EPA-450/2-89-013
                  August 1989
LOCATING AND ESTIMATING AIR EMISSIONS

FROM SOURCES OF PERCHLOROETHYLENE

AND TRICHLOROETHYLENE
                     By

                 Claire C. Most

               Radian Corporation

        Research Triangle Park, North Carolina

            Contract Number 68-02-4392


        EPA Project Officer: Anne A. Pope
     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.  Mention of trade names or commercial
products does not constitute endorsement or recommendation for use.
                  EPA 450/2-89-013

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                               TABLE OF CONTENTS
 Section                                                               paqe
   1       Purpose of Document 	   1
                References for Section 1	   4
   2       Overview of Document Contents 	   5
   3       Background 	   7
                Trichloroethylene	   7
                     Nature of Pol1utant	   7
                     Overview of Production and Use	   9
                Perch! oroethyl ene	  10
                     Nature of Pol 1 utant 	  10
                     Overview of Production and Use 	  13
                References for Section 3	    16
   4       Emissions  from Trichloroethylene and Perch!oroethylene
             Production  	  17
                Trichloroethylene Production 	  17
                     Process  Descriptions	  17
                     Emissions	  22
                     Source Locations	  27
                Perchloroethylene Production 	  27
                     Process  Descriptions  	  27
                     Emissions  	 31
                     Source Locations	 35
               References for Section 4	  37
JES/064
iii

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                        TABLE OF CONTENTS  (Continued)
Section
  5
                                                             Page
Emissions from Industries Producing Trichloroethylene
  or Perch!oroethylene as a By-product	  39
     Vinylidene Chloride Production 	  39
          Process Descri pti on	  39
          Emissions	  42
          Source Locati ons	  43
     Ethylene Dichloride/Vinyl Chloride Monomer
            Production	  43
          Process Descriptions	  45
          Emissions	  50
          Source Locations 		  54
     References for Secti on 5	  56
Emissions from Industries Using Trichloroethylene or
  Perchl oroethyl ene as Chemi cal Feedstock	  57
     Chi orof 1 uorocarbon Product i on	  57
          Process Descri pti on	  58
          Emissions	  60
          Source Locati ons 	  63
     Polyvinyl Chloride (PVC) Production 	  63
          Process Description 	  63
          Emissions	  67
          Source Locati ons 	  69
     References for Section 6	  72
JES/064
                           iv

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                        TABLE  OF  CONTENTS  (Continued)
Section                                                                Page

  7       Emissions  from  Industries  Using  Trichloroethylene and
            Perch!oroethylene  as  Sol vent  	   75
               Trichloroethylene  and Perchloroethylene  Use in
                 Organic  Solvent  Cleaning	   75
                     Process Description	   75
                     Emissions  	„	   77
                     Source Locations  „	   84
               Dry Cleaning	   84
                     Process Description	   85
                     Emissions	   87
                     Source Locations	   88
               Paints, Coatings,  and Adhesives  	   90
               Aerosols 	   91
               References for  Secti on 7	    92
  8       Other Potential Sources of Trichloroethylene  and
            Perchloroethylene  Emissions	   95
               Distribution Facilities 	   95
               Pub!icly Owned  Treatment Works (POTWs) 	   97
               Unidentified or Miscellaneous Sources of
                 Tri chloroethylene and Perchloroethylene  	   98
               References for  Section 8	   100
  9       Source Test Procedures  	   103
               References for  Section 9	   105
APPENDIX A - Derivation of Emission Factors 	 A-l

JES/064                               v

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JES/064
VI

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                                LIST OF TABLES

 Table                                                                 Page

   1        Physical  and Chemical  Properties of Trichloroethylene 	   8

   2        Physical  and Chemical  Properties of Perchloroethylene 	  12

   3        Trichloroethylene and  Perchloroethylene Emission Factors
             for an  Existing Plant Producing Trichloroethylene by
             Ethylene Bichloride  Chlorination 	  25

   4        Trichloroethylene and  Perchloroethylene Emission Factors
             for an  Existing Plant Producing Trichloroethylene and
             Perchloroethylene by Ethylene Dichloride
             Oxychlorination 	  26

   5        Domestic  Producers of  Trichloroethylene in 1988 	  28

   6        Emission  Factors  for the Release of Perchloroethylene
             from Perchloroethylene Production by  Ethylene
             Dichloride Chlorination 	  33

   7        Emission  Factors  for the Release of Perchloroethylene
             from Perchloroethylene Production by  Hydrocarbon
             Chlorinolysis Process 	  34

   8        Domestic  Producers of  Perchloroethylene in 1988 	  36

   9        Domestic  Producers of  Vinylidene Chloride  in  1988  	  44

 10        Trichloroethylene  and  Perchloroethylene Emission Factors
             for Three  Plants Producing Ethylene Dichloride/Vinyl
             Chioride Monomer 	   53

 11       .Domestic  Producers of  Vinyl Chloride Monomer  in  1988  	   55

 12        Estimated Controlled and  Uncontrolled Perchloroethylene
             Emission Factors for Existing  Facilities Producing
             Chlorofluorocarbon 113  and 114	   62

 13        Facilities Producing Chlorofluorocarbons 113, 114,  115,
             and/or  116  in 1988	   64

 14        Potential  Emission  Controls for  PVC Plants	   68

 15        Facilities Producing Polyvinyl Chloride Resins  in 1988 	   70
JES/064

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                          LIST OF TABLES (Continued)
 Table

  16


  17


  18


  19


 A-l
                                                            Page
Trichloroethylene and Perchloroethylene Emission Factors
  for Organic Solvent Cleaning: Schedule A	  80

Trichloroethylene and Perchloroethylene Emission Factors
 for Organic Solvent Cleaning:  Schedule B	  82

Emission Factors for the Perchloroethylene Dry Cleaning
  Industry	  89

Summary of Major Trichloroethylene and Perchloroethylene
  Di stri butors	 „	  95

Trichloroethylene and Perchloroethylene Emission
  Factors for Equipment Leaks from Selected
  Production Processes	A-6
JES/064
                          vi ii

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                                LIST  OF  FIGURES

Figure                                                                 paqe

  1       Chemical use  tree  for trichloroethylene  .„	   11

  2       Chemi cal use  tree  for perch! oroethyl ene  	   15

  3       Basic operations that may  be  used  for  trichloroethylene
             (TCE) and perch!oroethylene (PCE) production  by
             ethylene dichloride (EDC) chlorination	   19

  4       Basic operations that may  be  used  for  trichloroethylene
             (TCE) and perchloroethylene (PCE) production  by
             ethylene dichloride (EDC) oxychlorination	   21

  5       Basic operations that may  be  used  for  the production  of
             perchloroethylene by hydrocarbon chlorinolysis  	   30

  6       Basic operations that may  be  used  for  vinylidene chloride
             production  from  1,1,2-trichloroethane  	   41

  7       Basic operations that may  be  used  for  ethylene  dichloride
             production  by the balanced  process,  with air-based
             oxychlorination  	   46

  8       Basic operations that may  be  used  for  ethylene  dichloride
             production  by the oxygen process (oxychlorination step)  .   49

  9       Basic operations that may  be  used  for  vinyl chloride
             production  by ethylene dichloride dehydrochlorination  ...   51

 10       Basic operations that may  be  used  in the production of
             CFC-113 and CFC-114 	   59

 11       Basic operations for  polyvinyl chloride production by
             suspension  process  using trichloroethylene as a
             reaction chain transfer  agent 	„	   65

 12       Schematic of  a perchloroethylene dry cleaning plant 	   86

 13       Integrated bag sampling train	   104
JES/064
IX

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JES/064

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                                   SECTION 1
                              PURPOSE OF DOCUMENT

      The Environmental  Protection  Agency and  State  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.  Prior documents  in the  series are listed below:

                   Substance                   EPA Publication Number

          Acrylonitrile                          EPA-450/4-84-007a
          Carbon  Tetrachloride                   EPA-450/4-84-007b
          Chloroform                             EPA-450/4-84-007c
          Ethylene Dichloride                    EPA-450/4-84-007d
          Formaldehyde                           EPA-450/4-84-007e
          Nickel                                 EPA-450/4-84-007f
          Chromium                               EPA-450/4-84-007g
          Manganese                              EPA-450/4-84-007h
          Phosgene                               EPA-450/4-84-007i
          Epichlorohydrin                        EPA-450/4-84-007J
          Vinylidene Chloride                   EPA-450/4-84-007k
          Ethylene Oxide                        EPA-450/4-84-0071
          Chlorobenzenes                        EPA-450/4-84-007m
JES/064

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                  Substance                  EPA Publication Number

          Polychlorinated Biphenyls (PCBs)      EPA-450/4-84-007n
          Polycyclic Organic Matter (POM)       EPA-450/4-84-007p
          Benzene                               EPA-450/4-84-007q

     This document deals specifically with trichloroethylene and
perch!oroethylene.  Its intended audience includes Federal, State and local
air pollution personnel and others who are interested in locating potential
emitters of these compounds and making gross estimates of air emissions
therefrom.

     Because of the limited amounts of data available on some potential
sources of trichloroethylene and perch!oroethylene emissions, and since the
configurations 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 trichloroethylene and
perch!oroethylene, (2) process variations and release points that may be
expected within these sources, and (3) available emissions information
indicating the potential for trichloroethylene or perchloroethylene 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.  Because insufficient data are
available to develop statistical estimates of the accuracy of these emission
factors, no estimate can be made of the error that could result when these
factors are used to calculate emissions from any given facility.  It is
possible, in some extreme cases, that order-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 trichloroethylene or perchloro-
ethylene emissions is necessary, source-specific information should be
obtained to confirm the existence of particular emitting operations, the
OES/064

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  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.

       In  addition  to the information presented in this document,  another
  potential source  of emissions  data for perchloroethylene and
  trichlbroethylene is the Toxic Chemical  Release  Inventory (TRI)  form
  required by  Section 313 of Title III  of the  Superfund Amendments and
  Reauthorization Act of  1986 (SARA 313).l   SARA 313  requires  owners  and
  operators of certain facilities  that  manufacture,  import,  process or
  otherwise use certain toxic chemicals to report  annually their releases of
  these chemicals to  any  environmental  media.  As  part  of  SARA 313, EPA
  provides public access  to  the  annual  emissions data.  The  TRI data  include
.general  facility  information,  chemical, information, and  emissions data.  Air
  emissions data are reported  as total  facility release estimates, broken out
  into fugitive and point components.   No individual process or stack data are
  provided to EPA.  The TRI requires the use of available stack monitoring or
 measurement of emissions to comply with SARA 313.  If monitoring data are
 unavailable,  emissions are to be quantified based on best estimates  of
 releases to  the environment.  The reader is cautioned that the TRI will  not
 likely provide facility, emissions, and chemical  release data sufficient for
 conducting detailed exposure modeling and risk assessment.  In many  cases,
 the TRI  data  are based on annual  estimates  of emissions (i.e.,  on emission
 factors,  material  balances, engineering judgment).   The reader is urged  to
 obtain TRI data in addition to  information  provided  in this document to
 locate potential emitters of perchloroethylene and .trichloroethylene,  and to
make preliminary estimates  of air emissions from  these facilities.   To
obtain an exact  assessment  of air emissions from  processes  at a specific
facility,  source tests or detailed  material balance calculations  should be
conducted, and detailed  plant site  information should  be  compiled.
JES/064

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       For each  major industrial  source  category described  in  Sections  4
 through  8,  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 trichloroethylene and
. perch!oroethylene 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 trichloroethylene or  perchloroethylene based
 primarily on trade  publications.

      The final section of this  document  summarizes available procedures for
 source sampling and analysis of trichloroethylene and perchloroethylene.
 Details are not prescribed nor  is  any  EPA endorsement given or implied to
 any of these sampling and analysis procedures.   At this time, EPA has
 not generally 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 trichloroethylene or perchloroethylene,  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, Pollutant  Characterization Section (MD-15)
                Noncriteria Pollutant Programs Branch
                U.S.  Environmental Protection Agency
                Research Triangle Park,  N.C.  27711
JES/064

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                                  SECTION 3
                                  BACKGROUND
 TRICHLOROETHYLENE

 Nature of Pollutant
      Trichloroethylene (TCE)  is  a colorless,  sweet  smelling,  nonflammable
 liquid at normal  temperatures and pressures.   Trichloroethylene  is  also
 known as  ethylene trichloride, trichloroethene,  and trichlor.  The  structure
 of TCE is illustrated  below:
                                   H       Cl
                                   \     /
                                    C = C
                                   /    \
                                 Cl      Cl

 Physical and chemical properties of trichloroethylene are presented in
 Table  1.

     Trichloroethylene is miscible with most organic liquids including such
 common solvents as ether, alcohol, and chloroform, but is essentially
 insoluble in water.  It is relatively volatile, with a vapor pressure of
 7.6 kPa at 20°C.   The lower explosive limit of the vapor in air is
 11 percent, and the upper explosive limit is 41 percent.*  The liquid does
 not have a flash point.1'2

     Trichloroethylene decomposes by atmospheric oxidation and degradation
 catalyzed by aluminum chloride.1  The decomposition products include
 compounds that are acidic and corrosive,  such as hydrochloric acid.  To
 prevent decomposition,  commercial grades  of TCE contain stabilizers such as
 amines, neutral inhibitor mixtures, and/or epoxides.1
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       TABLE 1.  PHYSICAL AND CHEMICAL PROPERTIES OF TRICHLOROETHYLENE
         Property                                                Value

Structural Formula:  C2HC13, CHC1 - CC12
Molecular weight                                                131.39
Melting point, °C                                               -87.1
Boiling point, °C                                                86.7
Density at 20°C, g/mL                                            1.465
Vapor pressure at 20°C, kPa (mmHg)                             7.6 (57)
Viscosity (absolute) at 20°C, mPa S (=cP)                        0.58
Surface tension at 25°C, mN/m (=dyn/cm)                          26.4
Flash point (closed cup), °C                                     None
Upper explosive limit in air, % by volume                         41
Lower explosive limit in air, % by volume                         11
Heat of formation, liquid, MJ/(kg mo!)                           4.18
Heat of formation, vapor, MJ/(kg mo!)                          -29.3
Heat of combustion, MJ/kg                                        7.325
Solubility in water at 20°C, g/lOOg water                        0.107
Solubility of water in trichloroethylene at 20°C,
  g/lOOg trichloroethylene                                       0.0225

SOURCE:  References 1 and 2.
JES/064                               8

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     The  lifetime of TCE  in the  atmosphere  is slightly over  four  days, where
atmospheric lifetime is defined  as the time required for the concentration
to decay  to 1/e  (37%) of  its original value.3  This relatively  short
lifetime  indicates that TCE is not a persistent atmospheric  compound;
however,  it is continually released to the atmosphere.  The  relatively short
lifetime  of TCE  should prevent long-range global transport of significant
levels of TCE.   The major mechanism for destruction of TCE in the atmosphere
is reaction with hydroxyl radicals. '4  Some of the anticipated degradation
products  include phosgene, dichloroacetyl chloride, and formyl chloride.3

Overview  of Production and Use

     The  commercial production of trichloroethylene began in the United
States in 1925 for use as a metal degreasing and dry cleaning agent.1
Trichloroethylene is currently produced in the United States by two
companies at two manufacturing sites.   Domestic production  in 1987 was
about 91,000 Mg.  Approximately  23,000 Mg of trichloroethylene were exported
and 4,500 Mg imported.   Trichloroethylene production demand is expected to
decrease  because of improved industry recycling practices involving TCE and
the availability of inexpensive  imports.   Since 1980, imports have risen
steadily  and exports have fallen.

     Trichloroethylene is produced domestically by two processes:
(1) direct chlorination of ethylene dichloride,  and (2)  oxychlorination of
ethylene dichloride.  By varying raw material  ratios, trichloroethylene can
be produced separately or as a coproduct of perch!oroethylene (PCE).1'6  Of
the two companies currently producing TCE,  one company produces TCE
separately using the direct chlorination  process (PCE is  produced as a
by-product);, the other produces TCE and PCE as coproducts using the
oxychlorination process.  '   Trichloroethylene may also  be produced as a
by-product during vinylidene chloride or  ethylene dichloride/vinyl chloride
monomer manufacture.
JES/064

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      Figure 1  presents  a chemical  use  tree summarizing  the  production  and
 use  of TCE. The major  end use  of TCE  is  as an  organic  solvent;  for
 industrial  degreasing;  about  85 percent of the  TCE  supply is  used  in vapor
 degreasing  and another  5 percent is  used  in cold  cleaning.5  These processes
 are  used  in many industrial processes  such as the manufacture of
 automobiles, electronics,  furniture, appliances,  jewelry, and plumbing
 fixtures.

      Approximately  five percent of the TCE supply is  used as  a  chain-length
 modifier  in the production of polyvinyl chloride  (PVC).5  The remaining TCE
 (5 percent) is consumed in other solvent  and miscellaneous  applications.
 These applications  include use  (1) as  a solvent in  adhesive formulations;
 (2)  as a  solvent in paints and  coatings;  and (3)  in miscellaneous  chemical
 synthesis and  solvent applications.  '7

 PERCHLOROETHYLENE

 Nature of Pollutant

      Perchloroethylene  (PCE)  is  a colorless, nonflammable liquid with  an
 ethereal odor.'"   The  chemical  name for  perchloroethylene  is
 tetrachloroethylene; it  is  also  known  as  tetrachloroethene  and  perc.   The
 structure of PCE is illustrated  below:
           Cl
                                   \
                                          Cl
           Cl
                                        C
                                        \
                                         Cl
Perchloroethylene is practically insoluble in water, but is miscible with
the chlorinated organic solvents and most other common solvents such as
ethanol, diethyl ether, and oils.  It is a solvent for many substances,
including fats, oils and tars.9  At 20°C, PCE has a vapor pressure of
1.87 kPa (14 mmHg).'
properties of PCE.
Table 2 summarizes the physical and chemical
JES/064
                10

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       TABLE  2.   PHYSICAL AND  CHEMICAL  PROPERTIES OF  PERCHLOROETHYLENE
          Property                                                Value

Structural Formula:  C2C14, ClgC•- CC12
Molecular weight                                                 165.83
Melting point, °C                                                -22.7
Boiling point, °C                                                121.2
Density at 20°C, g/mL                                            1.62260
Vapor pressure at 20°C, kPa (mmHg)                             1.87 (14)
Viscosity at 25°C, mPa S  (=cP)                                   0.839
Surface tension at 15°C, mN/m  (=dyn/cm)                          32.86
Heat of formation, liquid, kJ/(mol)                              12.5
Heat of formation, vapor, kJ/(mol)                                -25
Heat of combustion at constant pressure
  with formation of aq HC1, kJ/(mol)                             679.9
Solubility in water at 25°C, mg/lOOg water                        15
Solubility of water in perch!oroethylene at 25°C,
  mg/120g perch!oroethylene                                        8

SOURCE:   References 2 and 9.
JES/064                               12

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      In the presence of light and air, perch!oroethylene slowly autooxidizes
 to trichloroacetyl chloride.  Stabilizers, such as amines or phenols,
 inhibit the decomposition process to extend solvent life and protect
 equipment and materials.  Compared to other chlorinated ethanes and
 ethylenes, PCE is relatively stable, and generally requires only small
 amounts of stabilizers.^

      The major mechanism that removes perch!oroethylene from the air is
 reaction with hydroxyl  radicals.3'4  The degradation products include
 phosgene and chloroacetyl  chlorides.  The atmospheric lifetime of PCE is
 estimated to range from 119 to 251 days,  where atmospheric lifetime is
 defined as the time required for the concentration to decay to 1/e (37%) of
 its original  value.3 The  relatively long lifetime of PCE in the atmosphere
 suggests that long-range global  transport is  likely.   Monitoring data have
 shown the presence of PCE  in the atmosphere worldwide and at locations
 removed from anthropogenic emission  sources.   Removal  of PCE from the air
 can also occur by washout.

 Overview of Production  and  Use

      Perch!oroethylene  was  first prepared in  1821  by  Faraday from
 hexachloroethane.    Industrial production began in the United States  in
 about 1925.   Perch!oroethylene is  currently produced  by  four companies at
 six locations.  The total domestic production was  about  200,000 Mg  in
 1987.     The  total  imports  of PCE  in  1987 were 54,000 Mg/yr,  and the  total
 exports  were  27,000 Mg/yr.10  Perchloroethylene production demand is
 expected to remain  the  same or decline slightly over the long term.

      Perchloroethylene  is produced domestically by three processes.  These
 are  (1)  the direct  chlorination of ethylene dichloride,  (2)  the
 oxychlorination of  ethylene dichloride, and (3) hydrocarbon  chlorinolysis.
 In the first two processes, PCE can be produced separately or as a coproduct
 of TCE with the raw material ratios determining the proportions of PCE and
TCE.   In the third process, PCE is manufactured as a coproduct with carbon
JES/064                               13

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tetrachloride.    Perchloroethylene may also be formed as a by-product
                                                              g
during ethylene dichloride/vinyl chloride monomer manufacture.   Perchloro-
ethylene is produced in purified, technical, USP, and spectrometric grades.
The various grades are produced for dry cleaning* technical, industrial, and
vapor-degreasing uses, respectively.

     The current uses of PCE are listed in Figure 2, along with the
percentage of the total product devoted to each use.  Perchloroethylene is
commercially important primarily as a chlorinated hydrocarbon solvent and as
a chemical intermediate.  The major end use of PCE is as a dry cleaning
solvent.  Perchloroethylene largely replaced carbon tetrachloride (which is
no longer used) in commercial, coin-operated, industrial and garment-rental
dry cleaning operations.  Some PCE is also used in textile processing as a
scouring solvent and as a carrier solvent.  Together these uses account for
about 50 percent of total domestic demand for PCE.    Approximately
25 percent of the PCE supply is used as a chemical intermediate in chloro-
fluorocarbon production (mostly for chlorofluorocarbon 113).    Another
15 percent is consumed in organic solvent cleaning operations such as vapor
degreasing and metal cleaning.    The remaining 10 percent of the PCE supply
is primarily consumed in other solvent applications.  These applications
include use (1) as a solvent in paints, coatings, and adhesives, (2) as a
solvent in aerosol formulations, and (3) in miscellaneous solvent
applications.
JES/064                               14

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 REFERENCES FOR SECTION 3

  1.   McNeil!,  W.  C.,  Jr.  Trichloroethylene.   (In)  Encyclopedia of Chemical
      Technology,  3rd  ed. Volume 5.   R.  E.  Kirk,  D.  F.  Othmer,  M.  Grayson,
      and  D.  Eckroth,  eds.   John Wiley and  Sons,  New York,  New York.   1978.
      pp.  745-753.

  2.   U.S.  Department  of Health  and  Human Services.   NIOSH  Pocket  Guide to
      Chemical  Hazards.   DHHS (NIOSH)  Publication No. 85-114.   National
      Institute for Occupational  Safety  and Health,  Cincinnati,  Ohio.
      1985.

  3.   Cupitt, L. T.  Atmospheric Persistence of Eight Air Toxics.
      EPA/600/3-87-004.   U.S.  Environmental  Protection  Agency,  Research
      Triangle  Park, North  Carolina.   1987.

  4.   Cupitt, L. T.  Fate of Toxic and Hazardous  Materials  in  the  Air
      Environment.   EPA-600/3-80-084.  U.S.  Environmental Protection Agency,
      Research  Triangle  Park,  North  Carolina.   1980.

  5.   Mannsville Chemical  Products Corp.  Chemical Products  Synopsis -
      Trichloroethylene.  Asbury Park, New  Jersey.   1987.

  6.   Standifer, R.  L.,  and  J. A. Key.   Report  4:  1,1,1-Trichloroethane  and
      Perch!oroethylene,  Trichloroethylene,  and Vinylidine  Chloride.   (In)
      Organic Chemical Manufacturing,  Volume 8:   Selected Processes.
      EPA-450/3-80-28c.   U.S.  Environmental  Protection  Agency, Research
      Triangle  Park, North Carolina.   1980.  pp.  III-8  to 111-14.

  7.   U.S.  Environmental  Protection Agency.  Survey  of  Trichloroethylene
      Emission  Sources.   EPA-450/3-85-021.   Office of Air Quality  Planning
      and Standards, Research  Triangle Park, North Carolina.   1985.

  8.   U.S.  Environmental  Protection Agency.  Survey  of  Perch!oroethylene
      Emissions Sources.  EPA-450/3-85-017.  Office  of  Air Quality Planning
      and Standards, Research  Triangle Park, North Carolina.   1985.

  9.   Keil, S.  L.  Tetrachloroethylene.  (In) Encyclopedia of Chemical
      Technology, 3rd ed. Volume  5.  R.  E. Kirk,  D.  F.  Othmer, M.  Grayson,
      and D. Eckroth, eds.   John  Wiley and Sons,  New York, New York.   1978.
      pp. 754-762.

 10.   Mannsville Chemical Products Corp.  Chemical Products  Synopsis -
      Perch!oroethylene.  Asbury  Park, New Jersey.   1987.

 11.   Hobbs, F. D., and C. W.  Stuewe.  Report 2:  Carbon Tetrachloride  and
      Perch!oroethylene by the Hydrocarbon Chlorinolysis Process.   (In)
      Organic Chemical  Manufacturing, Volume 8:   Selected Processes.
      EPA-450/3-80-28c.   U.S.  Environmental   Protection  Agency, Research
      Triangle Park, North Carolina.  1980.   pp.  III-l  to III-4.
JES/064   •    ;.                        16

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                                   SECTION 4
       EMISSIONS FROM TRICHLOROETHYLENE AND PERCHLOROETHYLENE PRODUCTION

      Sources of atmospheric emissions of trichloroethylene and
 perch!oroethylene related to their production are described in this section.
 Process flow diagrams are included as appropriate and the specific streams
 or vents in the figures are labeled to correspond to the discussion in the
 text.   Emission factors for the production processes are presented when
 available and control  technologies are described.   It is advisable for the
 reader  to contact specific sources in question to verify the nature of the
 process used,  production volume,  and control  techniques  in place before
 applying any of the  emission factors presented in this report.

 TRICHLOROETHYLENE PRODUCTION

     Trichloroethylene  (TCE)  i-s currently  produced domestically  by either
 direct  chlorination  or  oxychlorination  of  ethylene dichloride  (EDC)  or other
 chlorinated  ethanes.  Trichloroethylene, C12C=CHC1,  can  be  produced
 separately or  as  a coproduct  of perch!oroethylene  (PCE),  C12C=CC12,  by
 varying  raw  material ratios.1

     Trichloroethylene  was once manufactured predominantly  by the
 chlorination of acetylene.  However,  because of the  high  cost of acetylene,
 EDC chlorination  became  the preferred method for producing  TCE.  No domestic
 plants currently  use the acetylene-based process to  produce TCE.2

 Process Descriptions

 Ethylene Dichloride Chlorination Process--

     The major products of the EDC chlorination process are TCE and PCE.
Hydrogen chloride (HC1) is produced as a by-product.   The direct
chlorination process involves the reaction of EDC with chlorine to yield a
                                        »                                     •
JES/064                               17

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crude product from which marketable-grade TCE and PCE are derived following
distillation and purification.  The EDC/chlorine ratio determines which
product (TCE or PCE) will be produced in the greatest quantity.  The
following chemical equation characterizes the EDC chlorination process:

                                400-450°
          C1CH2CH2C1  +  C12    	>   HC1 + C1?CCHC1 + C12CCC12
                                 1 atm
             EDC       Chlorine                      TCE        PCE

     Basic operations that may be used in the production of TCE and PCE by
EDC chlorination are shown in Figure 3.  Ethylene dichloride (Stream 1) and
chlorine (Steam 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 C0 hydrocarbons or recycled chlorinated hydrocarbon by-products
                              1
may be fed to the chlorinator.

     The product stream from the chlorination reaction consists of a mixture
of chlorinated hydrocarbons and HC1.  Hydrogen chloride (Steam 3) is
separated from the chlorinated hydrocarbon mixture (Steam 4) and used in
other processes.  The chlorinated hydrocarbon mixture (Stream 4) is
neutralized with sodium hydroxide solution (-Stream 5) and is then dried.
Spent caustic is transferred to a wastewater treatment plant.

     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.

     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
JES/064                               18

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this column (Steam 15) are fed to a heavy ends column.  Overheads from the
heavy ends column (Stream 16) are recycled and bottoms, consisting of tars,
are incinerated.

Ethylene Bichloride Oxychlorination Process--

     The major products of the EDC oxychlorination process are TCE, PCE, and
water.  Side reactions produce carbon dioxide, hydrogen chloride, and
several chlorinated hydrocarbons.  The EDC oxychlorination process is based
on the use of a single step oxychlorination where EDC is reacted with
chlorine and/or HC1 to from TCE and PCE.  This reaction can be illustrated
by the following chemical equation:
C1CH2CH2C1 + C12
        EDC
                        HC1
                                   430°C
                                   CuCl,
C12CCHC1  + H20 + C12CCC12
                                          TCE
                   PCE
The crude product contains 85 to 90 weight percent PCE plus TCE and 10 to
15 weight percent by-product organics.  Essentially all by-product organics
are recovered during purification and are recycled to the reactor.  The
process is very flexible, so that the reaction can be directed toward the
production of either PCE or TCE in varying proportions by adjusting the EDC
to HC1/C12 ratio.1

     Figure 4 shows basic operations that may be used for EDC
oxychlorination.  Ethylene dichloride (Stream 1), chlorine or hydrogen
chloride (Steam 2), oxygen (Stream 3), and recycled by-products 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
JES/064
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JES/064
                           21

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(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 by-product hydrochloric acid.  The remaining inert gases are purged
(Vent A).1

     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.1

     Crude TCE (Steam 11) is sent to a TCE column, where the light ends
(Stream 13) are removed overhead and stored for recycle.  The bottoms
(Stream 14) are neutralized with ammonia and then dried to produce finished
TCE (Stream 15), which is sent to storage.

     The crude PCE (Stream 12) from the PCE/TCE is fed to a heavy ends
column where PCE and light ends (Stream 16) are removed overhead.  Heavy
ends (Stream 17), called "hex wastes," are sent to an organic recycle
system, where the organics that can be recycled (Stream 18) are separated
from tars, which are incinerated.  The PCE and light ends (Stream 16) from
the heavies column are fed to a PCE column, where the light ends (Stream 20)
are removed overhead and sent to the recycle organic storage tank.  The PCE
bottoms (Stream 21) are-neutralized with ammonia and then dried to produce
finished PCE (Stre.am 22) which is sent to storage.1

Emissions

     The major sources of emissions from EDC chlorination are storage tanks,
equipment leaks (fugitives) and handling operations.  Other potential
sources of emissions include process vents, equipment openings, and
JES/064                               22

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 secondary sources.  Potential sources of TCE and PCE process emissions for
 the EDC chlorination process (see. Figure 3) 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
 noncondensible gases.  Storage emission sources (Vents C) include recycle
 storage and product storage.  Handling emissions (Vents D) can occur during
 loading into drums, tank trucks, tank cars, barges, or ships for" shipment.
 The majority of emissions from production of TCE and PCE from EDC
 chlorination result from process fugitives or equipment leaks.   Fugitive
 emissions (E) 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.   One company reported that contaminant and immediate pickup procedures
 are practiced to control  fugitives.   Secondary emissions can occur  when
 wastewater containing VOCs (including TCE and PCE)  is  sent to  a wastewater
 treatment system or lagoon and the VOCs  evaporate  (F).   Another source of
 secondary emissions is the combustion of tars in the incinerator where VOCs
 are emitted with the flue gases  (G).1'3

     The major sources of emissions  from EDC oxychlorination are equipment
 leaks  (fugitives)  and secondary  sources.   Other potential  emission  sources
 include process  vents,  storage tanks,  handling  operations,  and  relief  device
 discharges.   In  the EDC oxychlorination  process  (see Figure  4),  the hydrogen
 chloride absorber  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  EDG process emissions are the
 drying  column  vent  (Vent  B) and  the  distillation column vents (Vents C),
 which release  primarily noncondensible gases, and the TCE  and the PCE
 neutralizer vents  (Vents  D)., which relieve excess pressure of the nitrogen
 pads on  the systems.   The  process vents are  typically controlled by water
 scrubbers, and the  relief  vent is uncontrolled.  Storage emission sources
 (Vents E) are recycle  storage and product storage tanks.  At one facility,
 the storage tanks are  fixed roof tanks that range in size from
JES/064                               23

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13,500 gallons  to  430,000 gallons with  an  average  size  of  55,000 gallons.
The tanks  are controlled by  condensers  with reported  efficiencies  ranging
from 75 to 77 percent.  Handling emissions (F) can occur during product
loading into drums,  tank trucks, tank cars, barges, or  ships  for shipment.
All of the handling  operations except drum handling are controlled by
submerged  pipe  filling technology.  Fugitive emissions  (G) occur when  leaks
develop in valves  or in pump seals.  Some of the fugitive  emissions
resulting  from  pressure relief valves are controlled  by rupture disks  at one
facility.  Secondary emissions (H and I) occur as described above  for  the
chlorination process (see Vents F and G in Figure 3).   No  controls are
reported for reducing secondary emissions. '

     Table 3 presents TCE and PCE emission factors for  the only existing
plant producing TCE  by the EDC chlorination process (PCE is produced as a
by-product only).  Table 4 presents TCE and PCE emission factors for the
only existing plant  producing TCE and PCE as coproducts by the EDC
oxychlorination process.  Each table lists various emission sources, the
control techniques used to reduce emissions from each source, and  the
corresponding emission factor.  The emission factors were derived  from
estimates  of the annual emission rate and the total production capacity for
each plant in 1983.  >4'5  As such, the  factors reflect  the overall level of
control at each plant in 1983.  The EPA does not have more recent  data on
emissions  or control  devices at these plants.

     The controls currently  used at each plant may differ.  For example,
process vent emissions could be reduced by as much as 98 percent through
incineration.  Fugitive emissions could be reduced through an
inspection/maintenance (I/M) program.   Storage tank emissions could be
reduced by installing internal floating roof tanks with primary and/or
secondary  seals and  by adding a refrigerated condenser system.  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.
JES/064
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 Source Locations

      Table  5  presents  a published  list  of major producers  of TCE.

 PERCHLOROETHYLENE PRODUCTION

      Perch!oroethylene (PCE)  is  produced  domestically  by three  processes.
 Two  of the  processes involve  the chlorination  and  oxychlorination  of
 ethylene dichloride  (EDC)  or  other chlorinated hydrocarbons  having two
 carbon atoms.   Perchloroethylene and 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.1
 Perchloroethylene is also  manufactured  as  a coproduct with carbon
 tetrachloride by the chlorinolysis  of hydrocarbons such as propane and
 propylene.

      Perchloroethylene 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.   No domestic plants  currently  use  the  acetylene-based  method to
 produce PCE.

 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.
A diagram of the process is shown in Figure 3.

 Ethylene Dichloride Oxychlorination Process--

     A discussion of the EDC oxychlorination process  for producing PCE and
TCE is presented in the subsection  titled TRICHLOROETHYLENE PRODUCTION.   A
diagram of the process  is shown in  Figure 4.

JES/064                               27

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        TABLE  5.   DOMESTIC  PRODUCERS OF TRICHLOROETHYLENE  IN 19883'6
  Manufacturer                Location                 Process
Dow Chemical, USA          Freeport, TX        Chlorination of Ethylene
                                                 Dichloride


PPG Industries,  Inc.       Lake Charles, LA    Oxychlorination of Ethylene
                                                 Dichloride


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 PCE or
       TCE 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.  These
       operating plants and locations were current as of January 1988.
JES/064                               28

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 Hydrocarbon Chlorinolysis Process--

      The majority of PCE produced in the United States  is formed  by  the
 hydrocarbon chlorinolysis process.  This process involves the simultaneous
 chlorination and pyrolysis of hydrocarbons in which chlorine is reacted with
 chlorinated hydrocarbon derivatives or with a hydrocarbon such as methane,
 ethane, propane, or propylene.  The major products of the hydrocarbon
 chlorinolysis process are PCE, carbon tetrachloride, and hydrogen chloride.
 The process yields a crude product from which marketable PCE is derived
 following distillation and purification.  The reaction can be represented by
 the following equations:

                            500°
                C3H8 + C12  	»   C12C = CC1? + CC1. + HC1
                            cat      *       '      *

                            500°
                C3H6 + C12 	>   C12C = CCU + CC1. + HC1
                            cat .     c       *   .   *

      Basic  operations  that may be  used  in this process are  shown  in
 Figure  5.   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.7   The reaction products,  consisting of  carbon
 tetrachloride,  PCE,  HC1,  and  chlorinated hydrocarbon  by-products  (Stream 3),
 pass  through a  cyclone for removal of entrained catalyst and then  are sent
 to  a  condenser.  Uncondensed  materials  (Stream  4), consisting of hydrogen
 chloride, unreacted  chlorine,  and  some carbon tetrachloride, are removed to
 the hydrogen chloride purification system.  The condensed material
 (Stream 5)  is fed to a hydrogen chloride and chlorine removal column, with
 the overheads (Stream 6) from this column going to hydrogen chloride
 purification.  The bottoms (Stream 7) from the column are fed to a crude
 storage  tank.  Material from crude storage is fed to a distillation column,
which recovers carbon tetrachloride as overheads (Stream 8).  The bottoms
 (Stream  10)  from the carbon tetrachloride distillation column are fed to a
JES/064                              29

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 PCE distillation column.  The overheads  (Stream  11) from the  PCE
 distillation column are taken to PCE storage and loading, and the  bottoms
 are incinerated.

      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 by-product hydrochloric acid storage are combined
 (Stream 14) and passed through a caustic scrubber for removal  of residual
 hydrogen chloride.   Inert gases  are vented from the scrubber.7

 Emissions

     The majority of PCE  emitted from  all  three processes  originate from
 fugitive emissions.   Storage  tanks  are  the second largest  source of PCE
 emissions.   Potential  emission sources  for the  EDC  chlorination and
 oxychlorination  processes  are  shown  in  Figures  3  and 4,  respectively,  and
 are discussed in  the TRICHLOROETHYLENE  PRODUCTION subsection.

     Potential emission sources  for  the  hydrocarbon chlorinolysis process
 are shown  in Figure  5.  Process  emission  sources  originate at  the carbon
 tetrachloride and PCE distillation condensers and caustic scrubber
 (Vents A).  Fugitive emission sources (F)  include process pumps, valves and
 compressors.  Corrosion problems caused by chlorine and hydrogen chloride
 can increase fugitive emissions.  Storage emission sources (B)  are  crude  and
 final product storage.  Several facilities reported using fixed roof tanks;
 a couple other facilities, however, considered storage tank information to
 be confidential.  Handling emissions (C) can occur during product loadings
 into drums, tank trucks, tank cars, barges, or ships for shipment.
 Secondary emissions of PCE can result from handling and disposal of process

JES/064                               31

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waste liquids.  Two sources of secondary emissions from the hydrocarbon
chlorinolysis process are the bottoms from the PCE distillation column (D),
commonly called hex wastes, and the waste caustic from the caustic scrubber
(E).7

     Perch!oroethylene emission factors for the EDC oxychlorination process
are shown in Table 4 and discussed in the TRICHLOROETHYLENE PRODUCTION
subsection.  Perch!oroethylene emission factors for PCE production by the
EDC chlorination and hydrocarbon chlorinolysis processes are shown in
Tables 6 and 7, respectively.  For the EDC chlorination process, the
emission factors presented are based on two facilities for which emissions
information was available.  Control information is considered confidential
and is not listed for either facility, except for control of handling
emissions by submerged fill pipes.  Perch!oroethylene emissions could be
reduced by using condensers on process vents.  For the chlorinolysis
process, the emission factors are based on five facilities.  Emission
factors for each individual plant were derived from the estimated annual
emission rate and the estimated PCE production capacity for that plant in
1983. '   As such, the factors presented in Tables 6 and 7 reflect the
overall level of control at PCE production facilities in 1983.  The EPA does
not have more recent data on emissions or control devices at these plants.

     Individual plants vary in the number of emission points reported and
the types of controls used.  Emissions from process vents can be controlled
by scrubbers; fixed roof tanks by installation of internal floating roofs
with primary and/or secondary seals and addition of refrigerated condenser
system; handling by use of submerged fill pipe technology; equipment
openings by purging/washing/cleaning prior to openings; fugitive sources by
employing an I/M program; and secondary sources by steam stripping and
incineration.  The reader is encouraged to confirm the existence of emitting
operations and control technology at a particular facility prior to
estimating emissions therefrom.
JES/064                               32

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        TABLE 6.  EMISSION FACTORS FOR THE RELEASE OF PERCHLOROETHYLENE
                  FROM PERCHLOROETHYLENE PRODUCTION BY ETHYLENE
                  DICHLORIDE CHLORINATION
    Type of
 Emission/Source
                                            Emission Factor
                                                           a,b
 Range
Average
Process Vents
Storage
Handling
Process Fugitivec'd
Equipment Openings6
Secondary
0.12
0.23
0.001
80 -
0.
0.0f -
-0.29 kg/Mg
-1.0 kg/Mg
- 0.051 kg/Mg
138 Mg/yr
003 kg/Mg
0.001 kg/Mg
0.21 kg/Mg
0.62 kg/Mg
0.026 kg/Mg
110 Mg/yr
0.003 kg/Mg
0.0005 kg/Mg
  _....-_..,..  . ,.„„,,. w  ,,,  vv.1 inw  wi  i\y/ i -|y  ICICI  I»U N I I UVJ I Ctllld Ul  TUC Clll I U LCU 06"
  megagram  of PCE production capacity.

  Based  on  emission  factors  calculated  for two facilities.   Emission factors
  for each  facility  were  based  on  the estimated annual  emission rate from
  Reference 4 and the  estimated PCE production capacity from Reference 5.
  The emission factors reflect  the total  emission  rate  from both uncontrolled
  and controlled  sources  at  the two facilities in  1983.   The number of emission
  points and the  types of controls used at each plant differs.   The EPA does
  not have  more recent data  on  emissions  or control  devices at these plants
  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.

  Fugitive  emissions rate  independent of  plant capacity.

  Based on  the average emission factor  method  for  estimating emissions from
  equipment leaks.  Used the equipment  count  provided by plants and SOCMI
  equipment leak  emission  factors;  represents  a relatively  uncontrolled
  facility  where  no significant leak  detection and repair programs  are in
  place to  limit  fugitive  emissions.  More  accurate  emission estimates can
  be obtained  by  using other methods  such  as the leak/no-leak or the three-
  strata emission factor method.   These methods use  other data  described in
  Protocols  for Generating Unit-Specific  Emission  Estimates  for Eaui oment
  Leaks of  VQC  and VHAP (EPA-450/3-.M-mn) - u— ^ -
p
 Uncontrolled; based on data from one plant only.

 Value reported by facility.
JES/064
33

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       TABLE  7.   EMISSION  FACTORS  FOR  THE  RELEASE OF  PERCHLOROETHYLENE
                  FROM  PERCHLOROETHYLENE  PRODUCTION  BY HYDROCARBON
                  CHLORINOLYSIS  PROCESS
                                            Emission Factor3'
   Type of
Emission/Source                      Range      .                Average


Process Vents                <0.00004  - 0.20 kg/Mg            0.06 kg/Mg

Storage                       0.013 -  0.69 kg/Mg              0.4 kg/Mg

Handling                       0.03 -  0.89 kg/Mg              0.06 kg/Mg

Process Fugitive0              0.41 -  60 Mg/yrd                34 Mg/yrd

Equipment Openings           0.00006 - 0.054 kg/Mg            0.02 kg/Mg

Secondary                    0.0025 -  0.013 kg/Mg             0.008 kg/Mg


Emission factors in terms of kg/Mg refer to kilograms of PCE emitted per
 megagram of PCE production capacity.

 Based on emission factors calculated  for five facilities.  Emission factors
 for each facility were based on the estimated annual emission rate from
 Reference 4 and the estimated PCE production capacity from Reference 5.
 The emission factors reflect the total emission rate from both uncontrolled
 and controlled sources at the five facilities in 1983.  The number of
 emission points and the types of controls used at each plant differs.  The
 EPA does not have more recent data on emissions or control devices at these
 plants.  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.

°Fugitive emissions rate independent of plant capacity.

 At one facility, fugitive emissions were estimated to be 0.41 Mg/yr based on
 emissions testing.  At four other facilities, fugitive emission estimates
 ranged from 13.6 to 60 Mg/yr PCE.  These estimates were based on the average
 emission factor method for estimating emissions from equipment leaks.  The
 equipment counts provided by plants and SOCMI equipment leak emission factors
 were used.  More accurate emission estimates can be obtained by using other
 methods such as the leak/no-leak or the three-strata emission factor method.
 These methods use other data to obtain better emission estimates and are
 described in Protocols for Generating Unit-Specific Emission Estimates for
 Equipment Leaks of VOC and VHAP (EPA-450/3-88-010).
JES/064         :                      34

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 Source Locations
      Table 8 presents a list of perchloroethylene production facilities,
 their locations,  and production process.
JES/064                               35

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        TABLE 8.   DOMESTIC  PRODUCERS  OF  PERCHLOROETHYLENE  IN  1988
                                                                 4,5
   Manufacturer
   Location
        Process
Dow Chemical, USA
Occidental  Petroleum
  Corporation, Occidental
  Chemical  Corporation,
  subsidiary; electro-
  chemicals, detergent,
  and specialty products

PPG Industries, Inc.
  Chemicals Group

Vulcan Materials Co.
 Vulcan Chemicals Div.
Pittsburg, CA
Plaquemine, LA

Deer Park, TX
Lake Charles, LA
Geismar, LA
Wichita, KS
Chlorinolysis
Chlorinolysis

Chiorination of Ethylene
  Dichloride
Oxychlorination of Ethylene
  Dichloride

Chlorinolysis
Chlorinolysis
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 PCE or
       TCE 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.  These
       operating plants and locations were current as of January 1988.
JES/064
         36

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 REFERENCES FOR SECTION 4


 1.   Standifer, R. L., and J. A. Key.  Report 4:  1,1,1-Trichloroethane and
      Perchloroethylene, Trichloroethylene, and Vinylidine Chloride.  (In)
      Organic Chemical Manufacturing Volume 3:  Selected Processes.
      EPA-450/3-80-28c.  U.S. Environmental Protection Agency, Research
      Triangle Park, North Carolina.  1980.  pp. III-8 to 111-14.

 2.   Mannsville Chemical  Products Corp.  Chemical  Products Synopsis -
      Trichloroethylene.  Asbury Park, New Jersey.   1987.

 3.   U.S.  Environmental Protection Agency.  Survey of Trichloroethylene
      Emission Sources.  EPA-450/3-85-021.  Office  of Air Quality Planning
      and Standards, Research Triangle Park, North  Carolina.   1985.

 4.   U.S.  Environmental Protection Agency.  Survey of Perchloroethylene
      Emission Sources.  EPA-450/3-85-017.  Office  of Air Quality Planning
      and Standards, Research Triangle Park, North  Carolina.   1985.

 5.   SRI International.  1983 Directory of Chemical  Producers.   Menlo Park,
      California.   1983.

 6.   SRI International.  1988 Directory of Chemical  Producers.   Menlo Park,
      California.   1988.

 •7.   Hobbs,  F.  D.,  and C.  W.  Stuewe.   Report  2:  Carbon  Tetrachloride and
      Perchloroethylene by  the Hydrocarbon Chlorinolysis  Process.   (In)
      Organic  Chemical  Manufacturing,  Volume 8:   Selected Processes
      EPA-450/3-80-28C.  U.S.  Environmental  Protection Agency, Research
      Triangle Park,  North  Carolina.   1980.  pp.  III-l to III-4.

 8.    Mannsville Chemical Products.  Chemical  Products Synopsis  -
      Perchloroethylene.  Asbury  Park,  New Jersey.  1987.
JES/064                               37

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JES/064
38

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                                   SECTION 5
             EMISSIONS FROM INDUSTRIES PRODUCING TRICHLOROETHYLENE
                     OR PERCHLOROETHYLENE AS A BY-PRODUCT

      This  section discusses TCE and PCE emissions  from two processes where
 TCE and/or PCE are produced as  a by-product.   Trichloroethylene is produced
 as  a by-product and may be emitted from vinylidene chloride production.
 Trichloroethylene and PCE are produced as by-products  and  may be emitted
 during  the production of vinyl  chloride monomer by the balanced process.
 Emission sources are identified and emission  factors are presented as
 available.   The reader is advised to contact  the specific  source in question
 to  verify  the  nature of the process,  production volume,  and control
 techniques  used before applying any of the  emission factors presented in
 this  report.

 VINYLIDENE  CHLORIDE PRODUCTION

      Trichloroethylene is formed  as  a  by-product in the  manufacture  of
 vinylidene  chloride (VDC).   Vinylidene  chloride  is produced domestically by
 the dehydrochlorination  of 1,1,2-trichloroethane with  sodium hydroxide.1
 Two plants  in  the  U.S.  produce  VDC;  each  of these produces  a number  of other
 chlorinated  hydrocarbons by  a variety of  processes.1'2

 Process Description

      Vinylidene  chloride  is  produced by the action of caustic on
 1,1,2-trichloroethane.   The  raw material  1,1,2-trichloroethane is produced
 as a  coproduct  in  the chlorination and oxychlorination of ethane, ethylene,
 and ethylene dichloride  (1,2,-dichloroethane) to produce chlorinated C?
JES/064                               39

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         o
 species.    The  reaction  for the dehydrochlorination  of 1,1,2-trichloroethane
 to  produce  VDC  is  as  follows:

     H       Cl                      H       Cl                     H        Cl
      \    /              water    \   /                      \    /
 Cl  - C - C - H + NaOH  	-*>   C =  C     +   NaCl   +  H00   +    C  =  C
      /    \              100°C    /   \                2        /    \
     H       Cl                      H       Cl                     Cl       Ct
 1,1,2-tri-         sodium              VDC                          TCE
 chloroethane    hydroxide
 The reaction is carried  out with 2  to 10 percent excess caustic  arid  product
 yields  range from  85  to  90 percent.

     Basic  operations that may  be used in  the production  of VDC  from
 1,1,2-trichloroethane are  shown in  Figure  6.  Concentrated sodium  hydroxide
 (Stream 1)  is diluted with water (Stream 2) to about 5  to 10 weight  percent
 and is  mixed with  the 1,1,2-trichloroethane feed (Stream  3) and  fed
 (Stream 4)  to the  dehydrochlorination reactor.   The reaction is  carried  out
 in  the  liquid phase at about 100°C  without catalysts.   Because the aqueous
 and organic reactants are  not miscible,  the reaction is carried  out  in a
 liquid  dispersion.  The  dehydrochlorination reactor is  continuously  purged
 with nitrogen (Stream 5) to prevent the  accumulation of monochloroacetylene
 impurity in the product  VDC.  The nitrogen is discharged  from Vent A.1

     The VDC-containing  product  from  the dehydrochlorination reactor
 (Stream 6)  is separated  in a decanter into an aqueous phase (Stream  7) and
 an  organic  phase (Stream 8).  The aqueous phase, comprising a sodium
 hydroxide/sodium chloride  solution, is divided.  One fraction (Stream 9) is
 recycled (Stream 4) to the hydrochlorination reactor, and the other  fraction
 (Stream 10)  is  steam  stripped to  remove organics and is discharged to a
wastewater  treatment  system (Discharge F).1

     The organics  from the  aqueous phase (Stream 11) are combined with the
 organic phase from the decanter  (Stream 8).  The combined organics
 (Stream 12)  are fed to a drying column, where residual  water is  removed  as a
OES/064                               40

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                                                 41

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 bottoms stream (Stream 13).   The water removed from the drying column is fed
 to the stream stripper with  the aqueous stream from the product decanter
 (Stream 10).1

      The organic stream from the drying column (Stream 14)  is  fed to a
 distillation  column,  which removes  unreacted  1,1,2-trichloroethane as
 overheads (Stream 15).   The  unreacted  trichloroethane  is recycled to the
 dehydrochlorination  reactor.   Purified VDC  product,  removed as bottoms from
 the finishing column  (Stream 16), is used onsite  or stored  in  pressurized
 tanks before  being shipped to users.

 Emissions

      Trichloroethylene  can be formed as  a by-product during VDC  production.
 Potential  sources of  process  emissions (Figure 6) are  the dehydrochlori-
 nation  reactor purge  vent  (A)  and the  distillation  column vents  (B),  which
 release primarily noncondensible gases.  Storage  emissions  (Source  C)  result
 from the storage of VDC product  and intermediates containing TCE.   Handling
 emissions  (Source D)  result  from the loading of VDC  into tank  trucks  and
 railroad tank cars.   Fugitive emissions  (E) result  from  leaks  in  valves,
 pumps,  compressors, and pressure relief  valves.  When  process  pressures  are
 higher  than the  cooling water pressure,  VOC can leak into the  cooling  water
and escape as fugitive emissions from the cooling tower.   Secondary TCE
emissions can occur from desorption of VOCs during wastewater treatment.
                                  1
     Emissions of TCE in 1983 have been estimated for one VDC manufacturing
facility.   The major source of TCE emissions at the facility was equipment
leaks (fugitive emissions).  Using the average emission factor method for
estimating emissions from equipment leaks, uncontrolled fugitive emissions
were estimated to be about 2.3 Mg/yr TCE based on an equipment count
provided by the plant and SOCMI equipment leak emission factors.4  More
accurate emission estimates can be obtained by using other methods such as
the leak/no-leak or the three-strata emission factor method.  These methods
use other data to obtain better emission estimates and are described in
JES/064
42

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  Protocols  for Generating Unit-Specific  Emission  Estimates  for Equipment
  Leaks  of VOC  and  VHAP (EPA-450/3-88-010).

      The plant reported  that  a monitoring  system was  already  in  place  that
  detected 75 to 80 percent of  all equipment leaks.4  Insufficient information
  was provided,  however, to determine the effectiveness of the  monitoring
  system in controlling fugitive emissions.  It was estimated that a  formal
  leak detection  and repair program would reduce fugitive emissions by about
  50 percent.

      Trichloroethylene emissions from one  process vent and one pressurized
  storage  tank at the facility were estimated to be 1 x 10"7 Mg/yr and
 4 x 10"  Mg/yr, respectively.4  The facility considers further information
 regarding the process vent and storage tank to be confidential.4  Production
 capacity data for the facility are also considered to be confidential.
 Therefore,  insufficient data are available to estimate TCE emission factors
 for the process and storage vents at this  facility.   No TCE emissions from
 other sources  were reported.  The EPA does not have  more recent data on
 emissions or control  devices at  this facility.

      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 producers and production locations  are listed
 in Table  9.^

 ETHYLENE  DICHLORIDE/VINYL CHLORIDE MONOMER  PRODUCTION

     Trichloroethylene and PCE may be formed as by-products during the
production of vinyl chloride monomer (VCM)   by the balanced process.  The
balanced  process involves two steps.   In the first step, ethylene dichloride

JES/064                               43        ;

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        TABLE 9.  DOMESTIC PRODUCERS OF VINYLIDENE CHLORIDE IN 1988'
   Manufacturer
                       Location
Dow Chemical, USA
                    Freeport,  TX
PPG Industries, Inc.

  Chemicals Group
                    Lake Charles,  LA
NOTE:  This listing is subject to change as market conditions change,
       facility ownership changes, plants are closed, etc.   The reader
       should verify the existence of particular facilities by consul-
       ting current listings and/or the plants themselves.   The level  of
       TCE 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.  These
       operating plants and locations were current as of January 1988.
JES/064
44

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 (EDC)  Is produced from ethylene and chlorine by direct chlorination, and
 from ethylene and hydrogen chloride (HC1)  by oxychlorination.  In the second
 step,  EDC is dehydrochlorinated to yield VCM and by-product HC1.   The
 by-product HC1  from VCM production via the direct chlorination/dehydrochlor-
 ination  process is used in the oxychlorination/dehydrochlorination process.

 Process  Descriptions

 Ethylene Dichloride Production--

     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,  although  some plants  use purified oxygen  as  feed material.5
 Trichloroethylene and  PCE  are  formed as  by-products of oxychlorination as
 shown  in  the following equation:

     C2H4  +  HC1 + 0? 	* CICH-CH-Cl + C1CHCC1, + Cl.CCCl.,
       *             d CuCl9     2   2            222
                                EDC         TCE        PCE

     Basic operations  that may  be  used in a balanced process  using air for
 the  oxychlorination  step are shown  in  Figure 7.   Actual flow  diagrams  for
 production facilities  will  vary.  The process  begins with  ethylene
 (Stream 1) being  fed by pipeline to  both the oxychlorination  reactor and the
 direct chlorination reactor.   In the oxychlorination reactor  the ethylene,
 anhydrous hydrogen chloride (Stream  2),  and air  (Stream 3) are mixed at
 molar proportions  of about 2:4:1, respectively, producing  2 moles of EDC and
 2 moles of water.  The reaction is carried out in the vapor phase at 200 to
 315 C in either a  fixed-bed or fluid-bed reactor.  A mixture  of copper
 chloride and other chlorides is used as  a catalyst.5
JES/064             '                  45

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      The products of reaction from the oxychlorination reactor are quenched
 with water, cooled (Stream 4), and sent to a knockout drum, where EDC and
 water (Stream 5) are condensed.  The condensed stream enters a decanter,
 where crude EDC is separated from the aqueous phase.  The crude EDC
 (Stream 6) is transferred to in-process storage, and the aqueous phase
 (Stream 7) is recycled to the quench step.  Nitrogen and other inert gases
 are released to the atmosphere (Vent A).   The concentration of organics in
 the vent stream is reduced by absorber and stripper columns or by a
 refrigerated condenser (not shown in Figure 7).5'6

      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.5  Trichloroethylene and  PCE are formed as
 by-products in the following equation:

                  38-49°C
      C2H4  + C12  	—>  C1CH2CH2C1 + CICHCCK  + Cl-CCCU +  HC1
                   FeCu                         tie.
                               EDC          TCE        PCE

      Products  (Steam  9)  from the  direct chlorination  reactor are cooled  and
 washed with water (Stream 10)  to  remove dissolved  hydrogen chloride before
 being transferred (Steam 11)  to the crude  EDC storage facility.  Any  inert
 gas  fed with the ethylene or chlorine is released  to the atmosphere from the
 cooler  (Vent B).   The waste  wash  water  (Stream  12)  is neutralized and  sent
 to the wastewater steam  stripper  along with neutralized wastewater
 (Stream 13)  from the oxychlorination quench area and the wastewater
 (Stream 14)  from the drying  column.  The overheads  (Stream 15) from the
wastewater  steam stripper, which  consist of recovered EDC, other chlorinated
hydrocarbons, and water,  are returned to the process by adding them to the
crude EDC (Stream  10) going to the water wash.5
JES/064                               47

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     Crude EDC  (Stream 16) from in-process storage goes to the drying
column, where water  (Stream 14) is distilled overhead and sent to the
wastewater steam stripper.  The dry crude EDC  (Stream 17) goes to the heads
column, which removes light ends  (Stream 18) for storage and disposal or
sale.  Bottoms  (Stream 19) from the heads column enter the EDC finishing
column, where EDC  (Stream 20) goes overhead to product storage.  The tars
from the EDC finishing column (Stream 21) are taken to tar storage for
disposal or sale.

     Several domestic EDC producers use oxygen as the oxidant in the
oxychlorination reactor.  Figure 8 shows basic operations that may be used
in an oxygen-based 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 7, and therefore, are not shown again
in Figure 8.  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 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 oxychlori-
nation reactor as part of the ethylene feed.  A small amount of the vent gas
(Vent A) from the knockout drum is purged to prevent buildup of the inert
gases entering with the feed streams or formed during the reaction.5
JES/064                               48

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Ethylene  Dichloride  Dehydrochlorination--

     A typical  flow  diagram .for  EDC  dehydrochlorination  is  shown  in
Figure 9.   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  to 60  percent conversion
of EDC to VCM  is  achieved in the reaction.    The reaction is  presented in
the following  equation:

                            450-620°C
                C1CH7CH9C1   	>  CH-CHC1 + HC1
                   * *     450-930 kPa     z
                  EDC                      VCM
No PCE or TCI-  are formed in this step.

     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 onsite, 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  the  EDC production process (generally onsite).6  The vinyl
chloride product is  stored  in pressurized vessels  for eventual shipment to
polyvinyl chloride (PVC) plants  or other facilities using vinyl chloride.
In instances where the PVC  plant is very close to  the vinyl  chloride
producers, vinyl chloride can be delivered by pipeline.7  Heavy ends are
incinerated.

Emissions

     Potential sources of TCE and PCE process emissions are the
oxychlorination vent (Vent  A, Figures 7 and 8) and the direct chlorination
vent (Vent B, Figure 7).  Other  potential sources of process  emissions are
gases released from  column  vents (Vent C, Figure 7), which include vents
JES/064                               50

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from the wastewater steam stripper, the drying column, the heads column, and
the EDC finishing column.   Many plants incinerate vent gases from the
oxychlorination reactor, direct chlorination reactor, and column vents to
reduce atmospheric emissions of volatile organics.   ' »

     Storage emission sources include in-process, liquid-waste stream, and
product storage (Sources D and E, Figures 7 and 8; source not shown in
Figure 9).  Refrigerated condensation, compression, and/or incineration may
                                     459
be used to control storage emissions. ''   In addition, vinyl chloride
product is generally stored in pressurized tanks.   Handling emissions may
occur during waste by-product loading operations. '   Fugitive emissions
(Source F in Figure 7) result from leaks in process valves, pumps,
compressors, and pressure relief valves.  Secondary emissions can result
from the handling and disposal of process waste-liquid streams (Source G in
Figure 7).5

     Table 10 presents TCE and PCE emission factors for three existing
EDC/VCM plants.  The table lists various emission sources, the control
techniques used to reduce emissions from each source, and the corresponding
emission factor.  The emission factors were derived from estimates of the
annual emission rate and annual VCM production capacity for each plant in
     4 9—11
1983. '      The EPA does not have more recent data on emissions or control
devices at these plants.

     Insufficient information was available to calculate TCE or PCE emission
factors for fugitive emissions at the three plants.  Fugitive emissions of
TCE and PCE may be minor at EDC/VCM plants, however,  because of control
measures which are taken to prevent emissions of vinyl  chloride.

     It is uncertain whether the emission factors for the three plants
presented in Table 10 are typical for the EDC/VCM industry.  These 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.

JES/064.                              52       ,

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Source Locations

     A list of vinyl chloride production facilities and locations is
presented in Table 11.
OES/064                               54

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       TABLE 11.  DOMESTIC PRODUCERS OF VINYL CHLORIDE MONOMER  IN  1988'
    Manufacturer
                                                              Location
 Borden Chemicals and Plastics


 Dow Chemical, USA


 Formosa Plastics Corporation, USA



 Georgia Gulf Corporation


 The BF Goodrich Company

   BF Goodrich Chemical  Group


 Occidental  Petroleum Corporation

   Occidental  Chemical Corporation,  Subsidiary

     PVC Resins and  Fabricated Products


 PPG Industries,  Inc.

   Chemicals Group


 Vista  Chemical  Company
                                                    Geismar, LA
                                                    Oyster Creek, TX
                                                    Plaquemine, LA

                                                    Baton Rouge,  LA
                                                    Point Comfort, TX
                                                    Plaquemine,  LA
                                                    Calvert  City,  KY
                                                    La  Porte,  TX
                                                   Deer Park, TX
                                                   Lake Charles, LA
                                                   Lake Charles, LA
NOTE:
This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc.  The reader
should verify the existence of particular facilities by consul-
ting current listings and/or the plants themselves.  The level of
TCE and/or PCE 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.
These operating plants and locations were current as of January 1988
JES/064
                              •55

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 REFERENCES FOR SECTION 5

  1.   Standifer, R.  L., and J. A. Key.  Report 4:  1,1,1-Trichloroethane,
      Perch!oroethylene, Trichloroethylene, and Vinylidene Chloride.  (In)
      Organic Chemical  Manufacturing, Volume 8:  Selected Processes.
      EPA-450/3-80-028c.  U.S. Environmental Protection Agency, Research
      Triangle Park,  North Carolina.   1980.

  2.   SRI International.  1988 Director of Chemical Producers.   Menlo
      Park,  California.  1988.

  3.   U.S.  Environmental Protection Agency.  Locating  and Estimating Air
      Emissions from  Sources of Vinylidene Chloride.   EPA-450/4-84-007k.
      Office  of Air Quality Planning  and Standards, Research Triangle Park,
      North  Carolina.   1985.

  4.   U.S.  Environmental Protection Agency.  Survey of Trichloroethylene
      Emission Sources.  EPA-450/3-85-021.   Office of  Air Quality Planning
      and Standards,  Research Triangle Park, North Carolina.   1985.

  5.   Hobbs,  F.  D., and J.  A. Key.  Report 1:   Ethylene Dichloride.   (In)
      Organic Chemical  Manufacturing, Volume 8:   Selected Processes.
      EPA-450/3-80-28c.  U.S. Environmental Protection Agency,  Research
      Triangle Park,  North  Carolina.   1980.

  6.   U.S. Environmental Protection Agency.  Locating  and Estimating  Air
      Emissions  from  Sources of Ethylene Dichloride.   EPA-450/4-84-007d.
      Office  of Air Quality Planning  and Standards, Research  Triangle Park,
      North Carolina.   1984.

  7.   TRW, Inc.   Vinyl  Chloride - A Review of  National  Emission Standards.
      EPA-450/3-82-003.  U.S. Environmental  Protection Agency,  Research
      Triangle Park,  North  Carolina.   1982.

  8.   U.S. Environmental  Protection Agency.  Locating  and Estimating  Air
      Emissions  from  Sources  of Carbon Tetrachloride.   EPA-450/4-84-007b.
      Office  of Air Quality Planning  and Standards, Research  Triangle Park,
      North Carolina.   1984.

  9.   U.S. Environmental  Protection Agency.  Survey of Perchloroethylene
      Emission Sources.   EPA-450/3-85-017.   Office  of  Air Quality  Planning
      and Standards, Research Triangle Park, North  Carolina.  1985.

10.   SRI International.  1983  Directory of Chemical Producers.  Menlo
      Park, California.   1983.

11.   Mannsville  Chemical Products  Corp.  Chemical  Products Synopsis  - Vinyl
      Chloride Monomer.  Asbury Park, New Jersey.   1984.
JES/064                               56

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                                   SECTION 6
               EMISSIONS FROM INDUSTRIES USING TRICHLOROETHYLENE
                  OR PERCHLOROETHYLENE AS CHEMICAL FEEDSTOCK

      Emissions from industrial processes using TCE and/or PCE as a raw
 material are described in this section.  These processes include
 chlorofluorocarbon production and polyvinyl  chloride production.

 CHLOROFLUOROCARBON PRODUCTION

      Perch!oroethylene is used as a chemical  intermediate in the synthesis of
 CFC-113 (trichlorotrifluoroethane),  CFC-114  (dichlorotetrafluoroethane),
 CFC-115 (chloropentafluoroethane),  and CFC-116 (hexafluoroethane).   CFC-113
 is used mainly as a solvent,  but also as a refrigerant.   The other  CFC
 compounds  are used chiefly as refrigerants.1'2  The  use  of CFCs  as  aerosol
 propel!ants  was  prohibited in 1979  because of their  potential  to contribute
 to stratospheric ozone depletion.

      CFC-113 and CFC-114  are  co-produced as part of  an integrated process
 within  the same  facility.   The  only  commercially important  domestic  process
 used  to  produce  these  two  compounds  involves  the liquid-phase  catalytic
 reaction of  anhydrous  hydrogen  fluoride  (HF)  with PCE.3  A  portion of  CFC-114
 produced by  this  method can be  isolated  for consumption  in  a separate
 reaction with  anhydrous hydrogen fluoride to  yield CFC-115  and CFC-116.4
 These reactions  are  illustrated by the following chemical equations:

                            45-200°C
                           100-3500 kPa
     C!2CCC12 + HF + C12  —_	»  C2C13F3 + C2C12F4 + HC1
                                 5       CFC-113   CFC-114

     C2C12F4 + C12   	*   C2C1F5  +  C2F6  +  HC1.
     CFC-114                    CFC-115    CFC-116

JES/064                              57

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No other data were found on the CFC-115/CFC-116 production process or
emissions therefrom.  Therefore, this section will focus on the production
of CFC-113 and CFC-114.

Process Descri pti on

     Basic operations that may be used in the chlorofluorocarbon production
process are shown in Figure 10.  Perch!oroethylene (Stream 1), liquid
anhydrous HF (Stream 2), and chlorine (stream 3) are pumped from storage to
the reactor, along with the recycled bottoms from the product recovery
column (Stream 15) and the HF recycle stream (Stream 9).  The reactor
contains antimony pentachloride catalyst and is operated at temperatures
ranging from 45 to 200°C and pressures of 100 to 3,500 kPa.

     Vapor from the reactor (Stream 4) is fed to a catalyst distillation
column, which removes hydrogen chloride (HC1), the desired fluorocarbon
products, and some HF overhead (Stream 6).  Bottoms containing vaporized
catalyst, unconverted and underfluorinated species, and some HF (Stream 5)
are returned to the reactor.  The overhead stream from the column (Stream 6)
                                                   3
is condensed and pumped to the HC1 recovery column.

     Anhydrous HC1 by-product is removed overhead (Stream 7) from the HC1
recovery column, condensed, and transferred to pressurized storage as a
liquid.  The bottoms stream from the HC1 recovery column (Stream 8) is
chilled until it separates into two immiscible phases:  an HF phase and a
denser fluorocarbon phase.  These are separated in a phase separator.  The
HF phase (Stream 9), which contains a small amount of dissolved
fluorocarbons, is recycled to the reactor.  The denser phase (Stream 10),
which contains the fluorocarbons plus trace amounts of HF and HC1, is
evaporated and ducted to a caustic scrubber to neutralize the HF and HC1.
The stream is then contacted with sulfuric acid and subsequently with
                                  3
activated alumina to remove water.
JES/064                              58

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JES/064
59

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     The neutralized and dried fluorocarbon mixture (Stream 11) is compressed
and sent to a series of two distillation columns.  CFC-113 is taken off the
bottom of the first distillation column and sent to pressurized storage
(Stream 13).  The overheads from the first distillation (Stream 12) are sent
to the second distillation column, where CFC-114 is removed overhead and sent
to pressurized storage (Stream 14).  The bottoms from the second distillation
(Stream 15) are recycled to the reactor.   The actual configuration of the
distillation train for recovery of CFC-113 and CFC-114 may differ from the
two-column operation presented in Figure 10.

     There are a number of process variations in chlorofluorocarbon
production.  For example, HF is commonly separated from product
chlorofluorocarbons prior to hydrogen chloride removal.  In addition, the
HC1 removal system can vary with respect to the method of removal and the
type of by-product acid obtained.

Emissions

     No PCE emissions have been reported from process vents during
chlorofluorocarbon manufacture.  Vents on the product distillation columns
emit only fluorocarbons. * '   A vent on the hydrogen chloride recovery
column accumulator purges noncondensibles and small amounts of inert gases
which enter the reactor with the chlorine feed stream.  No PCE emissions from
                             356
this vent have been reported. »'

     One major source of PCE emissions during CFC-113/CFC-114 production is
raw materia.1 storage (A in Figure 10).  The PCE feedstock is generally stored
in fixed-roof tanks. '   Table 12 presents uncontrolled emission factors for
storage emissions reported by one facility.  Also presented in this table are
potentially applicable control techniques and associated controlled emission
factors.  The uncontrolled emission factor, 0.28 kg/Mg, was calculated from
a PCE storage emission rate of 4,400 kg/yr  and an associated CFC-113
production rate of 16,000 Mg/yr  (calculated as shown in Appendix A).   If
emissions were controlled by a contact internal floating roof, the estimated
JES/064                              60

-------
 PCE  emission  factor would  be  0.0075  kg/Mg  CFC-113  produced.   This  estimate
 is based  on a controlled PCE  emission  rate of  660  kg/yr7  and  the associated
 CFC-113 production rate of 16,000 Mg/yr.1   If  emissions were  controlled  by a
 refrigerated  condenser, the estimated  PCE  emission factor would be
 0.041  kg/Mg CFC-113 produced.  This  emission factor was calculated from  the
 uncontrolled  PCE  emission  factor and an  assumed condenser control  efficiency
 of 85  percent.

     The  other major  sources  of PCE  emissions  during chlorofluorocarbon
 manufacture are leaks from equipment components, such as  pumps, valves,
 compressors,  safety relief valves, flanges, open-ended lines, and  sampling
 connections.   Table  12 presents PCE emission  rates from  equipment leaks  for
 two  CFC-113/CFC-114 production plants.   Based on  an equipment count provided
 by each plant  and SOCMI equipment leak emission factors,  the  uncontrolled
 equipment leak emission rates were estimated using  the average emission
 factor method.  More  accurate emission estimates can be obtained by using
 other  methods  such as the  leak/no-leak or  the three-strata emission factor
 method. 'These methods use  other data to obtain better emission estimates  and
 are  described  in Protocols  for Generating  Unit-Specific Emission Estimates
 for  Equipment  Leaks of VOC  and VHAP  (EPA-450/3-88-010).

     The control options available for equipment leaks include a monthly leak
 detection and  repair program, venting compressor degassing reservoirs to a
 combustion device, using rupture discs on pressure relief devices,  using
 closed-purge sampling, and capping open-ended lines.  For the two plants in
 Table  12,  the  implementation of all  these control  options would reduce
 equipment leak emissions overall  by roughly 60 percent.7

     Other potential  sources of PCE emissions include loading/handling
 operations and equipment openings.   One chlorofluorocarbon plant reported no
 emission from these sources. '7  Another plant reported annual PCE  emissions
 in 1983 of 0.02 Mg and 0.03 Mg from handling and equipment openings, respec-
 tively. '    These emissions together represented less than one percent of the
 total estimated PCE emissions from that facility.   Production data  were not
 available  to calculate emission factors for the plant.

JES/064                              61

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Source Locations
                                  •$ •

     A list of facilities producing CFC-113 and CFC-114  is presented  in
Table 13.  One plant producing CFC-115 and CFC-116 is also listed.

POLYVINYL CHLORIDE  (PVC) PRODUCTION

     Trichloroethylene is used in PVC production as a reaction chain  transfer
agent to create low molecular weight polymers.  The PVC  suspension process  is
the only process that uses TCE in this manner.  Trichloroethylene is  used by
about 15 percent of the companies employing the suspension process.   Most  of
the TCE is destroyed in the chain transfer reaction.

Process Description

     The suspension process for producing PVC resins is characterized by the
formation of polymers in droplets of the liquid vinyl chloride monomer (or
other co-monomers) suspended in water.  These droplets are formed by
agitation and the use of protective colloids or suspending agents.
Protective colloids are water-soluble polymers such as modified cellulose or
partially hydrolyzed polyvinyl acetate.

     A flow diagram for the suspension process is shown in Figure 11.  This
process is represented by the following equation:
  CH2CHC1 + C2HCHOCOC3H + HgO + C2HC13 - * [-CHgCHCl rCHgCHCl :CH2CHC1-]
   VCM     Vinyl Acetate          TCE                  PVC

Water, vinyl chloride monomer (VCM) and protective colloids are charged to
the polymerization reactor.  Trichloroethylene is also added to the reactor
in suspension processes using TCE as a chain transfer agent.  The initiator
is usually the last ingredient charged to the reactor.  The initiators are
soluble in VCM and allow formation of PVC in the monomer droplets.
JES/064                              63

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             TABLE  13.   FACILITIES PRODUCING CHLOROFLUOROCARBONS
                         113,  114, 115, AND/OR 116  IN 1988
                                                    Compounds Produced
     Company            Location           CFC-113  CFC-114  CFC-115 CFC-116
Allied-Signal,  Inc.   Baton Rouge, LA          X        X
 Allied Chemical
 Corp.


E.I. duPont           Deepwater, NJ                              XX
 de Nemours and
 Co., Inc.
                      Corpus Christi, TX       X        X

                      Montague, MI             X


NOTE:  This 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
       lists 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.  These operating plants and locations were current as of
      . January 1988.

SOURCE:  Reference 5.
JES/064                              64

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     Ingredients charged to the reactor must be carefully measured prior to
charging because a level indicator for reactors has not been developed
comrnercially.  In some cases, the reactor is on a scale and the amount of
material charged is weighed in the reactor.  More often, a separate weight
tank 1s-used to measure materials charged to the reactor.  Reactor operators
manually charge additives that are used in small proportions.

     After all materials are in the reactor, the batch is brought up to the
reaction temperature by passing steam through the reactor jackets which
allows free radical initiators to be formed.  Reaction temperatures are
varied to produce a resin grade of a particular molecular weight.  Once
polymerization is initiated, the reaction becomes exothermic and cooling
water must be circulated through the reactor jacket to remove the heat of
reaction.

     After approximately 6 hours in the reactor, the batch temperature
and pressure drop.  This signifies that nearly all the VCM has reacted
(75 percent to 90 percent of the VCM usually reacts).

     Polyvinyl chloride resin, unreacted VCM (in the water, in the headspace,
and trapped in the resin) and water are the constituents remaining in the
polymerization reactor.  Generally, this polymer slurry (Stream 1) is
stripped of unreacted VCM (Stream 2) using steam and vacuum.  This can be
done in the reactor itself or in a separate vessel.  The unreacted VCM is
purified and recycled (Stream 3), and noncondensible gases are vented.

     After stripping, the batch -(Stream 4) is transferred to blend tanks
which mix the batch with other batches to insure product uniformity.  The
mixed batches (Stream 5) are then fed to a continuous centrifuging operation
that separates the polymer from the water in the slurry.  Both mixing tanks
and centrifuges are vented to the atmosphere if stripping is used.  The
centrifuge water is recycled back to the process or discharged to the plant's
wastewater treatment system.
JES/064                              66

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      The wet cake (Stream 6) from centrifuging is conveyed to a rotary dryer
 for further removal of the remaining (usually 25 percent) moisture.
 Counter-current air temperatures in the dryer range from 65°C to 100°C.
 Drying time is generally short, but large volumes of air are released.
 After drying, the resin (Stream 7) may be screened to remove agglomerates.
 The resin (Stream 8) is then bagged or stored in piles for bulk shipment by
 trucks or rail car.

 Emissions

      Potential TCE emission sources during the PVC suspension process
 include:12'13

      o    TCE unloading and storage,
      o    opening of equipment  for cleaning and maintenance,
      o    pressure relief device discharges,
      o    process vents,  such as blending  tank vents, monomer recovery
           system  vents,  and dryer exhaust  vents,
      o    equipment  leaks  from  valves,  flanges, pumps, compressors,  relief
           devices,  sample  connections,  and open-ended lines,  and
      o    secondary  sources  such as wastewater.

To maintain compliance with NESHAP requirements for vinyl chloride,  many  of
these  emission  sources are controlled at PVC production plants.  This  has the
indirect  and added benefit of controlling  potential TCE emissions to some
extent.   Table  14  identifies control technologies that can be applied  to
reduce emissions  from PVC plants.10

     An estimated 130 Mg of TCE were emitted in 1978 from PVC production
processes using TCE as a reaction chain transfer agent.12  The total TCE used
in 1978 by these processes was estimated at 6,500 Mg.  From these two values,
total TCE emissions per unit TCE used in PVC production are estimated at 0.02
Mg/Mg.  Data are not available on the derivation of the total  annual TCE
JES/064                              57

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3
•4

-------
 emissions estimate, nor are sufficient data available to determine the level
 of control that the emissions estimate reflects.

      Reference 12 presents annual emissions estimates for one facility using
 TCE as a reaction chain inhibitor during the production of vinyl chloride/
 vinyl acetate co-polymer.  Total TCE emissions from the facility in 1983 were
 estimated to be 1.1 Mg.  Of this, about 55 percent were secondary emissions,
 about 45 percent were equipment leaks, and about 2 percent were from TCE
 storage.  Equipment opening emissions and relief device discharges each
 contributed less than one percent of total  plant emissions.   None of the
 emission sources were reported to be controlled.  The facility also reported
 that a process vent was controlled with an  incinerator and quench tank system
 with a control efficiency of greater than 98 percent.   However,  no TCE
 emissions were reported for this process  vent.

      The EPA does  not  have more  recent data on  emissions and  control  devices
 at PVC production  facilities  using TCE as a reaction  chain transfer agent.

 Source Locations

      Table  15 lists  producers  of PVC  resins.  Data  are not available  to
 identify  which facilities  use  TCE as  a chain transfer agent.
JES/064                              59

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      TABLE 15.,  FACILITIES PRODUCING POLYVINYL CHLORIDE RESINS IN 1988
        Company
                      Location
Air Products and Chemicals, Inc.
 Industrial Chemicals Division
Borden Chemicals and Plastics



CertainTeed Corporation

Formosa Plastics Corporation USA


Georgia Gulf Corporation
The BF Goodrich Company
 BF Goodrich Chemical Group
The Goodyear Tire & Rubber Company
 Chemical Division'

Keysor-Century Corporation

Occidental Petroleum Corporation
 Occidental Chemical Corporation, Subsidiary
  PVC Resins and Fabricated Products
                 Calvert City,  KY
                 Pensacola,  PL
                 Geismar,  LA
                 Illiopolis, IL

                 Lake Charles,  LA

                 Delaware  City, DE
                 Point Comfort, TX

                 Delaware  City, DE
                 Plaquemine, LA
                 Avon Lake,  OH
                 Deer Park,  TX
                 Henry,  IL
                 Louisville, KY
                 Pedricktown, NJ
                 Plaquemine, LA
                 Niagara Falls,  NY

                 Saugus, CA
                 Addis, LA
                 Burlington, NJ
                 Burlington, NJ
                 Pasadena, TX
                 Pottstown, PA
JES/064
70

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                            TABLE  15.   (Continued)
         Company                                            Location


 SHINTECH Incorporated                                 Freeport, TX

 Union Carbide Corporation
  Solvents and Coating Materials Division              Texas City, TX

 Vista Chemical Company                                Aberdeen, MS
                                                       Oklahoma City, OK

 V*9en CorP-                                           Ashtabula, OH



 NOTE:  This 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
        lists or the plants themselves.   These operating plants and locations
        were current, as of January 1988.


 NOTE:  Emissions only occur when TCE is used as a chain transfer agent.
        Data are not available to identify which facilities use TCEl   The
        level  of emissions from any given facility that uses TCE is a function
        or variables such  as throughput  and control  measures,  and should be
        determined through direct contacts with plant  personnel.

 SOURCE:  Reference 5.
JES/064                              71

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REFERENCES FOR SECTION 6


 1.  Mannsville Chemical Products Corp.  Chemical Products Synopsis -
     Fluorocarbons and Fluorocarbon Solvents.  Asbury Park, New Jersey.
     1984.

 2.  Hawley, G. G. The Condensed Chemical Dictionary, 10th ed.  Van Nostra-nd.
     Reinhold Company, Inc., New York, New York.  1981.

 3.  Pitts, D. M.  Fluorocarbons (Abbreviated Report).  (In) Organic
     Chemical Manufacturing, Volume 8:  Selected Processes.
     EPA-450/3-80-028c.  U.S. Environmental Protection Agency, Research
     Triangle Park, North Carolina.  1980.

 4.  U.S. Environmental Protection Agency.  Survey of Perchloroethylene
     Emission Sources.  EPA-450/3-85-017.  Office of Air Quality Planning-and
     Standards, Research Triangle Park, North Carolina.  1985.

 5.  SRI International. 1988 Directory of Chemical Producers.  Menlo Park,
     California.  1988.

 6.  Letter and attachments from J. E. Cooper, Allied Corporation, to
     J. R. Farmer, EPA:ESED, April 2, 1985.  Response to PCE Questionnaire.

 7.  Memorandum from K. Fidler, and L. Kinkaid, Radian Corporation, to Carbon
     Tetrachloride File, May 14, 1986.  Estimates of Carbon Tetrachloride,
     Chloroform, and Perchloroethylene Emissions from Chlorofluorocarbon
     Production Facilities and Emission Reductions Achievable with
     Additional Control.

 8.  Letter and attachments from J. B. Coleman, Jr., E. I. duPont de Nemours
     and Company, to J. R. Farmer, EPA:ESED, January 30, 1985.  Response to
     PCE Letter.

 9.  Telecon.  Barr, J., Air Products Co., with P. B. Murphy, Radian
     Corporation, July 18, 1985.  Information on TCE Usage in PVC
     Manufacturing.

10.  TRW, Inc.  Vinyl Chloride - A Review of National Emission Standards.
     EPA-450/3-82-003.  U.S. Environmental Protection Agency, Research
     Triangle Park, North Carolina.  1982.

11.  Khan, Z. S., and T. W. Hughes.  Source Assessment:  Polyvinyl Chloride.
     EPA-600/2-78-004i.  U. S. Environmental Protection Agency, Cincinnati,
     Ohio.  1978.

12.  U.S. Environmental Protection Agency.  Survey of Trichloroethylene
     Emission Sources.  EPA-450/3-85-021.  Office of Air Quality Planning and
     Standards, Research Triangle Park, North Carolina.  1985.
JES/064                              72

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 13.  Letter and attachments from R. R. Neugold, Tenneco Inc., to
      J.  R. Farmer, EPA:ESED, November 18, 1985.  Response to TCE Letter.
JES/064                              73

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JES/064
74

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                                   SECTION 7
                EMISSIONS FROM INDUSTRIES USING TRICHLOROETHYLENE
                       AND PERCHLOROETHYLENE AS SOLVENT

      This section discusses emissions from major processes using TCE and/or
 PCE as a solvent.  These processes include organic solvent cleaning; dry
 cleaning; paints, coatings, and adhesives manufacture and use; and aerosol
 products manufacture and use.  In the United States,  organic solvent
 cleaning (vapor)  is the primary source of TCE emissions and dry cleaning is
 the major source  of PCE emissions.

 TRICHLOROETHYLENE AND PERCHLOROETHYLENE USE IN ORGANIC SOLVENT CLEANING

      Organic solvent cleaning (degreasing)  is an  integral  part of many
 industrial  categories such  as automobile manufacturing,  electronics,
 furniture manufacturing,  appliance manufacturing,  textiles,  paper,  plastics,
 and glass manufacturing.  Organic solvent cleaners  use organic solvents to
 remove water-insoluble soils  (such as  oils,  greases, waxes,  carbon  deposits,
 fluxes,  tars,  or  other debris)  from  surfaces prior  to  processes  such  as
 painting, plating,  repair,  inspection,  assembly, heat  treatment  or
 machining.   Various solvents,  including  petroleum distillates, chlorinated
 hydrocarbons,  ketones,  and  alcohols, are used  alone or in  blends  for  solvent
 cleaning  operations.1   About  90 percent  of theJCE and  15  percent of  the PCE
 supply in 1987 was  used in  solvent cleaning.2'3  Both  PCE  and  TCE are
 especially applicable  to cleaning  and drying metal- parts in the  industries
 mentioned above.                                 :

 Process Description

     There are three basic types of solvent cleaning equipment:  open top
 vapor cleaners (OTVC), conveyorized (often called in-line) cleaners and cold
 cleaners.
JES/064                               75

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     A typical OTVC consists of a tank equipped with a heating system and
cooling coils.  Heating elements on the inside bottom of the tank boil
liquid solvent, generating the vapors needed for cleaning.  Cooling coils
located on the inside perimeter of the tank above the liquid level condense
the solvent vapors, creating a controlled vapor zone which prevents vapors
from flowing out of the tank.  Soiled.objects are lowered into the vapor
zone where solvent condenses on their surfaces and dissolves the soils.
Only halogenated solvents are used in the vapor phase for cleaning (or other
applications) because they have excellent cleaning properties, are
essentially nonflammable, and the heavy vapors produced can be easily
contained within the machine.
                             1,4
     In-line cleaners feature automated conveying systems for continuous
cleaning of parts.  In-line machines clean either by cold or vapor cleaning,
although most use the latter.  The same basic cleaning techniques are used
for in-line cleaning as with OTVC but usually on a larger scale.   Although
in-line cleaners tend to be the largest, they emit less solvent per part
cleaned than other types of cleaners because they are usually enclosed
systems, operate continuously, and feature automated parts handling. '

     Cold cleaners are usually the simplest and least expensive type of
cleaner.  Spraying, flushing, wiping, and immersion are often employed with
these cleaners to enhance cleaning ability.  It should be noted,  however,
that TCE and PCE use in cold cleaning appears to be limited.  Discussions
with the major cold cleaner manufacturers indicate that TCE and PCE are not
used in cold cleaning to a significant extent.  None of these manufacturers
currently sells, or has recently sold, units for use with solvents other
than methylene chloride (part of a carburetor cleaner solution) and
nonhalogenated solvents.  Although there may be some older units  that use
other halogenated solvents, the total number of these units nationwide is
negligible.
JES/064
76

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 Emissions

      Solvent evaporation occurs both directly and indirectly with all types
 of solvent cleaning equipment.  Major causes of emissions include loss of
 solvent vapor from the tank due to diffusion and convection, and evaporation
 of solvent on cleaned parts as they are withdrawn from the machine.  Leaks
 from the cleaner or associated equipment and losses from solvent storage and
 transfer are other significant sources of emissions.  The quantity of
 emissions varies, depending upon the type, design, and size of equipment,
 the hours of operation, operating techniques, and the type of material  being
 cleaned.  Emissions are ultimately a function of solvent use,  therefore,
 techniques and practices designed to conserve solvent use are  beneficial  in
 reducing atmospheric emissions.

      Potential  control  methods for organic solvent cleaners  include add-on
 equipment and improved  operating practices.   Add-on  equipment  can be as
 simple  as adding covers to  equipment openings,  enclosing equipment,
 increasing freeboard height,  adding freeboard refrigeration  devices,  and
 using automated  parts handling systems.   These  devices  limit diffusional  and
 convective losses from  solvent tanks and  evaporative losses  due  to  solvent
 carry-out.  More sophisticated control techniques  include carbon adsorption
 systems  to recover solvent  vapors.

      Operating practices can be improved  to limit  solvent emissions  from
 solvent  cleaning.   These improvements, characterized by  practices that
 reduce solvent exposure to  the atmosphere, include:  minimizing  open  surface
 area, keeping cleaner covers closed, fully draining parts prior  to removal
 from  cleaner, maintaining moderate conveyor speeds, keeping ventilation
 rates moderate,  using a coarse  spray or solid stream of solvent  instead of a
 fine  spray, not  using compressed air sprays to blow-dry parts or to mix
 cleaning baths,  and by placing wipe rags in a closed container and reusing
 them whenever possible.   The emission reductions achievable through the use
 of control devices vary depending on the operating schedule of the machine.
 For example, an OTVC that is used constantly throughout the day will have a
JES/054                               77

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greater reduction in total emissions from a control that reduces working
emissions (such as an automated parts handling system) than an OTVC that is
idle for the majority of the day.
     In vapor cleaning, improper heat balance, air currents, high water
content, and solvent degradation are the primary factors that cause solvent
losses and necessitate greater virgin solvent use.  Equipment configurations
and operational practices that abate the problems will be useful in reducing
potential solvent emissions from vapor cleaning.  Conservation practices for
vapor cleaners as recommended by a major cleaning solvent manufacturer are
summarized below.
     1.   Use least amount of heat necessary to keep solvent at a boil and
          provide adequate vapor production.
     2.   Regulate cooling level by water temperature or flow rate
          adjustments.
     3.   Monitor water jacket temperature and flow rate to prevent
          migration of hot solvent vapor up cleaner side walls.
     4.   Use cold coil traps to lessen vapor losses.
     5.   Use covers, especially during idle periods, on open-top cleaners.
     6.   Avoid drafts over the cleaner by locating the unit to minimize
          natural drafts or use baffles to prevent vapors from being
          disturbed.
     7.   Extend the freebound height of the cleaner.
     8.   Spray in the vapor zone of the cleaner to minimize the generation
          of a vapor-air mixture and the disruption of the vapor interface.
     9.   Use minimum exhaust velocity necessary to provide proper vapor
          control in the work area.
     10.  Arrange air movement in the room to minimize wind tunnel effects.
     11.  Avoid rapid parts or basket movement in the vapor zone,,
     12.  Minimize the level of dissolved water in the solvent.
JES/064                               78

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      13.  Minimize the introduction of water to prevent the depletion of
           solvent stabilizers.
      14.  Have a separate water trough for refrigerated coils.
      15.  Minimize corrosion and remove visible signs of it to minimize
           solvent decomposition.
      16.  Monitor and maintain solvent stabilizers,  inhibitors, and acid
           acceptors.
      17.  Remove metal parts,  fines,  and sludge to prevent stabilizer
           depletion and in turn solvent decomposition.
      18.  Avoid high  oil  concentration build-up.
      19.  Minimize solvent carry-out  on parts.
      20.  Bring parts to  vapor temperature prior  to  removal  to minimize
           dragout.
      21.  Do  not overload the  cleaning capacity of the  cleaner.
      22.  Use properly sized baskets  in the cleaner  to  reduce  vapor-air
           mixing.
      23.  Do  not expose heating coils  to solvent  vapor.
      24.  Use only  clean  or non-porous materials  in  the  cleaning  process.
      25.   Operate  a cleaner leak detection  and  repair program.

      Tables 16  and  17  present  uncontrolled  emission  factors, applicable
control  techniques, their associated control efficiencies, and controlled
emission factors for each type  of solvent cleaner.1'6  Table 16 presents
control  efficiencies and  controlled emission factors for solvent  cleaners
that  are used for a relatively  small fraction of the day (Schedule A).
Table 17 presents control  efficiencies,  and controlled emission factors for
solvent  cleaners that  are  used more regularly.  The controlled emission
factors  were derived using  a material  balance approach based on the
uncontrolled emission  factors reported  in Reference 5 and control
efficiencies reported  in  Reference 1.   See Appendix A for an example
calculation.
JES/064                               79

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     All the emission factors presented in Tables 16 and 17 are based on
fresh solvent input.  These factors account for the recovery and reuse of
solvent contained in cleaner waste solvent streams.  This recycling of waste
solvent results in a reduction in the amount of fresh solvent required for a
given cleaning application, but the percentage of fresh solvent usage that
is ultimately emitted from the cleaning process is higher.

     The controlled emission factors, like the uncontrolled factors, are
expressed as kg solvent emitted per kg fresh solvent used.  It is important
to note; however, that the emission controls for solvent cleaners cause both
a reduction in solvent use and a reduction in the fraction of solvent that
is emitted to the air (as illustrated in Appendix A, Section A-2).  The
controlled emission factors refer only to kg solvent emitted per kg of
controlled fresh solvent used; therefore, these factors should not be
applied to estimates of uncontrolled solvent use to derive estimates of
controlled emissions.

Source Locations

     Five major industry groups use TCE and PCE in degreasing operations.
These are furniture and fixtures (SIC 25), fabricated metal products
(SIC 34), electronic and electronic equipment (SIC 36), transportation
                                                                        7 8
equipment (SIC 37), and miscellaneous manufacturing industries (SIC 39).'
Because of the large number of vapor degreasers, the locations of individual
facilities are not identified.

DRY CLEANING

     Approximately 50 percent of the PCE consumed in the United States is
                               2
used as a dry cleaning solvent.
JES/064                               84

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 Process Description9'10

      The principle steps in the PCE dry cleaning process are identical to
 those of laundering in water, except that PCE is used instead of soap and
 water.  Two types of machines are used for PCE dry cleaning:  transfer and
 dry-to-dry.  For transfer machines, clothes are washed in one unit and then
 transferred to a separate unit to be dried.  For dry-to-dry machines,
 clothes are washed and dried in a single unit, which eliminates the clothing
 transfer step.

      A typical PCE dry cleaning plant is shown schematically in Figure 12.
 The dry cleaning process involves the following major process steps:
 charging,  washing,  extraction,  drying,  and aeration.   Before the cleaning
 cycle begins,  small  amounts of detergent and water are added to the cleaning
 solvent in the charging step.   The detergent and water remove water-soluble
 dirts and  soils from fabrics during washing,  and thus,  improve the  cleaning
 capability of  the solvent.

      To begin  the washing  step,  clothes  are loaded  manually  into the
 perforated steel  drum  of the washer.  Charged  solvent  is  added  and  then
 clothes and solvent  are agitated by rotation of  the drum.  After the  washing
 step  is complete, the  drum  spins at high  speeds  to  remove the  solvent through
 perforations in the  drum.   This  step  is called extraction.

      Next,  the  clothes  are  tumbled  dry.   In this  step, recirculating  warm air
 causes  most of  the remaining solvent  in the clothes to vaporize.  The  PCE-
 laden drying air  stream is  condensed  by the water condenser and  recycled to
 the tumbler, with no exhaust gas stream vented to the atmosphere.   Recovered
 solvent  is  returned to  the  pure  solvent tank for recycle.  After drying,
 fresh ambient air is passed through the machine to freshen and deodorize the
 clothes.  This  process  is called aeration.  The PCE-laden air from this step
 may be vented to a control  device or emitted directly to the atmosphere.
JES/064               '                85

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                  r
                                   Exhaust Gas/Solvent
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       Figure 12. Schematic of perchloroethylene dry cleaning plant.9
  JES/064
           86

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      Most machines are equipped with inductive fans that are turned on when
 the washer and dryer doors are opened.  During the loading and unloading of
 clothes, these fans divert the PCE-laden vapors away from dry cleaning
 operators and pull them through the dry cleaning machine.  The gas stream is
 then either vented directly out the stack or through a control device.

      Efficient operation of dry cleaning plants necessitates at least partial
 recovery and reuse of used solvent.  There are several  pieces of auxiliary
 equipment used at most dry cleaning plants for recovery and purification of
 PCE.  These include filters that remove dirt from the PCE circulating through
 the washer, and stills that purify the PCE by distillation.

      As shown in Figure 12, dirty PCE from the washer is typically passed
 through a filtration  system.   The filtration process  removes most insoluble
 soils,  nonvolatile residue and dyes.   For plants  using  regenerative or
 tubular filters,  the  solids or "muck"  are removed from  the  filters each  day.
 The muck contains solvent  that is recovered by distillation in  a  muck cooker.
 The recovered PCE is  condensed,  separated,  and then returned to the solvent
 storage tank.   The muck solid  waste is  stored and then  disposed of.   For
 plants  .using  cartridge filters,  spent  filters are generally drained and then
 disposed of.

      Following  filtration,  the solvent  may  either flow  back to the  solvent
 storage tank  or to the  distillation unit.   Distillation  removes soluble oil,
 fatty acids,  and  greases not removed by filtration.  During distillation, the
 PCE  is  vaporized  and the residues are retained  in  the distillation  bottoms.
 The  vaporized PCE is condensed, separated,  and  then returned to the solvent
 storage tank.   The distillation bottoms are stored prior to disposal.

 Emissions

     Potential  sources of process emissions include losses during aeration
 and emissions ducted out the stack during clothing transfer.  There are no
 process emissions during other parts of the dry cleaning cycle (i.e., wash
JES/064                               87

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cycle, dry cycle) because exhaust gases are not vented to the atmosphere
during those operations.    Two control techniques used by the industry for
process emissions are refrigerated condensers and carbon absorbers.  Carbon
adsorbers reduce process vent emissions by about 95 percent or more,
refrigerated condensers reduce emissions by about 70 percent.
                                and
     Fugitive emissions include PCE losses from leaky process equipment
(pumps, valves, flanges, seals, etc.), emissions of PCE from spent cartridge
filters and PCE-laden solid waste, and in-plant evaporative losses of PCE
during clothing transfer and handling.  Other potential emissions include
losses from water separators, emissions from distillation units and muck
                                                                    9 10
cookers, and losses from solvent retained in discarded solid wastes. '    The
control techniques used for fugitive emissions include housekeeping
procedures such as detecting, repairing, and preventing leaks, and
minimizing the exposure of PCE-laden clothes to the atmosphere.  These
procedures have been detailed in References 9 and 12 and are reported to be
widely used.

     Table 18 presents emission factors for transfer and dry-to-dry
machines.  The factors are shown for three levels of process emission
control:  uncontrolled trolled, refrigerated condenser-controlled, and carbon
adsorber-controlled.  Neither the amount of solid waste generated.nor
fugitive emissions are affected by the addition of process vent controls, so
they are equal for controlled and uncontrolled machines.

Source Locations

     The dry cleaning industry is composed of three sectors:  commercial,
industrial, and coin-operated.  Commercial plants are classified under
Standard Industrial Classification (SIC) code 7216.  Industrial and
coin-operated plants are classified under SIC 7218 and SIC 7215,
respectively.  Because of the large number of facilities in the United
States, no attempt has been made to identify the locations and names of
facilities.
JES/064
88

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JES/064
89

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      Commercial  facilities  account  for 71  percent  of the  PCE  used  in  dry
cleaning;  industrial  facilities  for 11 percent;  and  coin-operated  for
18 percent.   Coin-operated  facilities  are  usually  small self-service
facilities that  are associated with neighborhood laundromats.  Only synthetic
.cleaning solvents  (no petroleum  solvents)  are  used at coin-operated plants
and  PCE is the primary solvent used.   All  coin-operated plants have
dry-to-dry units where clothes are  washed  and  dried  in a  single unit.
Commercial dry cleaners are typically  small  facilities offering non-self-
service cleaning,  including small neighborhood shops, franchise shops,  and
specialty  cleaners.   Of commercial  dry cleaners, 73  percent use PCE,
24 percent use petroleum solvents,  and 3 percent use trichlorotriflouro-
ethane.  Host machines are  transfer machines where clothes are washed  in one
unit  and transferred  to a separate  unit for drying.   Industrial cleaners are
large facilities that clean items for  rental services.  Forty to 45 percent
of industrial cleaners have dry  cleaning equipment and 50 percent  of  these
use PCE.   A typical industrial facility has one  250  kg per load capacity
washer/extractor and  three  to six 38 kg capacity dryers.

PAINTS, COATINGS, AND ADHESIVES

      Both TCE and PCE are used as solvents in  paints, coatings, and
adhesives.  In 1983,  approximately  520 Mg of TCE and  1,700 Mg of PCE were
used  to manufacture paints  and coatings.  In addition, an estimated 420 Mg of
TCE and 2,800 Mg of PCE were used to manufacture adhesives.8'13

      Solvent  emissions  from paints, coatings,  and  adhesives occur through
evaporation upon application.  Therefore, it is  estimated that all TCE and
PCE used in these applications is eventually emitted to the atmosphere.7'8

      No data were found  on  the emissions of TCE  or PCE during the manufacture
of paints, coatings,  and  adhesives.  The Standard  Industrial  Classification
(SIC) code for paint  and  allied product manufacturing is 285; the SIC code
for adhesives and sealants  manufacturing is 2891.
JES/064                               90

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 AEROSOLS

      Perch!oroethylene  is used as a solvent and carrier  in  aerosol  products
 such as spray paints and cleaners.14'15  Facilities packaging  aerosols
 consumed about 2,630 Mg of PCE in 1985.16  Some aerosol  products contain
 TCE, but insufficient data exist to quantify the extent  of  TCE use.
 Overall, TCE use in these products is believed to be negligible.16
 Therefore, this section discusses only PCE emissions during aerosol
 packaging and use.

      The total PCE emitted in 1985 from five packaging facilities using PCE
 was about 5.4 Mg.15  The total PCE consumed by these facilities was about
 1,470 Mg.     From these two values,  the uncontrolled emission factor for
 aerosol packaging is estimated to be 3.7 kg/Mg consumed.   Of the
 uncontrolled emissions,  approximately 81  percent were from handling
 (primarily mixing tank)  operations,  17 percent were from equipment leaks,
 and 2 percent were from storage tanks.15   Other potential sources include
 wastewater emissions and accidental  releases.

      During use  of aerosol  products,  PCE  is  released  by evaporation after
 application (or  by direct release in  the  gaseous phase).   Consequently,  it is
 assumed that  100  percent of PCE used  in aerosol  applications is emitted  to
 the atmosphere.
JES/064             •                  91

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REFERENCES FOR SECTION 7
 1.  U.S. Environmental Protection Agency. Alternative Control Technology
     Document - Halogenated Solvent Cleaners. EPA-450/3-89-030. Office of Air
     Quality Planning and Standards, Research Triangle Park, North Carolina.
     August 1989.

 2.  Mannsville Chemical Products Corp.  Chemical Products Synopsis -
     Perch!oroethylene.  Asbury Park, New Jersey.  1987.

 3.  Mannsville Chemical Products Corp.  Chemical Products Synopsis -
     Trichloroethylene.  Asbury Park, New Jersey.  1987.

 4.  6CA Corporation.  Organic Solvent Cleaners - Background Information for
     Proposed Standards.  EPA-450/2-78-045a.  U.S. Environmental Protection
     Agency, Research Triangle Park, North Carolina.  1979.

•5.  Dow Chemical Company.  Waste Minimization for Chlorinated Solvent Users.
     Chemicals and Metals Department, Midland, Michigan. June 1988.

 6.  Memorandum from R. C. Mead, Radian Corporation, to D. A. Beck, U.S.
     Environmental Protection Agency, September 3, 1987.  Documentation of
     Emissions and Long-term Exposure Model Inputs for the Organic Solvent
     Cleaning Source Category.

 7.  U.S. Environmental Protection Agency.  Survey of Perch!oroethylene
     Emission Sources.  EPA-450/3-85-017.  Office of Air Quality Planning and
     Standards, Research Triangle Park, North Carolina.  1985.

 8.  U.S. Environmental Protection Agency.  Survey of Trichloroethylene
     Emission Sources.  EPA-450/3-85-021.  Office of Air Quality Planning and
     Standards, Research Triangle Park, North Carolina.  1985.

 9.  U.S. Environmental Protection Agency.  Perchloroethylene Dry Cleaners -
     Background Information for Proposed Standards.  EPA-450/3-79-029a.
     Emission Standards and Engineering Division, Research Triangle Park,
     North Carolina.  1980.

10.  Memorandum from R. L. Ajax and 8. R. Wyatt, U.S. Environmental
     Protection Agency, to J. R. Farmer, U.S. Environmental Protection
     Agency, August 27, 1986.  Information Memorandum - Emissions of
     Perchloroethylene from Dry Cleaning Operations.  Attachment A.

11.  Memorandum from E. C. Moretti, Radian Corporation, to Perchloroethylene
     Dry Cleaning Project File, March 25, 1988.  Documentation of Emission
     Factors for the Perchloroethylene Dry Cleaning Industry.

12.  U.S. Environmental Protection Agency.  Control of Volatile Organic
     Emissions from Perchloroethylene Dry Cleaning Systems.
     EPA-450/2-78-050.  Office of Air Quality Planning and Standards,
     Research Triangle Park, North Carolina.  1978.
JES/064
92

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  13.  Letter from D.  L. Morgan, Cleary, Gottlieb,  Steen,  and  Hamilton,  to
      5;™ « osenstee1' U'S'  Environmental  Protection Agency,  March  1,  1985
      HSIA Data on Perch!oroethylene  Production and Consumption.

  14.  Maklan, D. M    D. H. Steele, S. K. Dietz, G. L. Brown,  and  S.  Fallah.
      Household Products Containing Methylene Chloride and Other  Chlorinated
      Solvents:  "A Shelf Survey."  EPA-OTS 560/5-87-006.  U.S. Environmental
      Protection Agency, Washington,  D.C.   1987.

  15.  Memorandum from J. Martinez, R. Wassel, and  G. Bockol,  Radian
      Corporation, to File of Aerosol Manufacturing - Packagers,  Formulators,
      and Users Work Assignment, October 13, 1987.  Emission  Estimates  and
      Controls Memorandum for Emissions from those Aerosol Packaging
      Facilities Responding to Section 114 Questionnaires.

 16.  Memorandum from E. C. Moretti,  Radian Corporation,  to Aerosol Packaqers
      Project File,  January 19, 1988.  Documentation of Baseline  and
      Controlled Emission Parameters for Aerosol  Packagers.
JES/064                               93

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JES/064
94

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                                   SECTION 8
                 OTHER POTENTIAL SOURCES OF TRICHLOROETHYLENE
                        AND PERCHLOROETHYLENE EMISSIONS

      This section summarizes information on other potential sources of TCE
 and PCE emissions.  These sources include (1) distribution facilities,
 (2) publicly owned treatment works (POTW), and (3) unidentified or
 miscellaneous uses.

 DISTRIBUTION FACILITIES1'2

      Roughly 70 percent of PCE and nearly all  TCE produced is so-ld through
 chemical  distributors.   There are an  estimated 300 chemical distributors
 handling  chlorinated solvents.   Table 19 presents the five largest TCE
 distributors and the three largest PCE distributors.   Data are not available
 to identify all  distribution  facilities handling  these solvents.

      In general,  distributors maintain as  few  as  three to  as  many  as
 65 regional  distribution  facilities spread out  across the  nation.   Each
 regional  distributor receives chemicals directly  from the  producer by  tank
 truck or  railcar.   Transportation  is  provided by  the  distributor.   The
 received  chemicals  are  stored by  regional  distributors  in  8,000 to
 20,000 gallon  fixed-roof  storage  tanks.  The storage  tanks  used by the
 regional  distributor include  vertical,  horizontal, and  underground tanks.
 Turnover  times for  storage tanks typically range  from two weeks to a little
 over a month.  Although the exact  number of distributors and distribution
 facilities that handle TCE is not  known, it is estimated that there are
 96 TCE storage tanks  and  270  PCE storage tanks owned  by distributors.

     Emissions from distribution facilities can be categorized as  two  types:
 storage and handling.  Storage emissions include breathing and working losses
 from tanks.  Handling emissions result from vapor displacement when drums and
 tanks are filled.

JES/064                              95       -,

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              TABLE 19.  SUMMARY OF MAJOR TRICHLOROETHYLENE AND
                         PERCHLOROETHYLENE DISTRIBUTORS

Company
Ashland
McKesson
Chera-Central
Detrex
Thompson -Hayward
Number of
Storage
Facilities
61
63
31
25
26
Number of TCE
Storage
.Tanks
52
6
15
10
6
Number of PCE
Storage
Tanks
37
6
10
--
--
SOURCE:  References 1 and 2.
JES/064
96

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       In  References  1  and  2,  storage  and  handling  emissions  from distribution
  facilities were  estimated using AP-42  emission  factors  and  data supplied by
  major distributors.   An estimated  21 Mg  of TCE  and  27 Mg  of PCE were emitted
  by uncontrolled  storage tanks  at distribution facilities  nationwide  in  1983.
  Approximately 65,700  Mg of TCE and 162,000 Mg of  PCE were sold  through
  distributors in  1983.  From  these values, uncontrolled  storage  emission
  factors  are calculated to be 0.3 kg/Mg and 0.2  kg/Mg for  TCE and PCE,
  respectively.

      Total handling emissions  at distribution facilities  in 1983 were
 estimated at 18 Mg/yr for TCE  and 23 Mg/yr for PCE.  Using the TCE and PCE
 distribution estimates above,  the uncontrolled emission factors  for  handling
 operations are calculated to be 0.3 kg/Mg and 0.1 kg/Mg for TCE  and  PCE,
 respectively.

 PUBLICLY OWNED TREATMENT WORKS (POTWs)

      Trichloroethylene and PCE may  be emitted from publicly  owned treatment
 works,  depending  on  the type of waste streams received.   The primary source
 of these emissions is  believed to be  industrial  discharges containing TCE and
 PCE.   A recent  study used  emissions modeling  to  estimate compound-specific
 emission  factors  for a hypothetical average POTW that treats industrial
 wastewater.   Atmospheric  emissions of  TCE from  the  hypothetical  POTW were
 estimated to  be 62 percent of the TCE in  the  POTW  influent;  atmospheric
 emissions of  PCE  were  estimated to  be 70  percent of  the  influent PCE.

      Characteristics of the hypothetical  POTW were based on  data  obtained in
 a previous study  of  1,600  POTWs nationwide identified as treating industrial
 discharges.  The  hypothetical POTW included the four most  common  major unit
 operations identified  in the  database of  1,600 industrial  POTWs:   1}  aerated
 grit  chamber, 2)  primary clarifier,  3) mechanically aerated basin, and
 4) chlorine contact chamber.  The average flowrate of the  1,600 POTWs was
 0.5906 cubic meters per second, so this was the flowrate selected for the
 hypothetical POTW.
JES/064                              97

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UNIDENTIFIED OR MISCELLANEOUS SOURCES OF TRICHLOROETHYLENE AND
PERCHLOROETHYLENE

     Trichloroethylene and PCE are used in miscellaneous chemical synthesis
and solvent applications.  For example, TCE is used as a reactant to produce
pesticide intermediates.  An estimated 3,670 Mg of TCE were consumed for this
purpose by the pesticide industry in 1984.   Trichloroethylene may also be
used in the chemical synthesis of f1ame-retardant chemicals; as a solvent in
pharmaceutical manufacture; as a solvent in waterless preparation, dying, and
finishing operations in the textile industry; and as a carrier solvent in
formulated consumer products such as insecticides, fungicides, typewriter
                                                       5-8
correction fluids, paint removers, and paint strippers.

     The known miscellaneous uses of PCE primarily include solvent
applications.  The pharmaceutical industry consumed about 7 Mg of PCE solvent
in 1985.   In textile processing, PCE functions as a scouring solvent,
removing oils from fabrics after knitting and weaving operations, and as a
carrier solvent for fabric finishes and water repellants, and for sizing and
         q
desizing.   Perch!oroethylene is miscible with other common solvents and is
an ingredient in blended solvents.  Perchloroethylene is used as a carrier
solvent in many products such as printing inks, cleaners, polishes,
                          6 9
lubricants, and silicones. '   It is also used as a recyclable dielectric
fluid for power transformers, heat transfer medium, and pesticide
intermediate.

     No specific emission factors were found for TCE and PCE emissions from
these miscellaneous uses of TCE and -PCE.  National emissions of these
compounds from pesticide and pharmaceutical manufacture have been reported to
be negligible. *   It is assumed that all TCE and PCE used in consumer
products is eventually emitted to the atmosphere.

     Both TCE and PCE may also be emitted during solid and hazardous waste
treatment, storage and disposal.  Emissions of TCE and PCE have been reported
from hospital waste incineration, waste oil combustion, sewage sludge
JES/064
98

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  incineration, and landfills.10'13  The quantity of emissions depends on
  waste type and disposal techniques.  The reader is encouraged to investigate
  specific sites to determine the potential for TCE or PCE emissions from
  these sources.
JES/064                              gg

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REFERENCES FOR SECTION 8
 1.  U.S. Environmental Protection Agency.  Survey of Perch!oroethylene
     Emission Sources.  EPA-450/3-85-017.  Office of Air Quality Planning and
     Standards, Research Triangle Park, North Carolina.  1985.

 2.  U.S. Environmental Protection Agency.  Survey of Trichloroethylene
     Emission Sources.  EPA-450/3-85-021.  Office of Air Quality Planning and
     Standards, Research Triangle Park, North Carolina.  1985.

 3.  White, T. S., Radian Corporation.  Volatile Organic Compounds Emissions
     from Hazardous Waste Treatment Facilities at Downstream POTW (Final
     Report).  Prepared under EPA Contract No. 68-02-4378.  U.S. Environmental
     Protection Agency, Research Triangle Park, North Carolina.  1987.

 4.  Memorandum from R. Pandullo, and R. Nash, Radian Corporation, to
     Methylene Chloride File, July 24, 1986.  Estimates of Hazardous Compound
     Emissions from Pesticide Facilities and Emission Reductions Achievable
     with Additional Controls.

 5.  Mannsville Chemical Products Corp.  Chemical Products Synopsis -
     Trichloroethylene.  Asbury Park, New Jersey.  1987.

 6.  Maklan, D. M., D. H. Steele, S. K. Dietz, 6. L. Brown, and S. Fallah.
     Household Products Containing Methylene Chloride and Other Chlorinated
     Solvents:  "A Shelf Survey."  EPA-OTS 560/5-87-006.  U.S. Environmental
     Protection Agency, Washington, D.C.  1987.

 7.  Memorandum from R. Pandullo, R. Nash, and P. Murphy, Radian Corporation,
     to Methylene Chloride File, September 17, 1986.  Estimates of
     Potentially Hazardous Compound Emissions from Pharmaceutical Facilities
     and Emission Reductions Achievable with Additional Controls.

 8.  McNeil!, W. C., Jr.  Trichloroethylene.  (In) Encyclopedia of Chemical
     Technology, 3rd ed., Volume 5.  R. E. Kirk, D. F. Othmer, M. Grayson,
     and D. Eckroth, eds.  John Wiley and -Sons, New York, New York.  1978.
     pp. 745-753.

 9.  Mannsville Chemical Products Corp.  Chemical Products Synopsis -
     Perch!oroethylene.  Asbury Park, New Jersey.  1987.

10.  Pope, A. A., P. A. Cruse; and C. C. Most.  Toxic Air Pollutant Emission
     Factors -• A Compilation for Selected Air Toxic Compounds and Sources.
     EPA-450/2-88-006a.  U.S. Environmental Protection Agency, Research
     Triangle Park, North Carolina.  1988.

11.  Harkov, R., S. J. Gianti, J. W. Bozzeli, and J. E. LaRegina.  Monitoring
     Volatile Organic Compounds at Hazardous and Sanitary Landfills in New
     Jersey.  Journal of Environmental Science and Health.  A20(5):491-501.
     1985.
JES/064
100

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 12.  Wood, J. A., and M. L. Porter.  Hazardous Pollutants in Class  II
      Landfills.  Journal of the Air Pollution Control Association.
      37(5):609-615.  1987.

 13.  Fennelly, P. F., M. McCabe, J. M. Hall, M. F. Kozik, M. P. Hoyt,
      G. T. Hunt, GCA Corporation.  Environmental Characterization of
      Disposal of Waste Oils by Combustion in Small Commercial Boilers.
      EPA-600/2-84-150.  U.S. Environmental Protection Agency, Cincinnati,
      Ohio.  1984.
JES/064

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JES/064
102

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                                   SECTION 9
                            SOURCE TEST PROCEDURES

      Trichloroethylene and perch!oroethylene emissions can be measured using
 EPA Reference Method 18, which was added in the Federal Register on
 October 18, 1983.   This method applies to the analysis of approximately
 90 percent of the total gaseous organics emitted from industrial sources.1

      In Method 18, a sample of the exhaust gas to be analyzed is drawn into
 a Tedlar® or alumized Mylar® bag as shown in Figure 13.  The bag is placed
 inside a rigid leak proof container and evacuated.   The bag is then
 connected by a Teflon* sampling line to a sample 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 seven
 days  of sample collection.   The GC  operator  should  select  the column and  GC
 conditions that provide good  resolution and  minimum analysis  time for the
 compounds  of interest.   One recommended 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®.1   Zero helium or nitrogen  should  be used as  the carrier gas at
 a  flow  rate  that optimizes  good resolution.

      The peak  areas corresponding to the retention  times of
 trichloroethylene  and perchloroethylene are measured and compared to  peak
 areas for  a  set  of standard gas mixtures to determine  the  trichloroethylene
 and perchloroethylene concentrations.  The detection range of this method is
 from  about 1 ppm to the upper  limit governed by GC detector (FID) saturation
 or column  overloading; however, the upper limit can be extended  by diluting
 the stack  gases with an inert gas or by using smaller gas sampling loops.
JES/064                              103

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OES/064
104

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 REFERENCES FOR SECTION 9



 1.   Method 18:  Measurement of Gaseous Organic Compound Emissions by Gas
      Chromatography.  Federal Register 48(202}:4834A-4a3fii  1933.
JES/064                              105

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JES/064
106

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                                  APPENDIX A
                        DERIVATION OF EMISSION FACTORS
JES/064                              A_!

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JES/064                               A-2

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                                  APPENDIX A
                        DERIVATION OF EMISSION FACTORS

 A-l.  DERIVATION OF CFC-113 PRODUCTION RATE AT ALLIED CHEMICAL FACILITY
 (1)  -    U.S. sales of CFC-113 and CFC-11 = 125 x 106 Ibs in 19831
           CFC-113 is estimated to account for 95 percent of the sales1
           DuPont supplies about 70 percent of the CFC solvent market, with
           Allied Chemical selling the remaining 30 percent1
           Allied Chemical has only one facility that produces CFC-113
 (2)  -    Calculate CFC-113 production in 1983 at the Allied Chemical,
           Baton Rouge,  Louisiana,  plant as follows:
                    6                       Mg
           (125 x 10° Ibs) (0.95)  (0.30) (	-) =  16,000 Mg CFC-113
                                          2205 Ib
 A-2.   EXAMPLE CALCULATION:   RELATIVE SOLVENT  USAGE AND EMISSION  FACTORS
                             FOR CONTROLLED VS. UNCONTROLLED CLEANERS
 o     The  controlled  and uncontrolled emission factors  are  related  as
      fol1ows:
                                                             (Equation
     where,
          ec s controlled emission factor (kg emitted per kg fresh solvent
               feed)
          eu = uncontrolled emission factor (kg emitted per kg fresh solvent
               feed)
           n = efficiency of control device
JES/064                              A_3

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     The relative amount of fresh solvent used by a controlled cleaner
     relative to the amount used by an uncontrolled cleaner is:
              Lli
              1 - e.
relative solvent usage factor
(Equation 2)
     Example Case:  Open Top Vapor Degreaser (OTVD)
     Consider a situation where a cleaning job requires 1 kg/hr of fresh
     solvent in the uncontrolled situation.  The uncontrolled emission
     factor (with recycle) for OTVD using PCE is 0.93 kg emitted per kg
     fresh solvent used.
                                      Emissions 0.93 kg/hr solvent

                                                       t
     Fresh Solvent
     1.0 kg/hr
                            Degreaser
                                      Unrecoverable waste 0.07 kg/hr solvent
     Now assume controls are applied (refrigerated freeboard chiller) at a
     control efficiency of 40 percent.  Emissions are reduced by 40 percent
     but the amount of unrecoverable waste solvent does not change.
                             Emissions 0.93 x (1 - .40) = 0.56 kg/hr solvent

                                                       t
     Fresh Solvent
     ? kg/hr
                            Degreaser
                                      Unrecoverable waste 0.07 kg/hr solvent
New solvent usage = 0.56 + 0.07 = 0.63 kg/hr

New emission factor (ec), fresh solvent basis = 0.56/0.63 =0.89 kg/kg

Relative solvent usage, controlled vs. uncontrolled (r)  - 0.63/1.0 - 0.63
JES/064
             A-4

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 Check Equations 1 and 2:
            0.93 (1 - .40)
      ec s T;	I	" = °-89 kg/kg, which checks with the example
           (1 - 0.93 x 0.40)   calculation

           1 - 0.93
       r „ 	 = o.63, which checks with the example calculation
           1 - 0.89

 A-3.   DERIVATION OF EQUIPMENT LEAK EMISSION FACTORS AS A FUNCTION OF
       PRODUCTION CAPACITY FOR SELECTED PRODUCTION PROCESSES
      The fugitive emission rate is generally independent of plant capacity.
 Therefore,  Sections 4,  5, and 6 of. this document present equipment leak
 emissions as a function of time (Mg/yr) rather than capacity (kg/Mg).   In
 some  cases,  however,  the reader may find it necessary to use equipment leak
 emission factors expressed as a function of capacity.   These can be
 calculated  based on the estimated  annual  emission rate and the estimated
 total  production capacity.   Table  A-l  presents TCE and PCE emission factors
 (in kg/Mg)  for TCE,  PCE,  and CFC-113 production processes.   A sample
 calculation  is shown  below for TCE production  by ethylene dichloride
 chlorination:

   Estimated  TCE production  capacity at  one  plant in  1983:   54,000  Mg/yr4
   Estimated  TCE equipment leak emissions  from  plant  in  1983  (control status
   is considered confidential)  =24.1 Mg/yr
   Calculate  equipment leak  emission factor  as  follows:
   (24.1  Mg/yr)  (1000  kg/Mg)  =  0.45 kg TCE emitted/Mg TCE  production  capacity
       (54,000  Mg/yr)
JES/064                              A_5

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-------
 REFERENCES FOR APPENDIX A         ;


 1.   Mannsville Chemical Products Corp.  Chemical Products Synopsis -
      Fluorocarbon Solvents.  Cortland, New York.  1984.

 2.   U.S. Environmental Protection Agency.  Survey of Perchloroethylene
      Emission Sources.  EPA-450/3-85-017.  Office of Air Quality Planning
      and Standards,  Research Triangle Park, North Carolina.  1985.

 3.   U.S. Environmental Protection Agency.  Survey of Trichloroethylene
      Emission Sources.  EPA-450/3-85-021.  Office of Air Quality Planning
      and Standards,  Research Triangle Park, North Carolina.  1985.

 4.   SRI International.  1983 Directory of Chemical  Producers.   Menlo Park,
      California.   1983.

 5.   Memorandum from K. Fidler and L.  Kinkaid,  Radian Corporation, to Carbon
      Tetrachlpride File,  May 14,  1986.   Estimates of Carbon Tetrachloride,
      Chloroform,  and Perchloroethylene Emissions from Chlorofluorocarbon
      Production Facilities  and Emission Reductions Achievable with
      Additional  Control.
JES/064          .                    A-7

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
         IO.
      EPA-450/2-89-013
                                                            3. RECIPIENT'S ACCESSION NO.
 I. TITLE AND SUBTITLE
 Locating And  Estimating Air Emissions  From
 Sources of Perchloroethylene And Trichloroethylene
                                                            S. REPORT DATE
                                                              	August 1989
                                                            i. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
 Claire  C.  Most
                                                            8. PERFORMING ORGANIZATION REPORT NO.
 I. PERFORMING ORGANIZATION NAME AND AOOHESS
 Radian  Corporation
 Post Office Box 13000
 Research Triangle Park, NC  27709
                                                            1O. PROGRAM ELEMENT NO.
                                                            11. CONTRACT/GRANT NO.

                                                                  68-02-4392
12. SPONSORING AGENCY NAME AND ADDRESS
 Air Quality Management Division
•OAR, OAQPS-,''AQMD-,  PCS  (MD-15)       '
 Noncriteria Pollutant  Programs Branch (MD-15)
 Research Triangle  Park, NC  27711
                                                            13. TYPE OF REPORT AND PERIOD COVERED
                                                                   Final
                                                            t«. SPONSORING AGENCY'CODE
 5. SUPPLEMENTARY NOTES
      EPA Project Officer:  Anne A. Pope
                                                                      various  potentially
                                                                      as  this to  compile
 To assist  groups  interested  in  inventorying  air  emissions  of
 toxic substances,  EPA  is. preparing a  series  of documents such
 available information on  sources  and emissions of  these  substances.   This  document
 deals specifically with  perchloroethylene and  trichloroethylene.  Its intended
 audience includes  Federal,  State,  and  local  air  pollution  personnel  and others  in
 locating potential emitters  of perchloroethylene and trichloroethylene and  in
 making gross estimates of  air emissions  therefrom.

 This document presents information on (1) the  types  of sources that may  emit
 perchloroethylene and trichloroethylene, (2)  process variations  and  release  points
 that may  be expected within  these  sources  and (3)  available  emissions  information
 indicating the  potential  for  trichloroethylene and  perchloroethylene  releases  into
 the air from each operation.
7.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                                                                        c.  COSATI Field/Group
 Perchloroethylene
 Trichloroethylene
 Air Emission Sources
 Locating Air Emission  Sources
 Toxic Substances
8. DISTRIBUTION STATEMENT
     Unlimited
                                              19. SECURITY CLASS (This Report I
                                                    Unclassified
21. NO. OF PAGES
	124
                                              20. SECURITY CLASS (Tin'spage/

                                               	Unclassified
                                                                        22. PRICE •
EPA Form 2220-1 (R«v. 4-77) '  PREVIOUS EDITION is OBSOLETE

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