450484007d
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
Locating And
Estimating Air
Emissions From
Sources Of
Ethylene Dichloride
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EPA-450/4-84-007d
March 1984
Locating And Estimating Air Emissions
From Sources Of Ethylene Bichloride
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office Of Air And Radiation
Office Of Air Quality Planning And Standards
Research Triangle Park, North Carolina 27711
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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental
Protection Agency, and has been approved for publication as received from GCA Technology. 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.
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CONTENTS
Figures •" 1v
Tables v1
1. Purpose of Document 1
2. Overview of Document Contents 3
3. Background 5
Nature of Pollutant 5
Overview of Production and Uses 8
4. Ethylene Dichloride Emission Sources 11
Ethylene Dichloride Production 11
Vinyl Chloride Monomer Production 22
Methyl Chloroform Production 26
Ethyleneamines Production 32
Trichloroethylene Production 36
Perchloroethylene Production 43
Vinylidene Chloride Production 49
Ethyl Chloride Production 52
Polysulfide Rubber Production 55
Liquid Pesticide Formulation 56
Use of Ethylene Dichloride in Grain Fumigation ... .61
EDC Use in Leaded Gasoline 72
EDC Use in Paints, Coatings, and Adhesives 76
EDC Use as an Extraction Solvent 80
EDC Use in Cleaning Solvents 80
Miscellaneous EDC Uses 81
Volatilization from Waste Treatment, Storage and
Disposal Facilities 81
5. Source Test Procedures 83
References 85
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FIGURES
Number Page
1 Chemical use tree for ethylene dichloride 10
2 Basic operations that may be used for ethylene
dichloride production by the balanced process, with
air-based oxychlorination 12
3 Basic operations that may be used for ethylene
dichloride production by the oxygen process
(oxychlorination step) 15
4 Basic operations that may be used for vinyl chloride
production by ethylene dichloride dehydrochlorination. . . 23
5 Basic operations that may be used for methyl chloroform
production by the vinyl chloride hydrochlorination/
1,1-dichloroethane chlorination process 27
6 Basic operations that may be used for methyl chloroform
production by the vinylidene chloride
hydrochlori nation process 29
7 Basic operations that may be used in the production of
ethyleneamines 33
8 Basic operations that may be used for trichloroethylene
(TCE) and perchloroethylene (PCE) production by
ethylene dichloride chlorination 37
9 Basic operations that may be used for trichloroethylene
(TCE) and perchloroethylene (PCE) production by
ethyl ene dichloride oxychlori nation. . •. 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
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FIGURES (continued)
Number Page
13 Basic operations that may be used for liquid
pesticide formulation 57
14 Method 23 sampling train 84
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TABLES
Number
1 Physical Properties of Ethyl ene Di chloride
2 Ethyl ene Di chloride Emission Factors for a Hypothetical EDC
Production Plant (Balanced Process) ........... 17
3 Production of Ethyl ene Di chloride ............. 21
4 Production of Vinyl Chloride Monomer ............ 25
5 Production of Methyl Chloroform ......... ..... 31
6 Production of Ethyl eneamines ................ 35
7 Production of Trichloroethylene ........... ... 42
8 Production of Perch! oroethyl ene ...... ........ 48
9 Production of Ethyl Chloride ............ .... 54
10 ' Companies Which Hold Registrations on Pesticide
Formulations Containing Ethylene Dichloride ....... 58
11 Ethylene Dichloride Pesticide Brand Names ......... 62
12 Fumigant Application Rates ...... " ........... 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 ............ 75
17 Petroleum Refineries .................... 77
VI
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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 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.
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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 avail-able, 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 eech 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.
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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. At this time, EPA generally has not
evaluated these methods. 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
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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 C1CH2CH2C1, and
the structure is as follows:
H H
Cl - C - C - Cl
H H
Ethylene dichloride should be distinguished from 1,2-dichloroethylene which has
double-bonded carbon atoms and the molecular formula C1CH=CHC1. Ethylene
dichloride is soluble in hydrocarbon solvents, miscible with other chlorinated
solvents, and has a high solvency for fats, greases, and waxes. However, it
has only a limited solubility in water.1 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. It can thus corrode iron or steel containers. 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
2
chemical, EDC is usually not stabilized.
Both of the chlorine atoms in the ethylene dichloride molecule are
reactive and can be removed by heat 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 condensation polymers and ethylene diamine.
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TABLE 1. PHYSICAL PROPERTIES OF ETHYLENE DICHLORIDE
3,4
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 C1CH2CH2C1
CAS Registry Number 107-06-2
Molecular Weight 98.97
Boiling Point, °C 83.7
Melting Point, °C -35.3
Density at 20°C, g/1 1.2529
Refractive Index at 20°C,
for Sodium Light 1.4451
Viscosity at 20°C, mPa-s 0.84
Surface Tension at 20°C, mN/m 31.38
Specific Heat at 20°C, J/(g-K)
liquid 1.288
gas 1.066
Latent Heat of Vapor at 20°C, 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, °C
closed cup 17
open cup 21
Explosive Limits in Air at 25°C,
% by Vol. 6.2-15.6
Autoignition Temperature in Air, °C 413
Thermal Conductivity, liq. at 20°C, .
W/(m-K) 0.143
Heat of Combustion, kJ/g 12.57
Heat of Formation, kJ/Cg-mol)
.liquid 157.3
vapor 122.6
CONTINUED
6
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TABLE 1. (continued)
Dielectric Constant
liquid, 20°C 10.45
vapor, 120°C 1.0048
Dipole Moment, C-m 5.24 x 10"30
Coefficient of Cubical Expansion,
mL/g, 0-30°C 0.00116
Vapor Pressure, kPa
10°C 5.3
20°C .- . 8-5
30°C 13-3
Solubility at 20°C, g
1,2-dichloroethane in 100 g H20 0.869
H20 in 100 g 1,2-dichloroethane , 0.160
Azeotropes, bp, °C
with 19.5% H20 72
with 5% H20 and 17% ethanol 66.7
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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. Ethylene dichloride is produced in the United States
mainly by 12 manufacturers in 19 production facilities. 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 Megagrams while actual production in 1982 was estimated at a level
of 3,451,488 Megagrams. Exports of EDC in 1981 were estimated at
277,000 Megagrams.
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 40°C to 50°C
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.
Ethylene dichloride is also manufactured commercially by treating ethylene
with anhydrous hydrogen chloride and oxygen (or air) in a fluldized bed of
finely divided particles containing cupric chloride. Typically, the reactive
ti
1
pressure and temperature are maintained at 20 to 70 psig and 200°C to 315°C,
respectively.
8
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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 HC1. Manufacturers take
advantage of the byproduct HC1 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, perch!oroethylene, trichloroethylene, and vinylidene chloride
(1,1-dichloroethene) accounts for another 14 percent of consumption.
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 1 percent of the 1980 production.
However, this use declined by 30 percent in 1980 and is expected to decline
further because of the decreasing production of leaded gasolines.
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 clean-ing 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. Nearly 11 percent
is used in the preparation of polysulfide compounds. 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.
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ETHYLENE + CHLORINE
(CH2CH2) (C12)
CATALYST
ETHYLENE
(CH2CH2)
ETHYLENE DICHLORIDE-
(C1CH2CH2C1)
HYDROGEN CHLORIDE
(2HC1)
+ OXYGEN
CATALYST
HEAT
USE
VINYL CHLORIDE
METHYL CHLOROFORM
ETHYLENEAMINES
PERCHLOROETHYLENE
TRICHLOROETHYLENE
VINYLIDENE CHLORIDE
LEAD SCAVENGER
METAL DECREASING
ORE FLOTATION
ORGANIC SYNTHESIS
PAINT, VARNISH, AND
FINISH REMOVER
SOAPS AND SCOURING
COMPOUNDS
SOLVENT
WETTING AND PENETRATING
AGENTS
PERCENT
- 8155
- 3%
- 3%
- 3%
- 3%
- 2%
100%
Figure 1. Chemical use tree for ethylene dichloride.^
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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 (HC1) by oxychlori-
nation. 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 HC1. In the balanced process, byproduct HC1 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 HC1.
Oxygen for Oxychlorination generally is added by feeding air to the reactor,
Q
although some plants use purified oxygen as feed material.
Basic operations that may be used in a balanced process using air for
the Oxychlorination step are shown in Figure 2. Actual flow diagrams for
production facilities will vary. The process begins with ethylene (Stream 1)
11
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ro
TO ABSORBER /STRIPPER
OR REFRIGERATED CONDENSER
AIR
(BY PIPELINED
"Lf
(c)
IN-
PROCESS
STORAGE
~y
HEADS
COLUMN
DRYING
COLUMN
Y
<»
WATER
U
PRODUCT
STORAGE
EDC
FINISHING
COLUMN
TO VINYL
CHLORIDE
PROCESS
OR SALES
SECONDARY .(G
EMISSION T
POTENTIAL
WASTE-
WATER
TREATMENT
FUGITIVE
EMISSIONS
OVERALL
PLANT
WASTE-
WATER
STRIPPER
HCI
REMOVAL
jjr
LIQUID-
WASTE
STORAGE
TO
'SKULIT
TAR
STORAGE
_TO_
SALES'
LIQUID
CHLORINATED
HYDROCARBONS
INCINERATOR
NOTE: The lumbers in this figure refer to process streams, as discussed In the text,
and the letters designate process vents. The heavy lines represent final product
streMS through the process.
Figure 2. Basic operations that may be used for ethyl ene
di chloride production by the balanced process,
with air-based oxychlorination.8
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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 315°C in either a
fixed-bed or fluid-bed reactor. A mixture of copper chloride and other
g
chlorides is used as a catalyst.
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 1s separated from the aqueous phase. The crude EDC (Stream 6) is
transferred to in-process storage, and the aqueous phase (Stream 7) 1s recycled
to the quench step. Nitrogen and other inert gases are released to the atmosphere
(Vent A). The concentration of EDC 1n the vent stream is reduced by absorber
2 8
and stripper columns or by a refrigerated condenser (not shown 1n Figure 2). '
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 49°C 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.
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
Q
to the water wash.
Crude EDC (Stream 16) from in-process storage goes to the drying column,
where water (Stream 14) 1s distilled overhead and sent to the wastewater steam
stripper. The dry crude EDC (Stream 17) goes to the heads column, which
13
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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
Q
column (Stream 21) are taken to tar storage for disposal or sale.
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 chlorination 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
jse
2
Q
considered to have integrated processes. Another producer uses only the
oxychlorination process and does not use direct chlorination.
Figure 3 shows basic operations that may be used in an oxygen-based
Q
oxychlorination process as presented in the literature. 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 HC1 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
8
direct chlorination step for recovery of dissolved organics.
- - The vent gases (Stream 6) from the knockout drum go to a caustic scrubber
for removal of HC1 and carbon dioxide. The purified vent gases (Stream 9) are
then compressed and recycled (Stream 10) to the oxychlorination reactor as
14
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REFRIGERATED
CONDENSER
OR
KNOCKOUT
DRUM
(BY PIPELINE)
HCI \y
(BY PIPELINE)
ETHYLENEV/
(BY PIPELINE)
CAUSTIC
SCRUBBER
DECANTER
NoOH
' COMPRESSOR
FROM DIRECT
CHLORINATION
STEP
TO PURIFICATION
IN-PROCESS
STORAGE
STEP
NOTE: The lumbers in this figure refer to process streams, as discussed in the text,
and the letters designate process vents. The heavy lines represent final product
streams through the process.
Figure 3. Basic operations that may be used for ethylene dichloride
production by the oxygen process (oxychlorination step).8
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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.
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, 215,000 Mg/yr is produced by direct chlorination and
q
185,000 Mg/yr by oxychlorination. 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, Figures 2 and 3) and the
direct chlorination vent (Vent B, Figure 2). The level of EDC in the oxychlori-
nation vent gas is reduced by either an absorber/stripper combination or a
refrigerated condenser. Average EDC emission rates of 3.249 and
3.58 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. 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.
Many plants incinerate vent gases from the oxychlorination and direct
chlorination reactors to reduce atmospheric emissions of EDC and VCM. This
includes plants using the air-based as well as the oxygen-based oxychlorination
processes, although in air units a much larger incinerator must be used
because of high levels of nitrogen in the oxychlorination vent.2 Thermal
12
oxidation is estimated to reduce EDC emissions by 98 percent or more.
Incineration destruction efficiency varies with emission stream properties
16
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TABLE 2. ETHYLENE DICHLORIDE EMISSION FACTORS FOR A HYPOTHETICAL EDC PRODUCTION PLANT (BALANCED PROCESS)'
1
1
Emission
source
Oxychlorination
Air process
Absorber/stripper, or
Refrigerated condenser
Oxygen process
Direct chlorination vent
Column vents
Storage vents
In-process
Product
Process fugitive
Secondary
Wastewater biotreatroent
Source .
designation
A
A*
B
C
0
E
F
G
Uncontrolled
EDC emission
factor*:
(kg/Kg)
3.24d>e
2i40e>f
0.462d
1.0Bd
3.00d
0.0149d
J
0.0733
0.265d
0.002-0.061'"
Potentially
applicable
control technique
Thermal oxidizer
Catalytic oxidizer
Thermal oxidizer
Thermal oxidizer
Refrigerated condenser
Thermal oxidizer
Refrigerated condenser
' Thermal oxidizer
Thermal oxidizer
Refrigerated condenser
Thermal oxidizer
Refrigerated condenser
Detection 4 correction
of major leaks
None"
t
reduction
98+9
92. 2T
98+9
85k
98+9
86k
98+9
98+9
85k
98+9
85k
72k.l
Controlled
EDC emission
factorc
(kg/Mg)
i0.0648h
S0.280fh
£0.0480"
SO. 0092[J
0.0693"
<0.0216h
0.162h.
S0.0600h
<0.0003||
0.0022^
SO. 0015"
o.ouo"
0.106h
0.002-0
.0.171
0.26'
.061'"
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 Hegagram of EDC produced by balanced process. In cases where a particular
source designation applies to multiple operations, these factors represent combined emissions for all (not each) of these operations within the
hypothetical facility.
Reference 8. p.IV-3.
eThe 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, one producer reports uncontrolled EDC emissions of 40 kg/Mg. Emissions from newer plants are generally significantly lower.
Reference 10.
9the control efficiency for thermal oxidation (I.e. Incineration) varies depending on the design of the Incinerator and the compound which Is
burned. The 98 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 B70°C, for a compound which is difficult to incinerate. Incinerators operating at longer residence times and higher
temperatures may achieve higher efficlences. 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.
-------
and incinerator operating parameters. The 98 percent efficiency level is
based on incinerator operation at 870°C and 0.75 second residence time for a
12
compound which is difficult to incinerate. 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
12
higher operating temperatures. Catalytic incineration is used by one plant
to reduce EDC emissions from reactor vents by 92.2 percent. Refrigerated
vent condensers may also be used to control direct chlorination vent emissions,
2
as reported by one EDC producer.
In an oxygen process, the purge gas can be dried and the contained
ethylene can be chlorinated in a separate direct chlorinator 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
9 12
finishing column. Incineration reduces EDC emissions by at least 98 percent.
Storage Emissions —
Ethylene dichloride emissions result from the storage of EDC during
in-process and final product stages. Sources for the hypothetical plant are
shown in Figure 2 (Sources D and E). The emissions in Table 2 are based on
fixed-roof tanks, half full, and 11°C diurnal temperature variation.
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 20°C and a condenser operating temperature of -15°C.
Greater efficiency can be achieved by using a lower operating temperature.
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
o
result in additional emissions.
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
9
process valves handling EDC or other liquids. 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
2
system may result in substantial EDC air emissions. 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 aeration, and hydraulic retention time of the
2 10
system. ' EDC wastewater to a biotreater originates from several sources,
as designated in Figure 2, as well as from spills, drips, stormwater runoff
2 10
from concrete pads under process equipment and washing down of equipment.
In an activated sludge biotreating system, EDC is not a readily biodegradable
compound.
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. The emission factors were based on production rates
of approximately 1.1 x 10 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 01 in Corporation is listed as a producer
14
of EDC by the U.S. International Trade Commission.
20
-------
TABLE 3. PRODUCTION OF ETHYLENE DICHLORIDE
2,5
Manufacturer
Location
Atlantic Richfield Co.
ARCO Chem. Co., div.
Diamond Shamrock
Dow Chem. U.S.A.
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.
The BF Goodrich Co.
BF Goodrich Chem. Group
PPG Indust., Inc.
Indust. Chem. Div.
Shell Chem. Co.
Union Carbide Corp.
Ethylene Oxide Derivatives Div.
Vulcan Materials Co.
Vulcan Chems., div.
Port Arthur, TX
Deer Park, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Lake Charles, LA
Baton Rouge, LA
Pasadena, TX
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
La Porte, TX
Calvert City, KY
Convent, LA
Lake Charles, LA
Deer Park, TX
Taft, LA
Texas City, TX
Geismar, LA
Note:
This listing is subject to change as market conditions change, faci
lity 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). It is used primarily in the
production of polyvinyl chloride (PVC). Vinyl chloride has the following
structure:
"S = c"-cl
HX XH
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 620°C and pressures
of 450 to 930 kPa. About 50 percent conversion of EDC to VCM is achieved in
the reaction.
The product gas stream from the furnace (Stream 2), containing VCM, EDC,
and HC1 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.
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
-------
VINYL CHLORIDE
co
TO EDC
PRODUCTION
NOTE: The nmbers In this figure refer to process streams, as discussed In the text.
and the letters designate process vents. The heavy lines represent final product
streams through the process.
Figure 4. Basic operations that may be used for vinyl chloride production
by ethylene dichloride dehydrochlorination.15
-------
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, 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.
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.
Dow Chem. U.S.A.
Geismar, LA
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.
The BF Goodrich Co.
BF Goodrich Chem. Group
PPG Indust., Inc.
Chems. Group
Chem. Division-U.S.
Shell Chem. Co.
Lake Charles, LA
Baton Rouge, LA
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
Calvert City, KY
La Porte, TX
Lake Charles, LA
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 (C13C-CH3), also known as 1,1,1-trichloroethane, is
used predominantly as a metal-cleaning solvent. It is produced in the
United States by three processes. 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 vinylldene chloride. The remaining 10 percent
17
of methyl chloroform produced is derived from ethane. 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
*| O
in the presence of a catalyst to form methyl chloroform.
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 (HC1), recycled methyl chloroform, and ferric copper catalyst are
combined in a tower-type reactor. In the reactor, a hydrochlorination reaction
between vinyl chloride and HC1 takes place at temperatures of 35 to 40°C,
18
producing 1,1-dichloroethane.
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 400°C to produce methyl chloroform and byproduct hydrogen chloride.
The entire product stream from the chlorination reactor, containing methyl
chloroform, HC1, and a small amount of unreacted 1,1-dichloroethane, is
18
recycled to the hydrochlorinator reactor (Stream 3).
26
-------
-*• HYDROCHLORINATOR
VENT
VINYL CHLORIDE
HYDROGEN
CHLORIDE
ro
CONDENSER
HYDROCHLORINATOR
REACTOR
HCI8 METHYL CHLOROFORM
RECYCLE STREAM
CHLORINATOR
REACTOR
CHLORINE
PURIFICATION
COLUMN
DICHLORO-
ETHANE
STEAM
STEAM
STRIPPER
CRUDE
METHYL
CHLOROFORM
STEAM STRIPPER
I •>-
I GAS EFFLUENT
CONDENSER
METHYL CHLOROFORM
STEAM STRIPPER
WATER EFFLUENT
NOTE: The numbers In this figure refer to process streams, as discussed In the text.
and the letters designate process vents. The heavy lines represent final product
streams inrougn the process.
Figure 5. Basic operations that may be used for methyl chloroform production by the vinyl
chloride hydrochlorination/1,1-dichloroethane chlorination process.18
-------
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). The
product yield is over 95 percent.18 One company reports that it does not use
a steam stripper, eliminating Vents B and C, but has a solids dump (not shown
in Figure 5) from the hydrochlorinator filter.
Vinylidene Chloride Hydrochlorination Process-
Figure 6 shows basic operations that may be used for the production of
methyl chloroform from vinylidene chloride. Vinylidene chloride, hydrochloric
acid, and small quantity of ferric chloride catalyst are fed to the hydro-
chlorination reactor. The reaction is conducted in the liquid phase at 25 to
35eC. Crude methyl chloroform product is withdrawn continuously from the
hydrochlorination reactor (Stream 1) and purified by fractional distillation.
The purified product (Stream 2) is treated to remove moisture and is combined
with appropriate stabilizers to make the material suitable for commercial use.
The yield of product is over 98 percent.
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 hydrochlorinator vent condenser and the^steam
stripper vent condenser are 8.5 kg/Mg and 0.5 kg/Mg, respectively. 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,
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
-------
ro
vo
VINYLIDENE
CHLORIDE
HCI
FERRIC
CHLORIDE
HYDROCHLORINATION
REACTOR
RECYCLE
FRACTIONATOR
COLUMNS
METHYL
CHLOROFORM
HEAVY
ENDS
WASTE
MOTE: The nutters In this figure refer to process stream, as discussed in the text
The heavy lines represent final product streams through the process.
Figure 6. Basic operations that may be used for methyl chloroform production by
the vinylidene chloride hydrochlorination process.18
-------
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 CHLOROFORM
2,5
Manufacturer Location
Dow Chem. U.S.A. Freeport, TX
PPG Indust., Inc.
Indust. Chem. Div. Lake Charles, LA
Vulcan Materials Co.
Vulcan Chems., Div. Geismar, LA
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.
31
-------
ETHYLENEAMINES PRODUCTION
Ethyleneamines are used in the production of carbamate fungicides,
chelating agents, dimethylethylene urea resins, and diaminoethylethanol.
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. The major product of
both of these reactions is ethylenediamine. Byproducts of the reactions
include diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, and higher polymers.
In the vapor phase reaction, EDC and an excess of anhydrous ammonia are
reacted at 150°C and 9.0 MPa. Anhydrous ethylenediamine hydrochloride is
formed, which, on treatment with caustic soda at 100°C, yields free ethylene-
diamine (NH2CH2CH2NH2). Ethylenediamine vapors, steam, and unreacted ammonia
are fed to a dehydrating column (not shown) where the diamine is dried and
20
condensed.
In the liquid phase process, EDC is treated with excess aqueous ammonia
at 100°C 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
20
recycled to the reaction vessel.
The ethyleneamines are separated into a number of marketable products,
the composition of which varies from producer to producer.
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
20
unreacted EDC.
Emissions of EDC from ethyleneamine production facilities using typical
19
-controls have been estimated at 600 Megagrams for 1976. Typical control
techniques used by industry in the production of ethyleneamines are not
32
-------
RECYCLE AMMONIA
to
EDC
AMMONIA
CAUSTIC SODA
1
r
REACTOR
FRACTIONATING
COLUMN
1.
f v
^ — '
ETHYLENE
DIAMINE
OTHER
ETHYLENE
AMINES
Figure 7. Basic operations that may be used in the production of ethyleneamines.
-------
discussed in the published literature. The total production of ethyleneamines
in 1976 was estimated at a level of 66,012 Megagrams. 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 ETHYLENEAMINES2'5>a'b
Manufacturer Location
Dow Chem. U.S.A. Freeport, TX
Union Carbide Corp.
Ethylene Oxide Derivatives Div. Taft, LA
a£thylenediamine 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, C12C=CHC1, can be produced
separately or as a coproduct of perchloroethylene (PCE), C1~C = CCl/>, by
21
varying raw material ratios.
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. The last acetylene-based TCE
22
plant was shut down in late 1977.
Process Descriptions
Ethylene Dichloride Chlorination Process —
The major products of the EDC chlorination process are TCE, PCE, and
hydrogen chloride (HC1). 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
450°C), slightly above atmospheric pressure, without the use of a catalyst.
Other chlorinated C, hydrocarbons or recycled chlorinated hydrocarbon byproducts
21
-may be fed to the chlorinator.
The product stream from the chlorination reaction consists of a mixture
of chlorinated hydrocarbons and HC1. 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
21
to a wastewater treatment plant.
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.
36
-------
HYDROGEN CHLORIDE O
TO OTHER •*
PROCESSES
CHLORINE
to
J.
C2 CHLORINATED
ORGANICS FROM
OTHER PROCESSES
TARS TO
INCINERATION
-LOADING
• LOADING
©
FUGITIVE
EMISSIONS
OVERALL
PLANT
NOTE: The nunbers In this figure refer to process strews, as discussed In the text.
and the letters designate process vents. The heavy lines represent final product
stream through the process.
Figure 8. Basic operations that may be used for trichloroethylene (TCE)
and perchloroethylene (PCE) production by ethylene dichloride
chlorination.21
-------
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. Bottoms from this column
(Stream 15) are fed to a heavy ends column. Overheads from the heavy ends
21
column (Stream 16) are recycled and bottoms, consisting of tars, are incinerated.
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.
Ethylene Dichloride Oxychlorination Process —
The major products of the EDC oxychlorination process are TCE, PCE, and
water. Side reactions produce carbon dioxide, hydrogen chloride (HC1), and
several chlorinated hydrocarbons. Figure 9 shows basic operations that may
be used for EDC oxychlorination. 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
21
proportions.
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 425°C. The reaction
takes place "at pressures slightly above atmospheric. Copper chloride catalyst
is added continuously to the tube bundle. 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 HC1 is recovered by absorption in process
water to make byproduct hydrochloric acid. The remaining inert gases are
purged (Vent A).21
38
-------
HYDROCHLORIC ACID
BYPRODUCT
*O
I AQUEOUS WASTE
). f TO WASTE
t TREATMENT
&Jn
I «!> •
BED
TOR
Am tf rti ic
^
.©
1
n
Of
CO
CHLORINE OR
HYDROGEN" ,„.
CHLORIDE <2
AND CATALYST
FINES TO
WASTE TREATMENT
CO
VO
EOC
STORAGE
ORGANIC
RECYCLE
SYSTEM
Cz CHLORINATED ORGANICS __S3l
FROM OTHER PROCESSES
TARS TO
INCINERATION
DRYER
^
NEI
f
PROCESS
WATER
[FUGITIVE
EMISSIONS
I OVERALL
PLANT
LOADING
TCE
STORAGE
DRYER
LOADING
PCE
STORAGE
- PCE TRAIN •
NOTE: The numbers In this figure refer to process streins, as discussed In the text.
and the letters designate process vents. The heavy lines represent final product
streams through the process.
Figure 9. Basic operations that may be used for trichloroethylene (TCE) and
perchloroethylene (PCE) production by ethylene dichloride oxychlorination.
-------
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 (6). 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),
21
which is sent to storage.
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
21
PCE (Stream 22) which is sent to storage.
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
21
where VOCs are emitted with the flue gases (F).
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 drying
column vent (Vent B) and the distillation column vents (Vents C), which
release primarily noncondensable gases, and the TCE and the PCE neutralizer
vents (Vents D), which relieve excess pressure of the nitrogen pads on the
systems. Storage emission sources (Vents'E) are raw material storage and
recycle storage. Fugitive emissions (F) occur when leaks develop in valves
or in pump seals. Secondary emissions (G and H) occur as described above for
21
the chlorination process (see Vents E and F in Figure 8).
Atmospheric emissions of EDC in 1977 from the TCE production processes
23
were estimated at 610 Mg. The total domestic production of TCE in 1977 was
estimated at 135,000 Mg, of which 90 percent was from EDC. 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
2
is 100 percent in the reactor.
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. Lake Charles, LA
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.
42
-------
PERCHLOROETHYLENE PRODUCTION
Perch!oroethylene (PCE) is used primarily as a dry-cleaning and
textile-processing solvent. It is also used as a metal-cleaning solvent.
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
24
the chlorinolysis of hydrocarbons such as propane and propylene.
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. The last acetylene-based
25
PCE plant was shut down in late 1977.
Process Descriptions
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.
Ethylene Dichloride Oxychlorination Process —
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 chlorinolysis process are PCE,
carbon tetrachloride, and hydrogen chloride (HC1). Basic operations that may
be used in this process are shown in Figure 10. 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 500°C.
The reaction products, consisting of carbon tetrachloride, PCE, HC1, 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, and some
43
-------
CHLORINOLYSIS
REACTOR
CARBON TETRACHLORIOE
FROM METHANOL
HYDROCHLORINATION
HCiacu
REMOVAC
COLUMN
AND METHYLCHLORIDE
CHLORINATION PROCESS
CRUDE CARBON
STORAGE TETRACHLORIDE
DISTILLATIONS
CARBON
TETRACHLORIOE
STORAGE
YHEAVIES TO
DISPOSAL
PCE
DISTILLATION
OTHER SOURCES
I
LOADING
PCE
STORAGE
L
«~
HoO
,jr-~i
H
1
. CAUSTI
"~
CAUSTIC
SCRUBB
CHLORINE
ABSORPTION
COLUMN
HCI
ABSORBER
BY-PRODUCT
HCI
STORAGE
NOTE: The numbers In this figure refer to process strews, as discussed in the text.
and the letters designate process vents. The heavy lines represent final product
stream through the process.
Figure 10.
Basic operations that may be used for the production
of perchloroethylene by hydrocarbon chlorinolysis.^
-------
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 distillation column, which recovers carbon tetra-
chloride 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.
The feed streams (Streams 4 and 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
24
scrubber.
Emissions
Potential emission sources for the EDC chlorination and oxychlori-
nation processes are shown in Figures 8 and 9, respectively, and discussed
in the TRICHLOROETHYLENE PRODUCTION subsection. It is estimated that
910 Mg of EDC were released to the atmosphere from the PCE production
45
-------
process in 1977. The majority of these emissions were from EDC oxychlori-
nation and chlorination. The total domestic production of PCE in 1977
OC
was 279,000 Mg, of which 65 percent of PCE production was from EDC.
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.
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
27
Mg of PCE and carbon tetrachloride produced.
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, and the EDC
emissions from the dumping of the hex wastes are essentially zero.
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 Mg 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.
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® 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. It is manufactured domestically by a two step process as shown in
Figure 11. 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.
Most 1,1,2-trichloroethane is made by chlorination of EDC. The reaction
is carried out in the liquid phase at 120°C and 345 kPa. The major products
are hydrogen chloride (HC1) and 1,1,2-trichloroethane. Where 1,1,2-trichloroethane
is made by oxychlorination the reactants are EDC, HC1, and oxygen. Reaction
conditions vary from one process to another. Water and 1,1,2-trichloroethane
31
are the major products of this reaction. After 1,1,2-trichloroethane is
produced, it is dehydrochlorinated with aqueous sodium hydroxide at about
70°C. Major products of the reaction are vinylidene chloride, sodium chloride,
and water.
Emissions
The primary source of emissions from the EDC chlorination process are
the waste streams from the HC1 scrubber. Waste water streams may contain
chlorine, HC1, 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.
Emissions from the EDC oxychlorination process originate from waste
water and vent gases from the separator which contain a number of chloro-
hydrocarbons, including EDC, trichloroethane, and byproducts. Scrubbing of
the crude product to remove unreacted acid is another source of waste water
which may contain EDC.
49
-------
en
O
EDO
RECYCLE
1,1,2-TRICHLOROETHANE
NoOH
^XX^ SOLUTION
1,1,2-TRICHLORO-
ETHANE
PURIFICATION p.HC| SOLUTION
1
VINYUDENE
STORAGE
Ppnni.r.T I CHLORIDEf
PURIFKAl
PHASE
SEPARATION
STORAGE DEHYDROCHLORINATION
REACTOR
WASTEWATER
TO USERS
NOTE: The heavy lines represent final product streams through the process.
Figure 11. Basic operations that may be used for. the
production of vinylidene chloride.30»31
-------
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.
It is estimated that 600,000 kg of EDC were released to the atmosphere
from the production of vinylidene chloride in 1977. The total U.S.
production of vinylidene chloride in 1977 was estimated at 105,000 Mg.
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 availabe 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
5
are listed below.
• 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.
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. Hydro-
chlorination 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
34
for final product purification.
Emissions
There is little information available in the published literature on EDC
emissions from ethyl chloride production. Emissions may occur from process
air vents. EDC emissions from ethyl chloride production via ethylene hydro-
chlorination were estimated to be 2313 x 103 kg in 1978. 5 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
-------
MIXER
REACTOR
SEPARATOR
FRACTIONATING COLUMN
ALUMINUM
CHLORIDE
HCI
EDC
^-r^
en
CJ
SPENT
CATALYST
ETHYL
•*• CHLORIDE
POLYMER
BOTTOMS
WASTE
Figure 12. Basic operations that may be used in the production of
ethyl chloride by ethlene hydrochlorination.34
-------
TABLE 9. PRODUCTION OF ETHYL CHLORIDE*
Manufacturer
Location
Process
tn
Dow Chem. U.S.A.
E.I. duPont de Nemours & Co., Inc.
Petrochems. Dept.
Freon® Products Div.
Ethyl Corp.
Chems. Group
Hercules Inc.
Operations Div.
PPG Indust., Inc.
Indust. Chem. Div.
Freeport, TX
Deepwater, NJ
Pasadena, TX
Hopewell, VA
Lake Charles, LA
Hydrochlorination of ethylene
Hydrochlorination of ethylene
Hydrochlorination of ethylene
Hydrochlorination of ethylene
Hydrochlorination of ethylene
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, through-
put 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 Na»SA. The main products of the reaction
37
are the polysulfide rubber chain, (CH2CH2-S4)n> and sodium chloride.
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. 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, 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.
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
38
such as carbon tetrachloride and carbon disulfide.
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 o'f 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
n
prevents moisture from entering the tank. 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
39
device or directly to the atmosphere.
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
-------
01
HOOD
. PESTICIDE
155 GAL. DRUMI
I SCALE
PUMP
SOLVENT STORAGE
EXHAUST VENT
AGITATOR
MANHOLE
EMULSIFIEH
. .STEAM
- COOLING WATER
FILTER
PUMP
PRODUCT
ISS GAL. DRUMI
I
SCALE
PUMP
Figure 13. Basic operations that may be used for liquid pesticide formulation.39
-------
TARIF in COMPANIES WHICH HOLD REGISTRATIONS ON PESTICIDE
IHDLt iu< FORMULATIONS CONTAINING ETHYLENE DICHLORIDE40
Company
Location
Southland Pearson & Co.
Vulcan Materials Co.
Cardinal Chemical Co.
Cooke Laboratory Products
Coyne Chemical Co.
Dexol Industries
Hacienda Enterprises
Hockwaldchem, Division of Oxford Chemicals
James Chem Co.
Master Nurseymens Assn.
Dettelbach Chemicals Corp.
Hill Manufacturing, Inc.
Lester Laboratories
Oxford Chemicals
The Selig Chemical Industries
Stephenson Chemical Co., Inc.
Wool folk Chemical Works, Inc.
Riverdale Chemical Co.
Carmel Chemical Corp.
Brayton Chemicals, Inc.
Industrial Fumigant Co.
Research Products Co.
Central Chemical Corp.
Dow Chemical USA
Mobile, AL
Birmingham, AL
San Francisco, CA
Commerce, CA
Los Angeles, CA
Torrance, CA
San Jose, CA
Brisbane, CA
San Francisco, CA
Concord, CA
Atlanta, GA
Atlanta, GA
Atlanta, GA
Atlanta, GA
Atlanta, GA
College Park, GA
Ft. Valley, GA
Chicago Heights, IL
Westfield, IN
West Burlington, IA
Olathe, KS
Salina, KS
Hagerstown, MD
Midland, MIa
(CONTINUED)
58
-------
TABLE 10. (continued)
Company
Location
Haertel Walter Co.
E.H. Leitte Co.
The Agriculture & Nutrition Co.
Bartels & Shores Chemical Co.
Farmland Industries, Inc.
Ferguson Fumigants
The Huge Co., Inc.
Knox Chemical Co.
Patterson Chemical Co., Inc.
FBI-Gordon Corp.
Stewart Sanitary Supply Co., Ltd.
Falls Chemicals, Inc.
Ling Fuang Industries, Inc.
Rochester Midland Corp.
Prentis Drug & Chemical Co., Inc
Bernard Sirotta Co., Inc.
Big F Insecticides, Inc.
Weil Chemicals Co.
J-Chem, A Division of Fumigators, Inc.
The Staffel Co.
Voluntary Purchasing Group, Inc.
Atomic Chemical Co.
Chemical Formulators, Inc.
Minneapolis, MN
Stillwater, MN
Kansas City, KS
Kansas City, MO
Kansas City, MO
Hazelwood, MO
St. Louis, MO
St. Louis, MO
Kansas City, MO
Kansas City, MO
St. Louis, MO
Great Falls, MT
Gardnerville, NV
Rochester, NY
New York, NY
Brooklyn, NY
Memphis, TN
Memphis, TN
Houston, TX
San Antonio, TX
Bonham, TX
Spokane, WA
Nitro, WV
(CONTINUED)
59
-------
TABLE 10. (continued)
Note: The companies listed are registrants of pesticidal products contain-
ing 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
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USE OF ETHYLENE BICHLORIDE 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
38
the period from 1976 to 1979. °
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:
o Ethylene dichloride 64.6 percent, carbon tetrachloride 27.4 percent,
ethylene dibromide 5.0 percent
o Ethylene dichloride 10.0 percent, carbon tetrachloride 76.5 percent,
ethylene dibromide 3.5 percent, carbon disulfide 10.0 percent
o Ethylene dichloride 29.2 percent, carbon tetrachloride 63.6 percent,
ethylene dibromide 7.2 percent
o Ethylene dichloride 64.7 percent, carbon tetrachloride 27.4 percent,
ethylene dibromide 7.9 percent
o 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 reinfestation. 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
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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
Co-op New Activated Weevil Killer Fumigant
Crest 15 Grain Fumigant
De-Pester Weevil Kill
De-Pester Grain Conditioner and Weevil Killer
Diweevil
Dowfume EE-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
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TABLE 11. (continued)
FC-13 Mill Machinery Fumigant
Formula MU-39
Formula 635 (FC-2) Grain Fumigant
Fume-0-Death Gas No. 3
Fumi sol
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
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TABLE 11. (continued)
Pearson's Fumigrain 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
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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: small banked
concrete silos and flat storages. At mills, banked silos are predominant.
Terminal elevators are banked silos. Grain transportation vehicles 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.
Grain fumigants are applied primarily by the "gravity distribution"
method by either surface application or layering. This method is practiced
both on-farm and off-farm. 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
43
into the car with a power sprayer.
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.
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
38
facilities are typically more tight-fitting than on-farm storage.
After application of fumigants, grain generally is left undisturbed for
at least 72 hours. The usual practice is to leave the grain for a much
longer period. Fumigants are often left on the grain until the normal
turning procedure is undertaken. Alternatively, the grain may be aerated by
65
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TABLE 12. FUMIGANT APPLICATION RATES38
Application rate
(gal/10^ bu)
Grain On-farm Off-farm
Wheat 3-4 2-3
Corn 4-5 3-4
Rice, Oats, Barley, Rye 3-4 2-3
Grain sorghum 5-6 4-5
66
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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.
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.
Source Locations
The Standard Industrial Classification (SIC) code for farms at which
grain may be stored are as follows:
0111 - Agricultural production of wheat
0112 - Agricultural production of rice
0115 - Agricultural production" of corn
0116 - Agricultural production of soybeans
0119 - Agricultural production of other grains
0191 - General farms
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
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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
Lake States:
Michigan
Wisconsin
Minnesota
Corn Belt:
Ohio
Indiana
Illinois
Iowa
Missouri
Northern Plains:
North Dakota
South Dakota
Nebraska
Kansas
Appalachian:
Virginia
West Virginia
North Carolina
Kentucky
Tennessee
Southeast:
South Carolina
Georgia
Florida
Al abama
Capacity Regional
(103 bu) percentage
142,698 2%
2,866
0
0
9,654
0
222
39,204
5,190
62,498
' 2,057
21,007
1,357,597 17% ,
116,462
244,827
996,338
2,982,755 37% —801
225,279
429,981
947,208
1,071,203
309,084
2,132,264 26% —
681,397
394,381
715,594
340,892
236,607 3%
37,554
5,685
100,938
49,237
43,193
159,132 2%
31,437
87,720
12,145
27,830
CONTINUED
68
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TABLE 13. (continued)
Region
and State
Delta States:
Mississippi
Arkansas
Louisiana
Southern Plains:
Oklahoma
Texas
Mountain:
Montana
Idaho
Wyomi ng
Colorado
New Mexico
Arizona
Utah
Nevada
Pacific:
Washington
Oregon
.California
Capacity
(103 bu)
131,593
41,588
50,095
39,910
315,160
76,685
238,472
507,357
278,783
77,960
19,519
97,216
9,136
6,404
15,220
3,119
151,622
60,011
33,552
58,059
Regional
percentage
1% •
4%
6%
2%
Total
8,116,815
100%
69
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Table 14 lists the number of off-farm grain storage facilities and the total
capacity of these facilities by State.
70
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TABLE 14.
OFF-FARM GRAIN STORAGE42
State
Alabama
Arizona
Arkansas
California
Colorado
Delaware
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Mi ssouri
Montana
Nebraska
Nevada
New Jersey
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
Number of
facilities
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
Capacity
(103 bu)
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
Total
6,600,030
15,065
71
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EDO 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 (Pbf/L) 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 alky! 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 trans-
portation 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 Mg 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 trans-
portation 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
72
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TABLE 15. EDC EMISSIONS FROM BULK LOADING, STORAGE, AND
TRANSPORTATION OF LEADED GASOLINE4**
Emission rate
Emission source °r factor
Gasoline storage and loading
Fixed roof tanks K a
Floating roof tanks0 438 g/yr
Tank car/truck loading
Submerged loading normal service a
Submerged loading balance service a
Splash loading normal service 0.269 mg/1 transferred
Splash loading balance service 0.192 mg/1 transferred
Marine vessel loading
Ship loading
Cleaned tank a
Ballasted tank a
Uncleaned tank a
Average tank condition a
Ocean barge loading
Cleaned tank a
Ballasted tank a
Uncleaned tank a
Barge loading
Cleaned tank • a
Uncleaned tank . a
Average tank condition a
Tanker ballasting a
Information was not available to calculate emissions of EDC from these
sources.
DThe 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 Ib/gallon.
73
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loading of tank cars and trucks, and from floating roof 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 under-
ground 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
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48
TABLE 16. EDC EMISSIONS FROM SERVICE STATIONS °
Emission factor
Emission source (mg/1 transferred)
Filling underground tank
Submerged filling J
Splash filling °-26
Balanced submerged filling a
Underground tank breathing and emptying a
Vehicle refueling operations
Displacement losses (uncontrolled) n'n^i
Displacement losses (controlled) 0-021
Spillage °-016
alnformation was not available to calculate emissions of EDC from these
sources.
75
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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. Gasoline service stations can be found
within SIC 5541. 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. This amounts to about
0.03 percent of total EDC consumption. 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. 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
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TABLE 17. PETROLEUM REFINERIES
50
Company and location
Company and location
Alabama
Hunt Oil Co.—Tuscaloosa
Louisiana Land and Exploration
Co.—Saraland
Marlon Corp.—Theodore
Mobile Bay Refining Co.— Chlckasaw
Warrior Asphalt Co. of Alabama
Inc.—Holt
Atlantic Richfield Corp.—Prudhoe Bay
Chevron U.S.A. Inc.—Kenai
North Pole Refining, D1v. of
Mapco—North Pole
Tesoro Petroleum Corp.—Kenal
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
Colorado
Inc.~
Asamera Oil U.S.
Commerce City
Conoco Inc.—Commerce City
Gary Refining Co.—Fruita
Arizona Fuels Corp.—Fredonia
Arkansas
Berry Petroleum, Division of
Crystal Oil Co.—Stevens
Cross Oil & Refining Co. of
Arkansas—Smackover
Macnillan Ring-Free Oil Co.—
Norphlet
Tosco Corp.—El Dorado
California
Anchor Refining CI—McKlttrick
Atlantic Richfield Co.—Carson
Beacon Oil Co.— Hanford
ChampHn Petroleum Co.—Wilmington
Chevron U.S.A. Inc.—Bakersfield
El Segundo
Richmond
Douglas Oil Co.—
Santa Maria
Eco Petroleum Inc.—Signal Hill
Edgington Oil CI—Long Beach
Exxon Co.—Benicia
Fletcher Oil & Refining Co.—Carson
Getty Refining a Marketing Co.—
Bakersfield
Golden Bear Division, Witco Chemical
Corp.—Oildale
Golden Eagle Refining Co.—Carson
Gulf Oil Co.—Santa Fe Springs
Huntway Refining Co.—Benicia
Wilmington
Independent Valley Energy Co.—
Bakersfield
Kern County Refinery Inc.—
Bakersfield
Marlex 011 & Refining Inc.—
Long Beach
Mobil Oil Corp.—Torrance
Newhall Refining CI—Newhall
Oxnard Refinery—Oxnard
Pacific Oasis—Paramount
Pacific Refining Co.—Hercules
Powerine Oil Co.—Santa Fe Springs
Sabre Refining Inc.—Bakersfield
Getty Refining and Marketing Co.—•
Delaware City
Amoco Oil Co.—Savannah
Young Refining Corp.— Douglasville
Hawaii
Chevron U.S.A. Inc.—Barber's Point
Hawaiian Independent Refinery
Inc.—Ewa Beach
Illinois
Clark Oil 4 Refining Corp.—
Blue Island
Hartford
Marathon Oil Co.—Robinson
Mobile 011 Corp.— Jollet
Shell Oil Co.—Wood River
Texaco Inc.—Lawrenceville
Union 011 Co. of California—Lemont
Amoco Oil Co.—Whiting
Sladieux Refinery Inc.—Ft. Wayne
Indiana Farm Bureau Cooperative
Association Inc.—Mt. Vernon
Laketon Refining Coro.—Laketon
Rock Island Refining Corp.—
Indianapolis
Kansas
Derby Refining Co.—Wichita
Farmland Industries Inc.—
Coffeyville
Getty Refining & Marketing Co.—
El Dorado
Mobile Oil Corp.—Augusta
National Cooperative Refinery
Association—McPherson
Pester Refining Co.—El Dorado
Total Petroleum—Arkansas City
CONTINUED
77
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TABLE 17. (continued)
Company and location
Company and location
Kentucky
Ashland Petroleum Co.—Catlettsburg
Louisville
Somerset Refinery Inc.—Somerset
Louisiana
Atlas Processing Co., Division of
Pennzol1--Shreveport
Calumet Refining Co.--Princeton
Canal Refining Co.—Church Point
Celeron 011 & Gas—Mermentau
Cities Service Co.—Lake Charles
Clalbome 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 011 Corp.—Belle Chasse
H111 Petroleum Co.—Krotz Springs
Kerr HcGee Corp.—Oubach
Mallard Resources Inc.—Gueydon
Marathon 011 Co.— Garyvllle
Murphy Oil Co.—Meraux
Placid Refining Co.—Port Allen
Port Petroleum Inc.—Stonewall
Shell 011 Co.— Norco
Tenneco 011 Co.—Chalmette
Texaco Inc.—Convent
Chevron U.S.A. Inc.—Baltimore
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
Mississippi
Amerada-Hess Corp.—Purvis
Chevron U.S.A. Inc.-Pascagoula
Ergon Refining Inc.—Vlcksburg
Natchez Refining Inc.—Natchez
Southland Oil Co.—Lumber-ton
Sandersvllle
Montana
Cenex—Laurel
Conoco Inc.—Billings
Exxon Co.—Billings
Flying J Inc.—Cut Bank
Kenco Refining Inc.—Wolf Point
Simnons Refining Co.—Great Falls
Nevada
Nevada Refining Co.—Tonopah
New Jersey
Chevron U.S.A.—Perth Amboy
Exxon Co.—Linden
Mobil Oil Corp.—Paulsboro
Seavlew Petroleum Inc.—
Thorofare
Texaco Inc.—Westvllle
New Mexico
Slant Industries Inc.—Ciniza
Farmington
Havajo Refining Co.— Artesla
Plateau Inc.—Bloomfield
Southern Union Refining Co.—
Lovlngton
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
Allied Material Corp.—Stroud
Champlln 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
Oregon
Chevron U.S.A. Inc.—Portland
Pennsylvania
Atlantic Richfield Co.—Philadelphia
BP 011 Corp.—Marcus Hood
Gulf Oil Co.—Philadelphia
Kendall-Amalle Division
Witco Chemical Co.—Bradford
Penzoil Co.— Rouseville
Quaker State 011 Refining
Corp.—Fanners Valley
Sun CI—Marcus Hook
United Refining Co.—Warren
Valvollne Oil Co.. Division
of Ashland 011 Co.—Freedom
Delta Refining Co.—Memphis
CONTINUED
78
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TABLE 17. (continued)
Company and location
Company and location
Amber Refining Co.—Fort Worth
American Petrofina Inc.~
Big Spring
Port Arthur
Amoco Oil Co.—Texas City
Atlantic Richfield Co.—Houston
Champ 1 in 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 4 Gas Co.—Tyler
Liquid Energy Corp.—Bridgeport
Marathon Oil Co.—Texas City
Mobil 011 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.— AmaVillo
El Paso
Port Arthur
Port Neches
Texas City Refining Inc.—Texas City
Uni Refining Inc. — Ingleside
Union Oil Co. of California—
(Beaumont), Nederland
Utah
Amoco Oil Co.—Salt Lake City
Caribou Four Comers Inc.—Woods Cross
Chevron U.S.A.—Salt Lake City
Crysen Refining Co.—Woods Cross
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.—Tacoma
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
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 facilitie's 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
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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.
Source Locations
Standard Industrial Classification (SIC) codes for uses of extraction
solvents are listed below:
t 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 These solid wastes are generally incinerated.
80
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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
t 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.
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
t Copper ores mining - 102
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 California55 shows that significant quantities of EDC may be
contained in hazardous wastes, which may be expected to volatilize within
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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.
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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.
EPA has validated the method for ethylene dichloride in the laboratory
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. 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 ionization detection (FID). Analysis should be conducted within
one day of sample collection. 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.) The column temperature should be set at 100°C. 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. The
method does not apply when ethylene dichloride is contained in particulate
matter.
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FILTER
(GLASS WOOL)
PROBE
SAMPLE
LINE
STACK
WALL
SAMPLING
BAG
FLOW
METER
CHARCOAL
TUBE
RIGID
LEAKPROOF
CONTAINER
i
Figure 14. Method 23 sampling train.
59
84
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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. Environ-
mental Protection Agency, August 18, 1983.
3. Encylcopedia 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. Environ-
mental Protection Agency. Cincinnati, Ohio. July 1981.
5. 1983 Directory of Chemical Producers, United States of America. SRI
International. Menlo Park, California. 1983.
6. Synthetic Organic Chemicals, United States Production and Sales, 1982.
U.S. International Trade Commission. Washington, D.C. 1983. p. 261.
7. Chemical Products Synopsis - Ethylene Dichloride. Mannsville Chemical
Products. Cortland, New York. June 1981.
8. Hobbs, F.D. and J.A. Key. Report 1: Ethylene Dichloride. In: Organic
Chemical Manufacturing Volume 8: Selected Processes. U.S. Environmental
Protection Agency. Research Triangle Park, N.C. Publication No. EPA-450/3-80-28c.
December 1980. pp. III-l to III-9.
9. Reference 8, pp. IV-1 to IV-11.
10. Shah, Hasmukh, Chemical Manufacturers Association, Washington, DC.
Letter to D.C. Misenheimer, GCA Corporation, December 21, 1983.
11. Gasperecz, Greg, Louisiana Air Quality Division, Baton Rouge, LA.
Personal communication with D.C. Misenheimer, GCA Corporation, September 30, 1983.
12. "Thermal Incinerator Performance for NSPS," Memo and addendum from
Mascone, D., EPA, to Farmer, J., EPA. June 11, 1980.
13. Reference 8, p. V-2.
14. Reference 6, p. 294.
15. Bryson H., K. Durrell, E. Harrison, V. Hodge, L. Phuoc, S. Paige and K.
Slimak. Materials Balance: 1,2-Dichloroethane. U.S. Environmental
Protection Agency, Washington, D.C. Publication No. EPA-560/13-80-002.
February 1980. pp. 3-1 to 3-6.
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16. Standifer, R.L. and J.A. Key. Report 4: 1,1,1-Trichloroethane and
Perchloroethylene, Trichloroethylene, and Vinylidine Chloride. In:
Organic Chemical Manufacturing Volume 8: Selected Processes. U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-450/3-80-28c. December 1980. p. II-3.
17. Reference 15, pp. 3-23 to 3-30.
18. Reference 16, pp. III-l to III-8.
19. Reference 15, pp. 3-30 to 3-34.
20. Liepins, R. and F. Mixon. Industrial Process Profiles for Environ-
mental Use. Chapter 6 - The Industrial Organic Chemicals Industry.
U.S. Environmental Protection Agency. Cincinnati, Ohio. Publication
No. EPA-600/2-77-023f. February 1977. pp. 353-355.
21. Reference 16, pp. III-8 to 111-14.
22. Chemical Products Synopsis - Trichloroethylene. Mannsville Chemical
Products. Cortland, New York. November 1979.
23. Reference 15, pp. 3-8 to 3-12.
24. Hobbs, F.D. and C.W. Stuewe. Report 2: Carbon Tetrachloride and
Perchloroethylene by the Hydrocarbon Chlorinolysis Process. In:
Organic Chemical Manufacturing Volume 8: Selected Processes. U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-450/3-80-28c. December 1980. pp. Ill-1 to
III-4.
25. Chemical Products Synopsis - Perchloroethylene. Mannsville Chemical
Products. Cortland, New York. October 1979.
26. Reference 15, pp. 3-12 to 3-18.
27. Reference 24, p. IV-2.
28. Reference 24, p. V-2.
29. Reference 24, p. IV-1.
30. Reference 16, pp. 111-15 to 111-17.
31. Reference 20, pp. 359-363.
32. Reference 15, pp. 3-18 to 3-22.
33. Encyclopedia of Chemical Technology, 3rd Edition, Volume 5. Wiley
Interscience Publication, New York, New York. 1979. p. 717-719.
34. Faith, W.L., D.B. Keyes, and R.L. Clark. Industrial Chemicals,
3rd Edition. John Wiley and Sons, New York. 1965. p. 356-357.
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35. Eimutis, E.G., R.P. Quill, and G.M. Rinaldi. Source Assessment:
Noncriteria Pollutant Emissions (1978 Update). U.S. Environmental
Protection Agency. Research Triangle Park, N.C. Publication
No. EPA-600/2-78-004t. July 1978. p. 58.
36. U.S. International Trade Commission. Synthetic Organic Chemicals, U.S.
Production and Sales, 1978. U.S. Government Printing Office, Washington,
D.C. 1979. p. 313.
37. Reference 15, pp. 3-47 to 3-48.
38. Holtorf, R.C. and G.F. .Ludvik. Grain Fumigants: An Overview of Their
Significance to U.S. Agriculture and Commerce and Their Pesticide Regulatory
Implications. U.S. Environmental Protection Agency, Washington, DC,
September 1981.
39. U.S. Environmental Protection Agency. Development Document for Effluent
Limitations Guidelines for the Pesticide Chemicals Manufacturing Point
Source Category. EPA-440/1-78/060-6, Washington, DC, April 1978.
40. Salzman, V., U.S. Environmental Protection Agency, Washington, DC.
Letter with attachments to E. Anderson, GCA Corporation, July 21, 1982
concerning pesticide registrants.
41. Ludvik, G.F. Fumigants for Bulk Grain Protection: Biological Aspects
and Relevant Data. U.S. Environmental Protection Agency, Washington,
DC, August 1981.
42. Development Planning and Research Associates, Inc. Preliminary Benefit
Analysis: Cancellation of Carbon Tetrachloride in Fumigants for Stored
Grain. U.S. Environmental Protection Agency, Washington, DC, April 1980.
43. U.S. Environmental Protection Agency. Carbon Tetrachloride; Pesticide
Programs; Rebuttable Presumption Against Registration and Continued
Registration of Certain Pesticide Products. Federal Register 45(202):
68534-68584, October 15, 1980.
44. Reference 15, p. 3-49.
45. GCA Corporation. Survey of Substitutes of 1,2-Dichloroethane as a Lead
Scavenging Agent in Motor Fuel. Draft Final Report. Prepared for the
U.S. Environmental Protection Agency Under Contract Number 68-01-5960,
Technical Directive No. 7. Bedford, MA. p. 3.
46. U.S. Environmental Protection Agency. Regulation of Fuels and Fuel
Additives. Federal Register 47(210): 49322, October 29, 1982.
47. Reference 15, pp. 3-35 to 3-43.
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48. Transportation and Marketing of Petroleum Liquids. In: Compilation of
Air Pollution Emission Factors, Third Edition - Supplement 9. AP-42,
Research Triangle Park, NC. July 1979.
49. Compilation of Air Pollutant Emission Factors: Highway Mobile Sources.
U.S. Environmental Protection Agency, Office of Mobile Source Air Pollution
Control, Ann Arbor, MI. Publication No. EPA-460/3-81-005. March 1981.
p. 4.
50. Cantrell, A. Annual Refining Survey. Oil and Gas Journal. March 21, 1983,
pg. 128.
51. Reference 15, pp. 3-43 to 3-44.
52. Reference 15, pp. 3-44 to 3-45.
53. Reference 15, p. 3-46.
54. Reference 15, p. 3-51.
55. Scheible, Mike, et al. An Assessment of the Volatile and Toxic Organic
Emissions from Hazardous Waste Disposal in California. Air Resources
Board, State of California, February 1982.
56. GCA Corporation. Evaluation and Selection of Models for Estimating Air
Emissions from Hazardous Waste Treatment, Storage and Disposal Facilities.
Revised Draft Final Report. Prepared for the U.S. Environmental Protection
Agency Under Contract Number 68-02-3168. Assignment No. 77. Bedford,
MA. May 1983.
57. Pellizzari, E.D. Project Summary - Volatile Organics in Aeration Gases
at Municipal Treatment Plants. EPA-600/52-82-056, U.S. Environmental
Protection Agency, Cincinnati, OH, August 1982.
58. Fate of Priority Pollutants in Publicly Owned Treatment Works. U.S.
Environmental Protection Agency, Washington, DC. Publication No. EPA 440/
1-82-302. July 1982.
59. Method 23: Determination of Halogenated Organics from Stationary Sources.
Federal Register. 45(114)39776-39777, 1980.
60. Knoll, J.E., M.A. Smith, and M.R. Midgett. Evaluation of Emission Test
Methods for Halogenated Hydrocarbons: Volume 1, CCl^, C2H2C12, C2Cl,j, C2HC13,
EPA-600/4-79-025. U.S. Environmental Protection Agency, Research Triangle
Park, NC, 1979.
61. Field Validation of EPA Reference Method 23. Prepared for U.S. Environmental
Protection Agency by Scott Environmental Services under Contract 68-02-3405.
February 1982.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/4-84-007d
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF
ETHYLENE BICHLORIDE
5. REPORT DATE
March 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
GCA Corporation
213 Burlington Road, Bedford, MS
8. PERFORMING ORGANIZATION REPORT NO.
01730
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Office Of Air Quality Planning And Standards
U. S. Environmental Protection Agency
MD 14
Research Triangle, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer;
16. A8STI
Thomas F. Lahre
ACT — ' —
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such
as this to compile available information on sources and emissions of these
substances. This document deals specifically with ethylene dichloride. Its
intended audience includes Federal, State and local air pollution personnel
and others interested in locating potential emitters of ethylene dichloride
and in making gross estimates of air emissions therefrom.
This document presents information on 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 release into the air from
each operation.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Ethylene Dichloride
Air Emission Sources
Locating Air Emission Sources
Toxic Substances
19. SECURITY CLASS /This Report/
21. NO. OF PAGES
92
20. SECURITY CLASS (This page/
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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