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
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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
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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
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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.
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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.
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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.
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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
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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.
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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).
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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
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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
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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
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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. 260658)
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\«ts1
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).
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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.
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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.
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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
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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.
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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
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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.
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