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

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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

-------
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

-------
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

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                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

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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

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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

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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

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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.

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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

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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

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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

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      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

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                           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

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                          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

                                           81

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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.
                                      82

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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.
                                         83

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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
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     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.
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     February  1980.   pp. 3-1 to 3-6.

                                       85

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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-
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     U.S. Environmental  Protection Agency.   Cincinnati, Ohio.  Publication
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21.  Reference 16,  pp. III-8 to 111-14.

22.  Chemical Products Synopsis - Trichloroethylene.  Mannsville Chemical
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23.  Reference 15,  pp. 3-8 to  3-12.

24.  Hobbs, F.D. and C.W. Stuewe.  Report 2:   Carbon  Tetrachloride  and
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     Environmental  Protection  Agency.  Research Triangle Park, N.C.
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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.

                                        86

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35.  Eimutis, E.G., R.P. Quill, and G.M. Rinaldi.  Source Assessment:
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36.  U.S. International Trade Commission.  Synthetic Organic Chemicals,  U.S.
     Production and Sales, 1978.  U.S. Government Printing Office, Washington,
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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
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39.  U.S. Environmental Protection Agency.  Development Document for Effluent
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40.  Salzman, V., U.S. Environmental Protection Agency, Washington, DC.
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41.  Ludvik, G.F.  Fumigants for Bulk Grain Protection:  Biological Aspects
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42.  Development Planning and Research Associates, Inc.  Preliminary Benefit
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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):
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44.  Reference 15, p. 3-49.

45.  GCA Corporation.  Survey of Substitutes of 1,2-Dichloroethane as  a  Lead
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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.
                                       87

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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.
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     p. 4.

50.  Cantrell, A.  Annual Refining Survey.   Oil  and Gas  Journal.  March 21, 1983,
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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
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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.
                                      88

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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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