United States

Environmental Protection
Agency

Office of Air Quality

Planning And Standards
Research Triangle Park, NC 27711

EPA-450/4-84-007d
March 1984

AIR

EPA
LOCATING AND ESTIMATING AIR
EMISSIONS FROM SOURCES OF
ETHYLENE DICHLORIDE

L& E

EPA-450/4-84-007d
March 1984

LOCATING AND ESTIMATING AIR EMISSIONS

FROM SOURCES OF ETHYLENE DICHLORIDE

U.S. ENVIRONMENTAL PROTECTION AGENCY

Office of Air and Radiation
Office of Air Quality Planning an Standards
Research Triangle Park, North Carolina 27711

This report has been reviewed by the Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency, and approved for publication as received from the contractor. Approval does not signify
that the contents necessarily reflect the views and policies of the Agency, neither does mention of trade
names or commercial products constitute endorsement or recommendation for use.

ii

CONTENTS

Figures
Tables

. . . . . . . . . . . . . . . . . . . . . . IV
. . . . . . . . . . . . . . . . . . . . . . vi

1. Purpose of Document
. . . . . . . . . . . . . .
2. Overview of Document Contents
. . . . . . . . .
3. Background . . . . . . . . . . . . . . . . . . .
Nature of Pollutant . . . . . . . . . . . . .
Overview of Production and Uses: . . . . . . .
4. Ethylene Dichloride Emission Sources . . . . . .
Ethylene Dichloride Production . . . . . . . . .
Vinyl Chloride Monomer Production
. . . . . . .
Methyl Chloroform Production . . . . . . . . . .
Ethyleneamines Production. . . . . . . . . . . .
Trichloroethylene Production . . . . . . . . . .
Perchloroethylene Production . . . . . . . . . .
Vinylidene Chloride Production . . . . . . . . .
Ethyl Chloride Production
. . . . . . . . . . .
Polysulfide Rubber Production
. . . . . . . . .
Liquid Pesticide Formulation . . . . . . . . . .
Use of Ethylene Dichloride in Grain Fumigation .
EDC Use in Leaded Gasoline . . . . . . . . . . .
EDC Use in Paints, Coatings, and adhesives . . .
EDC Use as an Extraction Solvent . . . . . . . .
EDC Use in Cleaning Solvents . . . . . . . . . .
Miscellaneous EOC Uses . . . . . . . . . . . . .
Volatilization from Waste Treatment, Storage and
Disposal Facilities . . . . . . . . . . . . .
5. Source Test Procedures . . . . . . . . . . . . .

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. 1
. 3
. 5
. 5
. .8
.11
. 11
. 22
. 26
.32
.36
. 43
. 49
. 52
. 55
. 56
. 61
. 72
. 76
. 80
. 80
. 81

. . 83
. . 83

References . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

iii

FIGURES
Number

Page

Chemical use tree for ethylene dichloride

. . . . . 10

Basic operations that may be used for ethylene

dichloride production by the balanced process, with
air-based oxychlorination
. . . . . . . . . . . . . 12

Basic operations that may be used for ethylene

dichloride production by the oxygen process
(oxychlorination step) . . . . . . . . . . . . . . . 15

Basic operations that may be used for vinyl chloride

production by ethylene dichloride dehydrochlorination 23

Basic operations that may be used for methyl chloroform

production by the vinyl chloride hydrochlorination/
1,1-dichloroethane chlorination process
. . . . . . 27

Basic operations that may be used for methyl chloroform

production by the vinylidene chloride
hydrochlorination process
. . . . . . . . . . . . . 29

Basic operations that may be used in the production of

ethyleneamines . . . . . . . . . . . . . . . . . . . 33

Basic operations that may be used for trichloroethylene

(TCE) and perchloroethylene (PCE) production by
ethylene dichloride chlorination . . . . . . . . . . 37

Basic operations that may be used for trichloroethylene

(TCE) and perchloroethylene (PCE) production by
ethylene dichloride oxychlorination
. . . . . . . . 39

10 Basic operations that may be used for the production of

perchloroethylene by hydrocarbon chlorinolysis . . . 44
11 Basic operations that may be used for the production of
vinylidene chloride
. . . . . . . . . . . . . . . . 50
12 Basic operations that may be used in the production of
ethyl chloride by ethylene hydrochlorination . . . . 53
CONTINUED
iv

FIGURES (continued)

Page

Number

13 Basic operations that may be used for liquid

pesticide formulation . . . . . . . . . . . . . . 57
14 Method 23 sampling train

. . . . . . . . . . . . . . 84

TABLES
Number
1

Page
Physical Properties of Ethylene Dichloride

. . . .

Ethylene Dichloride Emission Factors for a Hypothetical

EDC Production Plant (Balanced Process) . . . . . 17

Production of Ethylene Dichloride

Production of Vinyl Chloride Monomer

Production of Methyl Chloroform

Production of Ethyleneamines

Production of Trichloroethylene

. . . . . . . . . . 42

Production

of Perchloroethylene

. . . . . . . . . . 48

Production

of Ethyl Chloride

. . . . . . . . . 21
. . . . . . . . 25

. . . . . . . . . . 31

. . . . . . . . . . . . 35

. . . . . . . . . . . 54

10 Companies Which Hold Registrations on Pesticide

Formulations Containing Ethylene Dichloride . . . 58
11 Ethylene Dichloride Pesticide Brand Names
12 Fumigant Application Rates

. . . . . 62

. . . . . . . . . . . . . 66

13 On-Farm Grain Storage

. . . . . . . . . . . . . . . 68

14 Off-Farm Grain Storage

. . . . . . . . . . . . . . . 71

15 EDC Emissions from Bulk Loading, Storage, and

Transportation of Leaded Gasoline . . . . . . . . 73
16 EDC Emissions from Service Stations
17 Petroleum Refineries

. . . . . . . . 75

. . . . . . . . . . . . . . . . 77

SECTION 1
PURPOSE OF DOCUMENT
EPA, States and local air pollution control agencies are
becoming increasingly aware of the presence of substances in the
ambient air that may be toxic at certain concentrations.

This

awareness, in turn, has led to attempts to identify source/receptor

relationships for these substances and to develop control programs to
regulate emissions.

Unfortunately, very little information is

available on the ambient air concentrations of these substances or on

the sources that may be discharging them to the atmosphere.
To assist groups interested in inventorying air emissions of
various potentially toxic substances, EPA is preparing a series of
documents such as this that compiles available information on sources
and emissions of these substances.

This document specifically deals

with ethylene dichloride. Its intended audience includes Federal,

State, and local air pollution personnel and others who are
interested in locating potential emitters of ethylene dichloride and
making gross estimates of air emissions therefrom.
Because of the limited amounts of data available on ethylene
dichloride emissions, and since the configuration of many sources
will not be the same as those described herein, this document is best
used as a primer to inform air pollution personnel about 1) the types
of sources that may emit ethylene dichloride, 2) process variations
and release points that may be expected within these sources, and 3)
available emissions information indicating the potential for ethylene
dichloride to be released into the air from each operation.
The reader is strongly cautioned against using the emissions
information contained in this document to try to develop an exact
assessment of emissions from any particular facility.

Since

insufficient data are available to develop statistical estimates of

1

the accuracy of these emission factors, no estimate can be made of

the error that could result when these factors are used to calculate
emissions from any given facility. It is possible, in some extreme
cases, that orders-of-magnitude differences could result between
actual and calculated emissions, depending on differences in source
configurations, control equipment and operating practices.

Thus, in

situations where an accurate assessment of ethylene dichloride

emissions is necessary, source-specific information should be
obtained to confirm the existence of particular emitting operations,
the types and effectiveness of control measures, and the impact of
operating practices.

A source test and/or material balance should be

considered as the best means to determine air emissions directly from

an operation.

SECTION 2
OVERVIEW OF DOCUMENT CONTENTS
As noted in Section 1, the purpose of this document is to assist
Federal, State, and local air pollution agencies and others who are
interested in locating potential air emitters of ethylene dichloride
and making gross estimates of air emissions therefrom.

Because of

the limited background data available, the information summarized in

this document does not and should not be assumed to represent the
source configuration or emissions associated with any particular
facility.
This section provides an overview of the contents of this
document.

It briefly outlines the nature, extent and format of the

material presented in the remaining sections of this report.

Section 3 of this document provides a brief summary of the
physical and chemical characteristics.of ethylene dichloride, its
commonly occurring forms and an overview of its production and uses.
A chemical use tree summarizes the quantities of vinylidene chloride
consumed in various end use categories in the United States.

This

background section may be useful to someone who needs to develop a

general perspective on the nature of the substance and where it is
manufactured and consumed.
Section 4 of this document focuses on major industrial source
categories that may discharge ethylene dichloride air emissions.
This section discusses the production of ethylene dichloride and its
use as an industrial feedstock.

For each major industrial source

category described in Section 4, example process descriptions and

flow diagrams are given, potential emission points are identified,
and available emission factor estimates are presented that show the
potential for ethylene dichloride emissions before and after controls
employed by industry.

Individual companies are named that are

reported to be involved with either the production or use of ethylene

dichloride, based primarily on trade publications.
3

The final section of this document summarizes available

procedures for source sampling and analysis of ethylene dichloride.
Details are not prescribed nor is any EPA endorsement given or
implied to any of these sampling and analysis procedures.
time, EPA generally has not evaluated these methods.

At this

Consequently,

this document merely provides an overview of applicable source

sampling procedures, citing references for those interested in
conducting source tests.
This document does not contain any discussion of health or other
environmental effects of ethylene dichloride, nor does it include any
discussion of ambient air levels or ambient air monitoring
techniques.
Comments on the contents or usefulness of this document are
welcomed, as is any information on process descriptions, operating
practices, control measures and emissions information that would
enable EPA to improve its contents.

All comments should be sent to:

Chief, Noncriteria Emissions Section

Air Management Technology Branch
U.S. Environmental Protection Agency
Research Triangle Park, N.C.

27711

SECTION 3
BACKGROUND
NATURE OF POLLUTANT
Ethylene dichloride (EDC) is a clear, colorless oily liquid with
a pleasant chloroform-like sweet odor and taste.

The chemical name

for ethylene dichloride is 1,2-dichloroethane, the molecular formula

is ClCH2CH2Cl, and the structure is as follows:
H

Cl - C - C - Cl
H

Ethylene dichloride should be distinguished from 1,2-dichloroethylene

which has double-bonded carbon atoms and the molecular formula
ClCH=CHCl.

Ethylene dichloride is soluble in hydrocarbon solvents,

miscible with other chlorinated solvents, and has a high solvency for
fats, greases, and waxes.
in water.1

However, it has only a limited solubility

Physical properties of EDC are listed in Table 1.

Dry EDC is stable at room temperature but decomposes slowly when

exposed to air, moisture, and light, forming hydrochloric acid and
other corrosive products.

The decomposing liquid becomes darker in

color and progressively acidic.

containers.

It can thus corrode iron or steel

Decomposition can be prevented by adding a small amount

of alkylamine.

EDC that is sold as a solvent is normally treated in

this manner; however, as an intermediate chemical, EDC is usually not

stabilized.2
Both of the chlorine atoms in the ethylene dichloride molecule
are reactive and can be removed by beat or replaced by other
substituents.

The economic importance of ethylene dichloride is

based in part on the ease with which hydrogen chloride can be removed
to form vinyl chloride with the application of heat.

The chemical

nature of EDC also makes it useful in the manufacture of ccndensation

polymers and ethylene diamine.1
5

TABLE 1.

PHYSICAL PROPERTIES OF ETHYLENE DICHLORIDE3,4

Synonyms: 1,2-Dichloroethane, EDC, glycol dichloride, ethylene chloride,

sym-dichloroethane, brocide, borer sol, destruxol borer-sol,
di-chlor-mulsion, dutch liquid, ent 1,656, freon 150, NCI-C00511
Chemical Formula

ClCH2CH2Cl

CAS Registry Number

107-06-2

Molecular Weight

98.97

Boiling Point, C

83.7

Melting Point, C

-35.3

Density at 20C, g/l

1.2529

Refractive index at 20C,

for Sodium Light

1.4451

Viscosity at 20C, mPas

0.84

Surface Tension at 20C, mN/m

31.38

Specific Heat at 20C, J/(gK)

liquid

1.288

gas

1.066

Latent Heat of Vapor at 20C, J/g

323.42

Latent Heat of Fusion, J/g

88.36

Critical Temperature, C

290

Critical Pressure, MPa

5.36

Critical Density, g/L

0.44

Flash Point,

closed cup

17

open cup

21

Explosive Limits in Air at 25C,

% by Vol.

6.2-15.6

Autoignition Temperature in Air, C

413

Thermal Conductivity, liq at 20C,

W/(mK)

0.143

Heat of Combustion, kJ/g

12.57

Heat of Formation, kJ/(gmol)

liquid

157.3

vapor

122.6

TABLE 1. (Continued)
Dielectric Constant
liquid, 20C

10.45

vapor, 120C

1.0048

Dipole Moment, Cm

5.24 x 10-30

Coefficient of Cubical Expansion,

0.00116

mL/g, 0-30C
Vapor Pressure, kPa
10C

5.3

20C

8.5

30C

13.3

Solubility at 20C, g
1,2-dichloroethane in 100 g H2O

0.869

H2O in 100 g 1,2-dlchloroethane

0.160

Azeotropes, bp, C
with 19.5% H2O

72

with 5% H2O and 17% ethanol

66.7

OVERVIEW OF PRODUCTION AND USES

Since the mid-1940s, ethylene dichloride has been used
principally as a raw material in the synthesis of other compounds,
particularly vinyl chloride, methyl chloroform, trichloroethylene,
perchloroethylene, vinylidene chloride, and ethyleneamines.1

Ethylene

dichloride is produced in the United States mainly by 12

manufacturers in 19 production facilities.5

The production of EDC

from these plants is flexible and highly responsive to economic

conditions. The combined annual capacity of these plants in 1983 was
estimated to be 9,205,700 Megagrams5 while actual production in 1982
was estimated at a level of 3,451,488 Megagrams.6

Exports of EDC in

198l were estimated at 277,000 Megagrams.7

Ethylene dichloride is manufactured in the United States by
direct chlorination of ethylene, oxychlorination of ethylene, or a
combination of these methods. In the direct chlorination process
ethylene is treated with chlorine in the presence of a catalyst to
produce EDC.

Either vapor- or liquid-phase reactions may be used,

but undesirable side products are obtained unless conditions are

controlled carefully.

In one vapor-phase procedure, product yields

of 96 to 98 percent are obtained by treating ethylene at 40C to 50C

with chlorine containing traces of ethylene dibromide, which acts as
a catalyst. Other direct chlorination procedures exist that differ
primarily in reaction conditions and catalyst.

Catalysts mentioned

most often in the patent literature include ferric, aluminum, cupric,

and antimony chlorides.

In 1974 the direct chlorination of ethylene

accounted for 58 percent of the U.S. production of ethylene

dichloride.1
Ethylene dichloride is also manufactured commercially by
treating ethylene with anhydrous hydrogen chloride and oxygen (or
air) in a fluidized bed of finely divided particles containing cupric
chloride.

Typically, the reactive pressure and temperature are

maintained at 20 to 70 psig and 200C to 315C, respectively.1

Where EDC is produced for use in the manufacture of vinyl chloride,

the oxychlorination and direct chlorination processes are often used
together in what is know as the balanced process. In the balanced process,
EDC is synthesized by the direct chlorination process and is then
dehydrochlorinated, resulting in the production of vinyl chloride monomer
and byproduct HCl. Manufacturers take advantage of the byproduct HCl by
using it in the oxychlorination process to produce more EDC.
Ethylene dichloride is used primarily as a chemical intermediate in
the synthesis of other compounds.

The current uses of EDC are listed in

Figure 1, along with the percentage of the total product devoted to each
use.

Synthesis of vinyl chloride accounts for 81 percent of the annual

United States consump- tion of EDC while the synthesis of methyl chloroform
(1,1,1-trichloroethane), ethyleneamines, perchloroethylene,
trichloroethylene, and vinylidene chloride (1,1-dichloroethene) accounts
for another 14 percent of consumption.4
Ethylene dichloride is also used as a scavenger for lead in gasoline.
The EDC decomposes during combustion, with the chlorine atoms binding to
the lead in the gasoline to form gaseous lead species.

Thus, engine

fouling with lead oxides or other solid lead species is prevented.

The use

of EDC as a lead scavenger in gasoline accounted for about l percent of the

1980 production.

However, this use declined by 30 percent in 198O and is

expected to decline further because of the decreasing production of leaded

gasolines.7
Minor uses of ethylene dichloride are in textile cleaning and
processing, in formulations of acrylic-type adhesives, as a product
intermediate for polysulfide elastomers, as a constitutent of polysulfide
rubber cements, in the manufacture of grain fumigants, and as a cleaning
and extraction solvent. Of the estimated consumption of EDC by minor uses,
about 28 percent is used in the manufacture of paints, coatings, and
adhesives.

Extracting oil from seeds, treating animal fats, and processing

pharmaceutical products account for 23 percent.

An additional 19 percent

is consumed in cleaning textile products and polyvinyl chloride

manufacturing equipment.
polysulfide compounds.

Nearly 11 percent is used in the preparation of

Grain fumigation requires about 10 percent.

The

remaining 9 percent is used as a carrier for amines in leaching copper

ores, in the manufacture of color film, as a diluent for pesticides and
herbicides, and for other miscellaneous purposes.1
9

Figure 1.

Chemical use tree for ethylene dichloride.4

SECTION 4
ETHYLENE DICHLORIDE EMISSION SOURCES
This section discusses ethylene dichloride (EDC) emissions from
direct sources such as production of EDC, production of chemicals
using EDC as a feedstock, and miscellaneous uses of EDC.

Process and

emissions information are presented for each source for which data
were available.
ETHYLENE DICHLORIDE PRODUCTION
Ethylene dichloride (EDC) Is produced from ethylene and chlorine
by direct chlorination, and from ethylene and hydrogen chloride (HCl)
by oxychlorination.

At most production facilities, these processes

are used together in what is known as the balanced process.

This

section discusses EDC emissions from this process.

The balanced process generally is used wherever EDC and vinyl
chloride monomer (VCM) are produced at the same facility.

As noted

in Section 1, about 81 percent of the EDC produced domestically is

used in the manufacture of VCM.4

In VCM production, EDC is

dehydrochlorinated to yield VCM and byproduct HCl.

In the balanced

process, byproduct HCl from VCM production via the-direct

chlorination/dehydrochlorination process is used in the
oxychlorination/dehydrochlorination process.
Process Description
The balanced process consists of an oxychlorination operation, a
direct chlorination operation, and product finishing and waste
treatment operations. The raw materials for the direct chlorination
process are chlorine and ethylene. Oxychlorination involves the
treatment of ethylene with oxygen and HCl. Oxygen for oxychlorination
generally is added by feeding air to the reactor, although some
plants use purified oxygen as feed material.8
Basic operations that may be used in a balanced process using
air for the oxychlorination step are shown in Figure 2.
diagrams for production facilities will vary.
11

Actual flow

The process begins

12

with ethylene (Stream 1) being fed by pipeline to both the oxychlorination

reactor and the direct chlorination reactor.

In the oxychlorination

reactor the ethylene, anhydrous hydrogen chloride (Stream 2), and air
(Stream 3) are mixed at molar proportions of about 2:4:1, respectively,
producing 2 moles of EDC and 2 moles of water. The reaction is carried out
in the vapor phase at 200 to 315C in either a fixed-bed or fluid-bed
reactor.

A mixture of copper chloride and other chlorides is used as a

catalyst.8
The products of reaction from the oxychlorination reactor are
quenched with water, cooled (Stream 4), and sent to a knockout drum, where
EDC and water (Stream 5) are condensed.

The condensed stream enters a

decanter, where crude EDC is separated from the aqueous phase. The crude
EDC (Stream 6) is transferred to in-process storage, and the aqueous phase
(Stream 7) Is recycled to the quench step.
are released to the atmosphere (Vent A).

Nitrogen and other inert gases

The concentration of EDC in the

vent stream is reduced by absorber and stripper columns or by a

refrigerated condenser (not shown in Figure 2).2,8
In the direct-chlorination step of the balanced process, equimolar
amounts of ethylene (Stream 1) and chlorine (Stream 8) are reacted at a
temperature of 38 to 49C and at pressures of 69 to 138 kPa.

Most

commercial plants carry out the reaction in the liquid phase in the
presence of a ferric chloride catalyst.8
Products (Stream 9) from the direct chlorination reactor are cooled
and washed with water (Stream 10) to remove dissolved hydrogen chloride
before being transferred (Stream 11) to the crude EDC storage facility.
Any inert gas fed with the ethylene or chlorine is released to the
atmosphere from the cooler (Vent B).

The waste wash water (Stream 12) is

neutralized and sent to the wastewater steam stripper along with

neutralized wastewater (Stream 13) from the oxychlorination quench area and
the wastewater (Stream 14) from the drying column.

The overheads (Stream

15) from the wastewater steam stripper, which consist of recovered EDC,
other chlorinated hydrocarbons, and water, are returned to the process by
adding them to the crude EDC (Stream 10) going to the water wash.8
Crude EDC (Stream 16) from in-process storage goes to the drying
column, where water (Stream 14) Is distilled overhead and sent to the
wastewater steam stripper.

The dry crude EDC (Stream 17) goes to the heads

13

column, which removes light ends (Stream 18) for storage and disposal or
sale.

Bottoms (Stream 19) from the heads column enter the EDC finishing

column, where EDC (Stream 20) goes overhead to product storage.

The tars

from the EDC finishing column (Stream 21) are taken to tar storage for
disposal or sale.8
Two domestic EDC producers use oxygen as the oxidant in the
oxychlorination reactor.

The process details are considered to be

confidential by both producers.

Although conceptual descriptions of such

processes are given in the literature, it is not known how the actual
processes compare with those described in the literature.

One producer has

released data showing that the plant is not truly balanced; that is, the
ratio of EDC from oxychlorination and direct chlorlnation differs from that
of a balanced plant.

However, because both producers have direct

chlorination, EDC purification and cracking, and VCM purification steps at

the same site, both plants probably can be considered to have integrated
processes.8

Another producer uses only the oxychlorination process and

does not use direct chlorination.2

Figure 3 shows basic operations that may be used in an oxygen-based
oxychlorination process as presented in the literature.8

For a balanced

process plant, the direct chlorination and purification steps are the same
as those shown in Figure 2, and, therefore, are not shown again in Figure
3.

Ethylene (Stream 1) is fed in large excess of the amount used in the

air oxychlorination process, that is, 2 to 3 times the amount needed to

fully consume the HCl feed (Stream 2).

Oxygen (Stream 3) is also fed to

the reactor, which may be either a fixed bed or a fluid bed.

After passing

through the condensation step in the quench area, the reaction products
(Stream 4) go to a knockout drum, where the condensed crude EDC and water
(Stream 5) produced by the oxychlorination reaction are separated from the
unreacted ethylene and the inert gases (Stream 6).

From the knockout drums

the crude EDC and water (Stream 5) go to a decanter, where wastewater

(Stream 7) is separated from the crude EDC (Stream 8), which goes to
in-process storage as in the air-based process.

The wastewater

(Stream 7) Is sent to the steam stripper in the direct chlorination step

for recovery of dissolved organics.8
The vent gases (Stream 6) from the knockout drum go to a caustic
scrubber for removal of HCl and carbon dioxide.

The purified vent gases

(Stream 9) are then compressed and recycled (Stream 10) to the

14

oxychlorination reactor as part of the ethylene feed.

A small amount of

the vent gas (Vent A) from the knockout drum is purged to prevent buildup
of the inert gases entering with the feed streams or formed during the
reaction.8
Emissions
Uncontrolled EDC emission factors for the balanced process are listed
in Table 2.

Also listed in this table are potentially applicable control

techniques and associated emission factors for controlled emissions. The

emission factors were developed for a hypothetical plant with a total EDC
production capacity of 400,000 Mg/yr, based on 8760 hours of operation
annually.

Of the total production capacity, 2l5,000 Mg/yr is produced by

direct chlorination and 185,000 Mg/yr by oxychlorination.9

Because of

variations in process design, age of equipment, and so on, actual emissions

vary for each plant.
Process Emissions-Ethylene dichloride process emissions originate from the purging of
inert gases from the oxychlorination vent (Vent A, Figure 2 and Figure 3)
and the direct chlorination vent (Vent B, Figure 2).

The level of EDC in

the oxychlorination vent gas is reduced by either an absorber/stripper

combination or a refrigerated condenser.
9

3.24 and 3.58

10

Average EDC emission rates of

kg/Mg of EDC produced have been reported from the absorber

column. Emissions from the refrigerated condenser of one EDC producer were
calculated to be 2.40 kg/Mg of EDC produced.2

These emission factors are

presented in the "uncontrolled EDC emission factor" column in Table 2

because the use of either the absorber/stripper combination or the
refrigerated condenser is considered an integral part of the process design
of some EDC production facilities.

Somewhat higher oxychlorination and

chlorination pressures are also reported to help lower EDC emissions.2

Many plants incinerate vent gases from the oxychlorination and direct
chlorination reactors to reduce atmospheric emissions of EDC and VCM.
includes plants using the air-based as well as the oxygen-based
oxychlorination processes,11 although in air units a much larger
incinerator must be used because of high levels of nitrogen in the
oxychlorination vent.2

Thermal oxidation is estimated to reduce EDC

emissions by 98 percent or more.12

Incineration destruction efficiency

varies with emission stream properties and incinerator operating

16

This

TABLE 2.

Emission
source
Oxychlorination
Air process
Absorber/stripper, or

ETHYLENE DICHLORIDE EMISSION FACTORS FOR A HYPOTHETICAL EDC PRODUCTION PLANT (BALANCED PROCESS)a
Uncontrolled
EDC emission
Potentially
Source
factorc
applicable
%
designationb
(kg/Mg)
control technique
reduction

Controlled
EDC emission
factorc
(kg/Mg)

A
3.24d,e
3.58e,f
2.40e,f

Thermal oxidizer
Catalytic oxidizer
Thermal oxidizer

98+g
92.2f
98+g

<0.0648h
<0.280f
<0.0480h

Aj

0.462d

Direct chlorination vent

1.08d

Thermal oxidizer
Refrigerated condenser
Thermal oxidizer
Refrigerated condenser

98+g
85k
98+g
86k

<0.0092h
0.0693h, 0.17i
<0.0216h
0.162h,0.26i

Column vents
Storage vents
In-process

3.00d

Thermal oxidizer

98+g

<0.0600h

0.0149d

0.0733d

Thermal oxidizer
Refrigerated condenser
Thermal oxidizer
Refrigerated condenser

98+g
85k
98+g
85k

<0.0003h
0.0022h
<0.0015h
00110h

Process fugitive

0.265d

Detection & correction

of major leaks

72k,l

0.106h

Secondary
Wastewater biotreatment

0.002-0.06i,m

Refrigerated condenser
Oxygen process

Product

b
c

d
e

f
g

h
i
j
k
l

m
n

None

0.002-0.06i,m

Any given EDC production plant may vary in configuration and level of control from this hypothetical facility. The reader is encouraged to
contact plant personnel to confirm the existence of emitting operations and control technology at a particular facility prior to estimating
emissions therefrom.
Letters refer to vents designated in Figure 2.
Emission factors in terms of kg/Mg refer to kilogram of EDC emitted per Megagram of EDC produced by balanced process. In cases where a
particular source designation applies to multiple operations, these factors represent combined emissions for all (at each) of these operations
within the hypothetical facility.
Reference 8, p.IV-3.
The use of the absorber/stripper combination or refrigerated condenser is sometimes used for EDC recovery as an integrated part of the
process. Per Reference 2,2 one producer reports uncontrolled EDC emissions of 40 kg/Mg. Emissions from newer plants are generally significantly
lower.
Reference 10.
The control efficiency for thermal oxidation (i.e. incineration) varies depending on the design of the incinerator and the compound which
is burned. The 99 percent level is an estimate of the control efficiency of an incinerator with a residence time of about 0.75 seconds and a
temperature of about 870C, for a compound which is difficult to incinerate. Incinerators operating at longer residence times and higher
temperatures may achieve higher efficiences. Reference 12.
Calculated by applying the control efficiency to the uncontrolled emission factor.
Reference 2.
See Figure 3 for this vent source; see Figure 2 for all others.
Reference 13.
Detection and correction of major leaks is estimated to achieve emission reductions of 75 percent for pumps, 90 percent for vapor-service
valves, 70 percent for liquid service valves, and 62 percent for relief valves, for an overall reduction of 72 percent. Emission reductions
of up to 100 percent can be achieved for pumps and relief valves by installing double mechanical sealed pumps and rupture disks on relief
valves.
Emissions data are not available for deep well injection or neutralization. Reference 2.
Steam stripping is sometimes used as an integrated part of the EDC production process for the recovery of EDC from wastewater, as shown in
Figure 2. Information was not available on the use of controls beyond steam stripping.

parameters.

The 98 percent efficiency level is based on incinerator operation

at 870C and 0.75 second residence time for a compound which is difficult to
incinerate.12

The emission reduction may be greater than 98 percent for

incineration of EDC with these operating parameters. In addition, the

efficiency may be higher for longer residence times or higher operating
temperatures.12

Catalytic incineration is used by one plant to reduce EDC

emissions from reactor vents by 92.2 percent.10

Refrigerated vent condensers

may also be used to control direct chlorination vent emissions, as reported by

one EDC producer.2
In an oxygen process, the purge gas can be dried and the contained
ethylene can be chlorinated in a separate direct chloripator to produce
additional EDC.

The small vent from this direct chlorinator can be combined

with the vent from the other direct chlorinator and other vents from the
process and incinerated.

This treatment is reported to essentially eliminate

all emissions of EDC and VCM.2

Process emissions of EDC also result from the release of gases from the
column vents (Vent C, Figure 2).

Column vents include vents from the

wastewater steam stripper, the drying column, the heads column,and the EDC
finishing column.9
percent.

Incineration reduces EDC emissions by at least 98

12

Storage Emissions-Ethylene dlchloride emissions result from the storage of EDC during
in-process and final product stages.

Sources for the hypothetical plant are

shown in Figure 2 (Source D and source E).

The emissions in Table 2 are based

on fixed-roof tanks, half full, and 11C diurnal temperature variation.9

Emissions may be controlled by use of refrigerated vent condensers.

The

control efficiency for a refrigerated condenser is dependent on the properties

of the uncontrolled emission stream and on the condenser operating parameters.
The 85 percent efficiency level for storage vents is based on an uncontrolled
emission temperature of 20C and a condenser operating temperature of -15C.
Greater efficiency can be achieved by using a lower operating temperature.13
Handling Emissions-No handling emissions occur in the hypothetical plant, as all raw
materials, product, and waste byproducts are transported by pipeline.

This

may not be the case in existing plants, where loading and unloading operations
could result in additional emissions.9
18

Fugitive Emissions-Fugitive emissions of EDC and other volatile organics result

from leaks in process valves, pumps, compressors, and pressure relief
valves.

The plant is estimated to have 38 pumps handling EDC or

other light liquids.

There are an estimated 40 pressure relief

valves in volatile organics service and 900 process valves handling

EDC or other liquids.9

Fugitive emission quantities for specific

production facilities are dependent on age of equipment, level of

preventative maintenance, and leak detection programs.
Secondary Emissions-Secondary emissions can result from the handling and disposal of
process waste-liquid streams (Source G in Figure 2).

Wastewater

treatment at an EDC production plant may consist of neutralization

and steam stripping followed by either deep well injection or
biotreating.

Use of an open-pit neutralization system may result in

substantial EDC air emisslons.2

Handling of wastewater prior to deep

well injection may also result in EDC emissions; however, emissions

after injection are negligible.
Emissions of EDC from a biotreater are affected strongly by the
biotreater process configuration, temperature of ambient air and
wastewater, type of aeration device used, degree of aeratlon, and
hydraulic retention time of the system.2,10

EDC wastewater to a

biotreater originates from several sources, as designated in Figure

2,

as well as from spills, drips, stormwater runoff from concrete

pads under process equipment and washing down of equipment.2,10 In an

activated sludge biotreating system, EDC is not a readily
biodegradable compound.2
Most biotreater activated sludge systems consist of an open tank
with surface mixers for aeration and mixing.

The removal of EDC by

air stripping in these systems can be extremely high (over 99

percent).

The emisssion factor range in Table 2 is from biotreater

emission data reported by two EDC production facilities.2

The

emission factors were based on production rates of approximately 1.1

x 103 Mg/day.

Emission data were not available for neutralization or

deep well injection.

19

Source Locations
Major EDC producers and production locations are listed in Table
3.

In addition, the Chemical Division of Olin Corporation is listed

as a producer of EDC by the U.S. International Trade Commission.14

20

TABLE 3.

PRODUCTION OF ETHYLENE DICHL0RIDE2,5

Manufacturer

Location

Atlantic Richfield Co.

ARCO Chem. Co., div.

Port Arthur, TX

Diamond Shamrock

Deer Park, TX

Dow Chem. U.S.A.

Freeport, TX
Oyster Creek, TX
Plaquemine, LA

E.I. duPont de Nemours & Co., Inc.

Conoco inc., subsid.
Conoco Chems. Co. Div.
Ethyl Corp.
Chems. Group
Formosa Plastics Corp., U.S.A.
Georgia-Pacific Corp.
Chem. Div.

Baton Rouge, LA
Pasadena, TX
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA

The BF Goodrich Co.

BF Goodrich Chem. Group

La Porte, TX
Calvert City, KY
Convent, LA

PPG indust., Inc.

Indust. Chem. Div.

Lake Charles, LA

Shell Chem. Co.

Deer Park, TX

Union Carbide Corp.

Ethylene Oxide Derivatives Div.
Vulcan Materials Co.
Vulcan Chems., div.
Note:

Lake Charles, LA

Taft, LA
Texas City, TX
Geismar, LA

This listing is subject to change as market conditions change,

facility ownership changes, plants are closed down, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of EDC
emissions from any given facility is a function of variables such as
capacity, throughput and control measures, and should be determined
through direct contacts with plant personnel.

21

VINYL CHLORIDE MONOMER PRODUCTION

Vinyl chloride monomer (VCM) Is produced domestically by the
dehydrochlorination of ethylene dichloride (EDC).
in the production of polyvinyl chloride (PVC).

It is used primarily

Vinyl chloride has the

following structure:

Process Description
A typical flow diagram for EDC dehydrochlorination is shown in
Figure 4.

Ethylene dichloride (Stream 1) is introduced into the

pyrolysis furnace where it is cracked in the vapor phase at

temperatures of 450 to 620C and pressures of 450 to
930 kPa.
reaction.

About 50 percent conversion of EDC to VCM is achieved in the

15

The product gas stream from the furnace (Stream 2), containing
VCM, EDC, and HCl is quenched with liquid EDC, and fed to a condenser.
Hydrogen chloride is removed from the condenser in the gas phase, and
is recovered for use on site, generally in EDC production.

The liquid

stream from the condenser (Stream 4) is fed to a distillation column,

where it is separated into VCM product, unreacted EDC, and heavy ends.
The unreacted EDC (Stream 5) is recycled either to the quench column or
to the finishing section of an EDC plant (generally onsite).

Vinyl

chloride product is used either on-site or sold, and heavy ends are
incinerated.15
Emissions
In the EDC dehydrochlorination process, losses of EDC to the
environment can occur in the heavy ends from the vinyl chloride
separation unit (Source A in Figure 4).

Uncontrolled EDC emissions

from the heavy ends stream are reported as 0.6 - 0.8 kg/Mg.2,15
22

The heavy ends usually are incinerated along with other solid
wastes generated by the VCM manufacturing process.

Assuming that a

removal efficiency of at least 98 percent is achieved by

incineration,12 the controlled emission factor for EDC would be <0.016
kg of EDC per Mg of vinyl chloride produced.

Fugitive and process vent

emissions of EDC from VCM production are expected to be minor because

of control measures which are taken to prevent emissions of vinyl
chloride.15
VCM production plants may vary in configuration and level of
control. The reader is encouraged to contact plant personnel to confirm
technology at a particular facility prior to estimating emissions
therefrom.
Source Locations
A list of vinyl chloride production facilities, and locations is
presented in Table 4.

24

TABLE 4.

PRODUCTION OF VINYL CHLORIDE MONOMER2,5

Manufacturer

Location

Borden inc.
Borden Chem. Div.
Petrochems. Div.

Geismar, LA

Dow Chem. U.S.A.

Oyster Creek, TX
Plaquemine, LA

E.I. duPont de Nemours & Co., Inc.

Conoco inc., subsid.
Conoco Chems. Co. Div.

Lake Charles, LA

Ethyl Corp.
Chems. Group

Baton Rouge, LA

Formosa Plastics Corp. U.S.A.

Baton Rouge, LA
Point Comfort, TX

Georgia-Pacific Corp.
Chem. Div.

Plaquemine, LA

The BF Goodrich Co.

BF Goodrich Chem. Group

Calvert City, KY
La Porte, TX

PPG indust., Inc.

Chems. Group
Chem. Division-U.S.

Lake Charles, LA

Shell Chem. Co.

Deer Park, `TX

Note: This listing is subject to change as market conditions change,

facility ownership changes, plants are closed down, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of EDC
emissions from any given facility is a function of variables such as
capacity, throughput and control measures, and should be determined
through direct contacts with plant personnel.

25

METHYL CHLOROFORM PRODUCTION

Methyl chloroform (Cl3C-CH3), also known as 1,1,1-trichloroethane, is
used predominantly as a metal-cleaning solvent.16
United States by three processes.

It is produced in the

It has been estimated that about 60

percent of the methyl chloroform produced in the U.S. Is derived from vinyl
chloride and about 30 percent is made from vinylidene chloride.

The

remaining 10 percent of methyl chlorform produced is derived from ethane.17

Because Because there are no documented EDC emissions from the production of
methyl chloroform from ethane, this process is not discussed in this section.
Methyl chloroform may be produced from vinyl chloride by a two-step
process involving the hydrochlorination of vinyl chloride to form
1,1-dichloroethane and the thermal chlorination of this intermediate to
produce methyl chloroform. In the vinylidene chloride process, vinylidene
chloride is hydrochlorinated in the presence of a catalyst to form methyl
chloroform.18
Process Description
Vinyl Chloride Hydrochlorination/1,1-Dichloroethane Chlorination Process---Basic operations that may be used for production of methyl chloroform
from vinyl chloride are presented in Figure 5.

Vinyl chloride, hydrogen

chloride (HCl), recycled methyl chloroform, and ferric copper catalyst are
combined in a tower-type reactor.

In the reactor, a hydrochlorination

reaction between vinyl chloride and HCl takes place at temperatures of 35 to

40C, producing 1,1-dichloroethane.18
After being cooled in a condenser, the reaction products (Stream 1) are
fed to a purification column.

The dichloroethane fraction is removed as an

overhead stream (Stream 2) from the column, and fed to a chlorination

reactor. There, the dichloroethane is reacted with chlorine gas at
atmospheric pressure and about 400C to produce methyl chloroform and
byproduct hydrogen- chloride. The entire product stream from the chlorination
reactor, containing methyl chloroform, HCl, and a small amount of unreacted
1,1-dichloroethane, is recycled to the hydrochlorinator reactor (Stream 3).18
26

The recycled methyl chloroform is removed in the purification column as

a high boiling fraction (Stream 4), and is sent to a stripper column where it
is steam-stripped and distilled to yield a purified product (Stream 5).
product yield is over 95 percent.18

The

One company reports that it does not use

a steam stripper, eliminating Vent B and vent C, but has a solids dump (not
shown in Figure 5) from the hydrochlorinator filter.2
Vinylidene Chloride Hydrochlorination Process-Figure 6 shows basic operations that may be used for the production of
methyl chloroform from vinylldene chloride.

Vlnylidene chloride,

hydrochloric acid, and small quantity of ferric chloride catalyst are fed to
the hydrochlorination reactor.
at 25 to 35C.

The reaction is conducted in the liquid phase

Crude methyl chloroform product is withdrawn continuously

from the hydrochlorinatlon reactor (Stream 1) and purified by fractional

distillation. The purified product (Stream 2) is treated to remove moisture
and is combined with appropriate stabllizers to make the material suitable
for commercial use. The yield of product is over 98 percent.18
Emissions
Figure 5 shows possible sources of gas and liquid wastes (Sources A,
B, and C) for the methyl chloroform production process from the vinyl
chloride method.

The two major sources of EDC emissions to the atmosphere

from the vinyl chloride method are:

(1) the hydrochlorinator vent (Vent A),

and (2) the steam stripper gas effluent vent (Vent B).

The emissions of EDC

may result from the presence of EDC as an impurity in vinyl chloride or the
production of EDC in the hydrochlorination and chlorination reactions.

The

emission factors for EDC emissions from the hydroctilorinator vent condenser
and the steam stripper vent condenser are 8.5 kg/Mg and 0.5 kg/Mg,
respectively.17

The emission factors refer to kg of EDC emitted per Mg of

methyl chloroform produced.

One methyl chloroform producer is reported to incinerate gases in the
hydrochlorinator vent.2

This would reduce EDC losses by at least 98

percent,12 resulting in an emission rate of <0.17 kg/Mg, and in some

facilities below 0.001 kg/Mg.2 No information was available on techniques
used by industry to control emissions from the stream stripper gas vent.
28

Information on EDC emissions from the vinylidene chloride-based

production process of methyl chloroform is not available.

It is thought that

EDC may be present in the heavy ends waste stream and the aqueous effluent
waste stream discharged by the vinylidene chloride-based process.17

Data are

not currently available to quantify atmospheric discharges from the handling

of these waste streams.
Methyl chloroform production plants may vary in configuration and level
of control.

The reader is encouraged to contact plant personnel to confirm

the existence of emitting operations and control technology at a particular

facility prior to estimating emissions therefrom.
Source Locations
A list of methyl chloroform production facilities and locations is
presented in

Table 5.

Manufacturing processes used in each of the

facilities are not listed in the available literature.

30

TABLE 5.

PRODUCTION OF METHYL CHLOROFORM2,5

Manufacturer

Location

Dow Chem U.S.A.

Freeport, TX

PPG indust., Inc.

Indust. Chem. Div.

Lake Charles, LA

Vulcan Materials Co
Vulcan Chems., Div.
Note:

Geismar, LA

This listing is subject to change as market conditions change,

facility ownership changes, plants are closed down, etc.

The reader

should verify the existence of particular facilities by consulting

current listings and/or the plants themselves.

The level of EDC

emissions from any given facility is a function of variables such as

capacity, throughput and control measures, and should be determined
through direct contacts with plant personnel.

31

ETHYLENEAMINES PRODUCTION
Ethyleneamines are used in the production of carbamate fungicides,
chelating agents, dimethylethylene urea resins, and diaminoethylethanol.19
Process Description
The only reported process used in the production of ethyleneamines is
shown in Figure 7.

Ethyleneamines may be produced by reacting EDC with

ammonia in either the liquid phase or the vapor phase.

both of these reactions is ethylenediamlne.

The major product of

Byproducts of the reactions

include diethylenetriamine, triethylenetetramine, tetraethylenepentamine,

pentaethylenehexamine, and higher polymers.20
In the vapor phase reaction, EDC and an excess of anhydrous ammonia are
reacted at 150C and 9.0 MPa.

Anhydrous ethylenediamine hydrochloride is

formed, which, on treatment with caustic soda at 100C, yields free ethylenedlamine (NH2CH2CH2NH2).

Ethylenediamine vapors, steam, and unreacted ammonia

are fed to a dehydrating column (not shown) where the diamine is dried and
condensed.20
In the liquid phase process, EDC is treated with excess aqueous ammonia
at 100C and 1.0 MPa.

The aqueous product solution containing

ethylenediamine hydrochloride, ammonium chloride, and ammonia is heated with

caustic soda and fractionated.

The ethylenediamine is drawn off and the

ammonium chloride is recycled to the reaction vessel.20

The ethyleneamines are separated into a number of marketable products,
the composition of which varies from producer to producer.10
Emissions
Reactor pressure vents, dehydration columns, and fractionating
(distillation) columns are possible sources of unreacted EDC emissions.
Waste water streams from dehydrochlorination and drying operations may
contain quantities of unreacted EDC.20
Emissions of EDC from ethyleneamine production facilities using typical
controls have been estimated at 600 Megagrams for 1976.19

Typical control

techniques used by industry in the production of ethyleneamines are not

32

discussed in the published literature.

The total production of

ethyleneamines in 1976 was estimated at a level of 66,012 Megagrams.19

From these two values, average EDC emissions per unit ethyleneamine
production are estimated at 9.09 kg per Mg.

Data are not available on the

derivation of the total nationwide emissions estimates, nor are data

available to break down EDC emissions between specific sources.
Ethyleneamine production plants may vary in configuration and level of
control.

The reader is encouraged to contact plant personnel to confirm the

existence of emitting operations and control technology at a particular

facility prior to estimating emissions therefrom.
Source Locations
A list of major ethyleneamine production facilities and locations is
presented in Table 6.

34

TABLE 6.

PRODUCTION OF ETHYLENEAMINESa,b

Manufacturer

2,5

Location

Dow Chem. U.S.A.

Freeport, TX

Union Carbide Corp.

Ethylene Oxide Derivatives Div.
a

Taft, LA

Ethylenediamine is the principal product, although a mixture of various

ethyleneamines is obtained.

This listing is subject to change as market conditions change, facility

ownership changes, plants are closed down, etc.

The reader should verify

the existence of particular facilities by consulting current listings

and/or the plants themselves.

The level of EDC emissions from any given

facility is a function of variables such as capacity, throughput and

control measures, and should be determined through direct contacts with
plant personnel.

35

TRICHLOROETHYLENE PRODUCTION
Trichloroethylene (TCE) is used primarily as a metal-cleaning solvent
and is produced domestically by either chlorination or oxychlorination of EDC
or other chlorinated ethanes.

Trichloroethylene, Cl2C=CHCl, can be produced

separately or as a coproduct of perchloroethylene (PCE), Cl2C=CCl2, by

varying raw material ratios.21
TCE was once manufactured predominantly by the chlorination of
acetylene. However, because of a decrease in the supply of acetylene, EDC
chlorination became the preferred method for producing TCE.
acetylene-based TCE plant was shut down in late 1977.

The last

22

Process Description
Ethylene Dichloride Chlorination Process-The major products of the EDC chlorination process are TCE, PCE, and
hydrogen chloride (HCl).

Basic operations that may be used in the production

of TCE and PCE by EDC chlorination are shown in Figure 8.

EDC (Stream 1) and chlorine (Stream 2) vapors are fed to a chlorination
reactor.

The chlorination is carried out at a high temperature (400 to

450C), slightly above atmospheric pressure, without the use of a catalyst.

Other chlorinated C2 hydrocarbons or recycled chlorinated hydrocarbon
byproducts may be fed to the chlorinator.21
The product stream from the chlorination reaction consists of a mixture
of chlorinated hydrocarbons and HCl.

Hydrogen chloride (Stream 3) is

separated from the chlorinated hydrocarbon mixture (Stream 4) and used in

other processes. The chlorinated hydrocarbon mixture (Stream 4) is
neutralized with sodium hydroxide solution (Stream 5) and is then dried.
Spent caustic is transferred to a wastewater treatment plant.21
The dried crude product (Stream 7) is separated by a PCE/TCE column
into crude TCE (Stream 8) and crude PCE (Stream 9).

The crude TCE (Stream 8)

is fed to a TCE column, where light ends (Stream 10) are removed overhead.
Bottoms from this column (Stream 11), containing TCE and heavies, are sent to
the finishing column, where TCE (Stream 12) is removed overhead and sent to
TCE storage.

Heavy ends (Stream 13) are combined with light ends (Stream 10)

from the TCE column and stored for eventual recycling.21

36

The crude PCE (Stream 9) from the PCE/TCE column is fed to a PCE
column, where PCE (Stream 14) goes overhead to PCE storage.
this column (Stream 15) are fed to a heavy ends column.

Bottoms from

Overheads from the

heavy ends column (Stream 16) are recycled and bottoms, consisting of tars,
are incinerated.21 These bottoms, called "hex wastes", may be processed
further or heated to recover more volatilizable materials, with the resulting
tars sent to disposal, often by incineration.

This additional step recovers

80 to 90 percent of the bottoms.10

Ethylene Dichloride Oxychlorination Process-The major products of the EDC oxychlorlnation process are TCE, PCE, and
water.

Side reactions produce carbon dioxide, hydrogen chloride (HCl), and

several chlorinated hydrocarbons.

be used for EDC oxychlorination.

Figure 9 shows basic operations that may

The crude product contains 85 to 90 weight

percent PCE plus TCE and 10 to 15 weight percent byproduct organics.

Essentially all byproduct organics are recovered during purification and are
recycled to the reactor.

The process is very flexible, so that the reaction

can be directed toward the production of either PCE or TCE in varying

proportions.21
EDC (Stream 1), chlorine or hydrogen chloride (Stream 2), oxygen
(Stream 3) and recycled byproducts are fed to a fluid-bed reactor in the gas
phase.

The reactor contains a vertical bundle of tubes with boiling liquid

outside the tubes to maintain the reaction temperature at about 425C.

reaction takes place at pressures slightly above atmospheric.
chloride catalyst is added continuously to the tube bundle.

The

Copper
The reactor

product (Stream 4) is fed to a water-cooled condenser and then a refrigerated

condenser.

Condensed material and catalyst fines drain to a decanter.

The

noncondensed inert gases (Stream 5), consisting of carbon dioxide, hydrogen

chloride, nitrogen, and a small amount of uncondensed chlorinated
hydrocarbons, are fed to a hydrogen chloride absorber, where HCl is recovered
by absorption in process water to make byproduct hydrochloric acid.
remaining inert gases are purged (Vent A).

38

21

The

In the decanter the crude product (Stream 7) Is separated from an

aqueous phase.

The aqueous phase, containing catalyst fines (Stream 8), is

sent to a waste treatment plant (G).

Crude product is fed to a drying column

where dissolved water is removed by azeotropic distillation.

The water

(Stream 9) from the drying column is sent to the waste treatment plant (G)
and the dried crude product (Stream 10) is separated into crude TCE (Stream
11) and crude PCE (Stream 12) in a PCE/TCE column.21
Crude TCE (Stream 11) is sent to a TCE column, where the light ends
(Stream 13) are removed overhead and stored for recycle.

The bottoms

(Stream 14) are neutralized with ammonia and then dried to produce finished
TCE (Stream 15), which is sent to storage.21
The crude PCE (Stream 12) from the PCE/TCE is fed to a heavy ends
column where PCE and light ends (Stream 16) are removed overhead.

Heavy ends

(Stream 17), called "hex wastes," are sent to an organic recycle system,
where the organics that can be recycled (Stream 18) are separated from tars,
which are incinerated.

The PCE and light ends (Stream 16) from the heavies

column are fed to a PCE column, where the light ends (Stream 20) are removed
overhead and sent to the recycle organic storage tank.

The PCE bottoms

(Stream 21) are neutralized with ammonia and then dried to produce finished
PCE (Stream 22) which is sent to storage.21
Emissions
Potential sources of EDC process emissions for the EDC chlorination
process (Figure 8)

are the neutralization and drying area vent (Vent A),

which releases inert gases from the chlorine and EDC feeds, and the
distillation column vents (Vents B), which release noncondensable gases.
Storage emission sources (Vents C) include raw material storage and recycle
storage.

Fugitive emissions (D) occur when leaks develop in valves or in

pump seals.

When process pressures are higher than the cooling-water

pressure, VOCs can leak into the cooling water and escape as fugitive
emissions from the quench area.

Secondary emissions can occur when

wastewater containing VOCs is sent to a wastewater treatment system or lagoon

and the VOCs evaporate (E).

Another source of secondary emissions is the

combustion of tars in the incinerator where VOCs are emitted with the flue
gases (F).21
40

In the EDC oxychlorination process (Figure 9), the hydrogen chloride

asbsorber vent (Vent A), which releases the inert gases from the oxygen,
chlorine, and hydrogen chloride feeds, is a potential source of EDC process
emissions.

Other potential sources of EDC process emissions are the dr.ying

column vent (Vent B) and the distillation column vents (Vent C), which
release primarily noncondensable gases, and the TCE and the PCE neutralizer
vents (Vent D), which relieve excess pressure of the nitrogen pads on the
systems.

Storage emission sources (Vent E) are raw material storage and

recycle storage.
or in pump seals.

Fugitive emissions (F) occur when leaks develop in valves

Secondary emissions (G and H) occur as described above for

the chlorination process (see Vent E and Vent F in Figure 8).21

Atmospheric emissions of EDC in 1977 from the TCE production processes
were estimated at 610 Mg.23

The total domestic production of TCE in 1977 was

estimated at 135,000 Mg, of which 90 percent was from EDC.23

The emission

factor for the controlled EDC emissions from the production of TCE can be
calculated by dividing the EDC emissions by 90 percent of the total TCE
production quantity.

From these values, the controlled emission factor is

about 5.0 kg of EDC per Mg of TCE produced.

Data are not available on the

derivation of the total annual EDC emissions estimate, nor are sufficient
data available to break down EDC emissions between various sources.

One

reference states that EDC emissions for the process as a whole are
practically zero when volatiles are recovered from the hex wastes and since
EDC conversion is 100 percent in the reactor.2
TCE production plants may vary in configuration and level of control.
The reader is encouraged to contact plant personnel to confirm the existence
of emitting operations and control technology at a particular facility prior
to estimating emissions therefrom.
Source Locations
A list of trichloroethylene production facilities and locations is
presented in Table 7.

41

TABLE 7.

PRODUCTION OF TRICHLOROETHYLENE5

Manufacturer

Location

Dow Chem U.S.A.

Freeport, TX

PPG indust., Inc.

Indust. Chem. Div.
Note:

Lake Charles, LA

This listing is subject to change as market conditions change,

facility ownership changes, plants are closed down, etc.

The reader

should verify the existence of particular facilities by consulting

current listings and/or the plants themselves.

The level of EDC

emissions from any given facility is a function of variables such as

capacity, throughput and control measures, and should be determined
through direct contacts with plant personnel.

42

PERCHLOROETHYLENE PRODUCTION
Perchloroethylene (PCE) is used primarily as a dry-cleaning and
textile-processing solvent.

It is also used as a metal-cleaning solvent.16

PCE is produced domestically by three processes.

Two of the processes

involve the chlorination and oxychlorination of EDC or other chlorinated

hydrocarbons having two carbon atoms.

PCE and trichloroethylene (TCE) are

manufactured separately or as coproducts by the chlorination or

oxychlorination process with the raw material ratios determining the
proportions of PCE and TCE.21

PCE is also manufactured as a coproduct with

carbon tetrachloride by the chlorinolysis of hydrocarbons such as propane and

propylene.24
PCE was once manufactured predominantly by the chlorination of
acetylene. However, as acetylene production declined, EDC chlorination and
hydrocarbon chlorinolysis became the preferred methods of production.
last acetylene-base PCE plant was shut down in late 1977.

The

25

Process Description
Ethylene Dichloride Chlorination Process-A discussion of the EDC direct chlorination process for producing PCE
and TCE is presented in the subsection titled TRICHLOROETHYLENE PRODUCTION.
A discussion of the EDC oxychlorination process for producing PCE and
TCE is presented in the subsection titled TRICHLOROETHYLENE PRODUCTION.
Hydrocarbon Chlorinolysis Process-The major products of the hydrocarbon chlorlnolysis process are PCE,
carbon tetrachloride, and hydrogen chloride (HCl).
be used in this process are shown in Figure 10.

Basic operations that may

Preheated hydrocarbon feed

material (Stream 1) and chlorine (Stream 2) are fed to a chlorinolysis

reactor, which is a fluid-bed reactor maintained at about 500C.24
The reaction products, consisting of carbon tetrachloride, PCE, HCl,
and chlorinated hydrocarbon byproducts, (Stream 3) pass through a cyclone for
removal of entrained catalyst and then on to a condenser.

Uncondensed

materials (Stream 4), consisting of hydrogen chloride, unreacted chlorine,

43

and some carbon tetrachloride, are removed to the hydrogen chloride

purification system.

The condensed material (Stream 5) Is fed to a

hydrogen chloride and chlorine removal column, with the overheads

(Stream 6) from this column going to hydrogen chloride purification.
The bottoms (Stream 7) from the column are fed to a crude storage
tank.

Material from crude storage is fed to a distlllatibn column,

which recovers carbon tetrachloride as overheads (Stream 8).

The

bottoms (Stream 10) from the carbon tetrachloride distillation column

are fed to a PCE distillation column.

The overheads (Stream 11) from

the PCE distillation column are taken to PCE storage and loading, and
the bottoms are incinerated.24 These bottoms, called "hex wastes," may
be processed further or heated to recover more volatilizable
materials, with the resulting tars sent to disposal, often by
incineration. This additional step recovers 80 to 90 percent of the
bottoms.10
The feed streams (Stream 4 and Stream 6) to hydrogen chloride
purification are compressed, cooled, and scrubbed in a chlorine
absorption column with chilled carbon tetrachloride (Stream 9) to
remove chlorine.

The bottoms and condensable overheads (Stream 12)

from this column are combined and recycled to the chlorinolysis

reactor.

Uncondensed overheads (Stream 13) from the chlorine

absorption column are contacted with water to produce a hydrochloric

acid solution.

This solution is stored for eventual reprocessing and

use in a separate facility.

Overheads from the absorber and vented

gases from byproduct hydrochloric acid storage are combined (Stream

14) and passed through a caustic scrubber for removal of residual
hydrogen chloride.

Inert gases are vented from the scrubber.24

Emissions
Potential emission sources for the EDC chlorination and
oxychlorination processes are shown in Figure 8 and Figure 9,
respectively, and discussed in the TRICHLOR0ETHYLENE PRODUCTION
subsection.

It is estimated that 910 Mg of EDC were released to the

45

atmosphere from the PCE production process in 1977.26

The majority of

these emissions were from EDC oxychlorination and chlorination.

The

total domestic production of PCE in 1977 was 279,000 Mg, of which 65

percent of PCE production was from EDC.26 Thus, the nationwide
emissions estimate corresponds to a controlled EDC emission factor
for EDC chlorination and oxychlorination of about 5.0 kg of EDC per
Mg of PCE produced.

Data are not available on the derivation of the

nationwide annual EDC emissions estimate, nor are sufficient data

available to break down EDC emissions between specific emission
points. One reference states that EDC emissions for the process as a
whole are practically zero when the volatiles are recovered from the
hex wastes and since EDC conversion is 100 percent in the reactor.2
Potential emission sources for the hydrocarbon chlorinolysis
process are shown in Figure 10.

Since EDC is not used as a feedstock

in this process, as it is in the EDC chlorination and oxychlorination

processes, the only emissions of EDC can result from the handling and
disposal of hex wastes from the PCE distillation column (Source A in
Figure 10). The EDC is produced in the chlorinolysis reaction.

The

uncontrolled EDC emission factor for the hex waste handling is about
0.026 kg of EDC per Mg of PCE and carbon tetrachloride produced.27
Hex wastes may be processed further or heated to recover more
volatilizable materials, with the resulting tars sent to disposal.
This additional step recovers 80 to 90 percent of the bottoms,10 and
the EDC emissions from the dumping of the hex wastes are essentially
zero.2

Alternatively, a vapor-balance system and refrigerated

condenser have been used to control emissions from hex wastes with an
emission reduction of approximately 99 percent.28

Thus, the

controlled EDC emission factor for the secondary emissions is 0.00026

kg of EDC per fig of PCE and carbon tetrachloride produced.

These

EDC emission factors were developed for a hypothetical plant with the
capacity to produce 50,000 Mg/yr PCE and 30,000 Mg/yr carbon
tetrachloride operating 8760 hours per year.29
PCE production plants may vary in configuration and level of
control. The reader is encouraged to contact plant personnel to
confirm the existence of emitting operations and control technology
at a particular facility prior to estimating emissions therefrom.
46

Source Locations
A list of perchloroethylene production facilities and locations
is presented in

Table 8.

47

TABLE 8.

PRODUCTION OF PERCHLOROETHYLENE2,5

Manufacturer

Location

Diamond Shamrock Corp.

Indust. Chems. and Plastics Unit
Electro Chems. Div.

Deer Park, TX

Dow Chem. U.S.A.

Pittsburg, CA
Plaquemine, LA

E.I. duPont de Nemours & Co.,

Petrochems. Dept.
Freon(R) Products Div.

Corpus Christi, TX

PPG indust., Inc.

Indust. Chem. Div.

Lake Charles, LA

Vulcan Materials Co.

Vulcan Chems., Div.

Geismar, LA
Wichita, KS

Note:

This listing is subject to change as market conditions change,

facility ownership changes, plants are closed down, etc.

The reader

should verify the existence of particular facilities by consulting

current listings and/or the plants themselves.

The level of EDC

emissions from any given facility is a function of variables such as

capacity, throughput and control measures, and should be determined
through direct contacts with plant personnel.

48

VINYLIDENE CHLORIDE PRODUCTION

Process Description
Vinylidene chloride, or 1,1-dichloroethene, is used primarily in the
production of polyvinylidene copolymers such as Saran and some modacrylic
fibers.16
Figure 11.

It is manufactured domestically by a two step process as shown in

The first step involves the chlorination or oxychlorination of

EDC to produce 1,1,2-trichloroethane.

The second step is dehydrochlorination

of 1,1,2-trichloroethane to produce vinylidene chloride.

Little data are

available on the specific steps used in the production of

1,1,2-trichloroethane; however the process used to produce vinylidene
chloride from 1,1,2-trichloroethane is described extensively in published
literature.30
Most 1,1,2-trichloroethane is made by chlorination of EDC.
is carried out in the liquid phase at 120C and 345 kPa.
are hydrogen chloride (HCl) and 1,1,2-trichloroethane.

The reaction

The major products

Where

1,1,2-trichloroethane is made by oxychlorination the reactants are EDC, HCl,

and oxygen.

Reaction conditions vary from one process to another.

1,1,2-trichloroethane are the major products of this reaction.31

Water and

After

1,1,2-trichloroethane is produced, it is dehydrochlorinated with aqueous

sodium hydroxide at about 70C.

Major products of the reaction are

vinylidene chloride, sodium chloride, and water.30

Emissions
The primary source of emissions from the EDC chlorination process are
the waste streams from the HCl scrubber.

Waste water streams may contain

chlorine, HCl, spent caustic, and various chlorohydrocarbons, including EDC,

trichloroethane and reaction byproducts.

Hydrogen chloride and a number of

organic chlorides are probably present in the waste gas.31

Emissions from the EDC oxychlorination process originate from waste
water and vent gases from the separator which contain a number of
chlorohydrocarbons, including EDC, trichloroethane, and byproducts.
Scrubbing of the crude product to remove unreacted acid is another source of
waste water which may contain EDC.31

49

Potential sources of EDC emissions for the dehydrochlorination of

1,1,2-trichloroethane are the dehydrochlorination reactor purge vent (A in
Figure 11)

and the distillation column vents (B), which release

noncondensable gases.

Secondary EDC emissions can occur from desorption of

VOCs during wastewater treatment.30

It is estimated that 600,000 kg of EDC were released to the atmosphere
from the production of vinylidene chloride in 1977.32

The total U.S.

production of vinylidene chloride in 1977 was estimated at 105,000 Mg.32

From these values, the controlled EDC emission factor for vinylidene chloride
production is calculated to be 5.7 kg of EDC per Mg of vinylidene chloride
produced.

Data are not available on the derivation of the annual EDC

emissions estimate for vinylidene chloride production, nor are sufficient

data available to break down EDC emissions between specific emission points.
Vinylidene chloride production plants may vary in configuration and
level of control.

The reader is encouraged to contact plant personnel to

confirm the existence of emitting operations and control technology at a

particular facility prior to estimating emissions therefrom.
Source Locations
Major vinylidene chloride production facilities and their locations are
listed below.5

Dow Chemicals U.S.A.

Freeport, TX
Plaquemine, LA

PPG industries, Inc.

Lake Charles, LA

Industrial Chemicals Div.

This listing is subject to change as market conditions change, facility
ownership changes, plants are closed down, etc.

The reader should verify the

existence of particular facilities by consulting current listings and/or the

plants themselves.

The level of EDC emissions from any given facility is a

function of variables such as capacity, throughput and control measures, and

should be determined through direct contacts with plant personnel.

51

ETHYL CHLORIDE PRODUCTION

About 90 to 95 percent of ethyl chloride produced domestically is
manufactured by the hydrochlorination of ethylene.

This reaction takes place

in the presence of EDC and a catalyst such as aluminum chloride.

Ethyl

chloride is also produced by the thermal chlorination of ethane or by a

combination of ethane chlorination and ethylene hydrochlorination.

EDC is a

by-product of ethyl chloride production by both of these processes.33

Process Description
Basic operations that may be used in the production of ethyl chloride by
the hydrochlorination of ethylene are presented in Figure 12.

Ethylene gas

and hydrogen chloride are mixed in equimolar proportions before being fed to
a reactor which contains EDC or a mixture of EDC and ethyl chloride.
Hydrochlorination of ethylene occurs in the presence of an aluminum chloride
catalyst.

The gaseous reaction products are charged to a separation column

or flash drum to remove heavy polymer bottoms and then to a fractionation

column for final product purification.34
Emissions
There is little information available in the published literature on EDC
emissions from ethyl chloride production.
air vents.

Emissions may occur from process

EDC emissions from ethyl chloride production via ethylene

hydrochlorination were estimated to be 2313 x 103 kg in 1978.35

From this

total emission estimate and the level of ethyl chloride production for 1978
(244,800 Mg),36 the EDC emission factor for ethyl chloride production was
calculated to be 9.45 kg/Mg.
Ethyl chloride production plants may vary in configuration and level of
control.

The reader is encouraged to contact plant personnel to confirm the

existence of emitting operations and control technology at a particular

facility prior to estimating emissions therefrom.
Source Locations
Major ethyl chloride producers and locations are listed in Table 9.
52

TABLE 9.
Manufacturer

Dow Chem. U.S.A.

PRODUCTION OF ETHYL CHLORIDE5

Location

Freeport, TX

Process

Hydrochlorination of ethylene

E.I. duPont de Nemours & Co., Inc.

Petrochems. Dept.
Freon(R) Products Div.

Deepwater, NJ

Hydrochlorination of ethylene

Pasadena, TX

Hydrochlorination of ethylene

Ethyl Corp.
Chems. Group

Hercules inc.
Operations Div.

Hopewell, VA

Hydrochlorinaiion of ethylene

Lake Charles, LA

Hydrochlorination of ethylene

PPG indust., Inc.

Indust. Chem. Div.

Note:

This listing is subject to change as market conditions change, facility ownership changes,
plants are closed down, etc.

The reader should verify the existence of particular

facilities by consulting current listings and/or the plants themselves.

The level of

EDC emissions from any given facility is a function of variables such as capacity, throughput
and control measures, and should be determined through direct contacts with plant
personnel.

POLYSULFIDE RUBBER PRODUCTION

Process Description
Polysulfide rubber is a synthetic rubber polymer which is used in
the manufacture of caulking putties, cements, sealants, and rocket-fuel.
It is produced by the reaction between aliphatic halides, such as EDC,
and alkali polysulfides such as Na2S4.

The main products of the reaction

are the polysulfide rubber chain, (CH2CH2-S4)n, and sodium chloride.37

Emissions
Based on yields for similar industrial chemical reactions it has
been estimated that 94 percent of the EDC used during the manufacturing
of polysufide rubber becomes incorporated in the end product.37

It is

estimated that 5 percent of the EDC used in the process is released to

the atmosphere via leaks, spills and fugitive emissions associated with
the overall polysulfide manufacturing process.

The remaining 1 percent

of EDC remains dissolved in the mother liquor from which the polymer is
produced.

The mother liquor may be discharged as solid waste and stored

in landfills.37
From the stoichiometry of the polysulfide production reaction and
the percentages of EDC consumed and emitted,37 the average controlled EDC
emission factor for polysulfide rubber manufacture is 33.8 kg of EDC per
Mg of polysulfide rubber produced.
Source Locations
The Specialty Chemicals Division of Morton Thikol incorporated in
Moss Point, Mississippi, is currently listed as the only producer of
polysulfide rubber by the SRI Directory of Chemical Producers for 1983.5
This information is subject to change as market conditions change,
facility ownership changes, plants are closed down, etc.

The reader

should verify the existence of this or other facilities by consulting

current listings and/or the plants themselves.

The level of EDC

emissions from any given facility is a function of variables such as

capacity, throughput and control measures, and should be determined
through direct contacts with plant personnel.
55

LIQUID PESTICIDE FORMULATION

Ethylene dichloride is used in a number of liquid pesticide
formulations. These formulations generally are mixtures of EDC and other
active ingredients such as carbon tetrachloride and carbon disulfide.38
Process Description
Pesticide formulation systems are typically batch mixing operations.
A typical liquid pesticide formulation unit is presented in Figure 13.
Technical grade pesticide is usually stored in its original shipping
container in the warehouse section of the plant until it is needed.

If

the material is received in bulk, it is transferred to holding tanks for

storage.

Solvents are normally stored in bulk tanks.

Batch mixing tanks are typically closed vessels.

The components of

the formulation are fed into the tank, measured by weight, and mixed by
circulation with a tank pump.2

The formulated material is then pumped to

a holding tank before being put into containers for shipment.

The blend tank is vented to the atmosphere through a vent dryer,
which prevents moisture from entering the tank.2

Storage and holding

tanks and container-filling lines may be provided with an exhaust

connection or hood to remove any vapors.

The exhaust from the system may

be vented to a control device or directly to the atmosphere.39

Emissions
Sources of EDC emissions from pesticide formulation include storage
vessels, mixing vessel vents, and leaks from pumps, valves, and flanges.
insufficient information is available for the development of EDC emission
factors for liquid pesticide formulation facilities.
Source Locations
Registrants and applicants for registration of pesticide products
containing EDC are listed in Table 10.

Some of the listed companies may

buy a preformulated or prepackaged product from larger producers and,

therefore, may not be actual sources of emissions.

In addition, this

list may change as facility ownership changes or plants are closed down.
56

TABLE 10.

COMPANIES WHICH HOLD REGISTRATIONS ON PESTICIDE

FORMULATIONS CONTAINING ETHYLENE DICHLORIDE40

Company

Location

Southland Pearson & Co.

Mobile, AL

Vulcan Materials Co.

Birmingham, AL

Cardinal Chemical Co.

San Francisco, CA

Cooke Laboratory Products

Commerce, CA

Coyne Chemical Co.

Los Angeles, CA

Dexol industries

Torrance, CA

Hacienda Enterprises

San Jose, CA

Hockwaldchem, Division of Oxford Chemicals

Brisbane, CA

James Chem Co.

San Francisco, CA

Master Nurseymens Assn.

Concord, CA

Dettelbach Chemicals Corp.

Atlanta, GA

Hill Manufacturing, Inc.

Atlanta, GA

Lester Laboratories

Atlanta, GA

Oxford Chemicals

Atlanta, GA

The Selig Chemical industries

Atlanta, GA

Stephenson Chemical Co., Inc.

College Park, GA

Wool folk Chemical Works, Inc.

Ft. Valley, GA

Riverdale Chemical Co.

Chicago Heights, IL

Carmel Chemical Corp.

Westfield, IN

Brayton Chemicals, Inc.

West Burlington, IA

Industrial Fumigant Co.

Olathe, KS

Research Products Co.

Salina, KS

Central Chemical Corp.

Hagerstown, MD

Dow Chemical USA

Midland, MIa
(CONTINUED)
58

TABLE 10.

(Continued)

Company

Location

Haertel Walter Co.

Minneapolis, MN

E.N. Leitte Co.

Stlllwater, MN

The Agriculture & Nutrition Co.

Kansas City, KS

Bartels & Shores Chemical Co.

Kansas City, MO

Farmland industries, Inc.

Kansas City, MO

Ferguson Fumigants

Hazelwood, MO

The Huge Co., Inc.

St. Louis, MO

Knox Chemical Co.

St. Louis, MO

Patterson Chemical Co., Inc.

Kansas City, MO

PBI-Gordon Corp.

Kansas City, MO

Stewart Sanitary Supply Co., Ltd.

St. Louis, MO

Falls Chemicals, Inc.

Great Falls, MT

Ling Fuang industries, Inc.

Gardnerville, NV

Rochester Midland Corp.

Rochester, NY

Prentis Drug & Chemical Co., Inc

New York, NY

Bernard Sirotta Co., Inc.

Brooklyn, NY

Big F insecticides, Inc.

Memphis, TN

Weil Chemicals Co.

Memphis, TN

J-Chem, A Division of Fumigators, Inc.

Houston, TX

The Staffel Co.

San Antonio, TX

Voluntary Purchasing Group, Inc.

Bonham, TX

Atomic Chemical Co.

Spokane, WA

Chemical Formulators, Inc.

Nitro, WV
(CONTINUED)

59

TABLE 10.
Note:

(CONTINUED)

The companies listed are registrants of pesticidal products

containing EDC.

Some of these companies may buy a preformulated or

prepackaged product and, therefore may not be actual sources of

emissions.

In addition, the list is subject to change as market

conditions change, facility ownership changes, or plants are closed

down.

The reader should verify the existence of particular

facilities by consulting current listings or the plants themselves.

The level of emissions from any given facility is a function of
variables, such as throughput and control measures, and should be
determined through direct contacts with plant personnel.

60

USE OF ETHYLENE DICHLORIDE iN GRAIN FUMIGATION

Ethylene dichloride is used as a component of fumigant mixtures that
are applied to control insect infestations in grains during storage,
transfer, milling, distribution and processing.

Ethylene dichloride

comprises 7.1 percent of the total weight of fumigant active ingredients

applied to stored grain. Annual usage of EDC in grain fumigants ranged from
870 to 1570 Mg/yr during the period from 1976 to 1979.38
Due to its flammability, EDC is used in fumigant mixtures with carbon
tetrachloride, which decreases the fire and/or explosion hazard of the
mixture. A product containing three parts EDC to one part carbon
tetrachloride has been used widely.

Other grain fumigant formulations

containing EDC are:

" Ethylene dichloride 64.6 percent, carbon tetrachloride 27.4 percent,
ethylene dibromide 5.0 percent
" Ethylene dichloride 10.0 percent, carbon tetrachloride 76.5 percent,
ethylene dlbromide 3.5 percent, carbon disulfide 10.0 percent
" Ethylene dichloride 29.2 percent, carbon tetrachloride 63.6 percent,
ethylene dibromide 7.2 percent
" Ethylene dichloride 64.7 percent, carbon tetrachloride 27.4 percent,
ethylene dibromide 7.9 percent
" Ethylene dichloride 12.0 percent, carbon tetrachloride 83.8 percent,
ethylene dibromide 1.2 percent.38
Table 11 lists brand names of pesticide products containing EDC.
Process Description
Liquid grain fumigants are used on approximately 12 percent of the
grain grown in the United States.

Fumigants are used during binning

(placement in storage) and turning (shifting from one storage facility to

another) operations or at any time during storage when infestation occurs.
Fumigants have a period of effectiveness of only a few days.

Thus, they

kill existing insect populations but do not prevent later reinfestatlon.

Newly harvested grain typically is fumigated 6 weeks after binning.

Corn

grown in the southern regions of the U.S. usually is fumigated immediately

following binning, because of field infestation by weevils.41

61

TABLE 11.

ETHYLENE DICHLORIDE PESTICIDE BRAND NAMES40

Big F "LGF" Liquid Gas Fumigant

Best 4 Servis Brand 75-25 Standard Fumigant
Brayton 75-25 Grain Fumigant
Brayton Flour Equipment Fumigant for Bakeries
Brayton EB-5 Grain Fumigant
Bug Devil Fumigant
Cardinal Fume
Chemform Brand Bore-Kill
Cooke Kill-Bore
Coop New Activated Weevil Killer Fumigant
Crest 15 Grain Fumigant
De-Pester Weevil Kill
De-Pester Grain Conditioner and Weevil Killer
Diweevil
Dowfume EP-15 Inhibited
Dowfume 75
Dowfume EB-5 Effective Grain Fumigant
Dowfume F
Dowfume EB-59
Dynafume
Excelcide Excel fume
FC-7 Grain Fumigant
(CONTINUED)

62

TABLE 11.

(CONTINUED)

FC-13 Mill Machinery Fumigant

Formula MU-39
Formula 635 (FC-2) Grain Fumigant
Fume-O-Death Gas No. 3
Fumisol
Gas-o-cide
Grain Fumigant (Dettelbach Chemicals)
Grainfume MB
Hill's Hilcofume 75
Hydrochlor Fumigant
Hydrochlor GF Liquid Gas Fumigant
Infuco 50-50 Spot Fumigant
Infuco Fumigant 75
Iso-Fume
J-Fume-20
J-Fume-75
KLX
Koppersol
Leitte Spotfume 60
Max Spot Kill Machinery Fumigant
Max Kill 75-25
Max Kill Spot - 59 Spot Fumigant for Mills and Milling Machinery
Parson Lethogas Fumigant
Patterson's Weevil Killer
(CONTINUED)

63

TABLE 11.

(CONTINUED)

Pearson's Fumigraln P-75

Pioneer Brand Grain Fumigant
Riverdale Fumigant
Security Di-Chlor-Mulsion
Selig's Selcofume
Selig's Grain Fumigant No. 15
Selig's Grain Storage Fumigant
Serfume
Sirotta's Sircofume Liquid Fumigating Gas
Spray-Trol Brand insecticide Fumi-Trol
Spot Fumigant
Standard 75-25 Fumigant
Staffel's Boraway
Stephenson Chemicals Stored Grain Fumigant
Vulcan Formula 635 (FC-2) Grain Fumigant
Vulcan Formula 72 Grain Fumigant
Waco-50
914 Weevil Killer and Grain Conditioner

64

A variety of structures are used for grain storage.

Farm grain

storage facilities are mostly metal with some wooden bins of flat, older and
loose-fitting construction.

Country elevators are of two types:

banked concrete silos and flat storages.

small

At mills, banked silos are

predominant. Terminal elevators are banked silos.

Grain transportation

vehicle's include trucks, rail cars (box, freight, hopper), inland barges,
ocean barges and ships.

Subterminal and terminal elevators and shipholds

are usually almost air tight, while farm grain storage facilities generally
allow considerable air flow.38,41

On-farm facilities typically have a

capacity of about 3,000 bushels, while country elevators have a capacity of

about 300,000 bushels. Terminal elevators have an average capacity of 4
million bushels.42
Grain fumigants are applied primarily by the "gravity distribution"
method by either surface application or layering.
both on-farm and off-farm.

This method is practiced

A second method of fumigant application is

"outside of car" application, where the fumigant is either poured from one
or five gallon containers through vents located in the roof of the car or
sprayed into the car with a power sprayer.43
Equipment used to apply fumigants includes common garden sprinkling
cans with spray heads removed; 3 to 5 gallon capacity compressed air
sprayers from which the nozzles have been removed; high capacity motor
driven pumps which apply large volumes of liquid materials directly from
large drums; metering devices which treat streams of moving grain; and
distribution tube and pressure reduction valve systems for discharging of
liquids stored under pressure.41
The rate of application of fumigants is dependent on the type of grain
and the type of storage facility.

Table 12 presents general application

rates for various types of grain for both on-farm and off-farm storage.

The

application rates for off-farm storage are lower since these types of
facilities are typically more tight-fitting than on-farm storage.38
After application of fumigants, grain generally is left undisturbed
for at least 72 hours.
longer period.

The usual practice is to leave the grain for a much

Fumigants are often left on the grain until the normal

turning procedure is undertaken.

Alternatively, the grain may be aerated by

65

TABLE 12.

FUMIGANT APPLICATI0N RATES38

Application rate
(gal/103 bu)
__________________________
Grain

On-farm

Off-farm

Wheat

3 -

2 -

Corn

4 -

3 -

Rice, Oats, Barley, Rye

3 -

2 -

Grain sorghum

5 -

4 -

66

turning after completion of the required treatment period.

In tight-fitting

facilities equipped with recirculation or forced distribution blowers, the

fumigant is ventilated from the grain with fresh air by operating the
blowers for 3 to 4 hours.41
Emissions
Emissions of EDC from fumigant mixtures occur during fumigant
application and when fumigated grain is exposed to the atmosphere, for
instance, during turning or loading.

The rate of emissions of EDC from

fumigant use depends on a number of factors including the type of grain, the
type and concentration of fumigant applied, the type of storage (whether
loose or tight-fitting), the manner in which the grain is handled, and the
rate of release of fumigant residues in and on the grain.

Although high

sorption efficiencies (84 percent) have been reported for certain cereals,
it is generally concluded that by the time the grain is processed,
essentially all of the retained EDC will have been dissipated to the
atmosphere.44
Source Locations
The Standard industrial Classification (SIC) code for farms at which
grain may be stored are as follows:
0111
0112
0115
0116
0119
0191

Agricultural production
Agricultural production
Agricultural production
Agricultural production
Agricultural production
General farms

of
of
of
of
of

wheat
rice
corn
soybeans
other grains

Table 13 lists the on-farm grain storage capacity by state and the
percentage of total U.S. capacity by region.
SIC codes for off-farm storage facilities, are as follows:
4221 - Grain elevators, storage only
5153 - Wholesale grain merchants (includes country and terminal
elevators and other merchants marketing grain)
4463 - Marine cargo handling (includes terminal elevators

67

TABLE 13.

ON-FARM GRAIN STORAGE42

Region
and State
Northeast:
Maine
New Hampshire
Vermont
Massachusetts
Rhode island
Connecticut
New York
New Jersey
Pennsylvania
Delaware
Maryland

Capacity
(103 bu)
142,698
2,866
0
0
9,654
0
222
39,204
5,190
62,498
2,057
21,007

Lake States:
Michigan
Wisconsin
Minnesota

1,357,597
116,462
244,827
996,338

Corn Belt:
Ohio
Indiana
Illinois
Iowa
Missouri

2,982,755
225,279
429,981
947,208
1,071,203
309,084

Northern Plains:
North Dakota
South Dakota
Nebraska
Kansas

2,132,264
681,397
394,381
715,594
340,892

Appalachian:
Virginia
West Virginia
North Carolina
Kentucky
Tennessee

236,607
37,554
5,685
100,938
49,237
43,193

Southeast:
South Carolina
Georgia
Florida
Alabama

159,132
31,437
87,720
12,145
27,830

68

Regional
percentage
2%

17%

__

|
|
|
|
|
37%
|____80%
|
|
|
|
|
|
26% __|

3%

2%

TABLE 13.
Region
and State
Delta States:
Mississippi
Arkansas
Louisiana

ON-FARM GRAIN STORAGE

Capacity
(103 bu)
131,593
41,588
50,095
39,910

(Continued)
Regional
percentage
1%

Southern Plains:
Oklahoma
Texas

315,160
76,685
238,472

4%

Mountain:
Montana
Idaho
Wyoming
Colorado
New Mexico
Arizona
Utah
Nevada

507,357
278,783
77,960
19,519
97,216
9,136
6,404
15,220
3,119

6%

Pacific:
Washington
Oregon
California

151,622
60,011
33,552
58,059
=========
8,116,815

2%

Total

69

====
100%

Table 14 lists the number of off-farm grain storage facilities and the total
capacity of these facilities by State.

70

TABLE 14.

State
Alabama
Arizona
Arkansas
California
Colorado
Delaware
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New 3ersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
South Carolina
South Dakota
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Other States
Total

OFF-FARM GRAIN STORAGE42

Number of

Capacity

facilities

(103 bu)

37,290
33,890
179,180
115,710
91,500
17,200
6,070
56,700
64,070
775,260
245,550
635,000
830,000
49,580
87,010
36,940
90,240
366,440
76,350
204,140
54,000
484,600
300
2,200
17,550
70;270
63,420
140,070
228,800
203,520
65,530
26,900
33,470
83,820
43,180
720,350
17,170
29,920
186,370
530
118,920
5,580
5,170
6,600,030
71

178
76
283
226
209
27
27
344
231
1,177
804
1,141
1,086
202
131
64
351
894
183
611
298
740
4
24
27
243
465
580
713
400
238
337
177
386
106
896
55
241
324
9
428
49
80
15,065

EDC USE IN LEADED GASOLINE

General
Ethylene dichloride is used in conjunction with ethylene dibromide
(1,2-dibromoethane) as a lead scavenger in leaded gasoline.

The

addition of these compounds prevents the fouling of the engine combusion

chamber with lead oxides.

Ethylene dichloride and ethylene dibromide

react with lead during combustion to form lead chloride (PbCl2) and lead
bromide (PbBr2) which remain in the gas phase and-are expelled with
exhaust gases.

About 1.0 mole of EDC and 0.5 mole of ethylene dibromide

are added to gasoline per mole of alkyl lead added.45

Current EPA

regulations limit lead in gasoline to 0.29 grams (.0014 moles) per

liter.46

Thus, no more than 0.0014 moles or 0.14 grams of EDC are added

per liter. Higher lead and EDC levels were added in previous years.
Emissions
Sources of EDC emissions from its use in leaded gasoline include
blending oPerations at refineries, bulk gasoline marketing and
transportation service stations, gasoline combustion, and evaporation
from the vehicles themselves.
Blending-EDC emissions from blending operations at refineries result from
evaporation during storage and handling of EDC and blended product.

It

is estimated in the literature that about 1 kg of EDC is emitted to the

atmosphere per fig of EDC used in blending.47

This corresponds to an

emission factor of about 0.14 mg EDC/1 of leaded gasoline produced.

Bulk Marketing and Transportation-Estimates of EDC emissions from bulk loading, storage, and
transportation of leaded gasoline are presented in Table 15.

These EDC

emission factors were developed based on published VOC emission

factors.48

Data were not available to calculate emissions of EDC from

loading and ballasting of marine vessels, submerged loading of tank cars

and trucks, and storage and loading in fixed roof tanks.

Emissions of

EDC from splash loading of tank cars and trucks, and from floating roof
72

TABLE 15. EDC EMISSIONS FROM BULK L0ADING, STORAGE, AND

TRANSPORTATI0N OF LEADED GASOLINE48
Emission rate
or factor

Emission source
Gasoline storage and loading
Fixed roof tanks
Floating roof tanks

a
b

438 g/yr

Tank car/truck loading

Submerged loading normal service
Submerged loading balance service
Splash loading normal service
transferred
Splash loading balance service
transferred

a
a

0.269 mg/1
0.192 mg/1

Marine vessel loading

Ship loading
Cleaned tank
Ballasted tank
Uncleaned tank
Average tank condition

a
a
a
a

Ocean barge loading

Cleaned tank
Ballasted tank
Uncleaned tank

a
a
a

Barge loading
Cleaned tank
Uncleaned tank
Average tank condition

a
a
a

Tanker ballasting
a

Information was not available to calculate emissions of EDC from

these sources.

The following assumptions were made for floating roof tanks

emissions: external floating roof with metallic shoe primary seal,
diameter is 62 feet, height is 40 feet, shell condition is light
rust, 10 turnovers/year, wind speed is 10 miles/hour, gasoline
density is 6.1 lb/gallon.

73

tanks, were calculated using the assumption that the EDC concentration
in emissions is the same as that in the bulk liquid.
Service Stations-Estimates of EDC emissions from service stations are presented in
Table 16. These emission factors were developed based on published
emission factors for gasoline.

Data was not available for estimation of

EDC emissions from underground tank filling by submerged loading and

tank breathing.

Emissions from splash loading of underground tanks,

vehicle refueling, and spillage were developed with the assumption that
emissions have the same composition as the stored liquid.
Combustion in Motor Vehicles-Most of the EDC added to leaded gasoline is destroyed during
combustion, reacting with lead and oxygen to produce lead chloride,
hydrogen chloride, water, and carbon dioxide.

It is estimated in

published literature that about 1 percent of the EDC added is not

destroyed during combustion and is emitted to the atmosphere with
vehicle exhaust.47

This corresponds to an emission factor of about 1.4

mg EDC/liter of leaded gasoline burned.

Motor Vehicle Evaporation-In addition to EDC emissions from motor vehicle exhaust,
evaporative emissions occur in the crankcase, carburetor, and fuel tank.
Crankcase emissions result from the crankcase as the engine is running.
Hot soak losses are produced as fuel evaporates from the carburetor
system at the end of a trip.

Diurnal changes in ambient temperature

result in expansion of the air-fuel mixture in a partially filled fuel

tank.

As a result, gasoline vapor is expelled into the atmosphere and

EDC is emitted with the vapor.49

Evaporative EDC emission factors for motor vehicles are not
available.

74

TABLE 16.

EDC EMISSI0NS FROM SERVICE STATIONS48

Emission factor

Emission source

(mg/1 transferred)

Filling underground tank

a

Submerged filling
Splash filling

0.26
a

Balanced submerged filling

Underground tank breathing and emptying

Vehicle refueling operations

Displacement losses (uncontrolled)

0.21

Displacement losses (controlled)

0.021

Spillage

0.016

Information was not available to calculate emissions of EDC from these

sources.

75

Source Location
Blending of leaded gasoline generally occurs at petroleum
refineries. A list of active petroleum refineries in the United States and
their locations is presented in Table 17.
Bulk gasoline loading facilities and service stations are too
numerous to list here.

Terminal and bulk stations can be found within

Standard industrial Classifications (SIC) code 5171.

stations can be found within SIC 5541.

Gasoline service

Terminals and bulk plants are

commonly identified individually as point sources in many emission

inventories such as EPA's National Emissions Data System (NEDS).

Service

stations and other gasoline outlets are usually treated collectively as

area sources in these inventories, as are mobile sources.
EDC USE iN PAINTS, COATINGS, AND ADHESIVES
General
It is estimated that about 1,400 Mg of EDC per year are used in the
manufacture of paints, coatings, and adhesives.
0.03 percent of total EDC consumption.

This amounts to about

Although specific uses of EDC in

paints and coatings are not known, EDC is thought to be used as a solvent
in paints and coatings which use vinyl polymers, particularly polyvinyl
chloride. EDC use in adhesives is restricted to adhesives using acrylics.51
Emissions
Because EDC is used as a solvent in paints, coatings, and adhesives,
it is estimated that all of the EDC used in these products is eventually
emitted to the atmosphere.51

Data are not available on the relative

amounts of EDC emitted during formulation and use of these products.

Source Locations
Standard industrial Classification (SIC) codes for manufacturing and
uses of paints, coatings, and adhesives are listed below:

painting, paper hanging, decorating - 172

paint and allied product manufacturing - 285

adhesives and sealants manufacturing - 2891

76

TABLE 17.

PETROLEUM REFINERIES50

Company and location

Alabama
Hunt Oil Co.--Tuscaloosa
Louisiana Land and Exploration
Co.--Saraland
Marion Corp.--Theodore
Mobile Bay Refining Co.--Chickasaw
Warrior Asphalt Co. of Alabama
Inc.--Holt

Company and location

Shell Oil Co.--Martinez
Wilmington
Sunland Refining Corp.--Bakersfield
Texaco inc.--Wilmington
Tosco Corp.--Bakersfield
Martinez
Union Oil Co. of California-Los Angeles
Rodeo
USA Petrochem Corp.--Ventura

Alaska
Colorado
Atlantic Richfield Corp.--Prudhoe Bay
Chevron U.S.A. Inc.--Kenai
North Pole Refining. Div. of
Mapco--North Pole
Tesoro Petroleum Corp.--Kenai
Arizona
Arizona Fuels Corp. --Fredonia

Asamera Oil U.S. Inc.-Commerce City

Conoco inc. --Commerce City
Gary Refining Co.--Fruita
Delaware
Getty Refining and Marketing Co. -Delaware City

Arkansas
Georgia
Berry Petroleum, Division of
Crystal Dll Co. --Stevens
Cross Oil & Refining Co. of
Arkansas--Smackover
Macmillan Ring-Free Oil Co.-Norphlet
Tosco Corp.--El Dorado

Amoco Oil Co.--Savannah

Young Refining Corp.--Douglasville
Hawaii
Chevron U.S.A. Inc.--Barber's Point
Hawaiian independent Refinery
Inc. --Ewa Beach

California
Anchor Refining CI--McKittrick
Illinois
Atlantic Richfield Co.--Carson
Clark Oil & Refining Corp.-Beacon Oil Co. --Hanford
Blue island
Champlin Petroleum Co.--Wilmington
Hartford
Chevron U.S.A. Inc.--Bakersfield
Marathon Oil Co.--Robinson
El Segundo
Mobile Oil Corp.--Joliet
Richmond
Shell 011 Co.--Hood River
Douglas Oil Co.-Texaco inc.--Lawrenceville
Santa Maria
Union Oil Co. of California--Lemont
Eco Petroleum inc.--Signal Hill
Edgington Oil CI--Long Beach
Indiana
Exxon Co.--Benlcia
Fletcher Oil & Refining Co.--Carson
Amoco Oil Co.--Whiting
Getty Refining & Marketing Co.-Bakersfield
Gladieux Refinery inc. --Ft. Wayne
Golden Bear Division, Wltco Chemical
Indiana Farm Bureau Cooperative
Corp. --Oildale
Association inc.--Ht. Vernon
Golden Eagle Refining Co.--Carson
Laketon Refining Corp. --Laketon
Gulf Oil Co.--Santa Fe Springs
Rock island Refining Corp.-Huntway Refining Co. --Benicia
Indianapolis
Wilmington
Independent Valley
Kansas
Energy Co.-Bakersfield
Derby Refining Co.--Wichita
Kern County Refinery inc.-Farmland industries inc. -Bakersfield
Coffeyville
Marlex Oil & Refining inc.-Getty Refining & Marketing Co. -Mobil Oil Corp.--Torrance
El Dorado
Newhall Refining CI--Newhall
Mobile Oil Corp.--Augusta
Oxnard Reflnery--Oxnard
National Cooperative Refinery
Pacific Oasis--Paramount
Association--McPherson
Pacific Refining Co.--Hercules
Pester Refining Co.--El Dorado
Powerine Oil Co.--Santa Fe Springs
Total Petroleum--Arkansas City
Long Beach
Sabre Refining inc.--Bakersfield

77

TABLE 17.
Company and location

PETROLEUM REFINERIES (Continued)

Company and location

Kentucky
Ashland Petroleum Co.--Catlettsburg
Louisville
Somerset Refinery inc.--Somerset
Louisiana
Atlas Processing Co., Division of
Pennzoil--Shreveport
Calumet Refining Co.--Princeton
Canal Refining Co.--Church Point
Celeron Oil & Gas--Mermentau
Cities Service Co.--Lake Charles
Claiborne Gasoline Co.--Lisbon
Conoco inc.-Lake Charles
Cotton Valley Refinery (Kerr-McGee
Refining Corp.)--Cotton Valley
CPI Refining inc.--Lake Charles
Exxon Co.--Baton Rouge
Gulf Oil Corp.--Belle Chasse
Hill Petroleum Co.--Krotz Springs
Kerr McGee Corp.--Dubach
Mallard Resources inc.--Gueydon
Marathon Oil Co.--Garyville
Murphy Oil Co.--Meraux
Placid Refining Co.--Port Allen
Port Petroleum inc.--Stonewall
Shell Oil Co.--Norco
Tenneco Oil Co.--Chalmette
Texaco inc. --Convent
Maryland

New Jersey
Chevron U.S.A.--Perth Amboy
Exxon Co.--Linden
Mobil Oil Corp.--Paulsboro
Seavlew Petroleum inc.-Thorofare
Texaco inc.--Westville
New Mexico
Giant industries inc. --Ciniza
Farmington
Navajo Refining Co.--Artesia
Plateau inc.--Bloomfield
Southern Union Refining Co.-Lovington
Thriftway Co.--Bloomfield
North Dakota
Amoco Oil Co.--Mandan
Flying J inc.--Wllliston
Ohio
Ashland Petroleum Co.--Canton
Gulf Oil Co.--Cincinnati
Standard Oil Co. of Ohio--Lima
Toledo
Sun CI--Toledo
Oklahoma

Chevron U.S.A. Inc.--Baltimore

Allied Material Corp.--Stroud

Champlin Petroleum Co. --Enid
Conoco inc. --Ponca City
Kerr-McGee Refining Corp. -Wynnewood
Oklahoma Refining Co.--Cyril
Custer Country
Sun CI--Tulsa
Tonkawa Refining Co.--Arnett
Tosco--Duncan
Total Petroleum Corp. --Ardmore

Michigan
Crystal Refining Co.--Carson City
Lakeside Refining Co.--Kalamazoo
Marathon Oil Co.--Detroit
Total Petroleum inc.--Alma
Minnesota
Ashland Petroleum Co.--St. Paul Park
Koch Refining Co. --Rosemount

Oregon
Chevron U.S.A. Inc.--Portland

Mississippi
Pennsylvania
Amerada-Hess Corp.--Purvis
Chevron U.S.A. Inc.-Pascagoula
Ergon Refining inc.--Vicksburg
Natchez Refining inc.--Natchez
Southland Oil Co.--Lumberton
Sandersville

Atlantic Richfield Co.--Philadelphia

BP Oil Corp.--Marcus Hood
Gulf Oil Co.--Philadelphia
Kendall-Amalie Division
Witco Chemical Co.--Bradford
Penzoil Co. --Rouseville
Quaker State Oil Refining
Corp.--Farmers Valley
Sun CI--Marcus Hook
United Refining Co. --Warren
Valvoline Oil Co., Division
of Ashland Oil Co.--Freedom

Montana
Cenex--Laurel
Conoco inc.--Billings
Exxon Co.--Billings
Flying J inc.--Cut Bank
Kenco Refining inc.--Wolf Point
Simmons Refining Co.--Great Falls
Nevada

Tennessee

Nevada Refining Co.--Tonopah

Delta Refining Co.--Memphis

78

TABLE 17.
Company and location

PETROLEUM REFINERIES (Continued)

Company and location
Utah

Texas
Amber Refining Co.--Fort Worth
American Petrofina inc.-Big Spring
Port Arthur
Amoco Oil Co.--Texas City
Atlantic Richfield Co.--Houston
Champlin Petroleum Co.-Corpus Christi
Charter international Oil
Co. --Houston
Chevron U.S.A. Inc.--El Paso
Coastal States Petroleum Co.-Corpus Christi
Crown Central Petroleum
Corp.--Houston
Diamond Shamrock Corp. --Sunray
Dorchester Refining Co.-Mt. Pleasant
Eddy Refining Co.--Houston
Exxon Co. U.S.A. --Baytown
Flint Chemical Co.--San Antonio
Gulf Oil Co.--Port Arthur
Howell Hydrocarbons inc.--San Antonio
Koch Refining Co.--Corpus Christi
LaGloria Oil & Gas Co.--Tyler
Liquid Energy Corp.--Bridgeport
Marathon Oil Co.--Texas City
Mobil Oil Corp.--Beaumont
Phillips Petroleum Co.-Borger
Sweeny
Pride Refining inc.--Abilene
Quintana Petrochemical Co.-Corpus Christi
Saber Energy inc. --Corpus Christi
Shell Oil Co.--Deer Park
Odessa
Sigmor Refining Co.--Three Rivers
South Hampton Refining Co.--Silsbee
Southwestern Refining CI-Corpus Christi
Tesoro Petroleum Corp.-Carrizo Springs
Texaco inc.--Amarillo
El Paso
Port Arthur
Port Neches
Texas City Refining inc.--Texas City
Uni Refining inc.-- Ingleside
Union Oil Co. of California-(Beaumont), Nederland
Note:

Amoco Oil Co.--Salt Lake City

Caribou Four Corners inc.--Woods Cross
Chevron U.S.A.--Salt Lake City
Crysen Refining Co.--WoodsCross
Husky Oil Co.--North Salt Lake City
Phillips Petroleum Co.--Woods Cross
Plateau inc.--Roosevelt
Virginia
Amoco Oil Co.--Yorktown
Washington
Atlantic Richfield Co.--Ferndale
Chevron U.S.A. Inc. --Seattle
Mobile Oil Corp.--Ferndale
Shell Oil Co.--Anacortes
Sound Refining inc. --Taco:
Texaco inc. --Anacortes
U.S. Oil & Refining Co.--Tacoma
West Virginia
Quaker State Oil Refining Corp. -Newell
St. Mary's
Wisconsin
Murphy Oil Corp. --Superior
Wyoming
Amoco Oil Co.--Casper
Husky Oil Co.--Cheyenne
Little America Refining Co.--Casper
Mountaineer Refining CI--LaBarge
Sinclair Oil Corp.--Sinclair
Wyoming Refining Co. --Newcastle

This listing is subject to change as market conditions change,

facility ownership changes, plants are closed down, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of EDC
emissions from any given facility is a function of variables such as
capacity, throughput and control measures, and should be determined
through direct contacts with plant personnel.

79

EDC USE AS AN EXTRACTION SOLVENT

General
EDC is used in a number of solvent extraction applications.

Major

applications include the extraction of oil from seeds, the processing of

animal fats, and the processing of pharmaceutical products.

It is

estimated that EDC use as an extraction solvent accounts for about 1.1
Mg EDC/year or about 0.02 percent of total EDC consumption.52
Emissions
The solvent used in extraction processes is generally recovered by
low pressure distillation.

Some solvent is lost to the atmosphere from

valves, pumps, and compressors; in spills; and during transfer

operations.

It is estimated that in published literature that about 95

percent of the EDC consumed in solvent extraction processes is emitted

to the atmosphere, while about 5 percent is discharged with solid
wastes.

These solid wastes are generally incinerated.52

Source Locations
Standard industrial Classification (SIC) codes for uses of
extraction solvents are listed below:

Manufacturing of fats and oils - 207

Manufacturing of pharmaceutical preparations - 2834

EDC USE IN CLEANING SOLVENTS

General
Solvents containing EDC are used in cleaning equipment in the
polyvinyl chloride and textile manufacturing industries.

It is

estimated that this use accounts for about 910 Mg/year or about 0.02
percent of total EDC consumption.53

Data are not available on the

equipment cleaned, the specific nature of the cleaning operations, or

the compositions of the solvents used.
Emissions
Although no emissions data are available for solvent cleaning uses
of EDC, it is estimated in the literature that about 95 percent of the
EDC consumed is ultimately emitted to the atmosphere, while the
remaining 5 percent is discharged with solid wastes.53
wastes are generally incinerated.
80

These solid

Source Locations
Standard industrial Classification (SIC) codes for uses of cleaning
solvents are listed below:
!

Manufacturing of plastics materials and synthetics - 282

Manufacturing of textile mill products - 22

Manufacturing of apparel and other textile products - 23

MISCELLANEOUS EDC USES

General
EDC is used in the manufacture of color film, as a diluent in
pesticides and herbicides, and as an amine carrier in the leaching of
copper ores.

The total amount of EDC used in these applications is 460

Mg/year or about 0.01 percent of total domestic consumption.54

Very

little information is available in published sources regarding the

details of these processes.
Emissions
It is estimated in published literature that all of the EDC used in
the manufacture of pesticides, herbicides, and color film is emitted to
the atmosphere, while nearly all of the EDC used in copper leaching is
either consumed in the leaching process or emitted with waste water.54
Source Locations
Standard industrial Classification (SIC) codes for miscellaneous
uses of EDC are listed below:
!

Photographic equipment and supplies manufacturing - 3861

Agricultural chemicals manufacturing - 287

Copper ores mining - l02

VOLATILIZATION FROM WASTE TREATMENT, STORAGE AND DISPOSAL FACILITIES

Considerable potential exists for volatile substances, including
EDC, to be emitted from hazardous waste treatment, storage and handling
facilities. A study in Callfornia55 shows that significant quantities of
81

EDC may be contained in hazardous wastes, which may be expected to

volatilize within hours, days, or months after disposal by
landspreading, surface impoundment or covered landfill, respectively.
Volatilization of EDC and other substances was confirmed in this study
by significant ambient air concentrations of EDC over one site.
Reference 56 provides general theoretical models for estimating volatile
substance emissions from a number of generic kinds of waste handling
operations, including surface impoundments, landfills, landfarming (land
treatment) operations, wastewater treatment systems, and drum
storage/handling process.

If such a facility is known to handle EDC,

the potential should be considered for some air emissions to occur.

Several studies show that low levels of EDC may be emitted from
municipal wastewater treatment plants.

In a test at a small municipal

treatment plant (handling 40% industrial and 60% municipal sewage), EDC
emission rates from the aeration basins were measured at levels ranging
from 5 to 10 grams/hour.57

Tests at a larger municipal treatment plant

(handling about 50 percent industrial sewage) show that less than 92 to

184 grams/day of EDC are emitted, primarily from air stripping as part
of the activated sludge treatment process.

This emission rate was

calculated from the EDC content of the influent to the plant, and
assuming 50 to 100 percent volatilization as part of the overall
treatment process, which is the range of removal observed for other
volatiles.58 Too little data are available to extrapolate these test
results to other wastewater treatment plants.

82

SECTION 5
SOURCE TEST PROCEDURES
Ethylene dichloride emissions can be measured using EPA Reference
Method 23, which was proposed in the Federal Register on June 11, 1980.59
EPA has validated the method for ethylene dichloride in the
laboratory60 as well as in the field.61
In Method 23, a sample of the exhaust gas to be analyzed is drawn
into a Tedlar or aluminized Mylar bag as shown in Figure 14.

Tedlar is

considered a more reliable bag material than Mylar for EDC.61

The bag is

placed inside a rigid leak proof container and evacuated.

The bag is

then connected by a Teflon sampling line to a sampling probe (stainless

steel, Pyrex glass, or Teflon) at the center of the stack. Sample is
drawn into the bag by pumping air out of the rigid container.
The sample is then analyzed by gas chromatography (GC) coupled with
flame ionizatlon detection (FID).
one day of sample collection.

Analysis should be conducted within

The recommended GC column is 3.05 m by

3.2 mm stainless steel, filled with 20 percent SP-2100/0.1 percent

Carbowax 1500 on 100/120 Supelcoport.

This column normally provides an

adequate resolution of halogenated organics.

(Where resolution

interferences are encountered, the GC operator should select the column

best suited to the analysis.)
100C.

The column temperature should be set at

Zero helium or nitrogen should be used as the carrier gas at a

flow rate of approximately 20 ml/min.

The peak area corresponding to the retention time of ethylene
dichloride is measured and compared to peak areas for a set of standard
gas mixtures to determine the ethylene dichloride concentration.

The

range of the method is 0.1 to 200 ppm; however the upper limit can be
extended by extending the calibration range or diluting the sample.
method does not apply when ethylene dichloride is contained in
particulate matter.

83

The

84

REFERENCES
1.

Drury, J.S. and A.S. Hammons. Investigation of Selected

Environmental Pollutants: 1,2-Dichloroethane. U.S. Environmental
Protection Agency. Washington, D.C. Publication No.
EPA-560/2-78-006. April 1979.

2.

Cox, G.V., Chemical Manufacturers Association, Washington, DC.

Letter to Tom Lahre, Office of Air Quality Planning and Standards,
U.S. Environmental Protection Agency, August 18, 1983.

3.

Encyclopedia of Chemical Technology, Kirk Othmer, 3rd Edition,

Volume 5. Wiley interscience Publication, New York, New York. 1979.
p. 724-740.

4.

Chemical Producers Data Base System - 1,2--Dichloroethane. U.S.

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