MISCELLANEOUS INDUSTRIAL SOURCES
OF VINYL CHLORIDE EMISSIONS
IN THE U.S.

report to
U.S.  ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE  PARK, NORTH CAROLINA
by
ARTHUR  D. LITTLE, INC.
CAMBRIDGE. MASSACHUSETTS
MARCH, 1976
EPA CONTRACT NO.  68-O2-1332,
TASK 13 (PART  I - A, B, C)
ADL NO. 76O86-13
                           Arthur D Little, Inc.

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                                       950R76009
          MISCELLANEOUS INDUSTRIAL SOURCES
             OF VINYL CHLORIDE EMISSIONS
                   IN THE U. S.
                     Report to

       U. S.  Environmental  Protection Agency
      Research Triangle Park, North Carolina
                        by

                  Warren J. Lyman



                     76086-13

EPA Contact No.  68-02-1332, Task 13 (Part I - A, B, C)



                    March,  1976
               Arthur D. Little, Inc.
              Cambridge, Massachusetts
                Arthur D Little, Inc.

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                 ACKNOWLEDGEMENT
     The success of this program was totally dependent
upon our being able to obtain process and emissions data
from various chemical manufacturers.  Most manufacturers
were very cooperative.  We would like to acknowledge  this
help and to thank these manufacturers for their  time  and
effort.
                                                       Arthur D Little, Inc

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                         TABLE OF CONTENTS

                                                              Page

  I.  SUMMARY                                                   1

 II.  INTRODUCTION                                              7

      1.   Background                                            7
      2.   Scope of Work                                         7
      3.   Approach Used                                         8

III.  GENERAL FINDINGS                                         10
      1.   Literature Review                                    10
      2.   Contacts with Industry Associations                  -Q
          and Government Agencies
      3.   Contacts with Vinyl Chloride Producers               12
      4.   Contacts with Manufacturers of Copolymers            13
          and Terpdlymers
      5.   Categories of Vinyl Chloride Emissions Found         14

 IV.  USE OF VINYL CHLORIDE AS A CHEMICAL INTERMEDIATE         15

      1.   The Production of 1,1,1-Trichloroethane              -^
          (Plants A and B)
      2.   The Production of 1,1,2-Trichloroethane              ,Q
          (Plant C)
      3.   The Production of Other Chemicals from               -JQ
          Vinyl Chloride

  V..  USE OF VINYL CHLORIDE AS A MINOR CONSTITUENT IN          26
      CERTAIN COPOLYMERS AND TERPOLYMERS
      1.   Introduction                                         26
      2.   Vinyl Chloride - Vinylidene Chloride Copolymers      26
      3.   Other Vinyl Chloride Copolymers and Terpolymers      28

 VI.  PROCESSES PRODUCING VINYL CHLORIDE AS A BY-PRODUCT       30

      1.   Introduction                                         30
      2.   By-Product Vinyl Chloride from Industrial            31
          Processes Currently Used in the U. S.
      3.  By-Product Vinyl Chloride from Industrial            ^j
          Processes Not Currently Used in the U. S.
      4.  Perchloroethylene from Acetylene                     37

 APPENDIX I                                                    40

 REFERENCES                                                    42
                                                                Arthur D Little, Inc

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                                LIST OF  TABLES

                                                                    Page
   Table  1
       Estimated Vinyl  Chloride Emissions  in  the  U.  S.                3
   Table  2
       Emissions and  Emissions Control Summary  for  the                ,
       Plants  Identified
:   Table  3
       U.  S. Vinyl  Chloride  Manufacturers  Contacts                   13
'   Table  4
       Producers of Synthetic Polymers who were Contacted
       to  Determine Whether  They  Manufacture  Copolymers or          13
       Terpolymers  Incorporating  Vinyl Chloride
   Table  5
       Manufacture  of Methyl Chloroform  (1,1,1-TCE)                  15
       in  the  U. S.
   Table  6
       Comonomers Used  in the Commercial Production of               .5
       Vinyl Chloride Copolymers  in the  U. S.
   Table  7
       Ethylene Amine Production  in the  U. S.                       32
   Table  8
       Pollutant Concentrations  in Ethylene Amines                   ,
       Reaction System  Vent;  1975
                                                                     Arthur D Little, Inc

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                              LIST OF FIGURES
                                                                 Page
Figure 1
     Commercial Routes to 1,1,1-TCE, 1,1,2-TCE and                .,
     Vinylidene Chloride in the United States
Figure 2
     Process Flow Sheet for Use of Vinyl Chloride                 2i
     in Pesticide Production
Figure 3
     Vinyl Chloride Monomer Handling                              24
Figure 4
     Ethylene Diamine from Ethylene Dichloride                    34
Figure 5
     Ethylene Imine (Aziridine) from Ethylene Dichloride          36
Figure 6
     Tetrachloroethylene from Acetylene and Chlorine              39
                                                                   Arthur D Little, Inc

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I.   SUMMARY

     This report is the result of an.investigation undertaken to identify
and describe industrial sources of vinyl chloride emissions in the United
States other than those sources connected with the manufacture of vinyl
chloride or with the manufacture, compounding and fabricating of poly-
vinyl chloride.  The investigation focused on three general areas where
such other sources of vinyl chloride emissions were thought to exist.

     1.  Industrial processes where vinyl chloride is used as a chemical
         intermediate for the production of other chemicals.

     2.  Industrial processes where vinyl chloride is used as a minor
         constituent (< 50% by weight) for the production of resins.

     3.  Industrial processes where vinyl chloride is produced as a by-
         product of the chemical reaction involved.  (This area is given
         lowest priority.)

     The investigation did not cover possible vinyl chloride emissions
from aerosol spray cans*, from the transportation and storage of vinyl
chloride or from the use and disposal of polyvinyl chloride.

     The approach used in this investigation included the following:

     •   A literature search through several secondary sources, and a
         computer search of the recent literature;

     •   Contacts with several state and federal agencies, and with a few
         industry association, who were known to have interests in the
         vinyl chloride problem;

    "•"  Contacts with all U. S. vinyl chloride manufacturers;

     •   Contacts with all U. S. manufacturers of vinyl chloride copoly-
         mers or terpolymers (except for a few making copolymers with
         vinylidene chloride**);

     •   Contacts with other companies as necessary.

     No plant inspections or monitoring activities were carried out in
this investigation.  (Additional details on the approach used are given
in Sections II and III.)
 *While the use of vinyl chloride in spray cans was banned in October, 1974,
  some cans are still in the hands of the public and will eventually be used.

 **Vinylidene chloride was the subject of a separate investigation carried
  out at  the same time by ADL under the same Task order.
                                                                 Arthur D Little, Inc

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     The investigation identified sources of vinyl chloride emissions in
all three categories mentioned above.  A total of 8 companies* operating
a total of 15 plants** were identified.  The list of plants involved is
given in Appendix I.  It must be noted that, as is the case with vinyl
chloride and (to a lesser degree) polyvinyl chloride manufacturing plants,
a large portion of these plants (7 out of 15) are located in the states of
Louisiana and Texas.

     Table 1 gives a summary of the estimated annual vinyl chloride emis-
sions from the sources identified, and (for purposes of camparison) from
sources connected with the manufacture of vinyl chloride and polyvinyl
chloride.  In all cases except one, the estimated emissions from the
sources identified here are given for 1974 since the information obtained
related to that year.

     Table 2 lists the estimated annual emissions of vinyl chloride from
the 15 plants identified and gives a summary comment on the status, if
known, of emission controls at the plant.

     Some general comments and conclusions resulting from this program
follow.

     1.  Total estimated vinyl chloride emissions from the 15 plants
         identified were about 1.2 MM*** kg  (2.6 MM Ibs) in 1974.  This
         is about 1.2% of the total estimated vinyl chloride emissions
         from all other sources  (97.7 MM kg).

     2.  Over 80% of the emissions, documented here came from two plants
         (Plant M and N) where vinyl chloride was produced as a by-pro-
         duct.  Both plants are currently installing emission controls.

     3.  While it is not possible to predict accurately the extent of
         emissions reduction that can be expected for 1975 and following
         years, a significant reduction is  expected by 1976.  Vinyl
         chloride emissions in 1976 from the plants identified may drop
         below 0.3 MM kg(0.7 MM  Ibs) if the  construction of emission con-
         trols now in progress is completed.  Further reductions will not
         be as significant, but will occur  since several of the plants
         are expected to be covered by EPA  regulations for polyvinyl
         chloride plants.   (See  #4 below for details.)
  *The total is only 7 if subsidiary companies are counted with the parent
   company.

 **The word "plants" here is used loosely.  If a separate processing unit
   exists for each chemical or resin produced, then a total of 19 processing
   units is involved.  Some of these processing units are in the same "plant";
   further, three of the "plants" are in one town and thus may be in the same
   industrial complex.

***The abbreviation MM, for "million", is used throughout this report.
                                                                 Arthur D Little, Inc

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4.  Six of the plants identified, Plants F-K, are resin producers;
    emissions of vinyl chloride from these plants will be regulated
    under the EPA's proposed regulations for the manufacture of poly-
    vinyl chloride resins.  The other eight plants do not have any
    such connection to vinyl chloride monomer or polymer manufac-
    turing and thus would have to be considered individually for any
    proposed regulations.

5.  With respect to the eight plants that will not be covered under
    the regulations proposed by the EPA, a follow-up study should
    probably be conducted in the near future.  The study would center
    on an investigation of the types of emission controls in use,
    their effectiveness, their cost, and the resulting amounts of
    vinyl chloride lost to the atmosphere.

6.  The amount of detailed information obtained by ADL on chemical
    processes, characterizations of emission streams, emissions data,
    and emissions controls at the plants identified must be considered
    small.  In many cases, the information was either not available or
    was considered confidential.  Additional details would be neces-
    sary in these cases before any form of standards or regulations
    were to be considered.
                                                            Arthur D Little, Inc

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                                         TABLE 1
                   ESTIMATED VINYL CHLORIDE EMISSIONS IN THE U. S.
                                                                    (1)
Process

1.  Vinyl Chloride
    Monomer Production
    2,540 MM kg in 1974
    (5,596 MM Ibs)

2.  PVC Resin Production
    2,190 MM kg in 1974
    (4,821 MM Ibs)

3.  PVC Compounding and
    Fabricating
    2,300 MM kg in 1974
    (5,100 MM Ibs)
                       No. Companies  No. Plants
           Estimated Vinyl Chloride Emissions
           	1974	
                      1000 kg/yr
                            10
                            20
                         Several
                         Thousand
    SUBTOTAL
4.
Production of 1,1.1-
TCE and 1.1.2-TCE
Amount of Vinyl Chloride
Used in 1974 was ^107 MM kg  3
(236 MM Ibs)
5.  Production of Other
    Chemicals From Vinyl
    Chloride
    Amount of Vinyl Chloride
    Used in 1975 was 2.0 MM kg
    (4.3 MM Ibs)

6.  Production of Resins
    With Minor Amounts of
    Vinyl Chloride
    Amount of Vinyl Chloride
    Used in 1974 Roughly Esti-
    mated at 40 MM kg
    (90 MM Ibs)

7.  Production of Vinyl
    Chloride As A By-Pro-
    duct
    SUBTOTAL
   13
  -X35
Several
Thousand
11,400
85,700
   600
                                                                    (2)
                                                                    (3)
                                                                    (4)
                                                             97,700
                                                                 40 - 130
                                                                          (5)
                                                             <7
                                                                      (6)
                                                            116 -  122
                                                                      (7)
                                                              ^000
                                                                   (8)
                                                           1160-1260
    Footnotes on the following page
                                                                        Arthur D Little, Ihc

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                                   TABLE 1
                                   •
                                 (CONTINUED)
(1)   The reader should be cautioned that  the vinyl chloride emission figures given
     in this table are estimates;  in some cases the numbers are derived from actual
     measurements of  vinyl chloride in industrial process vents, while in other cases
     no such data were available and certain assumptions are involved.   Individual
     references and/or the appropriate sections of this report  should be consulted
     to determine the basis on which estimates were made.

(2)   Estimate is based on an emission rate of 0.448 kg/100 kg of product;  This is
     based on industry data submitted to  the EPA in response to Section 114 requests
     of May 31, 1974  from Don Goodwin, EPA,  Research Triangle Park,  N.C.  Data
     were obtained from all vinyl  chloride and polyvinyl chloride producers.

(3)   Estimate is based on an emissions rate of 3.92 kg/100 kg of product; This is
     based on industry data submitted to  the EPA in response to Section 114 requests
     of May 31, 1974  from Don Goodwin, EPA,  Research Triangle Park,  N.C.  Data were
     obtained from all vinyl chloride and polyvinyl chloride producers.

(4)   From Ref.  9.

(5)   This breaks down to an estimate of 10-100 MM kg from the production of 1,1,1-TCF,
     and 30 MM kg from the production of  1,1,2-TCE.

(6)   This estimate is not based on actual emissions data.  See  Section IV (2) for
     details.

(7)   Estimates were based on limited data.  Roughly 2/3 of the  emissions are from
     the manufacture  of resins containing vinylidene chloride.   Emissions estimate
     is for 1975.

(8)   Essentially all  of the emissions here are from the manufacture of ethylehe
     amines at one plant.
                                                                       Arthur D Little, Inc

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                                                           TABLE 2
C
a
             N
                              EMISSIONS AND EMISSION CONTROL SUMMARY FOR THE PLANTS IDENTIFIED

                                           Estimated Annual Emissions

Plant
A
B
C
D
E
Type of Process
(No. from Table 1)
4
4
4
5
5
of

}



Vinyl Chloride, 1974
(1000 kg/yr)
10.0 - 100
30.0
<.05
<7.0

Status of Emission Controls,
No information available
Confidential
No information available

1975


Vents go to a thermal oxidizer
Vent condensers used

F
6
71.9*
Efforts (unspecified) are underway to
reduce emissions.
G
H
I
J
K
L
M
6
6
6
6
6
7
7
4.5 - 11.0
39.0
}-<" ]
<1.0
No information
Confidential
None at present
are expected to
18 months.
No information
[ fVent goes to a
available



Incineration facilities
be installed during next
available
flare tower;

incineration
                                                  'vljOOO
j facility with a scrubber being built.

"None at present; construction is underway
 to allow incineration; solvent adsorption
_system is planned.

 Emission controls used; type not known.
           *Dei^iyed from hourly or daily emission rate; assumes 365 days/yr of operation.

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II.  INTRODUCTION

     1.  Background

     The discovery, in early 1974, of the link between worker exposure
to vinyl chloride and the development of angiosarcoma of the liver ini-
tiated action by the Environmental Protection Agency (EPA) and other
government agencies to determine the sources of vinyl chloride emissions
and investigate methods of control.  Aside from the action taken to pro-
hibit the use of vinyl chloride as a propellant in spray cans, most at-
tention was focused on the establishments (1) where vinyl chloride was
made; (2) where polyvinyl chloride was made; and, (3) where polyvinyl
chloride (PVC) resins were compounded and fabricated.

     It was clear, however, that these establishments were not the only
sources of vinyl chloride emissions.  First, there were indications that
perhaps only 97% of the vinyl chloride consumed in the United States was
for PVC production; there were suggestions that the remainder was used
as an intermediate in the production of other chemicals such as 1,1,1-
Trichloroethane (Refs. 1 and 2), 1,1,2-Trichloroethane (Ref. 2), vinyl-
idene chloride (Ref. 2), and chloroacetaldehyde (Ref. 3),  Second, there
was the possibility that vinyl chloride might be used as a minor consti-
tuent (i.e., less than 50% by weight) in certain copolymers and/or ter-
polymers, and thus have escaped notice since only polymers with more than
50% vinyl chloride (by weight) are generally called PVC resins.  Third,
since vinyl chloride is a relatively simple molecule, it seemed possible,
in fact likely, that vinyl chloride could be formed as a by-product in
one or more of the numerous industrial reactions involving low molecular
weight chlorinated hydrocarbons.

     Essentially, no published information was available on any of these
three possibilities, and thus their contribution to total vinyl chloride
emissions could not be assessed.   It was the purpose of this program to
investigate these possibilities and determine the nature and extent of
the vinyl chloride emissions associated with them.

     2.  Scope of Work

     The purpose of this program was to identify sources of vinyl  chloride
emissions from industrial processes other than the manufacture of  vinyl
chloride, and other than the manufacture, compounding, and fabrication
of PVC resins.  This was expected  to include processes  (1) where vinyl
chloride was used as an intermediate,  (2) where vinyl chloride was used
as a minor constituent in certain  copolymers or  terpolymers,  and  (3)
where vinyl chloride was produced  as a by-product.  The last  possibility,
by-product production, was  to be  given  the  lowest priority.

     For each source of vinyl chloride  identified, we were to provide,
where possible, certain information including plant  location, process
description,  characterization of  emission streams  (volume, composition,
temperature,  etc.), estimates of  vinyl  chloride  emissions, and  control
                                                                 Arthur D Little, Inc

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 techniques  that have been, or could have been, applied to each source in
 order  to  reduce emissions.  The costs, and resulting emissions reduction,
 connected with the  installation of emission controls were to be determined
 where  possible.  During  the course of  the project we found  that we could
 not  obtain  much of  these data.

     Our  scope of work did not include an investigation of  possible emis-
 sions  from  aerosol  spray cans, from the transportation and  storage of vinyl
 chloride, or  from the use and disposal of polyvinyl chloride.

     3.   Approach Used

     The  approach used in this investigation started with four basic items
 and  then  expanded or contracted depending on the amount of  useful informa-
 tion found.   The four basic items were:

     a.   A  Literature Review;  This included a search through the large
 number of secondary sources in ADL's library and a computer search of the
 recent literature in such files as  (i) the National Technical Information
 Service,  (ii) Chemical Abstract Condensates, (iii) CHEMCON, and  (iv) CHEM
 70-71.

     b.   Interviews with Representative of State and Federal Agencies and
 Certain  Industry Associations;  These  contacts were made in part to obtain
 useful information.and in part to  ensure  that our program did not involve
 any  real duplication of  effort.  Contacts were made with the following
 agencies  or associations:

     Government Agencies

          Occupational  Safety  and Health Administration
          National Institute of Occupational  Safety and Health
          Consumer Product Safety Commission
          Food and Drug Administration
          Texas Air  Control Board

      Industry Associations

          Society  of the  Plastics Industry
          Manufacturing Chemists Association
          National Paint  and Coatings Association

      c.   Contacts with All Vinyl Chloride Producers  in  the  U.  S.:   Initial
 telephone interviews were  followed up, when  necessary, with written ques-
 tions.  No  personal visits  or plant inspections were made.

      d.   Contacts with Vinyl  Chloride  Polymer  or  Terpolymer Producers  in
 the U. S.:This  list  totals  about 18  companies.As above, initial tele-
1 phone interviews  were  followed up, when necessary, with written questions.
 No personal visits  or  plant  inspections  were made.   Producers  of copolymers
 with vinylidene chloride were not  specifically included  since  they  were sub-
                                                                  Arthur D Little, Inc

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ject, in part, of a separate investigation being carried out by ADL for
the U. S. EPA (Ref. 4).  However, data on vinyl chloride emissions from
polyvinylidene chloride plants that use vinyl chloride are included in
this report.

     When a source of vinyl chloride emissions was found that fell with-
in the scope of work of this project, written questions were submitted to
that particular establishment requesting the details about the process
and emissions as listed in subsection 2 above (Scope of Work).
                                                                  Arthur D Little, Inc

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III. GENERAL FINDINGS

     This section presents some of the more general findings of this in-
vestigation.  Additional information is given on the scope and approach
of our investigation, as is some detail on the quantity and quality of
information obtained from the various lines of approach used, and an out-
line of the areas of vinyl chloride emission sources found that fell with-
in the scope of work.  The process emission details about the sources
identified are given in Sections IV to VI.

     1.  Literature Review

     The literature review included a search through several secondary
sources (e.g., books, encyclopedias, index journals, chemical economics
compilations, and certain trade journals) and a computer search of the
recent literature.  The files searched by computer included the following:

                        FILE                           TIME PERIOD COVERED

         National Technical Information Service           1964 _•- Present*
         Chemical Abstract Condensates                    1972 - Present*
         CHEMCON                                          1972 - Present*
         CHEM 1970-1971                                   1970 - 1971

     The computer search was done at ADL using a remote computer terminal.
These files were searched by using key wrods as the "search elements."
For example, the files were asked to search for citations that combined
the words "vinyl chloride" and "emissions," or "vinyl chloride" and "in-
termediate."  Key words for each citation are obtained from the title of
the article and, in many cases, the abstract.  Several other combinations
of key words (including the names of other chemicals) were used in the
computer search.  Foreign publications were generally not considered.

     Relatively little useful information was obtained from the literature
review of the secondary sources and the computer files, but this was not
unexpected, since in most cases such data had not been published.

     The computer search did illuminate a continuing interest by several
chemical companies in copolymers or terpolymers made by the graft poly-
merization of vinyl chloride onto some other polymer.  This interest is
demonstrated primarily by the patent literature.  For example, the com-
puter search of the Chemical Abstract Condensates file (covering the period
of 1972 - February, 1975) yielded 11 patents on the graft polymerization
of vinyl chloride that had been assigned  to seven U. S. chemical companies:
GAF, Hooker Chemical, Air Products and Chemicals, Rohm & Haas, Stauffer
Chemical, Firestone Tire and Rubber, and  Dow Chemical.  Other patent
coverage is possible as several patents state only  the use of various
vinyl halides as  the monomer to be grafted.

     The investigations carried.out in this program indicated that no
graft polymerization of vinyl chloride (to make copolymers or terpolymers)
is being carried  out on a commercial scale in the United States.  This was
 *Since the search was  conducted  in  February,  1975, no  information put  in  the
  first three files  after  that  date  was  seen.	"

                                    10                           Arthur D Little, Inc

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determined after consultation with several in-house (ADL)  experts,  with
one ADL consultant, and with several companies who hold patents in this
area.

     2.  Contacts with Industry Associations and Government Agencies

     The three industry associations contacted (see Section II) did not
find it advisable to assist in this investigation.

     Relatively little information of direct relevance to  this program is
currently being gathered by the government agencies we contacted.  (See
Section II for a list of the agencies contacted.)  It was  determined that
there was no duplication of effort involved, i.e., none of the other agen-
cies were untertaking a broad investigation to determine other uses or
areas of occurence of vinyl chloride.  Some examples of the information
gathering activities of these agencies are listed below.

     a.  The Louisiana Air Control Commission has recently conducted a
         survey of vinyl chloride emission sources in their state.  A
         copy of a summary sheet from this survey was obtained; it lists
         11 sources in the state, two of which fell within the scope of
         this study.  One of these was an ethylene amines production
         plant from which by-product vinyl chloride was emitted; the
         second was an ethylene dichloride production plant also involving
         by-product vinyl chloride emissions.  Additional details on these
         plants are given in Section IV.

     b.  The Texas Air Control Board has an emissions inventory  questionnaire
         to which all manufacturing industries are supposed to respond.
         We were told that in a large number of cases, all organic chemi-
         cal emissions were reported only as "total hydrocarbons" and as
         a result we did not seek to review these questionnaires.

     c.  The Food and Drug Administration issued a notice in the Federal
         Register  (April 22, 1974) which required drug manufacturers to
         submit information on any of their drugs intended for human use
         that contained vinyl chloride  (e.g., as a propellant) or that
         were packaged in polyvinyl chloride.  One agency spokesman stated
         that he was not aware of any information that was submitted that
         was important to the scope of work of the ADL investigation.

     d.  The Consumer Product Safety Commission  issued a notice  in  the
         Federal Register  (May 19, 1974) requesting information  from com-
         mercial establishments on the  use of vinyl chloride as  a pro-
         pellant in spray cans.  None of the information obtained as a
         result of this notice, or other information  gathering activities,
         was important to  the scope of  the ADL study, primarily  because
         we had excluded the spray can  use  from  our scope of work.

     e.  The Occupational  Safety and Health Administration, aside  from con-
         ducting its own studies on vinyl chloride exposure in vinyl chlo-
         ride and  polyvinyl chloride plants  (which were not of  interest  in
                                     11                           Arthur D Little, Inc

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         this  study), mandated,  in  their new vinyl  chloride  regulations*,
         that  all  establishments handling  vinyl  chloride  or  polyvinyl
         chloride  that were  not  able  to keep vinyl  chloride  concentrations
         below the permissible exposure limit  had to  report  such  to  their
         OSHA  area director.  "Regulated areas"  were  to be set  up in such
         instances.

         ADL requested from  OSHA a  list of the companies  that had reported
         that  they had a  vinyl chloride "regulated  area." This information
         was obtained, but for several reasons it proved  to  be  of no use.
         First,  those establishments  not knowingly  using  vinyl  chloride or
         polyvinyl chloride  (e.g., those where  vinyl chloride might be  pro-
         duced as  a by-product)  did not have to  report.   Second,  those
         establishments that were able to  keep vinyl  chloride below  the
         permissable exposure limit did not have to report.  Third,  there
         are 25 "agreement states"  which have  the authority  to  administer
         OSHA  regulations; in these states reports  of "regulated  areas"
         need  only be submitted  to  the state.  Fourth,  it was suspected
         that  several establishments  had failed  to  report their "regulated
         areas" by the time  the  ADL request was  made  (in  mid-May, 1975).

         Because of the problems mentioned above it was decided that the
         25 "agreement states" would  not be contacted to  request  the in-
         formation submitted to  them.

         From  various OSHA offices  information was  obtained  relating to
         the existence of vinyl  chloride regulated  areas  at  about 40 plants
         as of the end of June,  1975. All of  these plants are  involved in
         the manufacture  or  processing of  vinyl  chloride  or  polyvinyl  chlo-
         ride.

     3.  Contacts  with Vinyl Chloride Producers

     All U. S. producers  of  vinyl chloride were  contacted by ADL  during
this investigation. All  companies  agreed  to cooperate with  ADL and  did
so, either by  answering  questions over  the phone, or  by answering ques-
tions submitted in writing.   The list of  companies  contacted is given
in Table 3.
*Published in the Federal Register, October 4, 1974; effective date of
 the regulations was April 1, 1975.
                                    12
                                                                 Arthur D Little, Inc

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                                TABLE 3
             U. S. VINYL CHLORIDE MANUFACTURERS CONTACTED
     Allied Chemical
     B. F. Goodrich Chemical Company
     Borden Inc.  (Monochem)
     Continental  Oil Company (CONOCO)
     Dow Chemical Company
    Ethyl  Corporation
    P. P.  G.  Industries,  Inc.
    Shell  Oil Company-
    Stauffer  Chemical Company
    Teneco Chemicals, Inc.
     4.  Contacts with Manufacturers of Copolymers and Terpolymers

     The list of companies contacted (see Table 4) is thought to include
all U. S. comapnies using vinyl chloride for copolymer or terpolymer pro-
duction on a commercial scale.  In addition, the list contains the names
of a few other companies who were contacted because information obtained
by ADL implied the possible use of vinyl chloride in copolymers or ter-
polymers.

     The majority of the companies listed in Table 4 do not produce any
polymers with minor amounts of vinyl chloride; some do not make vinyl
chloride copolymers or terpolymers of any kind (these companies are identi-
fied in Table 4) .
                                TABLE 4

    PRODUCERS OF SYNTHETIC POLYMERS WHO WERE CONTACTED TO DETERMINE

          WHETHER THEY MANUFACTURED COPOLYMERS OR TERPOLYMERS

                     INCORPORATING VINYL CHLORIDE
 Air  Products  &  Chemicals,  Inc.
 Atlantic  Tubing &  Rubber Company*
 Borden Inc.
 Dow  Chemical  Company
 Eastman Kodak*
 Firestone Tire  & Rubber Company
 GAF  Corporation
 B. F.  Goodrich  Chemical Company
 Goodyear  Tire & Rubber Company
 Hooker Chemical Corporation
Jennat Corporation, subsidiary of
   Union Carbide Corporation
Keysor-Century Corporation
Monsanto Company*
National Starch & Chemical Company
Olin Corporation*
The Pantasote Company of New York, Inc.*
Stauffer Chemical Company
Tenneco Chemicals, Inc.
Union Carbide Corporation
 *These companies do not make vinyl chloride copolymers or terpolymers
  of any kind.
                                    13
                                                                  Arthur D Little Inc

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     5.  Categories of Vinyl Chloride Emissions Found

     For the purpose of further documentation and discussion, the various
sources of vinyl chloride emissions found, other than those connected with
the manufacture of vinyl chloride and polyvinyl chloride, are categorized
as follows:

     1.  Use of Vinyl Chloride as a Chemical Intermediate

         a.  For the production of 1,1,1-Trichloroethane (1,1,1-TCE, or
             methyl chloroform) and 1,1,2-Trichloroethane (1,1,2-TCE).

         b.  For the production of other special chemicals, e.g., certain
             pesticides.

     2.  Use of Vinyl Chloride as a Minor Constituent in Certain Copolymers
         and Terpolymers

         a.  Those in which vinylidene chloride is not a major constituent.

         b.  Those in which vinylidene chloride is a major constituent.

     3.  Processes Producing Vinyl Chloride as a By-Product

         a.  Processes used in the United States.

         b.  Commercialized processes not currently used in the United
             States.

     The processes and emissions associated with items 1-3 above are
discussed in detail in Sections IV - VI, respectively.
                                    14
                                                                  Arthur D Little, Inc

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    IV.  USE OF VINYL CHLORIDE AS A CHEMICAL INTERMEDIATE

         1.  The Production of 1,1,1-Trichloroethane (Plants A and B)

         a.  Introduction

         A significant amount of vinyl chloride, estimated by ADL to be around
    80 MM kg/yr (175 MM Ibs/yr), is used for the production of 1,1,1-Trichloro-
    ethane (1,1,1-TCE, or methyl chloroform) in the United States.  This
    amount of vinyl chloride represents about 3 percent of the total amount
    of vinyl chloride produced in the U. S. currently.  Small amounts of 1,1,2-
    TCE are produced as a by-product in the chemical process.

         1,1,1-TCE is used primarily as an industrial solvent, e.g., for metal
    degreasing.  1,1,2-TCE is used primarily as a chemical intermediate for
    the production of other chlorinated solvents, and for the production of
    vinylidene chloride.  Table 5 summarizes production information for methyl
    chloroform from the Chemical Economics Handbook. . No similar information
    is available for 1,1,2-TCE.  PPG Industries and Vulcan Materials Company
    confirmed, in conversations with ADL investigators, that the respective
    intermediates shown in Table 5 for them were correct.  Figure 1 diagrams
    the various routes of interest to 1,1,1-TCE and 1,1,2-TCE for additional
    clarification.

                                    TABLE 5

           MANUFACTURE OF METHYL CHLOROFORM (1,1,1-TCE)  IN THE U.  S.
Manufacturer
Dow Chemical*
Ethyl Corporation
Plant Location
Freeport , Texas
Baton Rouge,
Reaction Via
Vinyl Chloride
Vinyl Chloride
1972 Capacity
MM kg (MM Ibs)
159 (350)
23 ( 50)
                            Louisiana

P. P. G. Industries       Lake Charles,         Vinylidene           80  (175)
                            Louisiana             Chloride

Vulcan Materials Company  Geismar,              Ethane               30  ( 65)

                            L°Uisiana                      TOTAL    292  (640)
     *Dow Chemical  is  currently building an additional plant  for  the production
      of  methyl  chloroform  in Louisiana.

     Source;   Chemical Economics Handbook, Stanford  Research  Institute,
              November,  1972.
                                                                      Arthur D Little, Inc.

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                                         FIGURE 1

                      COMMERCIAL ROUTES TO 1.1,1-TCE. 1.1.2-TCE*.

                      AND VINYLIDENE CHLORIDE IN THE UNITED STATES
               with estimates of 1974 production given for specific routes**
                               Ethylene
                              Dichloride
Vinyl
_8Q
t
Chloride
MM kg_
                                   I Plants
                                   IA & B
                                                       Vinyl  Chloride
                                                        Purification
                                                      Column  Overheads
                                                     26-28 MM kg of VC
                          1,1-Dichloroethane
                         (process  intermediate)
      Vinylidene
    Chloride  (VDC)
      79  MM kg
10 MM kg
Several
Companies
I
                PP
       Various
       Polymers
70 MM kg VDC
  £0-100 MM kg
      1.1.1-TGE
        Ethane
                                               "Small amount
                                                        as
lants       -by-product
 & B
150-170 MM kg
  of 1,1,1-TCE
                                                     Jlant C
                                                 1,1,2-TCE
                                                55-60 MM kg
                                                            DOfc
                                                       Vinylidene
                                                        Chloride
                                                       41-43 MM kg
                                  DOW &
                                 Others
                       1,1,1-TCE
                       268 MM kg
I
                                                                           Various
                                                                          Polymers
            Vulcan
            20-30 MM kg
            1,1,1-TCE
         *Union Carbide production of 1,1,2-TCE not shown.
        **A11 production values are ADL estimates except for the total production
          of 1,1,1-TCE which is from Ref 5.
                                              16
                                                                           Arthur D Little, Inc.

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     As  a result of  the limitations  involved in  the information supplied
by the other two manufacturers  (because of the proprietary nature of their
processes),  we have  been unable to document details of the processes in
which vinyl chloride is used as an intermediate.

     Some more generlized information and estimates are possible, however,
and  these are given  below.

     b.   Production  Processes

     The major process  used in  the production of 1,1,1-TCE involves first
a reaction between vinyl chloride and hydrogen chloride to produce 1,1-
dichloroethane followed by chlorination of the 1,1,-dichloroethane to
produce  1,1,1-Trichloroethane (1,1,1-TCE) and small amounts  of 1,1,2-Tri-
chloroethane (1,1,2-TCE).  These reactions are written as follows:
    CH2=CHC1    +    HC1 	^CHC12CH3                              (1)

 vinyl  chloride                1,1-dichloroethane
     CHC12CH3        +  C12 —	»> CC13CH3     (or  CHC12CH2C1) +  HC1    (2)

 1,1,-dichloroethane               1,1,1-TCE         1,1,2-TCE
 The overall reaction is essentially balanced:
 CH2=CHC1       +    C12	». CC13CH3     (or CHC12CH2C1)            (3)
      While manufacturers did  not supply process details,  it is likely  that
 the process involves steps  similar to thos  described in U.  S.  Patent Num-
 ber 3,059,035  assigned to Pittsburgh Plate  Glass Company  (October 16,  1962)
 The process is described as follows:
                                     3,059,035
                         CONTINUOUS PROCESS FOR PRODUCING
                               METHYL CHLOROFORM
                      Floyd E. BCIIIKT, Jr., Wadsworth, nod Douglas H. Elscn-
                        luhr and Donald A. Kcicli, Barbcrton, Ohio, assignors,
                        by mc.snc assignments, to Pittsburgh Plate Glass Com-
                        pany
                             Filed Dec. 8, 1960, Scr. No. 74,505
                                6 Claims.  (Cl. 260—658)
                        I. A method of  producing melhyl chloroform com-
                      prising introducing elemental chlorine and a vapor stream
                      containing l,l-dichloroeth;me into a first chlorination
                      zone, thoroughly mixing and reacting the elemental chlo-
                                       17
                                                                       Arthur D Little, Inc

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                      fine mill 1,1-ilicliloroi-lhaiic vapors in (lie chlorinalion
                      /.one In form IK'I :HU| methyl chloroform al a temperature
                      of between -)2()" I', anil 7(10" !•., inlrodiidns tlio gaseou*
                      reaelanls conlaininn I Id from the first chlorinalion zone
                      to a second ehlormalion /.one operating :il a temperature
                      at leasl 50° !•'. higher Iliim .said first chlorinalion /.one and
                      up to 900° !•'.. removing Hie gaseous material from (Mo
                      second elilorinalion /.one, introducing said material lo a
                      hydrochloi inalion /one operating al a temperature of .10*
                      F. to 120°  !•'., introducing vinyl eliloiide  to said hydro-
                      chlorinalion /.one in an amount siillicient lo react with
                      the HCI pn-scnt to thereby provide a 1,1-dichloroclhane-
                      melhyl chloroform liquid mixture, removing at least a
                      portion  of  the methyl  chloroform-1,1-dichlorocthane
                      liquid mixture, simultaneously neutralising and sleam dis-
                      tilling said mixlure to provide a methyl chloroform-dichlo-
                      rocthane product, drying said liquid mixture and subject-
                      ing it to fractional distillation to provide a  methyl chloro-
                      form bottoms and a 1,1-dichloroethane overhead, feeding
                      the l,l:dichloroclhane  overhead to the first chlorinalion
                      zone, and  recovering methyl chloroform from  said
                      bottoms.


             SOURCE:   Official Gazette of  the U. S. Patent  Office.
                       Vol. 783, October, 1972



      A ferric chloride catalyst is used in this  patented  process.   The
relative yields of  1,1,1-TCE and  1,1,2-TCE from the processes used by
U.  S.  industry is not known exactly,  but  the  balance is heavily  in favor
of  1,1,1-TCE.


      c.  Amounts of Vinyl Chloride Consumed and  1,1,1-TCE Produced


      In order to assess the size  of  the potential problem, i.e.,  vinyl
chloride emissions  from the production of  1,1,1-TCE,  it is useful to esti-

mate  the amounts of reactants (vinyl  chloride) and  products (1,1,1-TCE  and
1,1,2-TCE)  involved.


      Total  U. S. production of methyl  chloroform (1,1,1-TCE) in  1974 was
about 268 MM kg (591 MM Ibs)  (Ref. 5), up  from 166  MM kg  (366 MM Ibs) in
1970  (Ref.  1).  The portion of this  amount that  is  derived from  vinyl chlo-
ride  is not known.   If however, the  proportion is taken from the capacities
in  Table 5,  it can  be simply calculated that  about  62.5%  is produced from
vinyl chloride; this is equivalent to  168  MM kg  (369  MM Ibs) of  methyl  chlo-
form  production.  Assuming  no substantial  losses  in the manufacturing pro-
cess,  this  would require the consumption of 78.5  MM kg (173 MM Ibs) of  vinyl
chloride.


      The amount of  1,1,2-Trichloroethane  (1,1,2-TCE)  produced as a by-product
in  this process is  not known.   For the purposes  of  this report it is assumed
(see  subsection b above) that the process  yields  substantially all 1,1,1-
TCE.   The relatively small  amount of  by-product  1,1,2-TCE formed may In-
crease the  amount of vinyl  chloride  consumed  in  this  process to  around
80  MM kg (175 MM Ibs) at 1974 production rates.    This is  about 3% of the
amount of vinyl chloride produced in  the U.  S. last year, which  has been
reported as 2538 MM kg (5,596 MM  Ibs)  (Ref.  5).
                                         18
                                                                          Arthur D Little, Inc

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     d.  Estimates of Vinyl Chloride Emissions

     While there may be a process vent from the hydrochlorinator unit in
the 1,1,1-TCE production process; we  have been told by one company in-
volved that their process contains no continuous process vents which con-
tain vinyl chloride.  Fugitive emissions from pumps and seals thus may be
the major source of vinyl chloride emissions from this process.

     Actual emissions data were not available from manufacturers.  Thus,
we are not able to report here on actual vinyl chloride emissions from the
manufacture of 1,1,1-TCE.  Even a rough estimate is difficult to obtain
when fugitive emissions are involved.  A careful mass-balance and/or atmos-
pheric sampling must be carried out.  In this process it is likely that
fugitive emissions are no greater than 1% (of the vinyl chloride consumed)
and are more likely closer to 0.1%.  Since the amount of vinyl chloride
consumed in this process is about 80 MM kg/yr, the fugitive emissions are
estimated to be on the order of 0.01 to 0.1 MM kg/yr.

     2.  The Production of 1,1,2-Trichloroethane (Plant C)

     In one vinyl chloride monomer plant, located in Plaquemine, Louisiana,
1,1,2-Trichloroethance (1,1,2-TCE) is made via chlorination of vinyl chlo-
ride purification column overheads (see Figure 1).  It is estimated by ADL
that 55-60 MM kg (120-130 MM Ibs) of 1,1,2-TCE was produced at this plant
in 1974.  The company plans to expand the capacity of this plant during
1975.

     ADL did not obtain any details about this process.  Since the vinyl
chloride purification column overheads contains some vinyl chloride (as
well as some ethylene dichloride and perhaps other chemicals) the chlorina-
tion reaction may be similar to that given for the production of 1,1,1-TCE
in section 1 above.  If the reaction was only with vinyl chloride (to pro-
duce the 1,1,2-TCE), about 26-28 MM kg (57-62 MM Ibs) of vinyl chloride
would be consumed on an annual basis.

     Vinyl chloride losses from this process were said by the company to
be 0.5 kg per 1000 kg of 1,1,2-TCE produced.  Thus annual emissions at
this plant were about 0.03 MM kg in 1974.  No details about the use, if
any, of emission controls at this plant were available.

     3.  The Production of Other Chemicals from Vinyl Chloride

     a.  Introduction

     Two other industrial processes were identified in which vinyl chloride
is used as an intermediate for chemical manufacture; in both cases the  chem-
icals being manufactured are pesticides.  Total vinyl chloride consumption
is estimated to be  2.0 MM kg  (4.3 MM Ibs) annually; this is only 2% of  the
amount estimated to be used for the production of 1,1,1-TCE and 1,1,2-TCE.
                                    19
                                                                 Arthur D Little, Inc

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     It cannot be said for certain that there are no other industrial pro-
cesses in the U. S. where vinyl chloride is used as a chemical intermediate.
Indeed, there is a suspicion that there may be others, probably involving
production on a small scale.

     Details about the process and emissions from the two sources that were
identified are given below.

     b.  Pesticide Manufacture;  Plant D, Kansas City, Missouri

     This plant uses vinyl chloride as a raw material in a process which
produces an intermediate for use in the manufacture of an insecticide. The
specifics of the chemical process are considered proprietary and were not
supplied to ADL.  The company did, however, respond to detailed questions
about the process in general, the location and extent of vinyl chloride
emissions and the emissions control procedures used.  The information given
below is taken for the information supplied to ADL in June, 1975.

     Plant Location;  Kansas City, Missouri

     Vinyl Chloride Consumption;  4,037.kg (8,900 Ibs)/calendar day
                                  1.30 MM kg (2.87 MM Ibs)/year

     Process Description:  Vinyl chloride is received into storage (see
     Figure 2) and is charged to the reactor under its vapor pressure plus
     nitrogen blanketing.  Cooling is provided to maintain a negative pres-
     sure initially and 1/2 psig. at the completion of the reaction.  The
     intermediate contains 0.5 to 2.0% residual vinyl chloride.  After
     reaction of the intermediate to form the product, the crude product
     and the reaction water are sparged with nitrogen to 100 ppm vinyl
     chloride in the product and less than 0.1 ppm vinyl chloride in the
     water.  Intermediate process off gases, and the product sparge gases,
     are incinerated in a Thermal Oxidizer at 1200°F.  The combustion pro-
     ducts are discharged from a 265 foot stack.

         The product is vacuum dried and stream stripped to less than 1 ppm
     vinyl chloride in the space over the product; the liquid concentration
     is non-detectable.  The dryer off  gas is discharged to the Thermal
     Oxidizer with the general plant ventilation air  (point B in Figure 2)
     or, as a stand-by procedure, to the atmosphere.

         The process wastewater is further sparged with nitrogen at its
     boiling point and the off gases are discharged at point B.  The con-
     centration  in the liquid  is non-detectable; the  concentration over a
     closed sample 1 to 10 ppm.
                                    20                           Arthur D Little, Inc

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FIGURE 2
PROCESS FLOW SHEET FOR USE OF VINYL CHLORIDE IN PESTICIDE PRODUCTION AT PLANT D
21 Arthur D Little, 1

_
•
Ve
• „ i
, 	 -v» 	 J— 	 , — fc-1 	 , 	 » a, • (•
i"
H .
\l SPACE -
X VENTILATION
fl SCRUBBER — —

J
ffffffffftf.fi. S. . . i., ^—^- •' . f- 	 *
xg ~mj —
)^~J
r~^z.r>'

JO) )\ 	 1
!.«•«»« --> 	 ^CKI 	 S 	 — 	 1 	 i 	 J 	 1 - HC.ALHUN

1
11 A
S\ fS r-L-l ,1 !!> 1 ' ^
^2; V^; Q ^T & r
jO:Ooo v\i_ HOSE VCM V/CM VCM STCRACE ^ —
•y, rA>:.< f.VAC PUMP VAPOR 30.000 GAL. \J 	
'.-•vl.-.= 'r -OO roMo TOMO I'io p«.ir, pf v^M

SODIUM 1
™ HYF'OCHLORITt
i r-L_5_£j>-™^_..
^ M :
j
fTMl
i l^-U ,
xy
- I

/A VE55LL
*-•* 100 Pi IDE SIGN
v ^
73 J. J.f^-- v
• ««. -. I 1 "
.„. MK»I-T«>» | C.T. 0«. ! .».
"**-" PLANT D
OAK * """ •«• W
puotrris "1-7-73 TIT..' •••
BCFORE °*j.j.ft. SIMPLIFIED FLOW SHEET
-3Mtrw'u <="-(zeiC ENVIRONMENTAL CONTROL
«r^.
"»• OW5. MO.
If i y ~} i "? r~\
v....- -SK-/I3 p

-------
     Composition  of  Emission  Streams:   (See  Figure  2)

     Point  A:   Process  Stream to  Thermal Oxidizer

                 0-  40  CFM nitrogen
               200-400  Ibs./day vinyl  chloride

     Point  B:   Ventilation Air to Thermal  Oxidizer
               (Stand-by:   to atmosphere)

               300 CFM  air
                 3 Ibs./day vinyl chloride

     Point  C:   Wastewater  to  Sewer

               125,000  Ibs/day water
               less  than 0.01 Ibs./day vinyl chloride

     Point  D:   Intermediate Building Ventilation

               5,500 CFM air
               less  than 0.5  ppm vinyl chloride


         Assuming that  the Thermal Oxidizer  is  100% efficient in the des-
     truction  of  vinyl  chloride  (in  streams  from points  A and B),  then the
     only continuous emissions of vinyl chloride to the  atmosphere are from
     points B  and C. The  data supplied by the  company indicate that these
     emissions may be less than  0.14 kg (0.3 Ibs) per  day.

         In addition to the use  of the Thermal  Oxidizer  to eliminate emis-
     sions  of  vinyl  chloride  from process  vents, the company cites tight
     design and construction  standards, and close control and supervision
     of all vinyl chloride operations  as a key  to  their  control of vinyl
     chloride.

         Additionally,  the company uses a  number of analytical devices,
     including personnel monitors, to  keep informed of ambient vinyl chlo-
     ride concentrations.

     c.  The Manufacture of Endrin;  Plant E, Memphis, Tennessee

     Endrin is a broad  spectrum insecticide for a wide variety of field
crops, fruit,  and vegetables.  It is chlorinated insecticide that falls
into the same class  as  Aldrin, Chlordan,  Dieldrin,  Heptachlor, and Toxa-
phene.  Total U.  S.  production of these chemicals  in 1972 amounted to
64.35 MM kg (141.9 MM Ibs); individual production  figures for these pesti-
cides are not published.  The particular plant  involved  here, Plant E, is
the only manufacturer of Endrin in the U.  S.

     Very likely, the chemical reactions involved  are similar to those
described in a patent issured to Shell  Development  Company (U. S. Patent
No. 2,676,132; April 20, 1954).   The reaction is given as:
                                    22                           Arthur D Little, Inc

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Cl
ei
ci
ci
               CH2=CHC1
               Vinyl
                 Chloride
Hexachlorocyclo-
  pentadiene
           Cl
                                                                         (4)
           Endrin

      The amount of vinyl chloride used at this plant is about 0.67 MM kg
  (1.5 MM Ibs) per year.

      The manufacturer has told ADL that their reaction involving vinyl
  chloride has a very high yield and thus they do not expect much loss of
  vinyl chloride as a result of unreacted material.  The company has not
  done any stack sampling for vinyl chloride but has prepared a material
  balance for the process which is given, along with a diagram of the pro-
  cess, in Figure 3.  From this material balance, vinyl chloride emissions
  would be a maximum of 7440 kg (16,400 Ibs) per year.  The company is
  reasonably certain that by-products from the reaction consume vinyl chlo-
  ride, thereby reducing the potential emission losses below the above men-
  tioned maximum.

      The emission controls used at this plant consist of vent condensers.
  In addition, the company monitors all possible exposure points.
                                      23
                                                                   Arthur D Little, Inc

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@
             1
 T»MK
cr
Q_
                                               m«TEK\«ts—•1
                           r
                 r*- -;

                     TKMK
__.B-J^Ntzid
          *W*f aocOAYJL*
          °*r  *~rx~~~
                                 '1
                                   I
                                         JJ,
                                         wa*H
                                         T«tffc
                                                           7-£>
                                            Rl
                                           "pisessifc-eD)

                                            £^>
                                      *v\rrwnj«-
                                      l\>ml>
                                                  FIGURE 3
                                                    A MT   e.

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V.   USE OF VINYL CHLORIDE AS A MINOR CONSTITUENT IN COPOLYMERS AND TER-
     POLYMERS

     1.  Introduction

     Vinyl chloride can be polymerized with a large number of other mono-
mers.  In practice, however, commercial production of vinyl chloride co-
polymers and terpolymers is limited to a relatively small number of co-
monomers (see Table 6) with one comonomer, vinyl acetate, accounting for
the vast majority of vinyl chloride copolymer production.  The production
of vinyl chloride copolymers is estimated by ADL to account for about 15%
of the total PVC resin output in the United States, and an estimated 95%
of this copolymer production is comprised of vinyl chloride-vinyl acetate
copolymers with an average vinyl acetate content of 11-12%.

     The full list of monomers thought to be used in the commercial pro-
duction of copolymers or terpolymers with vinyl chloride is given in
Table 6.  Ranges and typical values are listed when known.

     The term "PVC resin" is used by industry to describe the family of
synthetic polymers in which the vinyl chloride monomer content is over
50% by weight*.  Vinyl chloride emissions from the manufacturing, com-
pounding and fabrication of PVC resins have been the subject of previous
investigations by the EPA (Refs. 6 and 7).  The scope of this task in-
cluded an investigation of only those copolymers and terpolymers in which
the vinyl chloride monomer content was less that 50% by weight.

     As Table 6 implies, there is only one comonomer, vinylidene chloride,
with which a substantial amount of vinyl  chloride copolymer is produced in
which the vinyl chloride monomer content  is less than 50% by weight.  This
investigation found only two manufacturers making resins with minor amounts
of vinyl chloride in which vinylidene chloride was not a comonomer; the
total use of vinyl chloride by these two manufacturers is relatively small.
Additional information on these two groups of resins that contain minor
amounts of vinyl chloride (i.e., those with, and those without vinylidene
chloride) is given in subsections 2 and 3 below.

     2.  Vinyl Chloride - Vinylidene Chloride Copolymers

     The investigation of possible emissions connected with the production
and fabrication of vinyl chloride-vinylidene chloride copolymers containing
minor amounts of vinyl chloride is covered under a separate ADL report.
Consequently, only a  summary of the vinyl chloride emissions will be given
here; additional details on the products, processes, emissions, and emis-
sion controls are presented in a separate report  (REf. 4).
 *For the  purpose  of  regulating vinyl  chloride  emissions  from polymer manu-
  facturing,  the EPA  expects  to define "PVC resin" as any resin  containing
  vinyl  chloride,  not matter how  small the amount involved may be.
                                    25
                                                                 Arthur D Little, Inc

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                                      TABLE 6
                    COMONOMERS USED IN THE COMMERCIAL PRODUCTION
                     OF VINYL CHLORIDE COPOLYMERS IN THE U. S.
                                               % of Comonomer in Resin
Comonomer
Vinyl acetate
Vinylidene chloride
Acrylonitrile
Propylene
Ethylene
              4
Ethyl acrylate
              4
Octyl acrylate
                4
n-Butyl acrylate
2-Ethylhexyl acrylate
Di-2-Ethylhexyl fumarate
Typical Value(a)
       12
    401, 852
       403
        5
        5
Normal Range
    3-20
    4-90

    1- 8
    1- 8
1.  This .refers  to the content of yinylidene chloride in a  typical lacquer  resin.
2.  This refers  to the vinylidene chloride in a  typical Saran  (e.g.,  Saran  Wrap,
    made by Dow  Chemical); other sarans may contain less vinylidene  chloride.
3.  This refers  to the content of acrylonitrile  in Dynel, the  modacrylic fiber
    manufactured by  Union Carbide.   This  is the  only known  use of a  vinyl chloride-
    aery lonitrile copolymer.  Union Carbide expects to stop production of Dynel
    in the near  future.
4.  In cases  where the comonomer content  is not  listed, it  can be assumed to be
    <  50%  by  weight.
                                          26
                                                                       Arthur D Little, Inc

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     a.  Plant F;  Midland, Michigan

     This company produces four vinyl chloride-vinylidene chloride co-
polymers; both emulsion and suspension polymerization processes are in-
volved.  The vinyl chloride monomer content is thought to range from 15 to
35%; Saran Wrap probably contains about 15% vinyl chloride while films
used in applications were greater heat shrinkage is desired probably con-
tain up to 30 to 45% vinyl chloride.

     The four resins are actually produced at four different plant in Mid-
land.  The company has reported to ADL that extensive efforts are underway
to reduce emissions from their plants.  Emissions data supplied to ADL in
March, 1975, listed the following vinyl chloride emissions:


                                   Total Vinyl             Residual Vinyl
Product                        Chloride Emissions      Chloride in Product
                               (kg/day)  (Ibs/day)            (ppm)
Saran Suspension Resins           54.        119                 <2

Saran Emulsion Resins            131.        288               4-10

Saran F  - resins                  2.          5 •                <2

Saran Latex                      10.         22                 <2
                    TOTAL         197.        434
     b.  Plant G;  Louisville, Kentucky

     This company produces two classes of resins (both terpolymers in-
volving vinylidene chloride, vinyl chloride, and a third monomer) one of
which  contains about 50% vinyl chloride and 25% vinylidene chloride and
is thus on the borderline of being called PVC resin; production of this
class  of resins is of the order of several hundred thousand pounds per
year.  The other class of resins contains about 75% vinylidene chloride,
with the remaining 25% comprising vinyl chloride and a third monomer.
Production of this class of resins is much less than the first class, on
the order of one hundred thousand pounds per year.

     Data on emissions of vinyl chloride from Plant G in Louisville, Ken-
tucky  have not been supplied to ADL at this time.  A crude estimate may
be made of the order of magnitude of these emissions by assuming (1) the
use of vinyl chloride is on the order of half a million pounds/year, and
(2) the emission rate from the polymerization process is in the range of
2 to 5 Ibs of vinyl chloride per 100 pounds of vinyl chloride used.*
The toal loss of vinyl chloride is thus estimated to be in the range of
4,500  to 11,000 kg (10,000-25,000 Ibs) per year.

*This  assumption is based on  the quoted losses in the PVC industry for
 polymerization of polyvinyl  chloride homopolymer.  Data given in Ref. 6
 shows loss rates from various vinyl chloride polymerization processes
 to range from  .018 to  .06 Ibs/lb of product.
                                    27
                                                                 Arthur D Little, Inc

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     3.  Other Vinyl Chloride Copolymers and Terpolymers

     Only two manufacturers were identified by this study who produced
resins with minor amounts of vinyl chloride in which vinylidene chloride
was not a comonomer; the total use of vinyl chloride by these two manu-
facturers is thought to be small.

     a.  Plant H;  Calvert City, Kentucky

     This plant produces a resin of the nature described above.  Process
deatils are proprietary.

     Total vinyl chloride emission from this plant have been calculated
based on an analysis of the vent emissions.. Data received by ADL in May,
1975, indicate total vinyl chloride emissions are just under 39,000 kg
(86,000 Ibs) per year.

     b.  Plant I;  Torrance, California; Plant J;  Tucker, Georgia;
         Plant K;  Somerset, New Jersey

     These planteaproduce resins with minor amounts of vinyl chloride.  All
are owned"by one company.  Previous to this investigation, the company sub-
mitted detailed information on the products, processes and vinyl chloride
emission involved to the EPA.

     Only three resins are produced by this company that contain vinyl chlo-
ride; in all cases the vinyl chloride is a minor constituent.  The latexes  .
produced are interpolymers which find uses in such products as paints and
adhesives.  The other monomers involved may include vinyl acetate and/or
acrylic esters.  Production for these three resins totals about 6.8 MM kg
(15 MM Ibs) per year.

     Total vinyl chloride emissions from 7 points  (including the unloading
of vinyl chloride from  tank cars) was given in July, 1974, as 0.017 kg/
100 kg of latex  (wet weight) produced.  Thus, total annual vinyl chloride
emissions are about 1,100 kg (2,500 Ibs)*.  A materials balance of their
use of vinyl chloride monomer  (VCM) indicates an over-all VCM efficiency
of 94%.  A  typical balance in  indicated below.
*This assumes that the production figures given above are also on a wet
 weight basis.
                                    28                           Arthur DLittleJnc

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                                                POUNDS
       Vinyl chloride monomer (VCM)              100

     OUTPUT

       Product (as PVC)           "               94.

       Product (VCM)                                0.30

       Heel returned  in truck (VCM)           ;     1.50

       Fugitive (VCM)                              4.10

       Waste (VCM and PVC)                          Q.05
                     TOTAL ACCOUNTED              99.95


     The average (weighted) VCM content in their resin products is said
to be 400 ppm.

     No vinyl chloride emission control devices are currently in service.
The company does, plant, however, to install incineration facilities during
the next 18 months at a rough cost estimate of $30,000-$50,000 per location.
                                    29
                                                                 Arthur D Little, Inc

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VI.  PROCESSES PRODUCING VINYL CHLORIDE AS A BY-PRODUCT

     1.  Introduction

     One part of this investigation involved a search for industrial pro-
cesses in which vinyl chloride was produced as a by-product.  Our search
involved a review of several secondary literature sources, a computer
search of the recent literature, discussion with knowledgeable ADL staff
members, discussions with industry representatives, and discussions with
representatives of several state and federal agencies interested in the
vinyl chloride problenu  (Details on most of these items are described in
Sections II and III of this report.)

     Because of the limitations of the approach and the time available, it
is possible that some industrial processes involving by-product vinyl chlo-
ride emissions were not identified.  This possibility is based on the fact
that reactions of two-carbon molecules (i.e., ones based on ethane, ethylene,
or acetylene) with, or containing, chlorine are common in the chemical in-
dustry; none of these chemical reactions ever gives a 100% yield of the
desired product(s).  Usually some amounts of unreacted initial chemicals,
as well as unwanted by-products of the reaction, are present.  Reaction
yields in cases of interest here will almost always be above 90% and more
usually above 95%, but this still leaves 5 - 10% of the material unaccounted
for, consisting of unreacted reactants and by-products.

      The number of ways in which vinyl chloride could be produced as a by-
product is probably fairly small, involving various types of addition, sub-
traction, or elimination reactions.  Because process paramenters such as
temperature, pressure, and catalyst use are so .important in determining
process yields, it is very difficult to predict"that a given type of reac-
tion will, or will not produce vinyl chloride as a by-product.

      The investigations carried out in this program led to the identifica-
tion of only three industrial processes currently used in the U. S. where
vinyl chloride is known to be a by-product.  They are:

      1.  The manufacture of ethylene dichloride via oxychlorination;
      2.  The manufacture of ethylene amines from ethylene dichloride; and,
      3.  The manufacture of ethylene imine from ethylene dichloride.

      In addition, two other industrial processes, not currently used in
the U. S., are known to involve the production of vinyl chloride as a by-
product.  They are:

      1.  The manufacture of ethylene glycol from ethylene dichloride; and,
      2.  The manufacture of chloroprene from acetylene.

      Additional details on the plants, processes, and emissions connected
with the first group mentioned above are given  in subsections 2 and 3 below.
Only brief background information  is given on the second group mentioned.
                                    30                           Arthur D Little, Inc

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     Subsection 4 below describes the results of our investigation into
another reaction, the production of perchlorethylene from chlorine and
acetylene, that seemed to hold the possibility of some by-product vinyl
chloride formation.  In this case, it is likely that no by-product vinyl
chloride is formed because of certain aspects of the process.

     2.  By-Product Vinyl Chloride from Industrial Processes Currently
         Used in the U. S.

     a.  Ethylene dichloride (EDC) via oxychlorination

     Ethylene dichloride is a major chemical in the U. S. chemical industry;
over 4 billion kg (9 billion Ibs) were produced in the U. S. in 1973.  One
of the major uses is an an intermediate for the production of vinyl chlo-
ride.  One EDC production process, called the oxychlorination process, pro-
duces a very small amount of by-product vinyl chloride.  While about 45%
of the EDC produced in the U. S. is made by this oxychlorination route
(by 11 companies) (Ref. 8) most of this production is in plants integrated
with the vinyl chloride production units.  These EDC-vinyl chloride inte-
grated plants are ourside the scope of this investigation as they are es-
sentially vinyl chloride monomer production facilities; as such, they have
been the subject of previous investigation (Ref. 6).  Two U. S. plants which
make EDC via the oxychlorination route are not integrated with vinyl chlo-
ride plants, but these plants were similarly excluded from our scope of work.

     b .  Ethylene amines from ethylene dichloride

     Ethylene amines are members of the series:
     The  first  5 members of the series are listed below.

     ii       Name                            Formula

     0       Ethylene  diamine                NH2CH2CH2NH

     1       Diethylene triamine             NH

     2       Triethylene tetramine           N

     3       Tetraethylene pentamine         N

     4       Pentaethylene hexamine          N
      End  uses  for  these chemicals include:  carbamate fungicides  (25%);  ex
 ports (25%); chelating agents  (13%); dimethylolethylene urea resins  (8%);
 aminoethyl  ethanolamine (8%);  and miscellaneous  (21%) (Ref. 9).
                                     31
                                                                  Arthur D Little; Inc

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     These chemicals are currently made at three plants in the U. S.  Ad-
ditional information is given in Table 7 below.
                                TABLE 7
                 ETHYLENE AMINE PRODUCTION IN THE U. S.
Plant Location
Freeport, Texas
.Taft, Louisiana
.Texas City, Texas
Capacity*
(MM kg/yr) (MM
13.6
16.3
10.9
TOTAL 40.8
Ibs/yr)
30
36
24
90
Plant Identity

  Plant L

  Plant M
  Plant N
  *Capacities are somewhat variable since the higher ethylene amines are
   made in the same units.

   SOURCE:  Ref. 9
     In addition to the above production plants, one other manufacturer
has an ethylene amines plant in Port Neches, Texas, with a capacity of
6.8 MM kg/yr (15 MM Ibs/yr) which is currently idle.  It is possible that
the plant may be reactivated in a few years.

     Actual U. S. production figures for all the ethylene amines are not
known, but the total was probably around 28 MM kg  (62 MM Ibs) in 1972 and
29 MM kg (64 MM Ibs) in 1973 according to the 'demand' figures given by
Chemical Profiles (Ref. 9).  Production of ethylene diamine, the lowest
member of the series, has been reported as 22 MM kg (48.6 MM Ibs) in 1972
(Ref. 10) and 24 MM kg (52.7 MM Ibs) in 1973 (Ref. 11).  There have been
reports that Plant M, in Taft, Louisiana, will be  expanded by 7.3 MM kg/yr
(16 MM Ibs/yr) by the end of 1975 (Ref. 12).

     The principal chemical reaction involved in the production of ethylene
diamine is:
 C1CH2CH2C1  +  2NH3  + 2NaOH  - >  NH^CH^  +  2NaCl  + 2H20

 Ethylene     Ammonia   Caustic       Ethylene
 Bichloride                           Diamine

     The ethylene diamine produced can then react further to produce  the
higher ethylene amines.
                                    32
                                                                 Arthur D Little, Inc

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  The  following  steps  are  involved  in  the production of ethylene amines.
Ethylene
  Bichloride
Ammonia
Caustic
                         Vent Stream
                        >With Vinyl
                         Chloride
EVAPORATION
   SYSTEM
REFINED
 AMINES
       Many details  of  this process  are proprietary.  Some additional  de-
  tails of  the  reaction system may,  however, be  close to  those  disclosed
  in a patent assigned  to  Olin Mathieson  Chemical  Corporation for  a  simi-
  lar process.  A diagram  of  the  Olin process  is shown  in Figure 4.  At re-
  latively  low  temperatures,  low  pressures  and high ammonia  concentrations
  the production  of  ethylene  diamine is apparently favored;  conversely, at
  higher pressures,  higher temperatures and lower  ammonia concentrations
  the production  of  higher members of the ethylene amines series is  favored.
  Additional details on the process  are given  in Ref. 6.

       The  ethylene  amines manufacturers  confirmed that vinyl chloride is
  produced  as a by-product in their  ethylene amines plants.  At Plant  L, the
  process vents for  the production of ethylene diamine  and ethylene  imine
  (see subsection C  below) are combined,  and losses to  the atmosphere  are
  said by the company to be less  than 0.01  kg  of vinyl  chloride per  100 kg
  of product.   Total annual emissions are thus estimated, by AOL., ' to be less
  than 1000 kg  (2,200 Ibs) .   Emission controls are used on this combined
  vent but  details were not available to  AOL.

       Emissions  data from the two other  plants  are given in Table 8.

       If no emissions  controls were used by these two  plants,  a total yearly
  vinyl chloride  emission  of  1.54 MM kg  (3.39  MM Ibs) would  result,  assuming
  365 days/yr of  operation.   Emissions controls  are, however currently in
  use at Plant  M  (Taft, Louisiana) and are  under construction at Plant N
  (Texas City,  Texas).   At the Taft, Louisiana,  plant vinyl  chloride is cur-
  rently being  burned in a flare  tower; an  incineration facility consisting
  of a thermal  combustion  chamber and a water  scrubber  will  reportedly be-
  come operational by August, 1975,  at an investment cost of $1.2  million.
  At the Texas  City, Texas, plant construction is  reportedly underway  for
  routing the vinyl  chloride  stream  to power-house boilers for  incineration,
  as an interim solution;  cost is estimated to be  $10,000.   Permanent  facil-
  ities for the Texas City plant  are being  designed  to  remove vinyl  chloride
  in a methyl  ethyl  ketone adsorber  at  the  Suspension Vinyls Unit, along with
  other vinyl  chloride vent streams  at  the  Texas City plant, cost  is estimated
  at $650,000.
                                      33
                                                                   Arthur D Little, Inc

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                                               FIGURE 4
                           ETHYLENE DIAMINE FROM  ETHYLENE  DICHLORIDE
      Reaction:
CH2CICH2C!  +  2NH3
H2NCH2CH2NH?  -i   211C I
Feed Materials:
      Ethylene Dichloride
      Ammonia
Coproducts:
      Vinyl Chloride
      Polyamines
      Hydrogen Chloride
               COOLER
                                                              SURGE
                                                              TANK
                                H20
                                NH3

                                No OH
                               (AQUEOUS)
                                                -FRACTIONATING TOWER
                                                    REBOILER
                                             2HCI
                                      +WATER
                                          OP
                                         WATER
                Catalyst:
                Phase:
                Reactor type:
                Solvent used:
                Temperature, "C:
                Pressure psi:
                Reaction time:
                Heat Required:
                Heat evolved:
                Product yield:
                Product purity:
                Materials of Construction:   Sleel
   Sodium Hydroxide
   Liquid
   Fractional ing Tower
   Walcr
   100-200
   15-300
   Yes
   65%
Major Product Uses:   Synthesi;. of surface ccHve and chelating agents; inhibitors; rubber accelerators; pesticides,  etc.
Reference:   U.S. Patent 2,805,25-1 b/ B.H. Nicolaisen (to Olin Mothieson Chemical Cop.) (Sept. 3, 1957)
       Source:  Organic Chemical  Process  Encyclopedia,  1969,  2    Edition,  by
                  Marshall  Sittig,  Noyes Development Corporation, Park  Ridge, N.J.,  1969
                                                    34
                                                                                         Arthur D Little; Inc.

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                                   TABLE 8
Pollutant



Vinyl chloride

Ammonia
Methane

Miscellaneous
  Organics
                POLLUTANT CONCENTRATIONS IN ETHYLENE AMINES

                         REACTION SYSTEM VENT:  1975
Plant
Wt %
60
20
20
M: Taft, LA
Amount
(kg/day) (Ibs/day)
2,555 5,632
851 1,877
851 . 1,876

Plant N:
Wt %
76*
23
1
Texas City.
TX
Amount
(kg/day)
1,656
501
10
(Ibs/day)
3,650
1,105
23
*Average flow rate for vinyl chloride at this plant is 31.2 SCFM

  SOURCE:   Private communication from the manufacturer, June,  1975.
       Because all three ethylene amines  plants  are  undergoing some form of
  revision,  it is  not  possible to estimate  accurately  current  or  future  vinyl
  chloride emissions.   Emissions  during 1974 were probably  of  the order  of
  1 MM kg (2 MM Ibs).   By 1976,  total  annual emissions from all three plants
  should be down around 3,000 kg  (7,000 Ibs) if  emission controls are com-
  pleted.                 :       .

       c.  Ethylene imine from ethylene dichloride

       Ethylene imine  is produced at only one  plant  (Plant  0)  In  the U.  S.
  It is located in Freeport,  Texas,  and has a  capacity of 1.4  MM  kg/yr (3 MM
  Ibs/yr) (Ref. 13).   Production  was stopped a few years ago for  an interim
  period after OSHA included  ethylene  imine on a list  of carcinogens for
  which the agency issued emergency  temporary  standards.  The  manufacture
  reportedly took  several measures to  reduce the exposure of workers to
  ethylene imine at that time (Ref.  11) and is now back in  production.

       The manufacturer confirmed that vinyl chloride  is a  by-product of
  their ethylene imine production and  said  that  vinyl  chloride losses to the
  atmosphere are less  than 0.01 kg/100 kg of product.   Total annual emissions
  are thus estimated by ADL to be less than 140  kg (300 Ibs).   As mentioned
  above, the process vents are combined with the process vents from the
  ethylene diamine unit; some form of  emission control is used.

       Some process details may be inferred from a patent issued  to Phillips
  Petroleum Company for this  reaction. Details  are given in Figure 5.
                                      35
                                                                   Arthur D Little Inc

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                                           FIGURE  5
                 ETHYLENE IMINE  (AZIRIDINE)  FROM ETHYLENE DICHLQRIDE
Reaction:
H
N
: / \
CICH2CH2CI -i- 3NH3 	 »- CH2-CH2 + 2NH4CI
OIHALOALKANE
.AMMONIA .X- —


( STORAGE ) (STORAGE) (| STORAGE j]
ill '
tJ-1 |COMPRESSOR|
1 AMMONIA ,
REAC'IOR p-~
	 ' s-*~^ J
TOLUENf~
S^ . i I
T ^
* l^- li.
nr T L___
         Feed Material*:
               Ethylene Dichloride
               Ammonio'
          Zoproducfs:
               Ammonium Chloride
Calcium Sulfate
Liquid
Jacketed Tank
Dimethylformamide
25-110

10 minutes to 2 hours
Catalyst:
Phase:
Reactor type:
Solvent used:
Temperature, °C:
Pressure psi:
Reaction time:
Heat Required:
Heat evolved:
Product yield:
Product purity:
Materials of Construction:   Stainless Slue I
                                                                           20-30% per Pass
         ,.->6Jor  Product Uses:   In the manufacture of textile treating agents.
         kuterence:   U.S. Patent 3,205,224 by J.S. Dix (to PhiIIips Petroleum Co.) (Sept. 7,  1965)

      SOURCE:  Organic  Chemical Process Encyclopedia, 1969,  2n   Edition, by
                Marshall Sittig, NOyes Development  Corporation,  Park  Ridge, N. J., 1969
                                                  36
                                                                                      Arthur D Little, Inc.

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     3.  By-Product Vinyl Chloride from Industrial Sources Not Currently
         Used in the U. S.

     a.  Ethylene glycol from ethylene dichloride

     Vinyl chloride is a by-product of the manufacture of ethylene glycol
from ethylene dichloride (EDC) acceding to a patent discolsure by the Shell
Development Company (U.:S. Patent No. 2,148,304; February 21, 1939).  This
route is not currently used by any U. S. manufacture of ethylene glycol.
The route involves a reaction of EDC with disodium phosphate (with proper
temperature and pressure control) as shown below.

C1CH2CH2C1   +   2Na2HPO,   +   2H20 	)  HOCH2CH2OH + 2NaH2P04 + 2NaCl

    EDC          Disodium                   Ethylene
                   Phosphate                  Glycol                  (g)
     b.  Chloroprene from acetylene

     In the U. S., chloroprene is made by DuPont (at plants in Kentucky,
Louisiana, and Texas) and Petro-Tex Chemical Corporation (Houston, Texas).
Petro-Tex has always made chloroprene from butadiene, a route that does not
involve any by-product vinyl chloride.  DuPont confirmed reports that all
of their U. S. chloroprene manufacturing plants now use the butadiene route
as well;they had been using the acetylene route up to about 1970 and pro-
bably completed the conversion by 1972.

     Vinyl chloride is cited as a by-product of the acetylene route in
Vinyl and Diene Monomers, Part 2 by E. C. Leonard (ed.) (Ref. 14).

     The acetylene route involved the following steps:

                    2CH=CH 	*  CH=C-CH"=CH

                    Acetylene            Vinyl Acetylene
                                            Cl
       CH=C-CH=CH2    +    HC1 catalys5  CH2=£-CH=CH2

       Vinyl Acetylene                   Chloroprene


     Additional process information is given in DuPont's patent disclosure
 (U. S. Patent No. 3,361,836; January  2, 1968).

     4.  Perchlorethylene from acetylene

     One industrial chemical reaction that was investigated was the pro-
 duction of perchloethylene  (CCl2=CCl2) from acetylene  (CH=CH) and  chlorine
 (0.2).  Only one  plant in the U. S.,  located in Taft,  Louisiana,  currently
 uses this process, Plant P.
                                     37                            Arthur D Little, Inc

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     The various steps in this process reportedly (Ref. 1) include the fol-
lowing reactions:

             CHECH  +  2C12  - - V   CHC12CHC12                      (9)

          Acetylene                   Tetrachloroethane
CHC12CHC12  gj--  r)   CCVCHC1  +  HC1
                         Trichloroethylene

                           CC13CHC12
                         Pen tachlo re thane
             CC12=CHC1  +  C12  - >   CC13CHC12                    (ID
           Ca(OH)
                  T>
                     Perchlorethylene
             CC13CHC12  - -^T>   CC12=CC12  +  HC1
     Some other process details may be inferred from a patent issued to
Solvay and Cie for a similar process.  Details are given in Figure 5.

     While there was no published information indicating that vinyl chlo-
ride was a by-product in this process, there seemed to be a possibility
if HC1 (a by-product in reactions 10 and 12 above) reacted with any resi-
dual acetylene.  The reaction of acetylene with hydrogen chloride (HC1)
is one process used in the U. S. today for the commercial production of
vinyl chloride.

     The perchlorination process used at the Taft, Louisiana, plant for
the production of perchlorethylene is operated in the presence of free
chlorine according to the manufacturer.  This free chlorine would react
with any traces of vinyl chloride if any of this material was somehow
formed as a by-product.  Thermal chlorination of vinyl chloride, in the
absence of any solvent or light, is effected at 100-250°C with yields of
90-95%of 1,1,2-Trichloroethane; higher yields can be obtained at lower
temperatures if a proper catalyst is used (Ref. 2).

     Thus, the probability of obtaining any emissions of by-product vinyl
chloride from this process would seem to be quite low.  No effort has been
made to look for vinyl chloride in the emissions from this process; such
sampling would be wise in order to settle the matter more firmly.
                                    38                           Arthur D Little, Inc

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                                                                               FIGURE  6
                                                       TETRACHLOROETHYLENE FROM ACETYLENE  AND CHLORINE
               Reaction:
                                       3CI
                                                                      2HCI
                             C'z
  u>
  VO
>
"^
r*
IT
J
_J
]
Fj
p


V-
^


ihnn'nnh
S:;:*::^v/£i;*:.S
i'fte
Mil


K
^ila • n,tr
yi&F
y:
ji

v :
/;.''':iv:-;;.:'^;.
.'.•! -• • -:. •.'-•j''"-'i'
'.VrS->:'W^''Air
T
11
i'.
3r
r=l
r
                                                                                               Feed  Materials:
                                                                                                      Acetylene
                                                                                                      Chlorine
                        Coproducts:
                              Trichlorethyiene
                              Hexochloroefhane
                              Hydrogen Chloride
                                                                                                                 Cotx;!' CVoriae on Carbon
                                                                                                                 V-jpor
                                                                                                                 Moving-Bed
                                                                                                                 Nor- "
                                                                                                                 300-350
                                                                                                                 At mospher Ic
                         Catalyst:
                         Phase:
                         Reactor type:
                         Solvent used:
                         Temperature, "C"
                         Pressure psi:
                         Reaction time:
                         Heat Required:
                         Heat evolved:
                         Product yield:
                         Product purity:
                         Materials of Construction-

Major  Product Uses:    For dry cleaning, metal degreasing, as a solvent fcr re?:.-is "~ rjbbers, etc.
Reference:   U.S. Patent 3.025,332 by C. Deprez (to Solvay & Cie) (May 13,  I?52'-
                                                                                                                   es
                                                                                                                  75%
                                      SOURCE:   Organic Chemical Process Encyclopedia,  1969, 2    Edition, by
                                                 Marshall Sittig, Noyes  Development  Corporation,  Park Ridge,  N.  J.,  1969

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                             APPENDIX I
        U. S. INDUSTRIAL PLANTS WITH VINYL CHLORIDE EMISSIONS
          (Excluding Those That Manufacture Vinyl Chloride,
             Polyvinyl Chloride, and Ethylene Bichloride)
1.  Plants Using Vinyl Chloride as a Chemical Intermediate
    a.  For the production of 1,1,1- and 1,1,2-Trichloroethane
        (1)  Plant A:  Freeport, Texas
                                             2
        (2)  Plant B:  Baton Rouge, Louisiana
        (3)  Plant C:  Plaquemine, Louisiana
    b.  For the production of certain pesticides
        (1)  Plant D:  Kansas City, Missouri
        (2)  Plant E:  Memphis, Tennessee
2.  Plants Using Vinyl Chloride as a Minor Constituent in Copolymers
    and Terpolymers
    a.  For the production of resins containing vinylidene chloride
        (1)  Plant F:  Midland, Michigan
        (2)  Plant G:  Louisville, Kentucky
    b.  For the production of resins not containing vinylidene  chloride
        (1)  Plant H:  Calvert City, Kentucky
        (2)- Plant I:  Torrence, California
        (3)  Plant J:  Tucker, Georgia
        (4)  Plant K:  Sommerset, New Jersey
3.  Plants Producing Vinyl Chloride as  a By-Product
    a.  From the production of ethylene amines via ethylene  dichloride
        (1)  Plant L:  Freeport, Texas
        (2)  Plant M:  Taft, Louisiana
        (3)  Plant N:  Texas City, Texas
1.  This plant integrated with a vinyl chloride production plant.
2.  This listing is base on information given in the Chemical Economic
    Handbook (Ref. 1) only.
                                    40                           Arthur D Little, Inc.

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b.  From the production of  ethylene  imine via ethylene dtchloride




    (1)  Plant 0:  Freeport,  Texas
                                41                            Arthur D Little, Inc

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REFERENCES
 1.  Chemical Economics Handbook,  Stanford Research Institute,  Menlo Park,
     California.

 2.  "Vinyl and Vinylidene Chloride,"  L.  G.  Shelton,  D.  E.  Hamilton, and
     R. H. Fisackerly, in Vinyl and Diene  Monomers, Part  3,  E.  C.  Leonard,
     Ed., Wiley Interscience,  New York, 1971.
 3.  Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,  1967.
 4.  "Vinylidene Chloride Monomer Emissions From The Monomer,  Polymer, and
     Polymer Producing Industries";  Draft Report to the  U.  S.  Environ-
     mental Protection Agency, Research Triangle Park, North Carolina,
     by Arthur D. Little, Inc. (Cambridge, Massachusetts), September, 1975
     (Contract No. 68-02-1332, Task 13).
 5.  "Preliminary Report on U. S.  Production of Selected  Synthetic Organic
     Chemicals-Preliminary Totals-1974," S* 0. C. Monthly Statistics:
     Series C/P-75-1, U. S. International  Trade Commission,  Washington,
     D. C., May 16, 1975.
 6.  Draft Document - "Standard Support-Environmental Impact Document; An
     Investigation of the Health Effects and Emission Reduction of Vinyl
     Chloride in the Vinyl Chloride Monomer and Polyvinyl Chloride In-
     dustries," U. S. Environmental Protection Agency, Office of Air
     Quality Planning and Standards, Emissions Standards  and Engineering
     Division, Research Triangle Park, North Carolina, March,  1975.

 7.  "Vinyl Chloride Monomer Emissions from the Polyvinyl Chloride Pro-
     cessing Industries," report to U. S.  Environmental Protection Agency,
     Research Triangle Park, North Carolina, prepared by Arthur D. Little,
     Inc., under Contract No. 68-02-1332  (Task 10); draft report submitted
     May, 1975.
 8.  "Engineering and Cost Study of Air Pollution Control for the Petro-
     chemical Industry, Volume 3:  Ethylene Dichloride Manufacture by
     Oxychlorination," U. S. Environmental Protection Agency,  Report No.
     EPA-450/3-73-006-C, November, 1974.
 9.  Chemical Profiles, Schnell Publishing Company, Inc., July, 1973.

10.  Synthetic Organic Chemicals-U. S. Production and Sales, 1972, U. S.
     Tarrif Commission, T. C. Publication 681, Washington, D. C., 1974.

11.  "U.  S. Production and Sales of Miscellaneous Chemicals-1973," U. S.
     Tarrif Commission, Washington, D. C., January, 1975.
12.  Chemical Marketing Reporter, August  12, 1974  (page 3); and Chemical
     Age, July 12, 1974  (page 11).

13.  Chemical Week, June 20,  1973  (page 9).

14.  "Chloroprene," by P. S.  Bachwitz, J. B. Finlay and C. A. Stewart, Jr.
     in  Vinyl and Diene Monomers, Part 2, E. C. Leonard, Ed., Wiley  Inter-
     science, New York, 1971.
                                                                  Arthur D Little Inc

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