction. SW-600.
U.S. Environmental Protection Agency. 1977g. Compilation of Air Pollutant
Emission Factors. Public Health Service Publication 999-AR 42. August
1977. .
8-4
-------
U.Si Environmental Protection Agency. 1978a. Personal Communication
citing U.S. Department of Commerce, 1970-1974.
U.S. Environmental Protection Agency. 1978b. Personal Communication
citing U.S. Department of Commerce, 1970-1974.
U.S. Environmental Protection Agency. 1978c. Air Pollution Assessment
of Vinylidene Chloride. EPA-450/3-78-015. Washington, D.C. pp. 49-.t6.
U.S. Environmental Protection Agency. 1978d. Monitoring of Ambient Levels
of Ethylene Dichloride (EDC) in the Vicinity of EDC Production and User
Facilities. Draft Report Under Contract No. 68-02-2722, Task 8.
U.S. Environmental Protection Agency. 1979a. Investigations of Selected
Environmental Pollutants: 1,2-Dichloroethane, fPA-560/2-78-006.
Washington, D.C. 172 pp.
U.S. Environmental Protection Agency. 1979b. An Assessment of the Need
for Limitations on Trichloroethylene, Methyl Chloroform, and
. Perchlorqethylene EPA-560/11-79-009, Washington, D.C. pp. 3-36 and
3-107. , .
:
U.S. Environmental Protection Agency. 1979c. Production and Use of
1,2-Dichloroethane. Draft Report Under Contract No. 68-01-3852,
Task 16.
U.S. International Trade Commission. 1973-1977. Synthetic Organic
Chemicals, U.S. Production and Sales.
Weast, R., ed. 1977. Handbook of Chemistry and Physics, 57th ed.
The Chemical Rubber Co., Cleveland, Ohio.
Windholtz, M., ed. 1976. The Merck Index, 9th ed. Merck and Co.,
Rahway, N.J. 1312 pp.
8-5
-------
APPENDIX A
PHYSICAL PROPERTIES OF
1,2-DICHLOROETHANE
-------
Physical Properties of 1,2-Dichloroethane
Molecular weight 98.96
Density ac 20*C 1.2351
Melting point, *C -35.36
Boiling poise, °C 83.47
Index of refraction at 20*C 1.4448
Vapor pressure, toFT
At -44.5*C 1
At -13.6*C 10
At 10.0'C 40
At 29.4*C 100
At 64.0*C 400
At 82.4'C 760
Solubility in water, ppo
At 20°C 8690
At 30'C 9200
Biochemical oxygon demand (5 days), X 0
Theoretical oxygen demand, mg/mg 0.97
Measured chemical oxygen demand, mg/mg 1.025
Vapor density (air - 1) 3.42
Flash point, closed cup, *C 13
Ignition temperature, *C 413
Explosive limit, Z by volume in air
Lower . 6.2
Upper 15.9
Specific resistivity 9.0 x 10*
Viscosity at 20*C, cP 0.840
Dielectric constant, e 10.45
Surface tension, dynes/cm 33.23
Coefficient of cubical expansion at 10"C to 30*C 0.0016
Latent heat of fusion, cal/g 21.12
Latent heat of vaporization at boiling point, cal/g 77.3
Specific heat, cal g" 'C'1
Liquid ac 20*C 0.308
Vapor, 1 atm, at 97.1*C 0.255
Critical temperature, *C 288
Critical pressure, acm 53
Critical density, g/on* 0.44
Thermal conductivity at 20*C, Btu hr~l ft*1 0.825
Heat of combustion at constant pressure, kcal/g-mole 296.36
Dlpole moment, esu 1.57 x 10~"
Conversion factors at 25*C and 760 torr 1 mg/liter • 1 g/m1 - 247 ppm
1 ppm ••4.05 mg/m' • 4.05 ug/liter
Source: Compiled from Faith, Keyes, and Clark, 1965a; Price, Waggy, and Conway, 1974;
Verschueren, 1977; Weast, 1977.
A-l
-------
APPENDIX B
EXCERPTED DESCRIPTIONS OF MAJOR
PROCESSES WHICH PRODUCE
OR USE EDC
-------
Various information on the 1,2-dichloroethane chemical
intermediate production processes are included in this appendix.
This information is excerpted from the following sources:
1. Gruber, G. I., Ghassemi, M., 1975. Assessment of
Industrial Hazardous Waste Practices: Organic Chemicals,
Pesticides, and Explosives Industries. EPA Contract No.
68-01-2919.
2. U. |3. Environmental Protection Agency, 1979. An
Assessment of the Need for Limitations on Trichloro-
ethylene, Methyl Chloroform, and Perchloroethylene.
EPA 560/11-79-009, Washington, D. C.
3. U. S. Environmental Protection Agency, 1978. Air
Pollution Assessment of Vinylidene Chloride. EPA
450/3-78-015, Washington, D. C.
4. Lowenheim, F. H., and M. K. Moran, 1975. "Ethylene
Diamine" In: Faith, Keyes, and Clark's Industrial
Chemicals, 4th edition. John Wiley & Sons, New York.
pp. 385-388.
5. McPherson, R. W., Starks, C. M., Fryar, G. J.,
"Vinyl Chloride Monomer". Hydrocarbon Processing, 58,
3, 1979.
B-l
-------
B.I Vinyl Chloride KonOT.er SIC ?B692^1M08'310'341) (Source: Gruber 1975)
The production rates 1n 1973 for vinyl chloride mono-.er (VCM) and for
ethylene dichloride (EOC). the intermediate used In the majority of manu-
facturing processes were 2,432,000 metric tons (5,351 million pounds) and
4,215,000 metric tons (9,293 million pounds)^ '. There were ten major
producers reported. ' Allied Chemical Corporation (Specialty Chemicals
Division), A.-erican Chemical Company, B. F. Goodrich Company (B. F. Goodrich
Chemical Company Division), Continental Oil Company, Dow Chemical Company,
Tenneco Chemicals Incorporated, Konochem Incorporated, Pittsburgh Plate Glass
Company, Shell Oil Company (Shell Chemicals Company Division) and Ethyl
Corporation. A typical plant size Is 136,000 metric tons per year, with
plant capacities which range from 27,000 metric tons to 317,500 metric tons
per year for the major process system employed.* '
The process flow diagram of Figure 5-14 is a composite typical department
for the production of vinyl chloride from ethylene and chlorine. -Ethylene
di chloride is produced continuously by the liquid phase catalyzed addition
chlorination reaction between ethylene and chlorine, fed as gaseous reactants
to a pressurized vessel. The reaction which takes place Is:
The catalyst employed -Is ferric chloride, suspended in liquid ethylene
dichloride. The product ethylene dlchloride Is liquified, scrubbed with dilute
caustic soda solution, filtered and distilled. Tie heavy ends from the still
(0.0104 kg per kg product VCM) are a hazardous process waste, sent to land
disposal. The heavy ends contain highly dangerous components— ethylene
dichloride (23 percent), 1,1 ,2-trichloroethane (38 percent) and tetrachloroethane
(38 percent) — which are bioaccumulable.
The purified EDC from the still 1s fed to the pyrolysls furnace for the
production of vinyl chloride monomer. In accordance with the following reaction:
C1CH2CH2C1 -JSQBQ'K > HC1
The reaction takes place in the vapor phase, at 450-620 x 103 newtons/meter
(50-75 pslg). The catalysts employed may be activated carbon or pumice. When
B-2
-------
mercuric chloride 1s employed as catalyst, lo-er \.&?~riratures '720°K) and
higher pressures (520-930 x 10 newtons/c.eter ) are u'.ed. Con.erslon per pass
Is 50 percent; with recycle, the pyrolysls yield Is 9> to 96 ptrcent.
The product gas stream from the furnace, contain ng VCH, EOC and HC1
Is quenched with recycled liquid EDC, and condensed. The hydrogen chloride
Is separated 1n the condenser, since It re~ains (as tde sole constituent) in
the gas phase, and Is sent to recovery, or to use In an oxy-chlorination unit
for the production of EOC by reaction with ethylene.
The liquid effluent from the condenser is sent to a still, where 1t is
separated into VCM product, recycle EDC, -and "heavy i nds" (about 0.038 kg/kg
VCH product). The "heavy ends" are a hazardous process waste sent to land
disposal. They are in this case composed of 'ilgher halogenated hydrocarbons
(97 percent), EDC (2 percent) and tars (1 percent), and are considered highly
dangerous. When mercuric chloride Is used as catalyst, there Is also a discharge
of mercuric "hydroxide" (hydrated oxide) to Und In the filter solids,
estimated at 5 x 10"6 kg/kg VCH.
B-3
-------
tun it| vmri CHiomoc
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aiCHlOROCTMAJIt
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I
It All
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Figure B-l. Typical Production Process for Vinyl Chloride Monomer
Iron 1.2-Dlchloroethan*
(Source: Crubcr, 197$)
B-4
-------
B.3 Perchloroethylene Production Tect.nologv (Source: EPA, 1979)
In 1973 nrarly all of the perchlorcethyl ene output In the U.ilted States
was derived from the oxychlor inat 1 on of ethylene dlchlorlde (about 3*>Z of out-
put), or by the sf^-jl taneous chlorlnatlon and pyrolysls of hydrocarbons lifout
63Z of output). Approximately 3Z -'as based on the use of acetylene as a raw
material (tovenhete and Koran, 1975).
B.3.1 Production Treat Ethylene Dlchlorlde--
.The typical process for manufacture of perchloroethylene and trlchloro-
ethylene from ethylene dichloride vas shown in Figure 3-6 and the process de-
scribed In Subsection 3.1.3.
B.3. 2 Production from Acetylene (Source: Cmber, 1975)
Production of perchloroethylene ("tetrachloroethylene*) In 1973 totalled
320,000 metric tons (706 million pounds). There were eight major producers--
Diamond Shamrock Corporation. Dow Chemical Company, and E. I. duPont de Nemours
and Company. Inc., Vulcan Materials Company (Chemical Division). Hooker
Chemical Corporation (Division of Occidental Petroleum), Pittsburgh Plate
Glass Company, Stauffer Chemical Company (Industrial Division), and Ethyl
Corporation. Typical plant sizes are In the range of 32.000 to 45,000 metric
tons (SO to 100 million pounds) per year.
About 2W of the perchloroethylene manufactured uses chlorine and
acetylene as starting materials. The chemistry of the reactions Is as follows:
2 C12 + HC s CH
C2H2C14 o* C1'CH • CC12 * HC1
C1CH - CC12 + C12 fa* C12CHCC1
onor
2C12CHCC13 + Ca(OH)2 ou u
Chlorine and acetylene, each Individually premised with a reaction medium of
recycled tetrachloroethane and antimony trichloride catalyst, are fed to a
pacVed chlorlnatlon tower. The reaction product (see Figure B-3 ) Is fed to •
still and separated Into spent antimony chloride catalyst, tetrachloroethane,
B-5
-------
The crude trlchloroethylene streirc ts fed Into * product sttll In
low boiling components, such as dichloroethylet.es, art r..=noved as an overhead
stream and recycled to the reartor. The purified product (99.9+ we. Z purity)
is retnoved from the bottom of the still, neutralized vtth a^rwnla, washed, and
dried. The overall yield of trlchloroethylene In this process ts 85 to 901.
By-products and wastes frc-a this process are hydrogen chloride (recovered
as hydrochloric acid); chlorln- (.produced frcra hydrogen chloride by the Deacon
process using a copper chloride catalyst); and atmospheric ('-ater vapor) emis-
sions frcss tie c-=jde oroduct dehjdrator unit (Lovrenheim and Moran, 1975).
t.CrcU
•rfr,
<
I
o
TJ
NHj Hj
u
TL
-ICI
'rLl
Tl
TJ
BH
"JO
l~
.in.
Source: Louenhein and Koran (1975).
Figure B-2. Production schematic for trlchloroethylene based on ethylene
dichloride.
B-6
-------
Source: EPA, 1.979
*
B.2 Trlchlorofthvlene Production Technology
In 1975, about 90Z of the commercial production of trlchloroethylene was
by the chlorlnatlon or oxyhydrochlorlnatlon of ethylene to fora the Intermedi-
ate ethylene dlchlorlde, which was in turn chlorinated and then dehydrochlorl-
nated to fora trlchloroethylene. The remaining 1OJ was still r-anufactured by
an older process which Involves chlorinatibn of acetylene in the presence of
a catalyst, followed by dehydrochlorination of the 1,1,2,2-tetrachloroethane
Intermediate.
B.2.1 Production From Ethylene Dlchlorlde--
A typical process for the manufacture of trlchloroethylene and perchloro-
ethylene from ethylene dlchloride Is shown In Figure B-2. There are several
other commercial processes based on ethylene dlchloride.
Trichloroethylene and perchloroethylene are produced as co-products in
a single-stage oxychlorinatIon process from ethylene dlchloride and chlorine.
As market demands dictate, the product ratios can be varied from nearly 1001
trlchloroethylene to 1001 perchloroethylene by adjusting the proportions of
raw materials and process conditions (Lowenheiro and Koran, 1975).
The principal reactions In this process are:
2C2H4C12 + 5C12 -> C2H2C14 + C2HC15 -r 5HC1
C2H2C14 + CjHClj > C2HC13 + 2HC1 + CjCl4
3.5H2O + 3.5C12 (Deacon)
Based on a final production of 1 kg of perchloroethylene and 0.793 kg of tri-
chloroethylene, the quantities of raw materials are 1.1VS kg of ethylene Ql-
chloride, 0.642 kg of chlorine, 0.388 kg of oxygen, and a snnrrt quantity "of
ojrychlorlnatlon catalyst (Lowenhein and Ho ran, 1975).
¥
Ethylene dlchloride, recycled chlorinated organic*, chlorine, and oxygen
are charged to a fluid bed reactor which is maintained under pressure and at a
temperature of about 625°C> The reaction product, containing trlchloroethylene,
perchloroethylene, and hydrogen chloride, Is passed through a vent scrubber.
After, vent scrubbing of the product gas stream with water, the weak hydro-
chloric acid and the condensed crude product, are phase separated. Aieotropic
distillation Is used to dry the crude; the overhead stream from this dehydra-
tion step Is vented to the atmosphere. The dehydrated crude Is fed to a perchlor-
trichlor still column In which the crude is spll Into .two streams, one rich In
trlchloroethylene and the other rich In perchlor >ethylene.
B-7
-------
and vent gas. The spent antimony trichloride catalyst Is sent to recovery;
overall catalyst loss Is sr.alr . and estimated as Ug/^'milllon kg product.
The tetrachloroethane 1s split Into a recycle stream, and a dehydro-
chlorinator feed stream. The deh>c!roch1or1 nation of the tetrachloroethane takes
place In a packed tower, filled with activated carbon catalyst, at 573°K (SOOT.).
The reaction products, trichlorcethylene and hydrogen chloride are cooled and
the liquid and gas phases separated. The gaseous phase hydrogen chloride 1s
absorbed In water, and sold as cccvr.&rdal grade muriatic acid.
The condensate trlchloroethylene Is fed to a degasser and then to a still
for purification. The tails from the purification column constitute a "heavy
ends" process waste stream. The corfiined heavy ends from this purification
column and the perchloroethylene purification column are approximately 0.30
kg per kg product; they are sent-to land disposal.
The purified trlchloroethylene 1s fed to a chlorlnation tower where
chlorination to pentachloroethane takes place at 343-353°K (70-80eC) In the
presence of a ferric chloride catalyst. The product pentachloroethane 1s
dehydrochlorinated, using aqueous slaked lime suspension, in a heated packed
tower maintained at 80°C. The aqueous phase, containing unreacted slaked
lime, calcium chloride and trace quantities of chlorinated solvents, Is
discharged after separation from the perchloroethane through an industrial
outfall.
The crude perchloroethylene after phase separation. 1s fed to a purifi-
cation column. Product refined "perc" (perchloroethylene) Is sent to storage.
The column bottoms, or 'heavy ends" are sent to land disposal. As noted
earlier, the combined "heavy ends from the trlchloroethylene and perchloroethylene
columns are about 0.30 kg per kg perchloroethylene product; analysis is about
77S hexachlorobutadiene, 7X chlorobe uenes, 7S tars and residues, 3X chloro-
ethanes. and 31 chlorobutadienes. These heavy ends constitute a hazardous
waste stream to land disposal; the constituents are bio-accumulable and are
therefore classified as highly dangerous. Other losses of chlorinated hydro-
carbons take place to the air at low levels from the reflux condensor (still).
the hydrochloric acid absorber, and the chlorination reaction reflux condensor;
they total slightly under 0.008 kg/kg product.
B-8
-------
B.4 K?thvl Chloroform Production Tec'r.noloer (Source: EPA, 1979)
In 1975, about 6&1 of the doraestic production of this chemical was derived
frtTi vinyl chloride, altsost 30^ was based on the use of vlnylldene chloride at
raw material, and the remainder was produced by thermal chlorlnatlon of ethane.
B.4.1 Production Froa Vinyl Chlorlde--
A representative process diagram for production of raethyl chloroform from
vtnyl chloride and chlorine Is presented In Figure 3-3. The principal reactions
in this process arc:
; CH2=CHCl + HC1 > C2H4C1?
C2H4C12 + Clj -* *>• CH3CC13 + HC1 Cby-product, reused
In process)
Based on 1 kg of methyl chloroform, the quantities of rav oaterial con*
su.-aed are 0.5 Vg vinyl chloride, 0.525 kg chlorine, and a snail quantity of
ferric chloride catalyse iGruoer, 1976).
Methyl chloroform is made in two steps: (a) hydrorhlorination of vinvl
chloride to form 1,1-dichloroethane, and (b) thermal chlorination of the lat-
ter to produce <-ne compound in yields greater than 95Z (Lovienheia and Koran,
1975). '
Vinyl chloride, recycled and make-up hydrogen chloride, recycled dichlo'ro-
ethane, recycled trichloroetbane, and ferric chloride catalyse are, fed to a
tower-type reactor where * catalyzed hydrochlorinatlon reaction between vinyl
chloride and hydrogen chloride at 35 to 40°C produces dlchloroethane (Cruber,
1976).
The reaction products are sent Co a purification column. The dlchloro-
ethane fraction Is separated as aa overhead stream from the colicnn and chlori-
nated (atmospheric pressure and abouc 600°C) with chlorine gas to produce
crude trichloroethane find by-product hydrogen chloride. The crude trichloro-
ethane, by-product hydrogen chloride, and excess dichloroethane are recycled
from the chlorlnator reactor Co the hydrochlorinacor reactor (lowenheln and
Koran, 1975).
f
The crude product, separated In the purification column as the high boil-
ing fraction, Is sent to a stripper column where 1C Is steam stripped and dis-
tilled Co yield purified methyl chloroform. The product yield Is over 951
(Lowenhelm and Koran, 1975). '
B-9
-------
,— rt
„ .A y,
o.s
CMofirf* -i ^ Rroclot
Ji«.l Up , , I I
HCI »tc,el« Slicon
fwlflce
Col-™.
Hvdtoc.K(ot!ixi1(M V«t< (Gail 1
OlcklarMlkxw O.OOU
TilchlofO«lkot«« O.OOf
Alt
CD
Ct Iwlro'or 1
«. .clor /^~*\
AJ
-J>^ . — I—. Olchlom-
r ^ L.J .i»>o"i
•
lion ^
U^3
1 '
t«a«i SlMpp,, Cat CHlMitf (Cm) 1
DicMatD.lt.rn 0.0005
Tilchlafo« 0.0005
Vlnrl 0-lo.idt 0.0001
Al,
| ~"l I ^" Strom Slftpf>«r
[To C"""""
5i.oi>-»> 1
Sl.on. (_ }
Woler tlllMnI
Cfud.
Itam Shipper Wain Elllutnl (Wain)
Organic CMo'ldti • T*octl '
HpJ.ocMo.lc AclJ - T»cn
W.l.r
Figure B-3 Production Process for Methyl Chloroform Based on Vinyl Chloride Method
(Cruber. 1975)
B-10
-------
Figure E-S shows Che gas and liquid waste streams for this process- the
qu.-uitlC5es of wastes are given In kilograms of waste constituents produced per
VIlogra--o of product. The water effluent fro™ the steam stripper cont.iins trace*
of organic chlorides. Currently (1,976) no land-desr Ined hazardous vastes are
discharged by this process (Cruber, 1976).
By-products and uaste material are hydrogen chlorid'.'; waste gas from hy-
drochlorlnator vent (Figure B-5 Item t) containing 0.0085 V.g of dlchloroethane
and 0.009 Vg of t rlchloroetl.ane for each kilogram of produce; waste gas from
steaa stripper (Figure B-5, Item 2) containing 0.0005 Vg each of dichloro-
ethane, trichloroethane, and vinyl chloride for each kllogra.ii of product; and
uaste water froa steaa stripper (Figure B-5 < Item 3) containing traces of or-
ganic chlorides 2nd hydrochloric acid.'
B.4.2 Production Froa Vlnylldene Chloride,—
The basic reaction Involved In this process Iss
HC1
On the basis of I Vg of produce, the rau material requirements are 0.727 kg
vinylIdene chloride, 0.27A kg hydrochloric acid, and a small quantity of ferric
chloride catalyst. A representative flow dlagraxu for this process Is shown In
Figure A-4 . .
Vinyjiciene— ^
Chloride •
HCI 0
Ferric 6»
CMoride
r
Hydrochlorinotor
t
•r
— — | Froctlonotor
Recycle
• fc-MC
w
a
15
S
u.
-
U Heov/
Ends
Wojte
Sourcel Louenheln and Mor«n (1975).
Figure B-4. Flow diagram for production of methyl chloroform from
vinylldene chloride by hydrochlorlnation.
B-ll
-------
The vlnylldene chloride used as rsJ iti:erlal Is obtained by: (a) chlori-
r.atlon of ethylene or 1,2-dlchloroetha.-.,; with chlorine to fora 1.1. ?-t rlchlo ro-
ethane and by-product hydrogen chloride; a/,d (b) dehydrochlorlnat icn of the.
1,1,2-lrlchloroethane to fora vinyl{dene chloride. The reaction of /Inylldene
chloride with the hydrojen chloride evolved In s:ep (a) yields netl ?l chloro-
fora (Lp-enhela and Horsn, 1975).
Reaction of vinylidene chloride vlth the by-product hydrogen chloride Is
Ideally conducted In the liquid phase vlth ferric chloride as a catalyst. The
cherMcal reaction Is conducted at 25 to 35°C under slightly superatnospherlc
pressure. Crude product Is continuously wlthdra--n frora 'he hydrochlorinat ion
step and purified by fraction distillation. The purlfiel product is treated
to remove noisture and is combined with appropriate stabilizers to make the
material suitable for various cc^r^erclal. uses. The ylel 1 of product is over
981 (Lo--enVieia and Koran, 1975).
Ko by-products are forced ia this process* A heavy ends waste stream is
discharged froa the fractionator*
B-12
-------
B-5 Vinylldene Chloride (Source: EPA, 1978)
The earliest and still cost widely used coc:
-------
resulting peroxide formation, '-'aier !s removed after separation.
The wet. Inhibited vlnylidene chloride Is dried by azeotroplc dis-
tillation and then fed to the finishing column "here, under a pressure
of 10 to 20 psl, the finished vlnylidene chloride Is withdrawn (Shel ton
et al., 1971>. yore Inhibitor Is added prior to storage.
The Initial Inhibitor, heavies and unconverted 1,1,2-trtchloro-
ethane are removed from the bottom of the finishing column and
processed through the recycling tcver. During recycling, vaste
products are reraoved from the bottom of the to--er and the phenolic
inhibitor drawn off Just slightly above the bottom for recycling.
The l|l,2-trichloroethane Is renewed from the top of the recycling
tower. After each batch. Is completed, a scall purge of this system
is also required to remove Inpurltles which vould othervlse accuciuiate.
producing chlorinated acetylenes and, hence, an explosion hazard
(Shelton et al., 1971). By the above process, if it is run continu-
ously at 98" Co 99*C, the overall yield of vinylldene chloride IB
approximately 90 percent (Wessllng and Edwards, 1971).
Domestic production losses .ire estimated to result In the release
of 3.355 million pounds per year of vinylident: chloride into the
environment* (tittle, 1975). The principal production losses are
through vents on the purification equipment and during recycling.
There Is also additional monomer loss during transportation and
storage.
'Additional monomer aay be lost during transportation and trans-
fer to and from storage facilities. Precautions to prevent these
losses are discussed briefly In Section E of this report. It it
difficult to quantify these losses. However, with the use of proper
handling techniques, they can be Vept «t a minimal level. The indus-
tries involved in vinylldene chloride monomer production are aware
of the potential handling problems and are actively enploylng these
techniques (Strasser, 19.75; Dehn. 1975).
B-14
-------
Figure B-6. PRODUCTION AND PURIFICATION OF VINYLIDENE CHLORIDE
Inhibitor
Cnustlc Solution
Fre5h Feed
l.l.l-
Trlchloro«lli«n»
Purge
J—Li. CoTtlni
**—r-M V,ter
Condenser
rinUhrd Vlnylldene
Chloride lo Storage
Strom
Recycle 1,1,2-Trlchloroctlmne
• Turge
B-15
-------
B.6 PRODUCTION PROCESSES OF EDC (Mo.Pherson, 1979)
Direct chlorinalion of elhylene. Direct chlorination of
ethylene to 1,2-dichloioethane is almost always conducted
in a liquid phase reactor by intimately mixing etlwlene
and chlorine in liquid EDC. Ferric chloride, a highly
efficient and selective catalyst for this rc.iction, is normally
used in commercial processes. AinMes, such as n,n-
dimcthylformamide, have been'reported to inciease 1'VC
selectivity.3 Oxygen, frequently present as an impurity in
chlorine, likewise increases EDC selectivity in direct
chlorination of ethylene by inhibition of free radical re-
actions that give 1,1,2-trichloroethane.
Direct chlorination reactions may be run rich in e (her
ethylene or chlorine, depending on the methods avai'able
to the plant for handling offgases from this reactor. Con-
version of the lean component is usually 100 percent,
and selectivity to EDC is greater than 99 percent.
1,2-DichIoroethane, as it comes from the direct chlori-
nation reactor, is frequently of sufficient purity for crack-
ing, except that it may contain ferric .chloride, which
would lead to rapid fouling of the cracking reactor. To
avoid expensive purification of this already pure EDC,
one may remove FeCl3 by adsorption on activated ctrbon'
or other solids.' Alternately, one may operate the direct
chlorinator at the boiling .point of EDC, takin;; pure
EDC overhead and using the heat of reaction to supply
the heat for vaporization.'•••'•B
Oxychlorinalion of elhylene to EDC. Ethylene oxy-
chlorination is normally conducted at temperatures of
225-325° C and at pressures of one to 15 atmospheres.
Catalysts for this reaction almost always contain copper
chloride and sodium or potassium chloride deposited on
alumina or other suitable supjort. The detailed mech-
anism of the catalyst's activity is not known, but it is
recognized that cupric chloride is the active chlorinating
agent. The cuprous chloride jroduced is rapidly recon-
verted to CuCl: under the reaction conditions, but the
presence of some cuprous chloride is thought to be
advantageous because it complexes with ethylene, bring-
ing it into contact with CuCI. for a long enough time for
chlorination to occur. The sodium or potassium chloride
serves to increase EDC selectivity, mostly by inhibiting
formation of ethyl chloride. Other catalyst components,
such as rare earth metal chlorides, sulfate salts, ferric
chloride and numerous other additives, have been de-
scribed in the patent literature.
B-16
-------
Good temperature control of the highly exotherni c oxy
reaction is a ley element in uccessful product! >n of
1,2-dichlorocthane. Temperatures higher than about
325°C lead to increased b\pn luct formation, mostly
through increased dehydrochlorii ation of EDC to vinyl
chloride followed by additional oxychlorination to give
products ha\-ing high levels of ch orine substitution. High
temperatures zilso increase the am >unt of ethylene bi rned
to carbon monoxide and carbon dioxide. Of equal im-
portance, high temperatures deactivate the catalyst by
highly accelerated coking and consequent powderii:7
of the catalyst units and by increased sublimation of
copper, chloride sway from the catalyst.
Temperature control in fluidized bed reactors is main-
tained by the excellent intermixing of the catalyst par-
ticles and by use of internal cooling surfaces.10 Tem.jera-
ture control in fixed bed reactors is more difficult since
"hot spots" tend to develop. To keep the hot spot
temperature below below 325° C, yet get maximum
utilization from the reactor, it is con mon practice to
pack the reactor tubes with active c.italyst and inert
diluent mixtures in proportions of each so adjusted as
to have low catalyst activity at the inlet, steadily in-
creasing to maximum activity at the outlet. This grading
of the catalyst activity flattens the temperature profile,
allowing for good temperature control with high produc-
tivity. For example, one patent* indicates the use of
four zones \vith 93 percent, 85 percent, 40 percent, and
0 percent, respectively, of the active catalyst pellets
replaced by inert graphite. As an alternate to using inert
materials in the catalyst bed, catalysts,""each with higher
levels of CuClj and consequently of increasing reactivity,
are sometimes used. •—
Fluid bed oxychlorination of ethylene, operated under
good control, results in 94-97 percent eth /lene conver-
sion, 95-97 percent HC1 conversion, and EDC selectivi-
ties in the range of 94-96 percent. Fbced bed oxychlori-
nations are normally run with excess ethylene relative
to HC1, resulting in 93-97 percent ethylene conversion,
94-95 percent HCI conversions, and EDC selectivities of
93-95 percent. These data do not include recovery of
excess ethylene in subsequent reaction steps. Excess ethyl-
ene in vent gases from oxychlorinalion is normally con-
verted to EDC by direct chlorination with chlorine,'1-"
although, if oxygen is used rather than air, the excess
ci'iylcnc may be recycled directly bick to oxychlorination.
B-17
-------
Byproducts of cthylcne oxychlorirption arc vinyl chlo-
ride, ethyl chloride, 1,1-dichlorocthane, vinylidcnc chlo-
ride, (is- and /rcnj-l^-dichloroclhylcnc-s, trichlorocthyl-
ene, ' chloroform, carbon tetrachloride, methyl chloride,
methylene chloride, chloral and high boiling compounds.
All of these byproducts present problems in one way or
another, such that their production needs to be minimi/":d
to lower raw material costs, to lessen the difficulties of
preparing pure EDC, and to prevent fouling in the
cracking reactor. Chloral, in particular, needs to be re-
moved since it pol\meri/rs readily in strong acids to
give solids which clog and foul operating lines and
controls. **
One must also take care to see that the feeds to
oxvchlorination are pure. Normally, the only problem is
with low levels (0.1 to 0.5 percent) of acetylene present
in the HC1 from cracking of EDC. Acetylene in the feed
leads .to the formation of considerable highly chlorinated
byproducts and tars. Selective hydrogenation of this
acetylene to ethylene and ethane is practiced by many
companies."
Oxychlorinalion with oxygen instead of air. Use of
oxygen instead of air for ethylene oxychlorination has
received much attention.1*"19 The .outstanding benefits
from using oxygen are avoidance of expensive facilities
to recover EDC, ethylene and other chemicals from the
large nitrogen vent gas stream; a large reduction in the
quantity of offgases that will probably need to be in-
cinerated; and the ability to use ethylene as a diluent for
oxychlorination, a procedure said to improve heat transfer
in tubular reactors.
B-18
-------
APPENDIX C
OCCURRENCE OF EDC IN
RAW AND FINISHED WATER
-------
TABLE C.I QUANTITY OF EDC IN RAW AND FINISH WATER SUPPLY
o
1.
1.
3.
4.
*
• •
;.
a.
».
10.
11.
12.
i).
14.
Utility nunbar ind na«a"
(plant n««a wtten applieftbla)
Lawrtnct Vatar Work*
Uatarbury lurtau of Uatir (Horrla •
Tr«at«nt Station)
Hatropollt.n Dlitrlct Coralaalon
Ntvport D«pt. of Uatar (South Pond
Authority (Sergio Cuavaa Vatar
Treatcant flanl)
Finite Valla? Ualar Connlaaion
To*i Rlvor Water Co.
Buffalo Vattr Dapt.
VllU|t of Rhlnabaek Water Dapt.
PhlUd.lpl.il Water (Mpc.
(Torrt«d«l« Pline)
Ullnlngton Suburban U«t«r Corp.
(Stinton Plane)
Artcilin W.t«r Co. (Llanfollin
U.ll rlild Flint)
u>thln|ton Aqutduet
(0
-------
TABLE C.I QUANTITY OF EDC IN RAW AND FINISH WATER SUPPLY (cont'd.)
o
to
IS.
16.
i;.
u.
it.
JO.
:i.
12.
i).
:«.
75.
16.
17.
1».
1«.
Utility niwber end at mm"
(plant n>M whan appllceble)
Baltimore City tureeu of Uater Supply
(Hontebello PltnC Ma. 1)
Weetern Penntylvenla Utter Co.
(Hi?! Hint Flint)
Streeburt. Borough Water Syateai
Palrfai County Water Authority
(Nfw Ucton Plant)
llopevall Dletrlct
Huntlnfton Water Co.
Wheeling Water Dept>
KUnl-OxU UKtr tnd Sever Authority
(Preeton Plant)
Jeckaonvllle Dcpt. of Public Worke
(Hlfhlende PuBplng Station)
Atlanta Vatarvorka
(Chattahoochaa Plant)
Ovcnaboro Municipal Utllltlaa
Crafnvllla Vatar Dapt.
Tannaaaaa Anarlean Water Co.
Hoplila Ll|ht, Caa end Vatar Olvlelon
(Hall«y Plant)
Matropolltan Uatar and Savarata Dapt.
(Lawranca Plant)
Content o(
1,»-
Dlehloro-
athana
KP
xr
Nt
NF
HP
HP
NP
NP
NK
Mf
<0.)
<0.t
<0.3
«!.<
-------
TABLE C.I QUANTITY OF EDC IN RAW AND FINISH WATER SUPPLY (cont'd.)
10.
11.
11.
13.
It.
13.
li.
1 ll*
J /a*
17».
38.
19.
to.
tl.
1 Utility mwbar and na»a4
(plant naa* whan applleabla)
Coulaalonara of Public Vorka
(Stonty riant)
Cincinnati Vatar Vorka
Chtciio Dapt. of Uatar and Savtri
(South Dlatrlct Vatar nitration
riant), two iaiplia
Clinton Public Vatar Supply
tndlanapolla Vatar Co.
(Vhlta Rlvar Plant)
Vhltlni Vatar Dapt.
Aflar pra Cl«
Bafora pra Clt
Datrolt Matro Vatar D«pt.
(Vatarvorka rack riant)
Ml. Claaana Vitar Purification
actlvatad carbon)
It. Paul Vatar Authority
Clavaland Dlvlalon of Watar
(Dlvlalon Filtration Plant)
City of Coluabua
(Dublin toad riant)
Dayton Vatar Vorka
(Ottawa riant)
Contant of
1.1-
Dlchloro- •
athana
NF
NF
NF
<0.t
NF/NF
<0.t
NF
NF
«0.1
NF
NF
NF
NF
0.3
O.t
NF
•«o.t
<0.2
NF
NF
NF
NF
NF
NF
NF
<0.l
aalactad compounda In raw and flnlahid watar (ui/llter)'1
Bromo-
dlchloro-
•athana
NT
9
NF
13
NF/«O.J
10
NF
0.3
NF
'a
u
int.l
or,»nlc
c* rbon
(ng/llt>r)
11. t
t.l
2.J
1.1
1.9/1.7
1.3
7.7
6. 7
5.1
2.6
2.0
1.9
l.J
2.6
1.2
7 0
1.4
6.7
t ^
7.9
4.4
2.2
i.a
f..6
2.)
0.9
0.7
-------
TABLE C.I QUANTITY OF EDC IN RAW AND FINISH WATER SUPPLY (cont'd.)
41.
4).
44.
4).
46.
47.
41.
4».
50.
31.
52.
5).
54.
55o.
55b.
Utility nuabar and naaa
Indian Hill Uatar Supply
FlQ.ua Uatar Supply
Kahonlng Vallay Sanitation Dlatrlet
Nllwiukaa Uatar Uorka (Howard
Avanua Purification Plant)
Oahkoah Uatar Utility
(Dlatrlet No. 1)
CaxJan Municipal Uatar Uorka
Town of Loianaport Uatar Syataa
City of Albuq.uaro.ua
Oklohou City Uatar Dapt.
(llafnar Plant)
Irownavllla Public Utility Board
(Plant No. 2)
Dallaa Uatar Utllltlaa
(Bachaan Plant)
San Antonio City Uatar Board
Ottuawa Uatanrarka (2/17/75)
Ottuawa Uatarworka (4/7/7S)
Content of
1.2-
Dlchloro-
athana
NP
NP
NP
-------
TABLE C.I QUANTITY OF EDC IN RAW AND FINISH WATER SUPPLY (cont'd.)
n
Ul
5*.
57.
it.
J».
(0.
61.
ti.
»J.
*
45.
66.
67.
68.
•«.
Utility mmber and nan
(plant na«« vhen applicable)
Clarluda ta»* Water Uorke
Davenport Water Co.
Topeka. Public Water Supply
(South Plant)
Hlaeourl Utility Co.
Kanaae City (Mo.) Water Dept.
St. LouU County Water Co.
(Central Plant)
Lincoln Municipal Water Supply
City Water Dept.
(Mareton Plant)
Putblo loard ol Ualervorka
(Ordntr Flint)
Huron Vittr Dept.
Salt Lake Water Dept.
City of Tucaon Water and Severe
Dept. (Plant No. 1)
City of Phoenli Water end Severe
Dept. (Verde riant)
Content of
1.2-
Dlchloro-
• ethane.
HP
NP
NF
<0.4
HP
NP
0.2
0.)
HP
NP
0.3
0.4
NP
NP
NF
NP
up
NP
HP
NF
NF
NF
<0.4
NF
NP
NF
NP
NF
eelected compound • In rav and flnlahed water (ug/ilt»r)f>
Brono-
dlchloro-
nethane
NP
19
NP
a
<0.«
18
NF
21
NP
a
NF
1}
NP
6
NP
1
NF
10
NF
2
NP
IK
NF
U
NP
<0.8
NP
15
Dlbrotno-.
chloro-
nethant
NP
4
NF
<0.«
NF
19
NP
2
HP
2
NP
"•3
NP
t
NF
NF
NF
3
NP
<2
NP
49
NP
a
. NP
2
NF
17
Brono- .
form
NF
NF
NF
NF
NF
3
NF
NF
NF
NP
NF
<1
NF
<2
NP
NP
NF
NF
HP
NP
NP
8
NP
NP
NF
13
NF
<4
Chloro-
form
«0.2
48
0.4
88
0.4
as
0.2
116
NF
24
NF
55
NF
A
NF
3
«rt 3
*u« *
14
<0.2
2
NF
309
0.2
20
<0.1
<0.2
<0.2
9
Carbon
tftrs-
chlorlde
UF
NF
NF
NF
NF
)
NP
2
HF
NF
NT
NF
NF
NF
NF
NF
ujr
NF
Mr
NF
NF
NF
NF
NF
NF
NF
NF
NF
Nonvolat 1 1«
total
orftintc
ca rbon
(mR/lU.r)
3.5
5.0
6.5
4.4
3.4
2.2
4.5
3.6
3.4
1.9
3.4
2.6
1.4
1.4
1.1
5.2
j 0
1.7
1.8
1.6
19.2
12.2
1.2
0.9
<0.05
<0.05
1.0
1.0
-------
TABLE C.I QUANTITY OF EDC IN RAW AND FINISH WATER SUPPLY (cont'd.)
o
•
70.
n.
71.
I).
7».
1
ft.
17.
7«.
79.
to.
Utility nuabar and na»«
(plant nanQ when applicable)
Dcpt. of Supply and Purification
Contra Coata County Uacar Dept.
(Bollun riant)
City of Doa Paloa Watar Dapt.
Loa Anialta Dcpt. of Wittr and Povar
San Dlfffo Watar Utllltlaa Dapt.
(Klraur Plant)
(Sin Andrea* Treatment Plant)
SvattU Water D*pC. (tnJ of
distribution ayatvn)
Douglaa Water Syate*
Idaho Falla Uat«r Ocpt.
City of CorvalHa Utllltlaa Dlvlalon
(Taylor Plant)
lluaco Municipal Uatar Dapt.
fUnga
fsc« Table 17 for location of utility
Flrat Una Indtcataa rav-vat«r data}
CHF — nona found.
Source) AJaptcd fro* Symona *t al.(
i.t-
Dlchloro-
athanv
NF
HF
nr
xr
Hf .
NP
NP
nr
NP
HP
ua
NP
NP '
NP
NP
NP
NF
HP
NP
W
HF
KP
Nf-J
NF-<
^
aacond Una ii
197). Tablt 5,
Brono-
dlchloro-
•ethana
NP
17
•.<•
2.9
1.2
1.3
2.9
2.B
j S
l.f>
0.9
n.9
3.4
2.8
O.S
0.3
1.0
0.4
7.5
3.1
<0. 05-19.
•0.05-12.
itn u,,tk.
2
2
Aaaoclatlon froa JOURNAL AWUA Voluaia 67, copyrighted 197].
-------
APPENDIX D
FLOW DIAGRAM OF EDC
-------
TECHNICAL REPORT DATA
{Please resa Ir.unicrions on ihe re:-ene before completing/
'caT NO.
EPA-560/13-80-002
3. RECIPIEMT'S ACC£SSiO'»NO.
4. TITLE AND SUBTITLE
Materials Balance - Task #11 - 1,2-Dichloroethane
5. REPORT OAT
ItfORT DATr i rn r>
January 4, 1979
6. PERFORMING ORGANIZATION CODE
7 AUTttal'3feryson, Kathleen Durrell, Eliot Harrison,
Virginia Hodge, Phuoc Le, Sidney Paige, Karen Slimak
8. PERFORMING ORGANIZATION REPORT NO
2-800-03-379-34
9. PERFORMING ORGANIZATION NAME AND ADDRESS
JRB Associates, Inc.
8400 Westpark Drive
McLean, Virginia 22102
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-'3793
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Pesticides and Toxic Substances
U.S. Environmental Protection Agency
Washington, B.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSOF ING AGENCY COOE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The 'purpose of ;.:the Level I materials balance for 1,2 dichLoroethane (EDC)
is to evaluate the sources of release of EDC to the environment. EDC is
produced via direct chlorination and oxychlorination of ethyLme. EDC is
used consumptively in the production of other chemicals such as vinyl
chloride, monomer, perchloroethylene, trichloroethylene, ethyl.eneamines and
vinylidene chloride. EDC is also used in the production of leaded gasoline
additives as lead scavenger. Releases of EDC from the production and
consumptive uses appear to be the major sources of EDC emissions.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
3. DISTRIBUTION STATEMENT
- Release unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
152
20. SECURITY CLASS -This page/
Unclassified
22. PRICE
GPA Form 2220-1 (9-73) •
-------
IUKKC
CHI. OK
I'Koci:
2.') 7 .
94 x U
,[
[
1
•"".-.
£x H/J
NAT 1 ON
S *
u."
*
,.vn ^"l.lx.n'
'.; MM'
- AIR
WATER ^^~ 4.4 x 10
«.'. xIO1
:'.(!') x in6
2.0 .x n,h
_> VIXYI. CHLORIDE
MIINOMER
XYCHLORIN
PROCES
2.08 x 1
]
f AIR
-0-
, ATR
.1.97 xIO
^ ATR
r ,.» ^l.-^
; 3.lxioJ
,6
AIR
1 WATER .S* 4.9xloJ
' 4.9xlOJ
- ATB
LAND
' 2.0xl03
^^ 99
VHM TMP1IRTTV
' _» ^ i
i.fi x in5 EX'uRi1 ' 1
5.1 x lu"
2.2 x III'
1 . 0 x n 5
1.2 x 103
i .-> x in5 (
9.7 x Id"
'..9 x 103
>.. _ «. — —
VIXYI. IRENE
i
.1 ,1-TRICIil.OROETHANK
I
TRK:III.CIROI;TIIYI.ENE
'
i~ ™* ~
Pl'KCII OROI- IHYLFME
WATER
> -0-
AIR
-— — -- — -— -^
* U.TPO "-1
-0-
-0-
AIR
—_ MC IMPURITY
UATPP 0,1
LAND
-0-
AIR
— .*
p-, -, , , - TCF IMPURITY
WATER 0.1
t -o-
-0-
AIR
910
WATER 0 . 1
-(>-
I'kiinivnoM ... , " r,-,
>
r
ETim.EXEAMlXES
LAND
-0-
AIR
610
WATER 0 . 1
-n-
»
C.ASOI IXI'
LAND
-0-
AIR
1.2xlOJ
WATER
»
MINOR USES:
- Jiou-riu lor paint.
LAND
-0-
AIR
4.9xlOJ
- Clc'.inin;; solvent
- Pcstlrlilu diluent
- Color (Urn cleaning ~*
solvent
LAND
-0-
- PnlysuHlile produc-
t inn
- Copper lenrhlnR
WATER
INDIRECT
PRODUCTION
- Natural-Source
- Imports
- Stockpiles
- Wastewater
Treatment
- By-Product of
Other Processe
- Miscellaneous
FIGURE D.I ENVIRONMENTAL FLOW DIAGRAM OF EDC
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