PB-243 641
SURVEY OF INDUSTRIAL PROCESSING DATA
TASK I - HEXACHLOROBENZENE AND HEXACHLOROBUTADIENE
POLLUTION FROM CHLOROCARBON PROCESSING
MIDWEST RESEARCH INSTITUTE
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
JUNE 1975
DISTRIBUTED BY:
National Technical Information Service
U. S. DEPARTMENT OF COMMERCE
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PB 243 641
EPA - 560/3-75-003
SURVEY OF INDUSTRIAL PROCESSING DATA
Task I - Hexachlorobenzene and Hexachlorobutadiene
Pollution From Chlorocarbon Processes
JUNE 1975
FINAL REPORT
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
4TH AND M STREETS, S.W.
WASHINGTON, D.C. 20460
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BIBLIOGRAPHIC DATA 1. Report No. 2. F
SHEET EPA 560/3-75-003 ' 1-
4. Title and Subtitle
Survey of Industrial Processing Data
Task I - Hexachlorobenzene and Hexachlorobutadiene Pollution
from Chlorocarbon Processing
7. Author(s) Charles E. Mumma
Edward W. Lawless
9. Performing Organization Name and Address
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri ? 64110
12. Sponsoring Organization Name and Address
Environmental Protection Agency
Office of Toxic Substances
Washington, B.C. 2D460
lf5
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EPA - 560/3-75-003
SURVEY OF INDUSTRIAL PROCESSING DATA
Task I - Hexachlorobenzene.and Hexachlorobutadiene
Pollution From Chlorocarbon Processes
by
Charles E; Murama
Edward W. Lawless
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
EPA Contract No. 68-01-2105
EPA Project Officer: Mr. Thomas E. Kopp
For
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
4TH AND M STREETS, ,'S.W.
WASHINGTON, D.C. 20460
JUNE 1975
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PREFACE
This report presents the results of the Task I study of a proj-
ect entitled "Survey of Industrial Processing Data." Task I, "Hexachloro-
benzene and Hexachlorobutadiene Pollution From Chlorocarbon Processes," was
performed by Midwest Research Institute (MRI) under Contract No. 68-01-2105
for the Office of Toxic Substances of the U.S. Environmental Protection
Agency. The MRI Project No.'was 3822-C. '••*'•'
Task I was conducted during the periods 27 June to 15 November
1973 and 1 March to 7 October 1974 with final revisions made in April 1975.
This program was under the supervision of Dr. E. W. Lawless, Head, Tech-
nology Assessment Section. Mr. C. E. Mumma, Senior Chemical Engineer, served
as project leader. Other MRI personnel who contributed significantly to this
study included: Mr. G. Kelso, Assistant Chemical Engineer; Mr. G. Cooper,
Assistant Chemist; Mr. J. Edwards, Assistant Chemist; and Ms. Cassandra
Collins, Junior Chemist. Dr. A. F. Meiners, Principal Chemist and Dr. Harold
Orel, Consultant on Technical Writing, reviewed drafts of this report and
provided technical and editorial assistance.
This final report for Task I was prepared by Mr.
Dr. Lawless.
Mumma and
Task II of this study is on brominated biphenyl compounds; it is
the subject of a separate report.
Approved for:
MIDWEST RESEARCH I
H. MTHubbard, Director
Physical Sciences
10 July 1975
iii
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TABLE OF CONTENTS
Page
List of Figures • • . . . . . . . . • ...... . . . . vi
List of Tables. . . .' , ;. . . . - .• . . . . . . ...;.•.'., V ••• ix
I. Introduction . .. . . . .... 1
II. Summary 3
III. Conclusions and Recommendation . ....*.. 11
IV. Discussion of Methodology. 13
A. Selection of Toxic Substances. . ....*...... 13
B. Identification of Production Sites and Estimated
Production Volumes ................. 13
V. Production Sites and Volumes . 15
Vt. Manufacturing Methods, By-Products, Contamination and Risks. 28
A. Processes Known to Produce HCB and/or HCBD ....... 28
B. Processes with Theoretical, But Not Proven, Production
of HCB and/or HCBD ................. 59
C. Methodology and Results of a Study to Estimate Quanti-
ties of HCB and/or HCBD Generated by Chemical
Industry ....... 73
VII. Waste Disposal . . 85
A. Waste Disposal for Chemical Processes Known to Produce
HCB and/or HCBD. ........ ..... 85
B. Waste Disposal for Chemical Processes with Theoretical,
But Not Proven, Production of HCB and/or HCBD. ... 88
C. Waste Disposal Technology. .............. 91
D. The Potential for HCB and HCBD Contamination of Indus-
trial Wastes, By-Products and Products .. ..... 95
VIII. Uses for Chemical Products ...;....... 98
IX. Environmental and Health Aspects . . • ... ... . . ... 107
X. Selection of Monitoring Sites 120
Preceding page blank
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TABLE OF CONTENTS (Concluded)
Appendix A - Plant Capacities, Production and Import Data for
Selected Chemicals ........ . . 127
Appendix B - Results of a Written Inquiry to Chemical Manufacturers . 146
Appendix C - Procedure for Selecting Monitoring Sites . ... . • • . • • 155
'Literature References ...... ...... 168
Subject Index for the Chemicals Studied ............... 172
vi
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LIST OF FIGURES
Figure Title Page
1 Production Sites for Hexachlorobenzene and Hexachloro-
butadiene 17
2 Operating Chlorine and Alkali Plants in the United States
and Canada. .... 18
3 Production Sites for Sodium Chlorate and Carbon Tetra-
chloride. . . 20
4 Production Sites for Perchloroethylene and Trichloro-
ethylene 21
5 Production Sites for Pentachlorophenol, HexachlorOethane,
Pentachlorobenzene, and Vinyl Chloride Monomer. ...... 23
6 Production Sites for Pentachloronitrobenzene, Dacthal,
Mirex, Atrazine, Propazine, Maleic Hydrazide and Synthetic
Rubber (Chloroprene) 24
7 Production Sites for Hexachlbrocyclopentadiene, Chlorinated
Biphenyls and Chlorinated Naphthalenes. ......... 26
8 Production Schematic for Hexachlorobenzene from Hexa-
chlorocyclohexane ........... 30
9 Production Schematic for Hexachlorobenzene by Chlorination
of Benzene and Chlorobenzenes ..... 31
10 Production Schematic for Chlorine in Diaphragm Cells. ... 34
11 Production Schematic for Chlorine in Mercury Cells. .... 36
12 Production Schematic for Carbon Tetrachloride by Reaction
of Carbon Disulfide with Chlorine ... . . . . ... . • 39
13 Production Schematic for Perchloroethylene frbm Methane,
Ethane, or Propane. • ............. 42
14 Production Schematic for Perchloroethylene from Acetylene . 44
15 Production Schematic for Trichloroethylene from Acetylene
Using Catalytic Dehydrochloririation ........... 47
16 Production Schematic for Trichloroethylene from Acetylene
Usin'g Milk of Lime. ................:... 49
vii
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LIST OF FIGURES (Coricluded)
.Figure Title
17 Flow Diagram for Dimethyl Tetrachloroterephthalate
Manufacture ..•-. .51
18 Production Schematic for Atrazine . .! . '. \ 53
19 Synthesis of Triazine Pesticides ; ....... 54
...-.; V. - . •
20 Production Schematic for Pentachlorobenzene by Chlorination
of Benzene or Chlorobenzene • • • .. . .. . • • • . ... . 56
21 Schematic of Reactions for Production of Mirex. ... .. • . 58
22 Production. Schematic for Sodium Chlorate. . . . . . . . . . 59
23 Production Schematic for Sodium Metal ........... 62
24 Schematic for Production of Vinyl Chloride by Pyrolysis of
Ethylene Dichloride •••..'. • . . •. '• ..... 63
25 Production Schematic for Acetylene Process for Vinyl
Chloride 65
26 Production Schematic for Pentachlorophenol by Chlorination
of Phenol . . . .' . .- . . ... . ... . . . 67
27 Production Schematic for Hexachloroethane from Per-
chloroethylene. . . 69
28 Chlorine Consumption Pattern (Major Chlorine Compounds
and Compounds of Special Interest) : . . 99
viii
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LIST OF TABLES
Table Title
S-l U.S. Chemical Production Volumes, Sites, and Manufac-
turers .
S-2 Estimated Total Quantity of HCB and HCBD Contained in U.S.
Industrial "Wastes, By-Products and Products in 1972. . . 7
I Summary of Number of Domestic Production Sites and Manu-
facturers and the Production Volumes for Selected
Chemicals 16
II Typical Raw Waste Loads from Mercury Cell Process. .... 38
III Production and Waste Disposal Data (1973) for Perchloro-
ethylene and Trichloroethylene ............. 74
IV Summary of Perchloro/Trichloro Estimates 78
V Waste Disposal Methods Used in Hexachlorocyclopentadiene
Manufacture 90
VI Hazardous Materials Expected in Waste Streams of Selected
Chemical Producers and Users 92
VII Waste Streams and Treatment Procedures for Selected
Chemicals. . . 93
VIII Waste Treating Processes Being Used for Selected
Petrochemical Wastes • • . . . 94
IX Estimated Total Quantities of HCB and HCBD Present in
Industrial Wastes, By-Products and Products in 1972. . . 96
X Estimated Quantities of HCB and HCBD Generated Per Ton of
Product in 1972 97
XE Distribution of Hexachlorobenzene and Degradation Products 109
XII Quantitative Values for Ecological Magnification (EM) and
Biodegradability Index (BI) for Eight Organochlorine
Pesticides in Fish and Snail . ; .....' 110
XIII Acute Toxicity of Hexachlorobenzene Following Single Dose
Administration . ... . 112
ix
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LIST OF TABLES (Concluded)
Tables Title Page
XIV Subacute and Chronic Toxicity of Hexachlorobenzene .... 113
XV Chlorine Plants Recommended as Monitoring Test Sites ,; . 121
.; ,' . / . • ' - ' ' ' ' . - ' ''•',' '
I • ' ' ' ' ' I' l
A-Ia Summary Data for the Chlor-Alkali industry ........ 128
A-Ib Chlor-Alkali Production. . i. ....... 129
A-Ic Domestic Chlorine Producers by EPA Region. . .' ,132
a • . '
A-II List of U.S. Producers of Selected Chemicals . 135
A-III U.S. Production and Import Data for Selected Chemicals . • 142
C-I Non-DSA Plants (Diaphragm Cells) 157
I; ' .
C-II Recommendations After Application of Criteria, By Type
. of Cells *. 159
C-III Non-DSA Plants (Mercury Cells) .............. 160
C-IV Non-DSA Plants (Miscellaneous Cell Types). ........ 161
C-V Graphite Consumption/Ton Cl2>for Different Types of Cells. 162
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I. INTRODUCTION
Hexachlorobenzene (HGB) and hexachlorobutadiene (HCBD) have aroused
concern because, of technical publications and reports by the news media that
these substances have been found as trace contaminants in the environment
and, in rare instances, in certain food supplies in the U.S. • •
During the summer of 1972, government inspectors identified HCB
in domestic meat and poultry supplies. HCB residues have been observed in
animal tissues from several widely separated locations!/ including Darrow,
Louisiana; Dimmitt, Texas; Phoenix, Arizona; and Westmoreland, California.
The Food and Drug Administration is investigating the extent of HCBD con-
tamination in various domestic food supplies.
Because of these reports of HCB-HCBD contamination, and concern
about the toxicity of these substances, the Office of Toxic Substances, EPA,
directed MRI to undertake this study. Much of the effort was designed to
identify possible sources and effects of HCB and HCBD. In addition to HCB
and HCBD, three other chemical products were initially selected for investi-
gation because it was considered likely that HCB and/or HCBD would escape
into the environment as a result of their production. These three chemicals
were hexachloroethane, pentachlorophenol, and pentachlorobenzene.
As the investigations of these five products progressed MRI iden-
tified, through discussions with industry representatives and surveys of
technical literature for chemical processing, a number of additional chem-
ical substances whose production was' considered to be potential sources
of environmental contamination by HCB and/or HCBD. During discussions with
EPA representatives, it was mutually agreed that 18 additional chemicals
• should be included in the project investigations because they also repre-
sent a proven or theoretical source of HCB and/or HCBD. Thus, a total of
23 chemicals and chemical product industries were of interest; they were:
*
*
*
*
*
*
*
*
*
*
*
*
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Pentachlorophenol
Pentachlorobenzene
Chlorine
Sodium chlorate
Sodium metal
Carbon tetrachloride
Perchloroethylene
Trichloroethylene
Vinyl chloride monomer
*
*
*
*
*
*
*
*
*
*
*
Synthetic rubber (chloroprene)
Atrazine
Propazine
Simazine
Pentachloronitrobenzene
Dacthal®
Mirex
Maleic hydrazide
Hexachlorocyclopentadiene
Chlorinated naphthalenes
Chlorinated biphenyls
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The scope ;of work included:
1. Identification of production sites and production volumes.
2. Description of manufacturing processes and environmental
and health aspects.
3. Characterization of waste disposal methods.
4. Identification of commercial uses for chemical products.
5. Recommendations concerning selected plant monitoring sites.
The following sections of this report discuss methodology, re-
sults obtained in each major assignment, and an evaluation conducted to
identify those chemical plants at which monitoring should be conducted. The
appendices provide further information on: manufacturing sites and produc-
tion and import volumes of the 23 substances; a written inquiry sent to
nine manufacturers; and the rationale for the process used to identify the
plants to be monitored.
The subject index included at the end of this report provides,
for each chemical of interest, a notation of the first page number for
the discussion of that chemical in each major report section.
This study of RGB and HCBD was Task I under this contract. Task
II of this program, a study of brominated biphenyl compounds, will be com-
pleted in June 1975 and will be the subject of a separate report.
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II. SUMMARY
On 5 July 1973, the Office of Toxic Substances of the U.S. En-
vironmental Protection Agency authorized Midwest Research Institute (MRI)
to initiate a project entitled "Survey of Industrial Processing Data" (EPA
Contract No. 68-01-2105). Primary objectives of this project were to col-
lect information on environmental aspects of U.S. production and use of
specific toxic substances, to be designated by EPA, and to organize this
information into a form which will assist EPA in assessing their environ-
mental impacts. The present study was made to help the EPA evaluate the
potential for environmental contamination by hexachlorobenzene (CgClg;
abbreviated HCB), and hexachlorobutadiene (04015; abbreviated HCBD). This
study was conducted during the period of 27 June 1973 to 7 October 1974.
Information acquisition and evaluation activities were designed
to identify proven or potential sources of HCB and HCBD and the environ-
mental and health effects of these substances. In addition to HCB and HCBD,
this study included 21 other domestically produced chemicals which were
either known sources of HCB and/or HCBD or theoretically capable of generat-
ing these substances as by-products, waste materials, or impurities in a
commercial product. These additional chemicals were identified through dis-
cussions with EPA, manufacturer's representatives and surveys of technical
literature; they were:
*
*
*
*
*
*
*
*
*
*
*
Chlorine
Vinyl chloride monomer
Carbon tetrachloride
Perchloroethylene
Trichloroethylene
Sodium chlorate
Synthetic rubber (chloroprene)
Atrazine
Hexachlorocyclopentadiene
Pentachloropheno1
Chlorinated blphenyls
* Simazine
* Chlorinated naphthalenes
* Propazine
* Maleic hydrazide
* Pentachloronitrobenzene
* Pentachlorobenzene
* Dacthal®
* Mirex
* Hexachloroethane
* Sodium metal
The scope of the study for each of these chemicals included iden-
tification of production sites and volumes, descriptions of manufacturing
processes and environmental and health aspects, description of waste dis-
posal methods, and identification of commercial uses for these products. An
important goal was the recommendation of specific plant sites that should
be monitored by EPA to determine if they were sources of significant dis-
charges or emissions of HCB and/or HCBD into the environment.
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Sources ,of the project team's information included several stand-
ard reference publications, technical literature for the chemical process
industry, telephone and letter inquiries to producers, trade organizations
and government agencies, and a written questionnaire submitted to nine
selected chemical producers.
The major findings in this study are briefly described in the
following subsections.
1. Chemical production volumes, sites and manufacturers; Pro-
duction data for the 23 chemicals of interest are presented in Table S-l.
The production rates, sites, and manufacturers range from none for
HCBD to nearly 20 billion pounds per year,- 65 sites and 32 manufacturers
for chlorine. Production sites for chemicals of interest are heavily con-
centrated in Louisiana, Texas, and Alabama. Chlorine manufacture represents
the most widely dispersed operations, with plants in 23 states. In contrast,
each of the pesticide chemicals listed is produced at only a few sites
(five or less).
2. Manufacturing processes that produce HCB or HCBD; Neither
HCB nor HCBD appear to be direct products of a commercial manufacturing
process—although synthesis routes are known—and both are normally ob-
tained in commercial quantities as by-products. HCB is a specialty chem-
ical reclaimed in domestic practice as a by-product of undisclosed (pro-
prietary) chlorinated hydrocarbon processes. In 1974, there was only one
active domestic HCB producer. Industry sources report that environmental
contamination by HCB does not occur in these manufacturing operations,
since all of the by-product HCB is recovered and sold. HCBD has been re-
covered domestically as a by-product in some chlorinated hydrocarbon pro-
cesses (e.g., perchloroethylene production). In 1974, no HCBD was produced
in the United States, but 200,000 to 500,000 Ib were reported to be im-
ported the same year .-2.'
In the study of manufacturing processes for the 21 other selected
chemicals, MRI identified 11 that are known to produce HCB and/or HCBD as
by-products, waste components, or impurities; they are;
* Chlorine * Dacthal® * Pentachlorobenzene
* Carbon tetrachloride * Atrazine * Pentachloronitrobenzene
* Perchloroethylene * Propazine * Mirex
•* Trichloroethylene * Simazine
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TABLE S-l
U,S. CHEMICAL PRODUCTION VOLUMES, SITES. AND MANUFACTURERS
a/
Chemical-
Total
Production
Vo lume
(106 Ib/year)-'
Chlorine
Vinyl chloride monomer
Carbon tetrachloride
Perchloroethylene
Sodium chlorate
Trichloroethylene
Synthetic rubber (chloroprene)
Atrazine
Hexachlorocyclopentadiene
Pentachloropheno1
Chlorinated biphenyls
Sittazine
Malgic hydrazide
Chlorinated naphthalenes
Propazine
Pentachloronitrobenzene
Dacthal®
Mi rex
Hexachlorobenzene
Hexachloroethane
Sodium metal
Pentachlorobenzene
Hexachlorobutadiene
19,;
5,089
997
734
428
427
396
100
5<#
49
38.6
8
4
3*7
0.4
0.15
< 0.002^7
e/
To ta 1
Production x,
Sites in
65
16
11
10
15
.5
6
2
4
4
1
1
4
1
1
2
1
1
3
1
5
3*7
Number of
Manu-
facturers-^
32
12
6
7
10
5 '
4.
1
2
4
1
1
4
1
1
1
1
1
3
1
3
6
2
a/ The chemicals are listed in descending order of total production vol-
ume.
1)7 1972 production volumes, except as otherwise noted (see Appendix A).
£/ Chlorine Institute Pamphlet No. 10, January 1974.
d/ MRI estimate. See Section III and Appendix A.
e/ No domestic production for commercial marketing (small amounts are
imported).
^/ SRI Chemical Information Service, Chemical Economics Handbook, Stan-
ford Research Institute (1974).
£/ Includes four plants which produce pentachlorobenzene as a by-product
and two specialty chemical companies.
h/ All three sites are inactive.
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HCB can be formed as a by-product in the production of chlorine
gas by electrolysis of sodium chloride^ in cells with carbon electrodes.
Both HCB and HCBD can be formed as by-products or waste material in the
manufacture of carbon tetrachloride, perchloroethylene, and trichloroethyl-
ene.1' The only domestic producer of Dacthal®has reported (see Appendix
B) that no HCBD is generated, that the pro'duct contains about: 0;3% HCB, and
that the process wastes contain about 84% HCB. The producer of ,'atrazine,
propazine, and simazine has reported (see Appendix B) that no ,HCBD is pro-
duced, but that each product and the related process waste materials con-
tain measurable amounts of HCB. HCB can be1 formed as a by-product in the
production of pentachlorobenzene.— Two pesticide products, pentachloro-
nitrobenzene and mirex, are known to be contaminated with HCB.—'
3. Evaluation of the HCB and HCBD pollution potential; An eval-
uation was made of the potential for environmental pollution by HCB and
HCBD on the basis of the information obtained on the production and use of
the 23 chemicals of interest. In this evaluation, MRI developed estimates
of the probable quantities of HCB and HCBD generated as by-products, con-
taminants in products, or components of waste materials in each of the
manufacturing processes and product industries.
The results, presented in Table S-2, show that production of
three related industrial chemicals, carbon tetrachloride, perchloroethylene,
and trichloroethylene, account for 89% of the HCB and more than 99% of the
HCBD that are formed in the U.S. The perchloroethylene industry alone gen-
erates about 72% of the total HCB and 60% of the total HCBD. Chlorine and
various pesticides (atrazine, propazine, simazine, Dacthal®, mirex, and
pentachloronitrobenzene) generate about 10% of the total HCB. Vinyl chlo-
ride accounts for the remaining 1% of the HCB.
For the 11 chemical processes considered in Table S-2, the total
HCB generated ranged from a low estimate of 2.4 million pounds to a high
estimate of 4.9 million pounds in 1972. The total estimated HCBD ranged
from about 7.3 to 14.5 million pounds.
4. Disposal methods for wastes containing HCB and/or HCBD; The
chlorine industry uses sanitary landfill or high-temperature incineration
methods. In the chlorinated hydrocarbon industries of interest (carbon
tetrachloride, perchloroethylene, trichloroethylene, pentachlorobenzene
and pentachloronitrobenzene), the disposal methods include landfill, in-
cineration, and deep-well injection. Incineration is reported to be a highly
effective disposal method in which practically all HCB and HCBD are de-
stroyed. The landfill operations pose a potential air pollution hazard,
since HCB is volatile in water vapor at low temperatures. Deep-well in-
jection systems are undesirable since they may create geological fractures
which can result in contamination of aquifers.
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TABLE S-2
ESTIMATED TOTAL QUANTITY OF HCB AND HCBD CONTAINED IN U.S.
INDUSTRIAL WASTES. BY-PRODUCTS. AND PRODUCTS IN 1972^
HCB (OOP Ib)-/ HCBD (OOQ
End-Products High Low High ,' .Low
Perchloroethylene 3,500 1,750 8,670 4,340
Trichloroethylene 450 230 3,000 1,500
Carbon tetrachloride
Chlorine
Dacthal®
Vinyl chloride
Atrazine, propazine, simazine
Pentachloronitrobenzene
Mirex
Total 4,884 2,429 14,530 7,280
a/ See Section V for description of waste disposal methods used.
t>/ Rounded to nearest 10,000 Ib—except for vinyl chloride, atrazine,
propazine, simazine, pentachloronitrobenzene, and Mirex.
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The pesticide process wastes of concern to this study (i.e.,
from production of-atrazine, propazine, simazine, and Dacthal®) are dis-
posed of by incineration.
5., Commercial uses of HCB, HGBD, and selected chemicals; A
brief discussion of the use patterns for selected products, which are known
to contain, or theoretically may contain, HCB and/or HCBD, follows.
Hexachlorobenzene; In 1972, th'e principal use for HCB was re-
ported to be as a fungicide to control wheat bunt and smut fungi of other
grains. The technical grade used in agriculture is reported to contain
98% hexachlorobenzene, t.8% pentachlorobehzene, and 0.2% of 1,2,4,5-tetra-
chlorobenzene. Commercial formulations applied as dusts contain 10 to 40%
hexachlorobenzene..1' Other applications include use as: additives for
pyrotechnic compositions for the military; a porosity controller in manu-
facture of electrodes; chemical intermediates in dye manufacture and or-
ganic synthesis; and a wood preservative.
In 1974, a spokesman for the only domestic producer (Stauffer
Chemical Company) reported that their entire HCB production capacity had
been committed on a multiyear contract basis for use only as a peptizing
agent in nitroso- and styrene-type rubber manufacture in automobile tire
plants.
Hexachlorobutadiene; The largest domestic use for HCBD is for
recovery of "snift" (chlorine-containing) gas in chlorine plants..?/ This
"snift" gas, which occurs at the liquefIcation unit, is cleaned by pass-
ing it through HCBD or carbon tetrachloride. HCBD is also used as a chemical
intermediate in the manufacture of rubber compounds. It has been used as
a fluid for gyroscopes and as a chemical intermediate to produce lubri-
cants.
Chlorine; A detailed materials flow diagram was prepared to
illustrate the utilization of chlorine values in various chemical process-
ing operations, intermediates, and end products. This schematic (see page 99)
shows all major compounds which use chlorine as a raw material. About 59%
of the total chlorine produced is consumed in the manufacture of chlori-
nated hydrocarbons (acyclic and cyclic)} these industries, as a group, have
the highest potential for generation of by-product HCB and HCBD. This chlo-
rine distribution diagram should be useful in any, future studies of chlorin-
ated hydrocarbons derived from these basic chemical industries.
Dacthal®; This product is a preemergence herbicide used for
cotton, peanuts, and a variety of vegetables.
8
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Atrazine, propazine, and simazine; Atrazine is a selective herb-
icide; the major use is for corn and sorghum crops. Less than 10% is used
by industry.
Propazine is a preemergence herbicide used to control broadleaved
and grassy weeds in millet, sorghum, and umbelliferrous crops.
Simazine is a herbicide widely used to control broadleaf and grassy
weeds in corn, citrus crops, deciduous fruits and nuts, established alfalfa,
perennial grasses, and nursery plantings. It is also applied as a nonselec-
tive herbicide for vegetation control on noncropland.
Pentachlorobenzene; This chemical is produced largely as a cap-
tive intermediate for synthesis of specialty chemicals. The estimated total
domestic sales in 1972 were less than 1 ton.
Pentachloronitrobenzene! This product is used as a soil fungi-
cide to control diseases of cotton, potatoes, tomatoes, and peppers. The
use of 20% pentachloronitrobenzene in dust also gives satisfactory results
as a seed disinfectant against smut.
Mirex; This insecticide is used for the control of some species
of ants, and most widely in the USDA's fire ant control program in the south-
eastern states. It has been used for control of cotton pests and some Hawaiian
pineapple growers have used it to control mealy bugs and ants.
6. Environmental and health aspects of HCB and HCBDt The tech-
nical literature^/ indicates that RGB is a hazard to man and to the environ-
ment. It appears to be readily dispersed through the atmosphere, is accu-
mulated in food chains, and is highly resistant to chemical, biological,
and physical degradation. Since HCB sublimes and is also volatile in water
vapor at low temperatures, it can be widely distributed by air transport.
In the U.S. it has been detected in poultry and meat from 20 states and in
marine ecosystems. HCB has a very low acute toxicity by single-dose admin-
istration; e.g., 500 mg/kg interperitoneal was nonlethal in rats, and the
oral lethal dose of a 15% suspension of HCB in female Japanese quail was
above 1 g/kg.,3/ In contrast, the subacute or chronic toxicity can be sig-
nificant;- serious physiological damage apparently can result from repeated
exposure of animals to small dosages of this chemical (see Section VII).
The literature!/ shows some data on the mortality rates for oral feeding
of HCB to rats; for a 30-day feeding period with 10 rats, 30% mortality was
observed at a dosage of 50 mg/kg/day and 60% mortality was reported for a
dosage of 150 mg/kg/day.
-------
HCBD is also a toxic substance and potentially hazardous environ-
mental pollutant that is resistant to chemical degradation. HCBD has greater
acute toxicity than RGB. Tests conducted by the Hazelton Laboratories (see
Section VII), indicate that the acute oral LD5Q of HCBD for male albino rats
is 178 M>l/kg of body weight, and that the acute dermal LD^Q for albino rabbits
is 1,780 ^1/kg.
10
-------
III. CONCLUSIONS AND RECOMMENDATION
The following conclusions are drawn on the basis of this study:
1. Production and processing of perchloroethylene, trichloro-
ethylene, and carbon tetrachloride accounts for an estimated 897o of the HCB
and 99% of the HCBD that are produced in the United States. Production of
chlorine and certain pesticides accounts for most of the remaining HCB,
with vinyl chloride monomer accounting for about 1%. The chlorine industry
also accounts for a small portion of the total amount of HCBD.
2. A review of waste-disposal technology and of discussions with
industry spokesmen indicates that one of the most effective and safest
methods for disposing of wastes containing HCB and HCBD involves the use of
a specially designed high-temperature incineration system. Use of such
special incinerators is increasing. Some deep-well injection and landfill-
ing disposal methods are still being used, but are not preferred methods.
3. HCB is a stable and potentially hazardous environmental pol-
lutant, which is highly resistant to chemical, biological, and physical
degradation. The single-dose acute toxicity is very low, but the subacute
or chronic toxicity can be significant. HCBD is also a stable environmental
pollutant, and has greater acute toxicity than HCB.
On the basis of our technical evaluation (see Section VIII), it is
recommended that sampling and analysis (monitoring) be conducted at several
plants known to be, or suspected of, discharging HCB and/or HCBD. Samples
should be taken from each plant's emissions, effluents, soil, solid wastes,
and products to characterize and quantify the types and levels of HCB and
HCBD. By industry class, the recommended monitoring sites and the products
produced there are as follows:
1. Perchloroethylene-trichloroethylene-carbon tetrachloride:
* PPG Industry, Inc.; Lake Charles, Louisiana; perchloro-
ethylene and trichloroethylene.
* Vulcan Materials Company; Wichita, Kansas; carbon
tetrachloride and perchloroethylene.
* Vulcan Materials Company; Geismar^ Louisiana; carbon
tetrachloride and perchloroethylene.
* E. I. du Pont de Nemours and Company, Inc.; Corpus Christ1,
Texas; carbon tetrachloride.
11
-------
2. Chlorine:
* Kaiser Aluminum and Chemical Corporation; Gramercy,
Louisiana; diaphragm cell operation.
i:
* Olin Corporation; Mclntosh, Alabama; mercury cell
operation.
3. Atrazine, propazine, simazine:
* Ciba-Geigy Corporation; St. Gabriel, Louisiana; atrazine,
propazine, and simazine.
4. Vinyl chloride monomer:
* PPG Industry, Inc.; Lake Charles, Louisiana.
5. Pentachloronitrobenzene:
* Olin Corporation; Mclntosh, Alabama.
6. Dacthal®:
* Diamond Shamrock Chemical Company; Greens Bayou, Texas.
If substantial HCB and HCBD contamination is shown to result from
operation of the chlorine plants previously listed, monitoring should also
be undertaken at:
* Champion International Corporation; Houston, Texas
(diaphragm cell).
* Linden Chlorine Products, Inc.; Linden, New Jersey
(mercury cell).
It is also recommended that samples of mirex and hexachlorpcyclo-
pentadiene be obtained and analyzed. If product contamination by HCB or HCBD
is demonstrated, monitoring should be undertaken at the Occidental Petroleum
Company's Niagara Falls plant.
12
-------
IV. DISCUSSION OF METHODOLOGY
A series of studies was conducted to develop information on the
potential hazards to man associated with the production and use of a class
of chemicals related to hexachlorobenzene and hexachlorobutadiene. A dis-
cussion of each major phase of the methodology employed in Task I follows.
A. Selection of Toxic Substances
At the beginning of the program, the EPA task officer designated
five chemical substances as subjects for the Task I investigations. As the
study developed MRI determined, through discussions with industry spokesj-
men and a survey of technical literature on the chemical process industry,
that production of several additional substances was a potential source for
escape of HCB and/or HCBD into the environment. During consultations with
the EPA task officer, it was mutually agreed that 18 additional substances
would also be investigated. These 18 substances were included because it was
established that their production posed either a proven or a potential source
of HCB and/or HCBD formation.
B. Identification of Production Sites and Estimated Production Volumes
1. Production sites; The domestic production sites for each sub-
stance were identified, using several standard reference publications, in-
cluding the following:
* Stanford Research Institute, Directory of Chemical Producers,
Chemical Information Services, Menlo Park, California (1973
and 1974).
* Stanford Research Institute, Chemical Economics Handbook,
Chemical Information Services, Menlo Park, California (1973
and 1974).
* Buyers Guide, Chemical Week (1973 and 1974).
* Manufacturing Chemists Association, Inc., Chemical Statistics
Handbook. 7th ed. (1971).
* U.S. Tariff Commission, Synthetic Organic Chemicals; U.S.
Production and Sales, T.C. Publication No. 479, U.S. Govern-
ment Printing Office, Washington, D.C. (1972).
13
-------
The last publication listed was^particularly helpful in distin-
guishing producers from other sources. In'some cases, telephone contacts
were made to confirm -information derived from the various references.
The names ;of the producers of each selected substance and the
geographic location of each production site in the United States were tab-
ulated. For all chemicals of special interest, maps were prepared showing
the geographical distribution of the production facilities and the corres-
ponding EPA regions. These maps are included with the discussions in.the
next section of the report.
2. Production capacity, production volumes, and imports; Some
problems were encountered in collecting the required data on production
capacities, production volumes, and projected production volumes by the
major producers of each chemical. Most of the standard reference publica-
tions do not list production data for some chemicals of interest to the
project (e.g., hexachlorobenzene, hexachloroethane and pentachlorobenzene)
which are either produced in very small quantities or as captive inter-
mediate chemicals or by-products. Several company spokesmen declined to
respond to telephone inquiries on this subject; they replied that such in-
formation was proprietary. Telephone and letter inquiries, made to chem-
ical trade organizations and chemical distributors, provided additional
data on production capacities and production volumes.
Information concerning imports was obtained from technical litera-
ture and the Kansas City, Missouri, Office of the U.S. Department of Com-
merce. .
14
-------
V. PRODUCTION SITES AND VOLUMES
This section provides a brief synopsis of plant locations and
production volumes for each of the 23 chemicals studied. Complete lists of
individual plant sites and production volumes, together with annual gross
production and import figures for as many years as are available, are ap-
pended to this report (Appendix A). Maps showing the plant locations appear
in this section, immediately after discussion of the substance(s) shown.
All production quantities are given in short tons for 1972, and the data
for number of production sites and number of manufacturers applies for
1973,' except as otherwise noted. '
Table I presents a summary of the number of domestic production
sites and manufacturers, and the production volumes for each of the chemicals
investigated. Individual discussions for each chemical are given in the '
following subsections.
A. Hexachlorqbenzene (HCB,
As shown in Figure 1, there were three production sites (Dover
Chemical Company, Dover Ohio; Hummel Chemical Company, South Plainfield,
New Jersey; and Stauffer Chemical Company, Louisville, Kentucky) operating
through 1973. In 1974, the Dover and Hummel plants were reported to have
been shut down, leaving Stauffer as the only domestic producer. The esti-
mated total production in 1973 was 350 tons. Efforts to obtain information
on whether Hummel and Dover have been repackaging or marketing HCB were
unsuccessful.
B. Hexachlorobutadiene (HCBD, CC1 =CC1-CC1=CC1 )
Hexachlorobutadiene has not been produced in the U.S. since 1970,
because of poor domestic demand. Prior to that time, HCBD was produced
domestically as a recovered by-product in the manufacture of perchloro-
ethylene and trichloroethylene. The technical literature indicates that
three HCBD production sites were used prior to 1970 (see Figure 1). In
1974, all commercial quantities (200,000 to 500,000 Ib) of HCBD, sold in
the U.S., were imported by Dynamit Nobel America from Germany^'
C. Chlorine (Cl.)
There are approximately 70 chlorine production sites and 32 manu-
facturing companies. As shown in Figure 2, these sites are concentrated in
the eastern one-third of the U.S., and along the coastlines. In addition
to chlorine, most of these sites also product coproducts, such as caustic
soda, caustic potash, soda ash, sodium metal, and magnesium. Louisiana ancj
Texas have the largest number of production sites (nine in Louisiana and
10 in Texas).
15
-------
TABLE I
SUMMARY OF NUMBER OF DOMESTIC PRODUCTION SITES AND MANUFACTURERS
AND THE PRODUCTION VOLUMES FOR SELECTED CHEMICALS
No. of Active
Production
Item Chemical SitesfL/
A Hexachlorobenzene 3
B Hexachlorobutadiene 0
C Chlorine 70£/
Sodium Metal 5
D Sodium Chlorate 15
E Carbon Tetrachloride 11
F Perchloroethylene 10
G Trichloroethylene 5
H Vinyl Chloride Monomer 16
I Hexachloroethane 1
J Pentachlorobenzene 6
K Pentachlorophenol 4
L Synthetic Rubber (Chloroprene) 6
M Atrazine 2
Propazine 1
Simazine 1
N Pentachloronitrobenzene 2
0 Dae thai 1
P Mirex 1
Q Maleic Hydrazide 4
R Hexachlorocyclopentadiene 4
S Chlorinated Naphthalenes 1
T Chlorinated Biphenyls 1
No. of
Manufac-
turers3.'
3
0
32
3
10
6
7
5
12
1
6
4
4
1
1
1
1
1
1
4
2
1
1
Production
Vo lutne
(short tons )-/
350d/
0
9,868,000
75-
214,000
498,500
367,000
213,500
2,544,500
200
< 1-^
24,500
178,000^
50,000
2,000
4,000
1,500
1,000
< 500
4,000
25,000
< 2,500
19,300
a/ Applies for 1973.
b/ Applies for 1972, except where otherwise noted.
c_/ Includes 5 sodium production sites at which
by-product.
d_/ Applies for 1973.
e_/ Applies for 1971.
f/ MRI estimate of domestic production in 1972
Appendix A (p. 126) for basis of estimate.
chlorine is
produced as
for commercial sales. See
16
-------
Legend:
o = Hexachlorobutadiene (Not Active)
. o = Hexachlorobenzene
Figure 1 - Production Sites for Hexachlorobenzene and Hexachlorobutadiene
-------
00
LEGEND --
(?) CHLOR
HE t SODIUM
SOD* ASH
CMLOAINE. CAUSTIC SOD* i sow *s
CHU»I«
CAUSTIC sou
CHLOT'NE '. CAUSTIC SOOA --- ^^ CrtlO'lNE. CAUSTIC SOOA ( SODIUM
CKLOA1NE ( CAUSTIC POTASH
0 «X> tOO 3OO «OO MX)
(Adapted from a fig-
..-»' ure provided by the
-~ Chlorine Institute,
Inc., New York, New
York)
9CAUI Or CXLEi
Figure 2 - Operating Chlorine and Alkali Plants in the United States and Canada (January 1, 1974)
-------
Total chlorine production was about 9,868,000 tons in 1972. In-
dividual reported plant production capacities range from 14,000 (Houston,
Texas) to 1,700,000 (Freeport, Texas) tons/year. Some production figures
were reported as a consolidated number for several plants; some plants'
capacities could not be determined.
Sodium metal production plants are included in this.category,
since chlorine is a by-product. The reported individual production capaci-
ties for the five sodium plants range from 15 to 23 tons/year. Total pro-
duction of sodium in "1972 was only 75 tons.
D. Sodium Chlorate (NaC103)
There are 10 manufacturers and 15 production sites for sodium
chlorate. Nine sites are located in southern states as shown in Figure 3.
An estimated total production for 1972 was 214,000 tons. The largest plant
capacity (Columbus, Mississippi) is 62,000 tons/year; the smallest capacity
(Beliingham, Washington, and Butler, Alabama) is 4,000 tons/year.
E. Carbon Tetrachloride (0014)
There are 11 production sites and six manufacturers of this chem-
ical. Figure 3 shows that five sites are located in southern states (Texas
- 2, Louisiana - 2, and Alabama - 1). Total production in 1972 was about
498,500 tons. The reported plant capacities range from 4,000 (Moundsville,
West Virginia) to 250,000 (Corpus Christi, Texas) tons/year.
F. Perchloroethylene
The seven producers and 10 production sites accounted for a total
production of about 367,000 tons of perchloroethylene in 1972. As indicated
in Figure 4, seven of the 10 plant sites are located in Louisiana and Texas.
Plant production capacities extend from a low of 10,000 (Pittsburg, California)
to a high of 100,000 (Lake Charles, Louisiana) tons/year.
G. Trichloroethylene (C2HC13)
This chemical is produced by five manufacturers and there are
five production sites. Figure 4 shows that Louisiana has three sites and
Texas has two. The total production of trichloroethylene in 1972 was about
213,500 tons. Individual plant capacities are reported to range from 20,000
(Taft, Louisiana) to 140,000 (Lake Charles, Louisiana) tons/year.
19
-------
Legend:
• ~ Sodium Chlorate
° = Carbon Tetrachloride
Figure 3 - Production Sites for Sodium Chlorate and Carbon Tetrachloride
-------
Legend:
• = Perch loroethylene
O = Trichloroethylene
Figure 4 - Production Sites for Perchloroethylene and Trichloroethylene
-------
H. Vinyl Chloride Monomer (CH2=CHC1)
Thirteen of the 16 production sites are located in Louisiana and
Texas (see Figure 5); there are 12 manufacturing companies. Total production
of vinyl chloride monomer amounted to about 2,544,500 tons in 1972. the
reported individual plant capacities range; from 75,000 (Pasadena, and Texas
City, Texas) to 500,000 (Calvert, City, Kentucky) tons/year.
I. Hexachloroethane
Hexachloroethane is produced at only one site (see Figure 5).
Total production in 1972 was about 200 tons. Production capacity of the
Hummel plant in South Plainfield, New Jersey, is estimated to be 250 tons/
year.
J. Pentachlorobenzene
In addition to captive production as a by-product by four com-
panies, this chemical is also produced in small quantities by two specialty
chemical companies in the New York City Area (see Figure 5). The estimated
domestic production for commercial sales in 1972 is less than 1 ton. Data
on individual plant capacities for captive production could not be obtained.
K. Pentachlorophenol (PCP, C6C15OH)
Four companies manufacture this chemical; and there are four pro-
duction sites (see Figure 5). Total production was about 24,500 tons in
1972. The individual plant production capacities are reported to range from
about 3,500 (Wichita, Kansas) to 13,000 (Sauget, Illinois) tons/year.
L. Synthetic Rubber (Chloroprene, CH2=011-CCL=CH2)
Since chloroprene appears to represent the only type of synthetic
rubber production which has potential for production of HCB and HCBD, this
was the only rubber process investigated. There are six manufacturing sites
(see Figure 6), and four producers for chloroprene. The estimated total
production for 1971 is 178,000 tons. Three of these plant sites have ca-
pacities' ranging from 22,500 (Houston, Texas) to 137,500 (Louisville,
Kentucky) tons/year. The total production capacity reported by the industry
for 1971 was 198,000 tons;
22
-------
tX)
I
Legend:
• = Pentachlorophenal
A = Hexachloroethane
A = Pentachlorobenzene
• = Vinyl Chloride Monomer
Figure 5 - Production Sites for Pentachlorophenol, Hexachloroethane,
Pentachlorobenzene, and Vinyl Chloride Monomer
-------
Legend:
0 Pentachloronitrobenzene
A Dacthal
O Mi rex
V Atrazine
O Propazine
• Simazine
A Maleic Hydrazide
x Chloroprene
Figure 6 - Production Sites for Pentachloronitrobenzene, Dacthal, Mirex, Atrazine, Propazine, Simazine,
Maleic Hydrazide and Synthetic Rubber (Chloroprene)
-------
M. Atrazine, Propazine, and Simazine
These chemicals are members of a family of triazine compounds
used in herbicide applications. They are now produced solely
by the Ciba-Geigy Corporation at St. Gabriel, Louisiana; atrazine was also
produced by the same company at Mclntosh, Alabama in 1973 (see Figure 6).
In 1972, the estimated production volumes for atrazi.ne, propazine, and
simazine were 50,000, 2,000, and 4,000 tons, respectively. .The Mclntosh,
Alabama, facility is reported to have a production capacity of over 75,000
tons/year; data on'capacities for other sites could not be ascertained.
N. Pentachloronitrobenzene (PCNB,
There are two production facilities and one manufacturer for
this product (see Figure 6). The estimated total production in 1972 was
1,500 tons, and the estimated production capacity for the same year was
2,000 tons.
0. Dacthal
As shown in Figure 6, this pesticide is produced at one plant
site (Greens Bayou, Texas); the production volume in 1972 was about 1,000
tons. The estimated production capacity for the same year was 1,300 tons.
P. Mirex (C1QC1]?)
Mirex was produced at only one plant site in 1973 (see Figure 6),
Two plants were in operation in 1972, and they had a combined annual pro-
duction of less than 500 tons. The total capacity was estimated to be less
than 600 tons/year.
Q. Maleic Hydrazide (NH-CO-CH=CH-CO-NH)
There are four production sites and four manufacturers for this
product (Figure 6). Total production in 1972 amounted to about 4,000 tons
and the plant capacity was estimated at 5,000 tons.
R. Hexachlorocyclopentadiene (HCP,
The locations of the four manufacturing plants for HCP are shown
in Figure 7; there are two manufacturers. The estimated total HCP volume
for all domestic producers in 1972 is 25,000 tons. Total plant capacity
for the same year was estimated to be 30,000 tons.
25
-------
Legend:
O Hexachlorocyclopentadiene
A Chlorinated biphenyl
D Chlorinated naphthalene
Figure 7 - Production Sites for Hexachlorocyclopentadiene, Chlorinated Biphenyls and Chlorinated Naphthalenes
-------
S. Chlorinated Naphthalenes (C,nEn Cl )
10 8-x x
The only domestic producer is the Koppers Company, which operates
a production facility at only one site (see Figure 7). The sales volume for
all of these products from 1969 to 1974 has averaged less than 2,500 tons/
year. Total plant capacity is estimated to be 3,000 tons/year.
T. Chlorinated Biphenyls (C10Hlrt Cl )
12 10-x x
Monsanto Company, the sole producer, operates only one produc-
tion facility (see Figure 7),.In April 1971, Monsanto closed its Anniston,
Alabama production plant for PCBs. The total domestic production of PCBs in
1972 was 19,300 tons, and the estimated total capacity was 24,000 tons.
27
-------
VI. MANUFACTURING. METHODS. BY-PRODUCTS. CONTAMINATION, AND RISKS
The following discussions cover 5the basic process technology for
each of the 23 chemicals^; with particular emphasis on the existing and
potential sources of HCB and HCBD. This section also discusses, in a general
manner, the operating parameters that affect the production of these chemi-
cals as by-products or wastes. Some of the: information in this section was
obtained from questionnaires (see Appendix] B).
The chemical production processes described in this section are
divided into two subsections.
A. Processes known to produce HCB and/or HCBD, and
B. Processes with theoretical, but not proven, production of
HCB and/or HCBD.
Following the discussion of Typef'A and B processes, a subsec-
tion (C) is presented which covers the methodology and results of a study'
conducted to estimate the quantities of HCB and/or HCBD contained in do-
mestic processing wastes, by-products, and products.
A. Processes Known to Produce HCB and/or HCBD
1. Hexachlorobenzene (HCB); Domestic producers of HCB have indi-
cated that manufacturing methods for this chemical are proprietary, and,
therefore, only a limited amount of information was obtained from processors
concerning the current production operations.
Representatives of the Stauffer Chemical Company have indicated
that at their Louisville, Kentucky, plant HCB is a by-product in the manu-
facture of perchloroethylene. The HCB is recovered from a by-product tar,
which contains 80% HCB and 10% HCBD, and the remainder of the tar is re-
ported to be recycled to the process. Under these operating conditions, the
possibility of HCB or HCBD entering the environment is considered to be
slight.
There are two basic processes described in the technical litera-
ture_L»Ji/ which could be used to produce HCB directly: (a) treatment of iso-
mers of hexachlorocyclohexane (C^H^Clg) with sufuryl chloride (S02C12)
and (b),reacting benzene (C^Hg) or chlorobenzenes with chlorine. These basic
processes are discussed in the following subsections.
28
-------
a. Production of hexachlorobenzene from hexachlorocyclo-
hexane4?6/
(1) Process flow diagram; A schematic production flow
diagram is shown in Figure 8.
(2) Process description; Hexachlorobenzene (HCB,
formula CfcClg) may be produced by refluxing isomers of hexachlprocyclo-
hexane (formula CgHfcC^) with sulfuryl chloride (S02Cl2> or chlorosulfonic
acid (HC1S03) in the presence of ferric chloride (FeCl^) or aluminum chlor-
ide (A1C13) as catalyst, at 130 to 200°C. Refluxing is continued for sev-
eral hours. The HCB, which crystallizes when the reaction medium is cooled,
is removed by filtration or centrifugation, and washed with water.
(3) Reaction;
Hexachlorocyclohexane + Chlorosulfonic Acid—•—;—^HCB + Hydrogen Chloride
+ Sulfurous Acid
(4) Raw materials;
Hexachlorocyclohexane isomers, normally from gamma-
hexachlorocyclohexane production (lindane)
Sulfuryl chloride or chlorosulfonic acid
Ferric chloride or aluminum chloride
(5) Resource requirements;
Water
(6) By-products and wastes;
Hydrogen chloride
Sulfurous acid (decomposes to ^0 and 802)
b. Production of HCB from benzene and chlorobenzenes—*—'
(1) Process flow diagram; A schematic production flow
diagram vis shown in Figure 9.
29
-------
C6H6CI6
isomers
Chlorosulfonic Acid ___
or Sulfuryl Chloride
Reflux -
Condenser -
Reactor with
FeClj as
Catalyst
Cooler
Filter
Drying
Packaging
Shipment.
Hexachlorobenzene
• - 4 6/
Figure 8 - Production Schematic for Hexachlorobenzene from Hexachlorocyclohexane—*—
-------
A patented process (U.S. Patent 2,269,600, January 1942) for
direct synthesis of HCBD involves the chlorination and dehydrochlorina-
tion of hexachlorobutene. An experimental method for preparation of HCBD
by chlorination of polychlorobutanes (at 425 to 500°C) is described in the
technical literature.Z' No evidence was found that either of these processes
have ever been used commercially in the U.S.
3. Chlorine;—' Chlorine (C12) is produced by electrolysis of
purified and concentrated sodium chloride (NaCl) brine. Two types of elec-
trolysis cells are used: the diaphragm cell and the mercury cell. A descrip-
tion of each process follows under separate headings.
a. Chlorine manufacture in diaphragm cells
(1) Process flow diagram; A schematic production flow
diagram is shown in Figure 10.
(2) Process description;—' Chlorine (C12) may be
produced by electrolysis of sodium chloride (NaCl) brine. The process be-
gins with obtaining, concentrating, and purifying a brine. The brine is
then passed into the diaphragm cell where C12 gas is evolved from the anode*
Previously, almost all anodes were made of graphite, but recently metal
oxide anodes (called dimensionally stabilized anodes, DSA) have been in-
troduced. The electrolysis produces hydrogen (H2) gas at the cathode,
rather than metallic sodium, and a caustic soda (NaOH) solution is formed.
The diaphragm serves to separate the anodic and cathodic solutions and
evolved gases. The spent brine proceeds to a concentration unit and the
caustic is recovered. The C12 and H2 are purified and dried for packaging.
(3) Reaction;
2 NaCl + 2H20 electrolvsis > ^ + R2 + 2 NaOH
(4) Raw materials;
Sodium chloride
(5) Resource requirements;
Sodium chloride
Water
(6) Energy requirements;
Electricity, 2,700 kw-hr/ton C12
33
-------
Chlorine Contaminated with HCB
NaCI
Brine Treatment
& Concentration
Electrolysis
Potential jr
HCB ^.Purification
Contamination-7 Mud (Waste)
/
Brine
NaCI,
NaOH
Evaporation
& Recovery
NaOH
Concentration
& Purification
I
Package
I
Shipment
NaOH
1
Heavy Ends
Containing
HCB
Compression
Package
Compression
Purification
Waste
Shipment
Hydrogen
Package
I
Shipment
Chlorine ~
(Adapted from a schematic in Reference 4)
Figure 10 - Production Schematic for Chlorine in Diaphragm Cells
-------
(7) By-products and wastes;
Hydrogen
Caustic soda
Processes using graphite anodes have potential for
production of by-product hexachlorobenzene. Plants that have converted
from graphite .anodes to metal oxide anodes (DSA) no longer have a prob-
lem with HCB formation.
b. Chlorine production in mercury cells
(1) Process flow diagram; A schematic production flow
diagram is shown in Figure 11.
(2) Process description;— Chlorine (C^) may be
produced by electrolysis of sodium chloride (NaCl) brine in mercury cells.
Brine is concentrated and purified and passed into the electrolytic cell
where Cl^ is evolved from the anode, which is usually graphite. The cathode
in a mercury cell is a flowing sheet of liquid mercury (Hg). The sodium forms
an amalgam with the mercury [Na(Hg)] and is continuously carried into the
amalgam decomposer. Normally the amalgam is then intimately contacted with
water to form caustic soda (NaOH) and hydrogen (H2) gas. The mercury regen-
erated is recycled to the cathode. Alternatively, the sodium can be recovered
as the metal, if preferred.
(3) Reaction;
electrolysis
2 NaC1 + 2 Hg
2 Na(Hg) + 2 H20 > 2 NaOH + H2 + 2 Hg
(4) Raw materials;
Sodium chloride
(5) Resource requirements;
Sodium chloride
Water
35
-------
Chlorine Contaminated with HCB
NaCI
Brine
Brine
Treatment
and
Concentration
Hg
Electrolysis
Brine
Potential
HCB Contamination1-^-Purification
Mud (Waste)
Hg
Na(Hg)
Decomposer
I
Concentration
& Purfication
I
Packaging
Shipment
NaOH
H2
1
Compression
& Packaging
I
Shipment
Hydrogen
Heavy Ends
Containing
HCB
Compression &
Purification
Waste
I
Packaging
T
Shipment
Chlorine
(Adapted from a schematic in Reference
Figure 11 - Production Schematic for Chlorine in Mercury Cells
-------
(6) Energy requirements;
Electricity - 1,200 kw-hr/ton C12
(7) By-products and wastes;
:' . Hydrogen
Caustic soda
Processes using graphite anodes have potential for
production of by-product hexachlorobenzene and hexachlorobutadiene. Some
plants have converted from graphite anodes to metal oxide anodes (DSA)
and no longer have a problem with HCB formation.
The process wastes from these electrolytic processes
(either diaphragm or mercury cell) have a significant potential for the
formation of HCB and other hydrocarbon waste materials in the crude Clo
gas when graphite anodes are used, as was previously the worldwide prac-
tice. In both processes, crude C12 gas is liquified and then purified by a
distillation step, so that most of the chlorinated hydrocarbons are sep-
arated from the C12 and remain as components of the "heavy ends" from the
distillation step. A minor potential exists for HCB contamination of the
recycled, spent brine, andvof the brine purification mud: the technical
literature indicates this is not a significant problem.—'
Industry spokesmen state that the substitution of a
metallized anode (DSA for dimensionally stable anode) for the graphite
anode in either process completely eliminates the HCB problems. Since
about 1969, many plants have been converted to the use of the DSAs. The
DSAs offer a substantial reduction in the consumption of electricity and
in maintenance requirements when used in the chlorine industry.
The typical chlorinated hydrocarbon wastes from the
Cl2 liquefication and purification steps of the diaphragm process range
from 0.70 to 1.4 Ib/ton of chlorine product.
The typical raw waste loads (based on 21 facilities)
from the mercury cell process^' are shown in Table II.
4. Carbon tetrachloride; The most important domestic production
route is the chlorination'of hydrocarbons, particularly methane.—' About
60% of the total production is accomplished by this method. About 40% of
the production involves a low temperature reaction between carbon disul-
fide and chlorine. A discussion of these production methods is given in
the following subsections.
37
-------
TABLE II
RAW WASTE LOADS FROM MERCURY CELL PROCESS^'
9
Purification muds, CaC03 and Mg(OH>2
NaOH
NaCl
KC1
H2S04
Chlorinated Hydrocarbons^'
Na2S04
C12 (as CaOCl2)
Filter aids
Mercury
Carbon, graphite
Waste Load
Mean
33
27
422
0
32
1.4
31
22
1.70
0.30
40.6
(Ib/ton Cl2 product^
Range
1.0-70
1.0-64
30-1,000
-
0-100
0-3.0
0-126
0-150
0-10
0.04-0,56
0.70-680
a/ Depends markedly on grade of chlorine produced (i.e., degree of puri-
fication).
38
-------
a. Production by chlorination of hydrocarbons;—' The
chlorination of aliphatic or aromatic hydrocarbons at pyrolytic tempera-
tures generally results in production of some carbon tetrachloride, along
with other chloromethanes and higher chlorination derivatives. Chlorina-
tion at such temperatures is often referred to as chlorinolysis, since it
involves a simultaneous breakdown of the hydrocarbons and chlorination of
the molecular fragments. This type of chlorination is highly favorable
to the formation of by-product HCB and HCBD. The quantity of carbon tetra-
chloride produced depends on the nature of the hydrocarbon starting mate.-
rial and the conditions of chlorination. When the hydrocarbon is methane,
conditions can be set to .obtain yields greater than 70% carbon tetrachloride.
In the Huls process, a 5:1 mixture (by volume) of chlorine
and methane is reacted at 650°C; this temperature is maintained by control
of the gas flow rate. The exit gas is cooled at 450°C and then passed to a
second reactor where more methane is added to the gas stream. The princi-
pal by-product is perchloroethylene. When ethylene is substituted for methane
in this process, perchloroethylene becomes the main product and carbon
tetrachloride is one of a group of coproducts, that also include hexachloro-
butadiene, hexachloroethane, and hexachlorobenzene.
In another methane chlorination process, the reactants are
brought into contact with a fluid catalyst bed, maintained at about 300 C
by the heat of the chlorination reaction. The crude product contains approxi-
mately equal quantities of carbon tetrachloride and perchloroethylene. Re-
cycle streams sent to the reactor suppress the formation of unwanted Co-
products by mass action.
b. Production from carbon disulfide and chlorine;—'
(1) Process flow diagram; A process flow diagram
is shown in Figure 12 below:
Mull
Neutrllizer]
and dryer
'Carbon '
tttracMoridt
(Adapted from a schematic in Reference 9)
Figure 12 - Production Schematic for Carbon Tetrachloride by Reaction
of Carbon Disulfide with Chlorine
39
-------
(i2) Process description; A solution of carbon disul-
fide in carbon tetrachloride (approximately 40% carbon disulfide, 50% car-
bon tetrachloride, and 10% sulfur monochloride) is charged into a chlori-
nator equipped with cooling coils. Chlorine is bubbled through the solution,
which contains iron powder added as a catalyst. The chlorination tempera-
ture is maintained at 30° C.
The reaction products consist primarily of carbon
tetrachloride (60%) and sulfur monochloride (40%) and are passed to a dis-
tilling column, where they are separated. The carbon tetrachloride distil-
late is sent to a neutralizer and dryer and the sulfur monochloride is re-
cycled. The low reaction temperature in this process is not considered to
be amenable to the formation of by-product HCB or HCBD.
(3) Reactions;
CS2 + 3C12 catllyst > S2C12 + CC14
CS2 + 2S2C12 > 6S + CC14
6S + 3C , > 3CS2
90% Yield
(4) Raw materials;
Basis—1 ton carbon tetrachloride
Carbon disulfide 1,100 Ib
Chlorine 2,300 Ib
5. Perchloroethylene; Numerous routes are available for manur
facture of perchloroethylene according to three broad categories: (a) the
dehydrochlorination of pentachloroethane derived from acetylene; (b) direct
processes based on acetylene or its chlorination products; and (c) the
cracking of other chlorohydrocarbons. Some processes typical of these categories
are described below.
a. Production from propane,'methane or ethane; One industry
source has estimated that approximately 40% of perchloroethylene production
in 1970 was based on ethane and propane. A process based on propane is de-
scribed below. '•!''•'•'.
40
-------
(1) Production from propane;—/.
(a) Process flow diagram; A process flow diagram
is shown in Figure 13.
• (b) Process description; Chlorine, propane, and
recycled distillation bottoms are mixed and fed to a chlorination furnace
held at 900 to 1200°F. Chlorination of the hydrocarbon takes place readily,
producing carbon tetrachloride and perchloroethylene. The perchloroethylene
is formed largely by pyrolysis of the carbon tetrachloride. Effluent gases
from the chlorination furnace are oil-quenched, and the chlorinated hydro-
carbons are separated from the quenching medium in a blowback column. The
chlorocarbon mixture is then fractionated with the carbon tetrachloride
going overhead to recovery and the distillation bottoms routed back toi the
furnace as recycle. Crude perchloroethylene is purified by distillation
and the bottoms are also recycled to the chlorination furnace. The process
by-products are carbon tetrachloride (CCl^) and hydrogen chloride (HC1).
There is a strong potential for the formation of HCB and HCBD in the chlori-
nation step; these coproducts concentrate in the still bottoms ("hex wastes").
(c) Reactions;
CsHs + 8 Cl2 - > CCl2=CCl2 + CC14 + 8 HC1
Propane + Chlorine - ^Perchloroethylene + Carbon Tetrachloride +
Hydrogen Chloride
2 C12
88% yield
(d) Raw materials;
Basis: 1 ton of perchloroethylene and 2,700
Ib hydrogen chloride
Propane 400 Ib
Chlorine 5,000 Ib
(e) Resource requirements;
Water (cooling)
41
-------
to
C3H8
Propane
••V^H
a.
Chlori nation
Furnace
1
ca,
H2Q-
Distillation
Column
Distillation
Column
Recycle Bottoms
I
Packaging
(Adapted from a schematic in Reference 9)
T
Shipment
Perchloroethylene
Absorption
Tower
I
cci4
Recovery
HCI — CGI,
By-Products
Figure 13 - Production Schematic for Perchloroethylene from Methane,TEthane, or Propane
-------
(f) By-products and wastes;
Hydrogen chloride
Carbon tetrachloride
Potential discharge of RGB and HCBD from
chlorination furnace
The HCBD formed averages a few percent (e.g.,
up to 2%) of product production.—' HCB is generally formed as a minor con-
taminant in the waste.
(2) Production from ethylene dichloride-t'
(a) Process description; Industry sources esti-
mate that approximately 50% of the per chloroethylene production in 1970
was based on ethylene dichloride (trichloroethylene may be coproduced with
the per chloroethylene). Chlorination of ethylene dichloride at 300 to 500°C
over coke or pumice gives perchloroethylene as the principal product. HCB
and HCBD can be formed in this chlorination reaction; these coproducts tend
to accumulate in the "hex waste" from the stills.
(b) Reaction; The chemical reaction may be repre-
sented as follows;
CH2C1CH2C1 + 3 C12 -J>CC12=CC12 + 4 HC1
Ethylene Dichloride >Perchloroethylene + Hydrogen Chloride
(3) Production from acetylene.2/
(a) Process flow diagram; A process flow dia-
gram is shown in Figure 14.
(b) Process description; Chlorination of acetyl-
ene (C2H2) is carried out in a reactor in the presence of a catalyst (antimony
trichloride, SbCl3) to form tetrachloroethane (CHC12CHC12). The tetrachloro-
ethane is then reacted with calcium hydroxide [Ca(OH)2] to produce trichloro-
ethylene and by-product calcium chloride (CaCl2). The trichloroethylene is
then treated with chlorine to form pentachlproethane (CHC12CC13). Penta-
chloroethane is reacted with calcium hydroxide to produce perchloroethylene
(CC12=CC12) and by-product calcium chloride. The perchloroethylene is dried
and packaged for shipment. In 1972 only 5% of U.S. production was based on
this processing method.
43
-------
CCI2-CCI2
C2 H2
Cl/
SbCI.
Reactor
r
Ca(OH)2
CI2
CHCI2-CHCI2
CHCI=CCI2
\\
CaCI2 H2O
Chlorinator
r
Ca(OH)2
CHCI2-CCI3
T
By-Product
Trichloroethylene
Waste
Shipment
(Adapted from a schematic in Reference 9) Perchloroethylene
Packaging
Packed,
Tower
1 CaCI:
H2O
Dryer
Figure 14 - Production Schematic for Perchloroethylene from Acetylene
-------
(c) Reactions;
HC=CH + 2 Cl >CHC12CHC12
Acetylene -j- Chlorine >1,1,2,2-tetrachloroethane
2 CHC12CHC12 t Ca(OH>2 -»2 CHCl=CCl2 + CaCl2 + 2
Tetrachloroethane + Calcium Hydroxide ^Trichloroethylene
I
!' + Calcium Chloride
2 CHC1=CC12 + 2 C12 >2 CHC12CC13
Trichloroethylene >Pentachloroethane
2 CHC12CC13 + Ca(OH)2 >2 CC12=CC12 + CaCl2 + 2 H20
Pentachloroethane ^Perchloroethylene
(d) Raw materials;
Basis: 1 ton perchloroethylene
Acetylene 380 Ib
Chlorine 3,000 Ib
Calcium hydroxide 900 Ib
Catalyst loss Small
(e) Resource requirements
Water (cooling and process)
45
-------
(f) 'By-products and wastes:
Trichloroethylene
Calcium chloride
Waste from-perchloroethylerie.decanter and
drier
6. Trichloroethylene
a. Production from acetylene using catalytic dehydrochlori-
nationZ'
(1) Process flow diagram: A process flow diagram
is shown in Figure 15.
(2) Process description; Acetylene and chlorine are
reacted (at 80 to 100° C) in the presence of tetrachloroethylene and a catalyst
(antimony chloride, SbC^) to produce tetrachloroethane
The tetrachloroethane prepared by this chlorination reac
tion is vaporized and sent to a catalytic reactor where it is dehydrochlori-
nated to produce trichloroethylene and hydrogen chloride. The standard
catalyst is barium chloride (307o) deposited on carbon. The reactor is heated
to 250 to 300°C to maintain the required pyrolysis reaction. Product gases
containing 90% trichloroethylene (TCE) and 10% tetrachloroethane are con-
densed, degassed to remove by-product HC1, and then sent to distillation
columns to separate TCE from the heavy ends. A small amount of trimethyl-
amine (20 ppm by weight) or proprietary neutral inhibitors (such as pyrrole-
based compounds) may be added to the product to stabilize it. The overall
process yield based on either acetylene or chlorine is 90%. This is the
only production process which appears to have a significant potential for
the formation of by-product RGB and HCBD.
(3) Reactions;
SbCl3 - >
CHC12
Acetylene + Chlorine - > Tetrachloroethane
CHCl2'CHCl2 > C1HC=CC12 + HC1
Tetrachloroethane - ^Trichloroethylene + Hydrogen Chloride
46
-------
BaCI,
f
C2HZ
CHCI2-CHCI2 _
C'2
Sbci3
' (Adapted from a sch
A*-"C-J IHCI
Reactor
CHCI2-CHCI2 R_tor
1
SbCI3
Recovery
_^ Piirifirnt
Absorption
Tower
1
ematic in Reference 9) By-Product
HCI
ion f- Packaging
Shipment
Trichloroethylene
Figure 15 - Production Schematic for Trichloroethylene from Acetylene
Using Catalytic Dehydrochlorination
-------
(4) Raw materials; >
Basis: 1 ton of trichloroethylene
.Acetylene " 440 Ib
: Chlorine 2,400 Ib
' •' '. V •,'•;,'• I ' '
Catalyst loss Small
>•
(5) Resource requirements;
Water (cooling)
(6) By-products and wastes;
Hydrogen chloride
Heavy ends from TCE purification still (waste)
Potential for formation of hexachlorobenzene in
the pyrolysis step
b. Production from acetylene using milk of lime-t'
(1) Process flow diagram: A schematic production flow
sheet is shown in Figure 16 (page 49).
(2) Process description: The method for providing the
intermediate, tetrachloroethane, is identical to that described in Process
1.
In this process the conversion of tetrachloroethane to
trichloroethylene is accomplished by contact with a milk of lime, Ca(OH)2»
suspension in a packed tower. The trichloroethylene distills overhead and
is then condensed, purified, and packaged for shipment.
(3) Reactions;
HC=CH + 2 C12 >CHC12CHC12
1,1,2,2-tetrachloroethane
2 CHC12CHC12 + Ca(OH)2 »2 CHC1=CC12 + CaCl2 + 2 H20
Tetrachloroethane >Trichloroethylene + Calcium Chloride
48
-------
•p-
vO
Acetylene
fCoHo)
v-2n2/
CHCI2-CHCI2_
SbCI3
Keactor
i
SbCI3
Recovery
Ca(O
CHCI2-CHCI2
C
H)2~l
Packed
Tower
1 1
aCI2 H2C
CHCI-CCh
)
r> 'i'
runtication
J
Can Lead
to Perchloroethylene
Production
Wastes
Shipment
(Adapted from a schematic In Reference 4) Trichloroethylene
Figure 16 - Production Schematic for Trichloroethylene from Acetylene
Using Milk of Lime
-------
(4) Raw materials; ;
Acetylene !
.f . .
Chlorine
Milk of lime '
(5) Resource requirements;
Water . '.'
(6) By-products and wastes;
Calcium chloride '
Wastes from the SbCl3 recovery system
I
7. Dacthal®; Dacthal® is the proprietary name for dimethyl tetra-
chloroterephthalate, a herbicide. A processing method described in the patent
literature is discussed in the following subsections.
\
a. Process flow diagram; A process flow diagram is pre-
sented in Figure 17.
b. Process description; An improved process route (U.S.
Patent No. 3,052,712, September 1962) involves the reaction of hexachloro-
£-xylene with terephthalic acid, followed by chlorination of the crude reac-
tion product, and finally, esterification of the crude chlorination product.
A spokesmani?-' for the Diamond Shamrock Corporation, the only
domestic producer, has reported that HCB is not an impurity in the feed-
stock <£-xylene), but is formed in the chlorination reaction. No HCBD is
formed in the process. The Dacthal® is reported to contain about 0.3% HCB
at present, but apparently contained much higher levels before 1972 (i.e.,
up to about 10% HCB). Information from a written inquiry (see Appendix B,
page 153) , shows that waste materials from production of Dacthal® at the
only domestic plant contain about 84% of HCB and that the product contains
about 0.3% HCB.
c. Reactions;
C6H4(COOH)2 + C6H4(CC13)2 >2 C6H4(COC1)2 + 2HC1 • .. ,
C6H4(COC1)2 + 4C12 »C6Cl4(COCl)2 + 4HC1
C6C14(COC1)2 + 2CH3ONa ->C6Cl4(COOCH3)2 > 2NaCl
50
-------
C*,0('HEXACHLORO-P-XYLENE [
[ TEREPHTHALIC ACID |
FUSION
|_I%_CCI4J
CHLORINE
J
[
•<
0.01-1.0% OF TOTAL
CHARGE, 100° -200* C.
[(PREFER 125°-150' C.)
MOLTEN CRUDE
TEREPHTHALOYL OICHLORIOE
CHLORINATION I-
|_METHAN_OL
NoOH
I50°-2IO° C.
0-200 PSIG. (PREFERABLY 100)
F«CI3 UP TO 1.0% OF TOTAL
CHARGE. USE EXCESS Clz
MOLTEN CRUDE
TETRACHLOROTEREPHTHALOYL
DICHLORIDE
ESTERIFICATION
SODIUM METHYLATE
IN METHANOL
f50-IOO°C. (AT REFLUX)
^0-25 PSIG.
[ALKALI + METHANOL
SLURRY OF CRUDE DIMETHYL 2,3,5,6
TETRACHLOROTEREPHTHALATE
IN METHANOL
METHANOL
MOTHER LIQUOR
TO ABOUT
20°-30° C.
OR LOWER
CENTRIFUGE|
1 -
H20
WASH
_L
NaCI + OTHER SOL. SALT
e C.
DIMETHYL 2,3,5,6
TETRACHLOROTEREPHTHALATE
I_P-XY_LENE _OR_
RECRYSTALLIZE j
IF DESIRED I
Source: U.S. Patent 3,052,712
Figure 17 - Flow Diagram for Dimethyl Tetrachloroterephthalate Manufacture
51
-------
8. Atrazine; Atrazine is one of a family of substituted triazine
herbicides; the other major members of the group are propazine and simazine.
A discussion of the'-process technology for-atrazine is given in. the follow-
ing subsections.
a. Process flow diagrams; A schematic production flow dia-
gram for atrazine is'presented in Figure 18, and Figure 19 shows flow dia-
grams for synthesis of various triazine pesticides.
b. Process description;— Cyanogen chloride is first pre-
pared by chlorination of hydrogen cyanide. Cyanuric chloride is then produced
by the polymerization of cyanogen chloride in the presence of activated car-
bon at 350 to 400°C, or in the liquid phase under pressure in various organic
solvents with the use of anhydrous aluminum chloride, etc., as catalysts.
The cyanuric chloride is rea'cted with ethylamine and sodium
hydroxide to form 2,4-dichloro-6-ethylamino-S-triazine, which by further
reaction with isopropylamine and sodium hydroxide gives atrazine.
The possible methods for HCB contamination during the pro-
duction of atrazine are;
* HCB may be contained as an impurity in cyanogen chloride
used as intermediate chemical.
* HCB may be formed during the production of cyanuric
chloride.
No evidence was found that any HCBD is formed in this industry.
Information obtained by a written inquiry (see pages 145 to
153) shows that atrazine products contain HCB (range of 0.025 to 0.25 ppm)
and that the liquid process wastes from the still bottoms also contain HCB
(range of 0.024 to 2,000 ppm). HCBtf is not produced in the process. Hydrogen
chloride, formed as a by-product of the process, is neutralized with caustic
soda to form a NaCl waste material.
c. Reactions;
Cl Cl
3HCN + 3C12 Nf)N C2E5m2 -^ (CH3)2CHNH2
z A ; , Solvent i I • r-
Cl
Cyanuric
Chloride
Cl
5HC1 or •>- "f ^
RNHoCl CoHcHN-^^N-^^NHCH^Ho),
•J . £. ^ • J £
Atrazine
: 52 . ; .
-------
Solvent
CI2.
HCN-
NaOH-
C3N3CI3.
Scrubber
and Filter
Deep Well
Disposal
(CH3)2CHNH2
Additives
I r—V-.-JV- z or Solvents
I 1 + i 1
Amination
Unit
T
Filtrate
Atrazine
Formulation
(Alternate)
L
Air Filters
and Scrubbers
Liquid
Wastes
Discharge
to River
Packaging
I
Product
Vent
Figure 18 - Production Schematic for Atrazineii'
-------
Dyrene
d
Cl
Slmazlne
NH
Cl^NpSu
C2HSNH TT NHC2H5
NH
3d
-------
d. Raw materials;
Hydrogen cyanide
"Appropriate" amines
Chlorine
Sodium hydroxide
e. By-products and wastes; By-product hydrogen chloride
(0.333 Ib HC1 produced per pound of atrazine).
Liquid wastes from cyanuric chloride productions unit.
9. Propazine
Process description; Propazine (i.e., the common name for 2-
chloro-4,6-bis-isopropylamino-l,3,5-triazine) is synthesized by the reac-
tion of cyanuric chloride with isopropylamine in the presence of an acid
acceptor. The technical product is more than 95% pure (molecular formula
is CgHi^^Cl). The process and the prospects for HCB formation are similar
to those discussed for atrazine, except that the production volume of the
latter is much greater (see page 153 for data from a written inquiry).
10. Simazine
Process description; Simazine (i.e., the common name for 2-chloro-
4,6-bis(ethylamino)-S-triazine) is synthesized by reacting cyanuric chloride
with ethylamine in the presence of an acid acceptor. The process and the
potential for HCB formation is similar to that for atrazine (see page 153
for data from a written inquiry).
11. Pentachlorobenzene; A discussion of a domestic process for
production of pentachlorobenzene is presented in the following subsections.
a. Process flow diagram; A schematic production flow dia-
gram is shown in Figure 20.
b. Process description;— Pentachlorobenzene (CgHCls) may
be produced by reacting chlorine (Cl2) with benzene (C^Hg) or partially
chlorinated benzenes (CgHcCl to C/rHoClA) in the presence of a catalyst,
ferric chloride (FeC^), at a temperature of 150 to 200°C. The reaction
products are scrubbed with water to remove hydrogen chloride (HC1) to pro-
duce by-product hydrochloric acid. The scrubber reaction products are then
55
-------
a-
v_,2 ^
C6H6 ^
Partially
Primary
Reactor
Scrubber
Chlorinated Benzenes
•- . '
i
\
i
Packaging
Shipment
HC1
Cooler &
Crystal lizer
•
Centrifuge
f
i
Separati
Chlorob
\
i
Purification
& Drying
on
r
enzenes -
Purification
& Drying
1- 4
Packaging
Packaging
\
(Adapted from a schematic in Reference 4)
Shipment of
Hexachlorobenzene
\
Shipment
Pentachlorobenzene
Figure 20 - Production Schematic for Pentachlorobenzene by Chlorination
of Benzene or Chlorobenzene
-------
cooled causing hexachlorobenzene (HCB, formula CfcClfj) to crystallize out.
HCB which is formed as a by-product, is removed by centrifuging or filter-
ing. Pentachlorobenzene separation from the less chlorinated benzenes
(C(jH5Cl to Cfc^Cl,!,.) and purification is effected by freezing point and sol-
vent extraction methods. The less chlorinated benzenes may be recycled or
become by-products.
Small quantities of pentachlorobenzene are produced as a
captive by-product in the U.S. The manufacturing process involves some risk
of HCB emission to the environment. Because of the captive production, how-
ever, it is considered unlikely that any serious HCB pollution problem is
created during production of pentachlorobenzene.
c. Reaction;
C6H6 + 5C12 "°°QC> CHC1 + 5HC1
d. Raw materials;
Benzene
Chlorine
Ferric chloride (catalyst)
e. Resource requirements;
Water
f. By-products and wastes;
Hexachlorobenzene
Monochlorobenzene (normally recycled in process)
Dichlorobenzenes (normally recycled in process)
Trichlorobenzenes (normally recycled in process)
Tetrachlorobenzenes (normally recycled in process)
Hydrochloric acid '
57
-------
12. Pentachloremitrobenzene;-/ Pentachloronitrobenzene (PCNB,
formula C^Cl^NC^) is synthesized by nitrating hexachlorobenzene or chlori-
nating various chloronitrobenzenes that are formed as by-products in the
production of m-chloronitrobenzene and 3,4-dichloronitrobenzene. The chlori-
nation is conducted in the presence of an iron-iodine catalyst. The complete
absence of moisture is an important condit'ion for the chlorination, since
even a trace of water sharply decreases the rate of the reaction.
The structural formula for PCNB is:
13. Mirex; Mirex is a trade name for dodecachloro-octahydro-
l,3,4-metheno-2H-cyclobuto(cd)pentalene. The production of this pesticide
is described in the following subsections.
a. Process flow diagram; A schematic production flow dia-
gram is shown in Figure 21 below.
Hydrocarbons
Partial
Chlorination
Cl, /Cl
Cl-
Cl
Cl
Cl
\ /
Cl
Cl
PCI5
AlCIa as
Catalyst
Cl
Cl
Mi rex
Figure 21 - Schematic of Reactions for Production of Mirex
58
-------
b. Process description; A dimer of hexachlorocyclopenta-
diene is first prepared by a process (U.S. Patent Re-Issue No.. 24,397,
15 February 1955), in which phosphorus pentachloride (PC^) is reacted with
decachlorotetrahydro-4,7-methanoindene. The Mirex is obtained by a condensa-
tion of hexachlorocyclopentadiene dimers.
Hexachlorobenzene contamination could occur in the
treatment step of this process. There is also a possibility that feed mate-
rials could contain RGB as an impurity.
B. Processes with Theoretical, But Not Proven, Production of HCB
and/or HCBD
1. Sodium chlorate; This chemical is produced in the United
States by the electrolysis of sodium chloride in aqueous solution. A dis-
cussion of this process follows.
a. Process flow diagram; A schematic production flow dia-
gram is shown in Figure 22 below.
Condensate rt^l
Sodium
dichrpmate Mother liquor
Hydrochloric
acid
Water
Sodium
chlorate
(Adapted from a schematic in Reference 9)
Figure 22 - Production Schematic for Sodium Chlorate
b. Process description;— Salt (sodium chloride) is
charged into a dissolving tank, where it is converted into a saturated
solution by the addition of soft water. Generally, some mud and salt im-
purities collect at the bottom of the dissolver, from which they are per-
iodically discharged. If the salt contains a high percentage of calcium
and magnesium salts, it is usually necessary to purify the solution by
precipitation, settling, and filtration of the foreign salts.
59
-------
The clarified saturated salt solution is transferred to a
feed tank, where it. is mixed with dilute hydrochloric acid. A concentration
of about 0.57, acid is usually maintained so that the average pH of the brine
solution in the cells will be approximately 6.5. Sodium dichromate (about
0.2%) is added to Inhibit cell corrosion caused by the liberated hypochlorous
acid (from the hydrochloric acid present).
The saturated acidulated brine is fed into banks of electro-
lytic cells, operating batchwise or continuously, maintained at,40 to 45°C
by cooling water. The construction and operation of the cells vary in dif-
ferent installations. Generally, the cell bodies are constructed of steel
and make use of steel cathodes and graphite anodes. There is no diaphragm
in the cell, and the electrodes are closely spaced to allow mixing of the
products. The electrolysis actually yields chlorine at the anode and sodium
hydroxide at the cathode. However, because of the foregoing conditions,
good mixing occurs, resulting in the formation of sodium hypochlorite
(NaCIO) and then sodium chlorate (NaClC^).' Hydrogen is liberated during the
electrolysis and may be either vented or recovered by suitable means.
The cell liquors, after electrolysis, are discharged into a
settler. In batch operations, generally 75% of the salt is converted. The
liquor in the settler may be heated to 90°C to destroy any residual hypo-
chlorite.
The chromate ions remain in the liquor and protect steel
equipment from corrosion further along in the process. Formates or urea
may be added to the liquors in the settler to convert the residual hypo-
chlorite to chlorate. Graphite mud from the anodes settles to the bottom
of the tank and is periodically removed.
The liquor contains about 50% sodium chlorate. It is de-
canted from the top of the settler, passed through a sand filter (if neces-
sary), and charged into double-effect evaporators. Here it is concentrated
to approximately 70 to 75% sodium chlorate and filtered. The unconverted
sodium chloride is less soluble than the chlorate at boiling temperatures.
and is thrown out of solution. Recovered salt (filter cake) is returned
to the dissolver for reuse.
The filtrate is passed into a crystallizer, where it is
cooled (below 30°C) to precipitate sodium chlorate crystals. The product
is centrifuged, washed, and dried in rotary dryers. The centrifuge mother
liquor and first wash liquors are generally returned to the evaporator for
subsequent concentration, although periodically they are returned to.the
cell feed tank for reprocessing.
60
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The dried product is ground to proper mesh size and screened
I to yield sodium chlorate crystals, which assay about 99.5%. Although the
initial conversion of sodium chloride to chlorate ranges from 50 to 75%,
the overall yield (based on the salt charged) is about 95%.
Sodium chlorate may be recovered from the cell liquors by
other methods than the previously described concentration process. These
. other procedures include direct crystallization by refrigerative cooling
(about 0°C) and salt exchange (isothermal crystallization) where the
chlorate is salted out by addition of sodium chloride.
The chief variations in electrolytic processes for sodium
chlorate are in recovery of the product from the cell liquors, which may
be accomplished by chilling, salting out, or evaporation. The particular
method used depends on conditions existing at a given plant. Considerable
.care must be taken in the operation of any chlorate plant, because of the
potential fire and explosion hazard.
c. Reaction;
d. Raw materials;
Sodium chloride, 1,130 Ib/ton of sodium chlorate
e. Resource requirements;
Sodium chloride
Water
f . Energy requirements
5,100 kw-hr/ton of sodium chlorate
2. Sodium metal; A minor source of chlorine is that produced
as coproduct with sodium metal production. Plants producing sodium metal
are included in the chlor-alkali listing in Table A-II, Appendix A).
61
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a. Process flow diagram; A schematic production flow
diagram is shown in Figure 23 below. -.'.•!'•
•CMwfh*
* ' ' ' '
^M
(Adapted from a schematic in Reference 9)
Figure 23 - Production Schematic for Sodium Metal
9/
b. Process description;— The electrolysis of salt to
produce sodium metal requires very high purity sodium chloride. A pure
sodium chloride brine is dissolved in water and treated with sodium hy-
droxide (to remove heavy metals), barium chloride (to remove sulfate), and
ferric chloride (as a coagulant). The brine is evaporated, filtered, and
dried.
The pure sodium chloride is mixed with calcium chloride in a
Downs Cell to obtain a low-melting fused-salt mixture. The composition is
about 58% CaCl2 and 42% NaCl which permits cell operation at 580°C. Addi-
tional calcium chloride can be added if lower operating temperatures is
desired. The electrolysis produces a sodium-calcium alloy (95% Na, 5% Ca).
Upon cooling, most of the calcium precipitates out in the cooled riser
pipe. The calcium falls back into the molten salt where it reacts with
chlorine to produce calcium chloride.
Sodium metal generated during the electrolysis operation is
distilled into a receiver. The material collected is filtered at 110°C.
The filtration removes most of the calcium carried over as well as sodium
and calcium chloride and oxides. The filtered sodium contains less than
0.04% calcium, and is sufficiently pure for most uses.
The filter cake produced during the sodium metal recovery
is usually solid waste. In some cases, it may contain sufficient chemical
reducing power (in the metallic calcium) to serve some specialized needs.
The chlorine generated during metallic sodium production is recovered by
the same processes and techniques used in the chlor-alkali industry.
No evidence Was found that HCB or HGBD are generated in
this process. , .
62
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3. Vinyl chloride monomer: This chemical is produced by: (a)
pyrplysis of ethyl dichloride; (b) reaction of ethylene dichloride with
caustic soda; and (c) the acetylene process as follows.
• - - . • '." •;'•.'-.' ' • 9/ •
a. Production by pyrolysis of ethylene dichloride~
(1) Process flow diagram; A schematic production
flow diagram is shown in Figure 24 below.,
Ethylene _ •„_ ^ . a.ckinn •' . .
dich
onde' ' furnace • | /J
Hz
Recycle ethylene dichloride
r-J
Dr~ '
Quencher
1 '
riid to absorber
i— +-Vln»l cMoridr
V 1
•H
f
•C
O
(J
L
-*•
He
Distillation
. . tower .
avy ends . • • •
(Adapted from a schematic in Reference 9) .
Figure 24 - Schematic for Production of Vinyl Chloride by
Pyrolysis of^ Ethylene Bichloride
(2) Description; Vaporized ethylene dichloride is
dried and passed over a contact catalyst (e.g., charcoal or pumice) con-
tained in tubes directly heated in a cracking furnace. At 50 psig, with
the effluent gases at 90 to 950°F, a yield of 95 to 96% is attained.
The effluent gases from the furnace are quenched by
direct contact with a stream of ethylene dichloride. Uncondensed gases are
sent to an indirect condenser to recover the remainder of the condensable
vapors arid the noncondensables are scrubbed with water to recover hydrogen
chloride.
The combined liquid streams from the condenser and
quencher are fed to a fractioriation tower operated under sufficient pres-
sure to yield vinyl chloride by condensing the overhead vapors in a water
condenser. The vinyl chloride is sent to storage. The still bottoms are
sent to a still where ethylene dichloride is separated from the "heavy
ends" and passed overhead. Condensed ethylene dichloride is recycled, part
to the quencher and part to the process feed tank. About 90% of the dom-
estic production of vinyl chloride is accomplished by this process. In
this process HCB may be formed in the thermal processing operation.
63
-------
(3) Reaction; •'•
CH=CHCi + HG1
.••;.' (4) . Raw mater ia Is; . •:•''•
Basis: 1 Lori, of .vinyl chloride
.Ethylene dichloride . 3,3.00 l.b . ,: ••'.'•' ' " .. . ••' .;
(5) By-products aiu'l wastes; . ,
HC1 (by-product)
The wastes are '"heavy ends" (chlorinated tars)
from the still. :
b. Production by reaction between ethylene dichloride and
caiu£t ic soda
(1) Process description;—' A process similar to the
pyrolysis process (a) involves heating ethylene dichloride in the presence
of caustic soda. Ethylene dichloride is mixed with a water solution containing
6% NaOH in a 2;1 ratio of dichloride to alkali. The mixture, is .charged to a
reactor held at 150 psig where it is allowed to react for 2 to 3 rain at
290°F.
The overflow from the reactor is cooled and sent to a
pressurized column where vinyl chloride passes overhead to storage. The
bottoms are discharged to separate unconverted ethylene dichloride and some
water vapor from the valueless bottoms. The ethylene dichloride is separated
from accompanying water in a decanter and recycled, the overall yield of
vinyl chloride based on ethylene dichloride is 90%.
. (2) Reaction; .
+ NaOH > CH^CHCl 4- tiaCl + H26
64
-------
(3) Raw materials
Ethylene dichloride
Sodium hydroxide
(4) By-products and wastes;
By-products; sodium chloride and water
Wastes: still bottoms (mixture of high boiling
,, organics and brine)
' . i '
1 Q/
c. Production by the acetylene process—'
(1) Process flow diagram;. A schematic production flow
diagram is shown in Figure 25 below.
Acetylene and HC1
Catalyst
Acttylene
II
i
Hydrogen chloride
I
cc
L
•HBH^^H
P
1
L
f (stabilized)
Phenol
(Adapted frora a schematic In Reference 9)
Figure 25 - Production Schematic for Acetylene Process
for Vinyl Chloride
(2) Process description; Dried acetylene (C2H2) and
anhydrous hydrogen chloride (HC1) are mixed and fed to a reactor containing
carbon pellets impregnated with mercuric chloride (catalyst). The reaction
is exothermic and the reaction temperature is maintained between 160 and
250°C.
Effluent gases from the reactor are cooled first by
heat exchange with cold reactants and finally condensed and fractionated
in a refrigerated column from which unreacted C2H2 and HC1 go overhead.
The acid-free monomer or "crude" is further fractionated in a second re-
frigerated column in which vinyl chloride goes overhead, and by-product
ethylidene chloride and aldehydes are removed as bottoms. The condensed
vinyl chloride is stabilized with a small amount of phenol and then sent
to storage. The yield, based on acetylene, is 99%. Because of the low reac-
tion temperature, it is unlikely that HCB or HCBD is formed in this process.
65
-------
(3) Reaction;
HeClo
C2H2 + HC1:—S—£» C2H3C1
(4) Raw materials; .
Basis; 1 ton of vinyl chloride
Acetylene 880 Ib
Anhydrous hydrogen chloride 1,200 Ib
(5) By-products and wastes
Ethylidene chloride and aldehydes are by-products
Wastes include;
* The carbon in the mixing chamber saturated
with chlorine and other impurities.
* The spent catalyst suspended in carbon.
* Hydrated solid" potassium hydroxide used to
dry the product before distillation.
12 /
4. Pentachloropheno1;—' The principal production process used
domestically involves the chlorination of phenol. A discussion of this
process follows.
a. Process flow diagram; A schematic production flow dia-
gram is shown in Figure 26.
b. Process description; Pentachloropheno1 (PGP, formula
C6C15OH) may be produced by reacting phenol (CfcH^OH) with chlorine (Cl2> in
the presence of aluminum chloride (AlCl^) at a temperature of 65 to 130 C.
The chlorination reactor is of two stage design, the second stage intended
to scrub excess Cl^. Separation of PGP from less chlorinated phenols is
effected by melting point. The product is dried for packaging and shipment.
Hydrogen chloride (HC1) produced by the process is absorbed by water to
produce by-product hydrochloric acid. Less chlorinated phenols may be re-
moved as by-products or recycled.
66
-------
HCI, CI2
HCI, CI2
Phenol J
CI2 _
-••
Primary
Reactor
i
rC6H5OH |H2° |C6H5OH
C6CI5OH Scrubber- Absorption
Reactor . Tower ;
'.I
X
Partially Chlorinated
Separation
&
Packaging
1
1
Phenols
f
Purification By-Product
Drying HCI
Packaging
Shipment
Partially Chlorinated
Phenols
I
Pentachlorophenol
C6CI5OH
127
Figure 26 - Production Schematic for Pentachlorophenol by Chlorination of Phenol—'
-------
I •, ' •-
c. Reaction;
65 130° C
C6H5OH + 5 C12 > C6C15OH + 5 HC1
A1C13 ',
d. Raw materials; ' , .
" . . ..;• r "••••''.-•• '• • •• ' ,,' . • :( ' . • •
Phenol '
Chlorine
Aluminum chloride (catalyst) ;
•>.-..
e. Resource requirements?
Water <
f . By-products and wastes;
Hydrogen chloride and the less chlorinated phenols are
by-products : . .
5. Hexach lo ro ethane ; The most commonly used process for produc-
tion of this chemical is based on the chlorination of perchloroethylene. A
discussion of this process is presented in the following subsections.
a. Process flow diagram; Figure 27 is a schematic flow
diagram for production of hexachloroethane by chlorination of perchloro-
ethylene.
b. Process description;—' Hexachloroethane (formula
is produced by reacting perchloroethylene (C2C1^) with excess chlorine
in the presence of a catalyst, ferric chloride (FeCl-j), in a lead-
lined vessel at 100 to 140°C. Any hydrogen chloride (HC1) produced is then
neutralized with caustic soda (NaOH). The reaction and neutralization prod-
ucts are then cooled. HCE crystallizes, precipitates from solution, and is
centrifuged out. The liquid phase is recycled after the water is removed.
\ . .
Because of the low chlorination temperature, it is unlikely
that this process poses any serious problem with regard to HCB Or HCBD
contamination.
c. Reaction;
Fed-}
C12 - - • - - — > C2C16
100-140°C
68
-------
HCI
FeCI
3
CCI2=CCI2
i
Reactor
(100-140° C)
NaOH
Neutralizer
vO
T
Centrifuge
Purification
Packaging
T
H2O
By-Product
NaCI
Shipment
Hexachloroethane
(Adapted from a schematic in Reference
Figure 27 - Production Schematic for Hexachloroethane from Perchloroethylene
-------
d. Raw materials;
.Perchloroethylene
Chlorine
Ferric chloride (catalyst) :
Caustic soda
e. Resource requirements;
Water (cooling) '
f. By-products and wastes
Sodium chloride
Water
6. Synthetic rubber (chloroprene); Of the seven major synthetic
rubbers currently produced in the United States, chloroprene production and
its polymerization to neoprene appears to present any potential problem in
regard to environmental contamination by HCB or HCBD.—'
Chloroprene is produced by chlorination and dechlorination steps,
some of which might produce by-product HCB or HCBD. All of the processing
methods are proprietary information, and therefore, no detailed process
data could be obtained on the production of chloroprene and its conversion
to neoprene. No evidence was found that any of the process operations gen-
erate HCB or HCBD. •
7. Maleic hydrazide;—' Maleic hydrazide (3-hydroxypyridazone)
is produced by heating equimolecular quantities of hydrazine salts and
maleic acid or maleic anhydride in aqueous solution. A typical production
reaction is;
0 P,
U ' I
' \ HC''0^
2HC 0 + (N2H4>2H2S04 —» 2 HJ, ^ + H2SO, + 2*1,0
HC /
^Pi Dihydrazine i (
0 Sulfate °
Maleic
Anhydride
70
-------
Generally the operation is carried out by mixing the reactants
and then heating to 75 to 110°C until the reaction has attained the required
degree of completion. After cooling, the product precipitates from the mix-
ture and is readily recovered by filtration and washing.
The principal possibility for HCB contamination in this process
would be by its introduction as an impurity in one of the raw materials
used. Since the maleic anhydride is conveniently made by air oxidation of
benzene, it does not appear to be a potential source. Hydrazine (N^N^)
is prepared by reacting elemental chlorine with caustic soda to form NaOCl,
forming N^Cl by oxidation of ammonia and finally reacting ammonia with
NH2C1. If hydrazinium chloride (^H^'HCl) were used in place of the sulfate,
the HCB might be formed in the reaction itself, but no data on such a reac-
tion were found.
8. Hexachlorocyclopentadienet—' Hexachlorocyclopentadiene (HCP)
is produced in the United States almost exclusively by the two-stage chlori-
nation of pentane, isopentane or cyclopentane. The first stage is a photo-
chemical chlorination of the hydrocarbon at 80 to 90°C which involves the
reaction of 1 mole of hydrocarbon with about 9 moles of chlorine. A crude
product (a mixture of noncyclic compounds) with an average formula of
C-jH^Cly, is continuously withdrawn and then subjected to a vapor-phase
chlorinolysis. In the chlorinolysis, the vaporized polychloropentanes and
excess chlorine are passed over a surface active catalyst at 300 to 430°C,
and then through a nickel tube at a temperature of 450 to 525°C. Octachloro-
cyclopentane is produced over the catalyst and is then dechlorinated to HCP
by the catalytic action of the nickel. Some information was obtained which
establishes a potential for the formation of HCB and HCBD in these processing
operations.
Another currently used industrial process involves chlorination
of cyclopentadiene with sodium hypochlorite. The low reaction temperature
of about 40°C precludes the formation of either HCB or HCBD.The cyclo-
pentadiene is produced on-site by vapor phase cracking of naphtha.
Detailed information concerning these proprietary processes could
not be obtained by inquiries to the producers.
9. Chlorinated naphthalenes; The Koppers Company, Inc., the
sole producer of chlorinated naphthalenes, uses a proprietary process for
the manufacturing operation. Our inquiries to this company did not develop
any information on the specific process operations involved. The technical
literature!/ reports that chlorination of naphthalene in the presence of
a catalyst (e.g., ferric chloride) is used to produce commercial quanti-
ties of 1-chloronaphthalene and mixtures of polychloronaphthalenes.
71
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The Koppers 'Company markets several different products under the
.trade name of "Halowax." These products contain various amounts of chlorine .
in the range of 22 to 61%. The products may?be either liquids (low chlorine
content) or waxlike solids (medium and high chlorine content).
1-Chloronaphthalene is produced industrially by passing chlorine
into molten naphthalene and fractionally distilling the product." For the
manufacture of higher chlorinated naphthalenes, the naphthalene is generally
chlorinated in the presence of ferric or antimony chloride. The initial
chlorination temperature is 80° C, and the temperature is slowly raised as
the reaction proceeds. The final temperatures may reach about 200°C. The
chlorinated product is neutralized by stirring in the molten state with
aqueous alkali, washed with water, and dried under vacuum. .
'4/
10. Chlorinated biphenyls (PCBs)t- In the United States, PCBs
are manufactured by a single producer, the Monsanto Company, and marketed
under the trade name of "Aroclor®." The different PCB products are dis-
tinguished by number designations in which the first two digits (12) specify
polychlorinated biphenyls and the last two digits indicate the P approxi-
mate percentage of chlorine in the mixture. The industrially important PCB
prodiicts ate formed by chlorination of biphenyl to give chlorine cofttShts
in the range of 21 to 60%.
The chlorination reaction can be accomplished by batch or con-
tinuous chlorination. The type of reactor used and the operating condi-
tions influence the composition of the Aroclor® product in regard to content
of isoraers and other compounds.
The chlorinators are generally steel towers equipped with chlorine
distributors at the bottom, heat transfer coils, and pumps for circulating
the liquid. The lower portion of the chlorinator is filled with ferric
chloride (catalyst).
For the manufacture of PCBs (1200 series Arochlor®), the chlori-
rator is charged with biphenyl, and chlorine gas is bubbled through the
liquid biphenyl. Throughout the chlorination, the temperature is kept well
above the melting point of the mixture, but below 150°C. Anhydrous hydrogen
chloride, which is evolved during chlorination is absorbed in water. The
time required for chlorination is 12 to 36 hr, depending upon the chlorine
content of the product.
72
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C. Methodology and Results of a Study to Estimate Quantities of HCB
and/or HCBD Generated by Chemical Industry
This section outlines the methodology and results for MRI esti-
mates of the quantities of HCB and/or HCBD contained in chemical process
wastes, by-products, and products. The results apply for 1972.
1. Perchloroethylene and trichloroethylene; The U.S. production
of perchloroethylene (perchloro) and trichloroethylene (trichloro) in 1972
was 734,800,000 and 427,000,000 Ib, respectively.
Information in the attached table (Table III), shows that the
waste quantity and composition varies widely from company to company. There-
fore, estimates of the HCB and HCBD generated were prepared for each company,
and then summed to obtain the total estimate for each industry. Assume that
production for each company corresponds to the percent of total U.S. capac-
ity represented by the company.
a. Diamond Shamrock Company
Perchloro: Production is 11.37. of total or 83.03 x 106 Ib,
the tar residue is 1% high or 0.5% low (assumed) of product and it con-
tains 107. HCB (assumed) and 757. HCBD.
High HCB = (83.032 x 106) (0.01) (0.10) = 83,032 Ib
Low HCB = (0.5) (high) = 41,516 Ib
High HCBD = (83.032 x 106) (0.01) (
Low HCBD = (0.5) (high) =311,370 Ib
High HCBD = (83.032 x 106) (0.01) (0.75) = 622,740 Ib
Trichloro; Production is 11.37. of total or 48.251 x 106 Ib,
the tar residue is 17. high or 0.57. low (assumed) of product and contains
10% HCB and 757. HCBD.
High HCB = (48.251 x 106) (0.01) (0.10) = 48,250 Ib
Low HCB = (0.5) (high) = 24,126 Ib
High HCBD = (48.251 x 106) (0.01) (0.75) = 361,880 Ib
Low HCBD = (0.5) (high) = 180,940 Ib
b. Dow Chemical Company
Perchloro; Production is 27.77.. of total or 203.5396 x 106
Ib. Assume the tar residue produced is 17. high and 0.5% low of product and
that the residue contains 15% HCB and 70% HCBD.
73
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TABLE III
PRODUCTION AND WASTE DISPOSAL HA^A (1973) FOR PERCHLOROETHYLENE AND TRICHLOROETHYLENE
Compar.y
Diamond Shamrock
Chemical Company
Dow Chemical
Company
-
E. I. du Pont de
Nemours and Company
Ethyl Corporation
PPG Industry, Inc.
Stauffer Chemical
Company
Vulcan Materials
Company
Vulcan Materials
Company
Hooker Chemical
Corporation
Total
a_/ Capacities of some
j>/ Hexachloroethane .
Location
Deer Park, Texas
Freeport, Texas
Plttsburg,
California
Plaquemlne,
Louisiana
Corpus Christ!,
Texas
Baton Rouge,
Louisiana
Lake Charles,
Louisiana
Louisville,
Kentucky
- . '
Geismar,
Louisiana
Wichita, Kansas;
Taft, Louisiana
Capacity-'
MM Ib/yr
Products 1972
Perchloro 100
Trlchloro 60
Perchloro 120
Trlchloro 150
Perchloro 20
—
Perchloro 105
• -- .
Perchloro (500)
— • __
Perchloro 75
Trichloro 50
Perchloro 160
Trichloro 200
Perchloro 70
. —
Perchloro 150
• ... — . -'
Perchloro 40
Perchloro 45
Trlchloro 70
885 530
plants are very flexible, since the same equipment
Source: (1) SRI Chemical Economics Handbook
(capacity data) 1973.
Waste or
By-product
Composition Waste Disposal
75% HCBD, 10% HCB, plus Ship to Rollins for Inclnera-
other chlorobutadlenes tion. Gases from latter
scrubbed with NaOH and dumped
without treatment.
NA Company prefers not to Identify
NA past or current methods but
incinerators comparable to
Plaquemine are either planned ' .
or under construction.
70% HCBD, 5-15% HCE,£/ Incineration with loss to
remainder HCB environment of less than 11
Ib/day. ( •
Unknown Unknown' x-
66.5% HCBD; 6.3% HCE, ^J Deep well disposal (8,000 ft
1.0% HCB deep)
•NA • Landfill until completion :
NA of Incinerator in July 1973.
10% HCBD, 80% HCB, HCB recovered for sale, re-
HCE, etc. , mainder recycled to chlbr-
Inator.
70% HCBD, 20% HCB, Geismar disposes under water
HCE, etc. " . seal In lagoon. Plan Incin-
eration within 2 years. Air
above lagoon less than 1 ppb
. .HCBD. . .
35% HCBD, 60% HCB, Unknown.
HCE,. etc. .
Is used to make other chlorinated solvents.
.-_-•- ,..
Remarks
Tar Is 1% of product output
'Due on stream late 1973
Company claims HCBD, etc.,
waste will "present no
problems."
Monitor plant and workers
for HCB and HCBD.
Tar production 5% of per-
chloro output
(2) Industry and government contacts (all other data).
-------
High HCB = (203.9596 x 106) (0.01) (0.15) = 305,939 Ib
Low HCB = (0.5) (high) = 152,970 Ib
High HCBD = (203.9596 x 106) (0.01) (0.7) = 1,427,717 Ib
Low HCBD = (0.5) (high) = 713,859 Ib
Trichloro; Production is 28.3% of total or 120.841 x 106
Ib. Assume other conditions are the same as for perchloro.
High HCB = (120.841 x 106) (0.01) (0.15) = 181,262 Ib
Low HCB = (0.5) (high) = 90,631 Ib
High HCBD = (120.841 x 1Q6) (0.01) (0.7) = 845,887 Ib
Low HCBD = (0.5) (high) = 422,944 Ib
c. Ethyl Corporation
Perchloro; Production is 8.5% of total or 62.458 x 10
Ib. Assume the tar is 1% high and 0.5% low of product, and that tar con-
tains 1% HCB and 66.5% HCBD.
High HCB = (62.458 x 106) (0.01) (0.01) =6,246 Ib
Low HCB = (0.5) (high) = 3,123 Ib
High HCBD = (62.458 x 106) (0.01) (0.665) = 415,346 Ib
Low HCBD = (0.5) (high) = 207,673 Ib
Trichlorot Production is 9.4% of total or 40.138 x 106
Ib. Assume other conditions are the same as for perchloro.
High HCB = (40.138 x 106) (0.01) (0.01) = 4,000 Ib
Low HCB = (0.5) (high) = 2,000 Ib
High HCBD = (40.138 x 106) (0.01) (0.665) =266,900 Ib
Low HCBD = (0.5) (high) = 133,450 Ib
d. PPG Industry, Inc.
Perchlorot Production is 18.1% of total or 132.999 x 10
Ib. Assume the tar is 1% or 0.5% of product and that tar contains 10% HCB
and 70% HCBD.
High HCB = (132.999 x 106) (0.01) (0.1) =133,000 Ib
Low HCB = (0.5) (high) = 66,500 Ib
High HCBD = (132.999 x 106) (0.01)
Low HCBD = (0.5) (high) = 465,500 Ib
High HCBD = (132.999 x 106) (0.01) (0.7) = 931,000 Ib
75
-------
.'• ' ' "'•',• f\
Trichloro; Production is .37.8% of total or 161,406 x 10
Ib. Assume other conditions are the same as for perchloro.
High HCB = (161.406 x 106) (0*01) (0.1) =161,400 Ib V:
Low RGB =(0.5) (high) =80,700 Ib
.High HCBD = (161.406 x 10^} ,(0.01). (0.7) = 1,129,900' Ib
, Low HCBD =(0.5) (high) = 565,000 Ib . . . :.
e. StaufEer Chemical Company . .
Perchloro; Production is 7.9% oi' total or 58.049 x 106
Ib. Assume by-product is 600,000 Ib (high) or 300,000 (low) perchloro pro-
duction and that by-product contains 80% HCB and 10% HCBD.
High HCB = (58.049 x 106) (0.0151) (0.8) -700,000 Ib
Low HCB = (0.5) (high) = 350,000 Ib —
High HCBD = (58.049 x 106) (0.0151) (0.10) = 87,700 Ib
Low HCBD = (0.5) (high) = 43,900. Ib .
f. Vulcan Materials Company
> ~ '
Perchloro; At the Geismar, Louisiana, plant the production
is 16.9% of total or 124.181 x 106 Ib. Assume tar production is 5 or 2.5%
of perchloro output, and that tar contains' 20% HCB and 70%,HCBD.
High HCB = (124.181.x 10^) (0,05) (0.2) =1,241,800 Ib
Low HGB = (0.5) (high) = 620*900 Ib
High HCBD = (124.181 x 106) (0.05) (0.7) = 4,346,400 Ib
Low HCBD = (0.5) (high) = 2,173,200 Ib
At the Wichita, Kansas, plant the production is 4.5% of
total or 33.066 x 10 Ib. Assume tar production is 5 or 2.570 of perchloro
and that tar contains 60% HCB and 35% HCBD.
High HCB = (33.066 x 106) (0.05) (0.6) = 992,000 Ib
Low HCB = (0.5) (high) = 496,000 Ib
High HCBD = (33.066 x 10 ) (0.05) (0.35) =578,700 Ib
Low HCBD = (0.5) (high) = 289,400 Ib
Trichloro; None produced.
76
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g. Hooker Chemical Corporation
Perchloro; Production is 5.17. of total or 37.4748 x 106
Ib. Assume the tar residue is 1 or 0.5% of product, and that tar contains
10% HCB and 70% HCBD (assumed composition).
High HCB = (37.4748 x 106) (0.01) (0.1) = 37,5qp Ib
Low HCB = (0.5) (high) = 18,750 Ib
High HCBD = (37.4748 x 106) (0.01)
Low HCBD = (0.5) (high) = 131,150 Ib
High HCBD = (37.4748 x 106) (0.01) (0.7) = 262,300 Ib
Trichloro; Production is 13.2% of total or 56.364 x 10
Ib. Assume other conditions are the same as for perchloro.
High HCB = (56.364 x 106) (0.01) (0.1) = 56,400 Ib
Low HCB = (0.5) (high) = 28,200 Ib
High HCBD = (56.364 x 1Q6) (0.01) (0.7) = 394,500 Ib
Low HCBD = (0.5) (high) = 197,250 Ib
Table IV presents the summary data for the perchloro and tri-
chloro estimate. These data show the estimated range (high and low values)
for HCB and HCBD generation and the estimated percentage distribution of
HCB and HCBD by company.
2. Carbon tetrachloride (CCl^): The U.S. production of CC14 in
1972 was 997 million pounds per year. About 60% of this production was by
the CS2 process which precludes the formation of HCB or HCBD.
In the absence of information on the composition of the process
hex wastes, and because of the similarity of processing operations, assume
that the CCU wastes are identical to the hex wastes produced in perchloro-
ethylene-trichloroethylene production.
Industry spokesmen have reported. **•"' that the tarry hex resi-
due in perchloroethylene-trichloroethylene operations can range in quantity
from about 0.5. to 1% of the product depending on the depth of chlorination.
Also, the average composition of the hex waste is reported to be about 10%
HCB and 70% HCBD. .
77
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Company
Diamond
Dow
Ethyl
PPG
Stauffer
Vulcan (1)
Vulcan (2)
Hooker
Total
Company
Diamond
Dow
Ethyl
PPG
Hooker
Total
TABLE IV
SUMMARY OF PERCHLORO/TRICHLORO ESTIMATES
Data For Perchloro Operations in 1972
High
(103 Ib)
83.0
305.9
6.2
133.0
700.0
1,241.8
992.0
37.5
3,499.4
High
(103 Ib)
48.3
181.3
4.0
161.4
56.4
HCB
Low
(103 Ib)
41.5
153.0
3.1
66.5
350.0
620.9
496.0
18.8
1,749.8
Data For
HCB
Low
(103 Ib)
24.1
90.6
2.0
80.7
28.2
Percent
of Total
2.37
8-74
0.18
3.80
20.00
35.49
28.35
1.07
100.00
Trichloro
Percent
of Total
10.70
40.16
0.8'9
35.76
12.49
High
(103 Ib)
622.7
1,427.7
415.3
931.0
87.7
4,346.4
578.7
262.3
8,671.8
Operations
High
(10-3 Ib)
361.9
845.9
266.9
1,129.9
394.5
HCBD
Low
(103 Ib)
311.4
713.9
207.7
465.5
43.9
2,173.2
289.4
131.2
4,336.2
in 1972
HCBD
Low
(103 Ib)
180.9
422.9
133.5
565.0
197.3
Percent
of Total
7.18
16.46
4.79
10.74
1.02
50.12
6.67
3.02
100.00
Percent
of Total
12.07
28.21
8.90
37.67
13.15
451.4
225.6
100.00
2,999.1 1,499.6
100.00
78
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The estimated RGB formed is:
High = (0.4) (997,000,000) (0.01) (0.10) = 398,800 Ib
Low = (0.4) (997,000,000) (0.005) (0.10) = 199,400 Ib
The estimated HCBD formed is:
High = (0.4) (997,000,000) (0.01) (0.70) = 2,791,600 Ib
Low = (0.4) (997,000,000) (0.005) (0.70) = 1,395,800 Ib
3. Chlorine (C12):
Production in 1972 = 9,873,000 tons of C12.
Diaphragm cells = 72.4% of production capacity. — /
Mercury cells = 24.2% of production capacity. — '
Assume that:
63.3% of mercury cells have been converted to DSA.
34.7% of diaphragm cells have been converted to OSA.
The converted cells do not form HCB or HCBD.
Then, total C12 production from polluting mercury cells = (0.242)
(1-0.633) (9,873,000 tons/year) = 877,000 tons/year.
And the .total €!„ production from polluting diaphragm cells =
(0.724) (1-0.347) (9,873,000 tons/year) = 4,668,000 tons/year.
Mercury cells
Assume that;
1. The heavy ends waste amounts to 1.4 Ib/ton C^.— Then, waste
chlorinated hydrocarbons = (1.4 Ib/ton C12) (877 x 10 ton Cl2/year) =
1,288 x 103 Ib/year.
2. The crude chlorine and purified chlorine are same quantities
(no losses in purification).
79
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3. The waste contains from 2 to 5% RGB, plus varying amounts of
HCBD, carbon tetrachloride, and r.hinrnfnrm. 15,18,19/
4. The HCB content of product chlorine ranges from 5 to 1 ppb. * '.
HCB in chlorinated hydrocarbon waste stream
High = (0.05 Ib HCB/lb waste) (1,228,000 lb waste/year) = 61,400
Ib RGB/year '
Low = (0.02 lb HCB/lb waste) (1,228,000 lb waste/year) = 24,560
RGB/year
RGB in product chlorine
High = (877 x 103 tons Cl2/year) (2,000 Ib/ton) (5 x 10'9 tons
RGB/ton C12) =z 9 lb RGB/year
Low = (877 x 103 tons C12 /year) (2,000 Ib/ton) (1 x 10'9 ton
RGB/ton C12) si 2 lb RGB/year
Total HCB from mercury cells
High = 61,400 + 9. ss 61,400 lb RGB/year
Low = 24,560 + 2 s- 24,600 lb RGB/year
Diaphragm cells
Assume conditions are the same as in the mercury cell process.
Then, the waste chlorinated hydrocarbons = (1.4 Ib/ton C12) (4,668 x 103
tons Cl2/year) = 6,535 x 103 Ib/year
HCB in chlorinated hydrocarbon waste stream
High = (0.05 Ib/HCB/lb waste) (6,535 x 103 lb waste/year) =
326,800 lb RGB/year
Low = (0.02 lb HCB/lb waste) (6,535 x 103 lb waste/year) =
130,700 lb RGB/year
80
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HCB in product chlorine
High = (4,668 x 103 tons Cl2/year) (2,000 Ib/ton) (5 x 10'9 Ib
HCB/lb C12) = 47 Ib HCB/year
Low = (4,668 x 103 tons Cl2/year) (2,000 Ib/ton) (1 x KT9 Ib
HCB/lb C12) = 9 Ib HCB/year
Total HCB from diaphragm cells .. .
High = 326,800 + 47 s: 326,800 Ib HCB/year !
. - . • . j .
Low = 130,700 + 9 ~ 130,700 Ib HCB/year
Total HCB formed in all C12 plants
High = 61,400 + 326,800 =388,200 Ib HCB/year
Low = 24,600 + 130,700 = 155,300 Ib HCB/year
Total HCBD formed in all C12 plants
An industry spokesman has reported that HCBD— present in waste
is less than 1% of'the by-product HCBD formed in all domestic perchloro-
ethylene and trichloroethylene plants (i.e., < 1% of 8,130,000 or 81,300
Ib/year). Assume 0.5 to 0.9% for a range of values.
High = 8,130,000 x 0.009 = 73,170, say 73,200 tons/year
Low = 8,130,000 x 0.005 = 40,650, say 40,700 tons/year
4. Dacthal®; An industry spokesman—' has indicated that the
total domestic production of Dacthal® in 1972 was 2 million pounds, and
that this product contains an average of about 0.3% of HCB and no HCBD.
Also, according to this spokesman, the total Dacthal®process wastes in
1972, amounting to about 100,000 Ib, contain an average of 84% HCB and
no HCBD.
Assume that:
1. The HCB contamination in Dacthal® ranges from a high of 0.4%
to a low of 0.2%.
2. The HCB content in Dacthal® process wastes ranges from a high
of 88% to a low of 80%. .
81
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Then, quantities of HCB formed are:
•' ) ' . • . .
For Dacthal product;
High = (2,000,(000 Ib) (0.004) - 8,000 Ib HCB
Low = (2,000,000 Ib) (0.002) = 4,000 Ib HCB
For HCB contained in wastes: I .
High = (100,000 Ib) (0.88) = 88,000 Ib HCB
Low = (100,000 Ib) (0.80) =80,000 Ib HCB
Total HCB formed;
High = 8,000 + 88,000 = 96,000 Ib
Low = 4,000 + 80,000 = 84,000 Ib
5. Vinyl chloride monomer; U.S. production in 1972=2,247,000
tons/year, or 4,494,000,000 Ib/year.
According to the technical literature, 927° of vinyl chloride
production capacity uses the ethylene and ethylene-oxychlorination pro-
cesses, which involve the high reaction temperatures conducive to forma-
tion of HCB.
Industry spokesmen have indicated that HCBD is not formed in the
manufacture of vinyl chloride and that heavy ends waste sent to incineration
or other disposal is about 6.5% of the product. A potential does exist for
the formation of HCB; however, no analytical data on this subject could be
obtained.
Assume that heavy ends waste from the process contains a maxi-
mum of 0.01% HCB and a minimum of 1 ppm HCB. Then range of HCB formed is:
High = (0.92) (4,494 x 106 Ib) (0.065) (0.0001) = 26,900, say
27,000 Ib
Low = (0.92) (4,494 x 106 Ib) (0.065) (0.000001) = 269 Ib
6. Atrazine, propazine, and simazine; In response to a written
inquiry (see Appendix B), Ciba-Geigy Corporation, the sole producer of
these products, reported that HCB is contained in the products and in the
waste material. Geigy also reports that:
82
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1. The total HCB leaving their plant in liquid, gaseous, and
solid waste streams is 15.4 Ib/day.
2. The total HCB leaving the plant as impurities in products
is 0.006 Ib/day.
3. No HCBD is formed in these production operations.
Assume 300 operating days per year. Then, the total HCB emitted is:
300 x 15.406 = 4,622 Ib HCB/year
Assume 4,622 to be the low value for operations with the high value
equal to 4,622 x 2 or 9,244 Ib HCB per year.
7. Pentachloronitrobenzene; The estimated U.S. production of
pentachloronitrobenzene (PCNB) in 1972 was 3 million pounds.
PCNB is reported— to be contaminated with HCB, but no specific
information concerning the extent of contamination in this product could
be ascertained.
On the basis of data reported in the industry for similar pesti-
cide products (e.g., Dacthal® , atrazine, etc.), assume a high HCB contami-
nation of 0.2% and a low of 0.1%, and that no HCBD is formed.
Then, HCB formed is:
High = (3,000,000) (0.002) = 6,000 Ib HCB
Low = (3,000,000) (0.001) = 3,000 Ib HCB
8. Mirex; Estimated U.S. production for 1972 is ^ 1 million
pounds.
An EPA representative has indicated— that this pesticide is con-
taminated with HCB. No evidence was obtained that HCBD is formed.
On the basis of data reported in the industry for similar pest-
icides, assume a high HCB contamination of 0.2% and a low of 0.1% in Mirex.
Then, estimated HCB formed is:
High = (1,000,000) (0.002) = 2,000 Ib
Low = (1,000,000) (0.001) = 1,000 Ib
83
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9. Other chemical industries; No evidence was found that a sig-
nificant environmental contamination by HCB or HCBD could occur in the fol-
lowing industries. Therefore, these industries were not included in these
estimates. ^ ' '
* Hexachlorobenzene;
* Hexachlorobutadiene; . : '
* Sodium chlorate; ; .
* Pentachlorophenol;
* Pentachlorobenzene (very limited production for marketing
^ 1 ton/year);
* Hexachloroethane;
* Synthetic rubber;
* Maleic hydrazide;
* Chlorinated naphthalene;
* Chlorinated biphenyl; and
* Hexachlorocyclopentadiene.
84
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VII. WASTE DISPOSAL
The generation and characterization of process wastes which may
contain HCB and/or HCBD are described in Section IV for each of the 23
chemicals investigated. The following discussion deals with waste treat-
ment and disposal practices currently used for these waste materials, a
general description of waste disposal technology used for chlorinated hy-
drocarbon products, and an estimate of the potential for HCB and HCBD con-
tamination of industrial wastes, by-products and products.
During the course of these studies, an unsuccessful attempt was
made to determine the breakdown of the various corporate waste disposal
methods (i.e., percentages using incineration, landfill or deep-well in-
jection) used in each of the chemical industries of interest. MRI inquiries
(e.g., telephone and written communications) failed to develop the required
data to support this type of analysis. Some companies failed to respond
because such waste disposal information was considered to be proprietary;
other companies, which did not supply this requested information, gave no
reasons for their refusal to respond.
The waste disposal operations described in this section are sepa-
rated into two categories:
A. Waste Disposal for Chemical Processes Known to Produce HCB
and/or HCBD
B. Waste Disposal for Chemical Processes with Theoretical, But
Not Proven, Production of HCB and/or HCBD
A. Waste Disposal for Chemical Processes Known to Produce HCB and/or HCBD
1. Hexachlorobenzene; The Stauffer Chemical Company, the only
domestic producer of this chemical in 1974, has indicated that at their
Louisville, Kentucky, facility, HCB is recovered for sale from a by-product
tar formed during production of perchloroethylene. The remainder of this
tar is reported to be recycled to the process (see Table III, p. 74).
2. Hexach1orobutadiene; This chemical is not currently produced
in the U.S., and therefore, there are no domestic waste disposal operations
for this industry.
3. Chlorine; The "heavy ends" waste from purification (distil-
lation) of liquified chlorine contain chlorinated hydrocarbons and possi-
bly some HCB and HCBD. This waste is generally disposed of by sanitary
landfill or high temperature incineration.
85
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The technical literature indicates that the estimated destruc-
tion efficiency of high temperature incineration units is almost 100%,
and that the estimated installation time required for chlorinated hydro-
carbon wasteburners in the chlorine industry is about 2 years."
4. Carbon tetrachloride; The procedures for waste disposal
generally include incineration or landfill.
Vulcan Materials Company at their carbon tetrachloride plants
in Wichita, Kansas, and Geismar, Louisiana, dispose of these "hex residues"
(solids containing HCB and HCBD) by impounding the waste within the plant
sites in an earth-covered groundfillJ=-2'
Dow Chemical Company disposes of its carbon tetrachloride produc-
tion wastes at Freeport, Texas, Plaquimine, Louisiana, and Pittsburg,
California, by on-site incineration. Dow reports that the incineration
operating conditions are proprietary and that the incineration effective-
ness is excellent (99.9f% destruction).!!/
5. Perchloroethylene; Industry disposal practices for the.tarry
residues (hex wastes) produced in production of perchloroethylene include
on-site or off-site incineration, deep-well disposal and landfill as shown
in Table III, p. 74.
The Diamond Shamrock Chemical Company (Deer Park, Texas) packages
its "hex" residues, which contain HCBD and HCB, in sealed containers and
ships them to a private waste disposal organization (Rollins International,
Inc., Houston, Texas) for incineration.±H' Exhaust gases from incineration...
are scrubbed with sodium hydroxide solution; the scrubbing solution is
discharged to the environment without further treatment (see Appendix B).
At Plaquemine, Louisiana, Dow Chemical Company incinerates their
"hex" waste from their perchloroethylene operations. Dow reportsJJ)/ that
for their perchloroethylene plants at Freeport, Texas, arid at Pittsburg,
California, plans are under way to install similar type incinerators (see
Appendix B).
The Vulcan Materials Company plants in Wichita, Kansas, and
Geismar, Louisiana, produce "hex" residues containing HCBD and HCB con-
taminants. These residues are impounded within .the plant sites in an
earth-covered groundfill (see Appendix B).
21/
In 1973, an Ethyl Corporation spokesman reported^— that the
"hex" residues from their perchloroethylene-trichloroethylene production
operations (containing about 67% HCBD and 1% HCB) were.disposed of in a
deep well (8,000 ft deep).
86
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PPG Industries, Inc., at Lake Charles, Louisiana, was scheduled
to have a waste incinerator in operation by July 1973 to dispose of "hex"
wastes from perchloroethylene production operations. Prior to that date,
the wastes were landfilled.
Representatives at the Louisville, Kentucky, perchloroethylene
plant, operated by Stauffer Chemical Company, have reported that the by-
product contains about 80% HCB and 10% HCBD. The HCB is recovered for sale,
and the remainder of the by-product is recycled to the process.
6. Trichloroethylene; The waste disposal methods conducted
in this industry, as shown in Table III, p. 74, are similar to those used
for perchloroethylene processes. Incineration appears to be the preferred
method for waste disposal. In 1973, one facility disposed of trichlbro-
ethylene process wastes by deep-well injection, another facility used
landfill operations, and a third shipped all of its waste to an off-site
treatment plant (operated by an independent contractor) for disposal by
incineration.
7. Dacthal®; The only domestic Dacthal® manufacturing facility,
located at Greens Bayou, Texas, ships the liquid waste (containing 84% HCB
and no HCBD) in sealed containers to an independent company site (Rollins,
International, Deer Park, Texas) for final disposal by incineration. Docu-
mentation for this disposal method is given in the results of a written
inquiry (see Appendix B).
8. Atrazine; The still bottoms, consisting of reject heavy
residue liquid containing 2,000 ppm by weight of HCB and no HCBD are shipped
to an independent processor for final disposal by incineration. The vent
scrubber emissions, consisting of a vapor containing only 0.024 ppm of HCB
and no HCBD is vented to the atmosphere. These data were obtained from a
written inquiry (see Appendix B).
9. Propazine and simazinet These chemicals are produced do-
mestically in the same single facility used for atrazine production and
the wastes involved also contain HCB. The process wastes from manufacture
of propazine and simazine are disposed of by the methods used for atrazine
(see Appendix B).
10. Pentachlorobenzene; No information was obtained concerning
disposal of waste materials from production of pentachlorobenzene as a
captive by-product. It is probable that the disposal methods are similar
to those used for other chlorinated wastes, e.g., incineration.
11. Pentachloronitrobenzenet Our inquiries to producers failed
to develop any specific disposal information for this chemical production
process.
87
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f 'I
12. Mirex; MRI inquiries to industry spokesmen did not develop
any specific information! concerning waste disposal practices used in the
production of this pesticide.
B. Waste Disposal .for Chemical Processes with Theoretical, But Not Proven,
Production of ,HCB and/or HCBD
1. Sodium chlorate; Waste control techniques vary considerably
as indicated in the following description of methods provided by Hooker
Chemical Company and Pennwalt Corporation-=•='
Hooker Chemical Company's plant, at Columbus, Mississippi, reported
that carbon from the electrodes is lost at a rate of 15 Ib/ton of NaCIO
produced. Approximately 12 Ib of carbon is recovered to be sold. Most or
the remaining 3 Ib ends up in the "mud" waste stream of the process.
Plant emissions consist primarily of the "mud" and gaseous ef-
fluents. The mud consists of the bottoms of the cells and the settling and
filtration systems following the addition of BaC^ to the cells' liquor.
The most important mud constituents are barium chromate, barium sulfate,
and graphite from the electrodes. This mud is discharged into the river
nearby. Hooker plans to start landfilling this "mud" by 1975.
Gaseous emissions come from the cells in the form of hydrogen,
C02 (less than 1% of hydrogen) and traces of chlorine. They are vented
directly to the atmosphere. Hooker is not aware of any chlorinated hydro-
carbons being formed in the cells.
Pennwalt apparently does not have the same kind of mud disposal
problem as other chlorate producers. They treat the brine prior to electrol-
ysis with sodium carbonate in order to precipitate most of the magnesium
and calcium. This precipitated material, also called "mud," is presently
allowed to accumulate at the Pennwalt chlorate plant. Evidently, they have
plenty of space and this disposal technique is acceptable.
2. Sodium metal: The waste disposal methods for the sodium
metal industry are similar to those used in the chlorine industry.
3. Vinyl chloride monomer; The major wastes of interest to this
study are the "heavy ends" from fractionation steps. Because of the high
cracking temperature, it is possible that significant amounts of HCB are
formed as by-products in the process and concentrated in the "heavy ends"
(waste material). Industry spokesmen from Dow Chemical Company and Ethyl .
Corporation have reported that HCBD is not generated in this industry.—*—
Waste disposal is accomplished by methods similar to those used
in the perchloroethylene industry. Incineration is reported by the industry
to be a principal method of waste disposal.
88
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4. Pentachlorophenol; Little information is available from the
literature and industrial sources pertaining to disposal of pentachloro-
phenol waste streams. No specific data on waste-disposal practices were
obtained.
5. Hexachloroethane! Sodium chloride solution which is the only
major waste, is disposed of by deep-well injection or through controlled
dilution to streams.
6. Synthetic rubber; Waste disposal information for the chlo-.
roprene manufacturing industry was obtained from one company spokesman.—
A sizable quantity of solid waste is produced during chloroprene production.
This waste consists largely (90%) of reject rubber in the form of "coagulum,"
a nondegradable, insoluble, and nonflammable material which is disposed of
by landfill operations at the Du Pont chloroprene facility. Du Pont has a
chemical waste incinerator at its facility, which it uses to dispose of
certain liquid chlorinated hydrocarbon wastes formed in chloroprene process-
ing. Hydrogen chloride formed in the waste-burning operation is absorbed
by scrubbing with water and the hydrochloric acid solution formed is then
injected into a deep well operated by Du Pont. Du Pont has reported^?-' that
no HCB or HCBD is contained in any of these wastes.
7. Maleic hydrazide; No specific data were obtained pertaining
to waste disposal in this industry.
8. Hexachlorocyclopentadiene: Waste disposal methods used in
hexachlorocyclopentadiene (HOP) manufacture are shown in Table V. The
Hooker Chemical Corporation incinerates HCP plant wastes at the Niagara
Falls, New York, site«=l' The Velsicbl Chemical Corporation incinerates
plant wastes at the Memphis, Tennessee, site and uses deep-well injection
for waste disposal at Marshall, Illinois.-"
9. Chlorinated naphthalenes: The Koppers Company, Inc., is the
only domestic producer of these chemicals. The inert distillation residue,
which is produced in small quantities during the Koppers Company process
operations, is hauled to a plant landfill. This residue has not been anal-
yzed for toxic substances, but a company pollution abatement officer has
indicated that he does not believe that this disposed waste creates any
pollution problems or health hazards involving HCB or HCBD*25/
The Koppers Company process uses liquid separators, absorbers,
packed columns, total condensers, and a wet scrubber to prevent atmospheric
emissions. The company has reported that stack testing by an ASTM method
showed that no hydrogen chloride (HC1) or chlorine (C^) was present. Based
on the detection limits for this testing, the emission is reported to be
less than 3 ppm by volume of HC1 and less than 0.2 ppm by volume of .Cl^* On
a weight basis, the total emission is less than 0.01 lb/hr.li/
89
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TABLE V
WASTE DISPOSAL METHODS USED IN HEXACHLOROCYCLOPENTADIENE MANUFACTURE
23.247
Manufacturer
Hooker Chemical Corporation
vO
o
Velsicol Chemical Corporation
Location
Montague, Michigan
Niagara Falls, New York
Memphis, Tennessee
Marshall, Illinois
(captive HCP
production)
Waste Disposal Method
Shipped by tank car to Niagar.
Falls, New York, and incin-
erated.
Incineration
Incineration
Deep we'll, injection
-------
10. Chlorinated biphenyls: The Monsanto Company is the only
domestic producer. In Monsanto's waste disposal operation, scrap liquids
containing chlorinated biphenyls are incinerated at about 2700°F for a
1.5 sec retention period and the off-gases are scrubbed to remove hydro-
gen chloride. This extremely high incineration temperature damages the
incinerator refractory and necessitates above average repair work (e.g.,
about three times the normal frequency of repairs to refractories). How-
ever, Monsanto considers this damage a reasonable sacrifice to ensure to-
tal destruction of PCBs and prevent environmental pollution.—'
C. Waste Disposal Technology
A review of the technical literature served to identify some
waste disposal technoIogy28/ which may have application, directly or in-
directly, to some of the waste problems which exist for the chemical pro-
cesses investigated in this study. This information is also useful in
characterizing the type of treatment methods and waste disposal techniques
now being used in the petrochemical industry which produces many types of
chlorinated hydrocarbon products. This information is presented in Tables
VI, VII, and VIII.
The waste treating processes being used for selected petrochemi-
cal wastes are indicated in Table VIII. The polychloroethane wastes and
ethylene dichloride are incinerated. Sodium chloride wastes are sent to
deep wells or disposed of by controlled dilution to streams and bays.
Incineration of chlorinated hydrocarbons is generally carried
out at about 1300°F with a residence time of approximately 1/4 sec. High
energy scrubbers are used to remove HC1. A caustic or lime solution is
used to partially neutralize HC1<29/
There are several types of incinerators:
* Liquid incinerators - require the feed material to be in the
liquid form.
* Rotary kiln type - particularly suited if the material to be
disposed of is collected in combustible
fiber drums or if material is viscous.
* Tray-type incinerators - well suited for solids. Material
falls from one tray to another until
there is almost complete combustion.
* Fluidized sand bed incinerators - HCB and HCBD are viscous
liquids at ambient tempera-
tures and are usually incin-
erated in rotary kilns or
fluidized bed Incinerators.
91
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TABLE VI
HAZARDOUS MATERIALS EXPECTED IN WASTE STREAMS OF SELECTED CHEMICAL PRODUCERS AND USERS
Waste Source
Description
Alkalies and Chlorine
Industry
I' •
. Vinyl Resins • ;
Cyclic Intermediates
Industrial Organic .
Chemicals
. Phenol Production
. Ethylene. via Pyro lysis
. Ace t aldehyde via
Ethylene Oxidation
. Methanol via Carbon
Monoxide Systems
. Ethylene Bichloride
via Oxy-Chlorlnatlon
of Ethylene
Acrylics
Description of
Hazardous Compounds
Cell Process Waste
. Calcium oxide
. Sodium carbonate
. Chlorinated hydro-
carbons
. Purification mud
Raw Water
. Phenols
. Carbon tetra-
chlorlde
. Chloroform
. Benzene
Process Waste
. Polychlorlde
benzene
. Tar
Chlorlnatlon of
Benzene Process
. Organic chloride
Raw Waste
. Organic chlorides
Ace t aldehyde Still
Bottoms
. Organic chlorides
. Organic chloride
Raw Waste
. Organic chlorides
Raw Waste
. Organic chlorides
Raw Waste
General Quantification
Factors
' •
0.8 Ib/ton of, down
pell C12 ' :
2 Ib/ton of down
cell C12
1 Ib/ton
50 Ib/ton
1.5 gal/lb product
-- -
'. — '..••••
' --
•
• ;
--
-- •
670 gal/1,000
product :
50 lb/1,000 Ib
product
0.02 lb/1,000 Ib
product
—
46 lb/1,000 Ib
product
0.16 lb/1,000 Ib
product
0.18 lb/1,000 Ib
product
320 gal/1,000 Ib
product
32 ib/ 1,000 Ib
product
0.13 gal/lb product
Annual Production
Units for Total U.S.
N.A.
' • ' ' N.A.
1,000 Ib 10,000
1,000,000 Ib 500
1,000,000 gal. 4,500
1,000 gal. 90,000
1,000 Ib 7,000
1,000 Ib 300
1,000 Ib 76,000
1,000 Ib 800
•• -
1,000 Ib 1,200
1,000,000 gal. 2,400
1,000 gal. 24,300
1,000 gal. 25,700
Source: Adapted from information contained in Reference 28.
92
-------
•CABLE VII
WASTE STREAMS AND TREATMENT PROCEDURES FOR SELECTED CHB1ICALS
Waste Media
Water
(The wastes
listed are ex-
amples of typi-
cal waste
streams)
Air
Product
Air
Hydrochloric
acid (2 million
tons/year)
Chlorine (9
million tons/
year)
Type Waste
Chlorinated hy-
drocarbon
wastes
Polymerization
wastes
Ethylene oxide
wastes
Hydrocarbons
Residuals of all
organic chemi-
cals packed and
shipped
Chlorinatlon
waste gases
Waste gases
Typical Disposal Collectable General Quantification
Pretreatment General Treatment Media . Residue Factors
Cyclic Intermediates - SIC- 28 15
Industrial Organic Chemicals - SIC-2818
Distillation Neutralization Water Spent ana- > 1 x 108 Ib/year
lysts
solids
Distillation Neutralization Landfill Slimes > 1 x 108 Ib/year
lagooning
Neutralization Water No Unknown
Scrubbers Landfill Filter cakes > 2% of volatile
. filters scrubber products — esti-
sollds mated as
10 x 109 Ib/year
Municipal land- Landfill Yes < 1-2% of total produc-
flll incinera- air No tion (120 x 10? Ib)
tion .
Industrial Inorganic Chemicals - SIC-2819
Recycling Recovery Air No 0.1-0.3% loss
Absorbers .
Scrubbers
Scrubbers Air No 1-2% loss
Absorbers
By-product
production
Fully
Potential Treated
Hazard On-Slte
Chlorinated
hydro-
carbons
Phosphates
Organic
chemicals
Air pol- Unknown
lutant
Toxic, flam- Unknown
mable ex-
plosive
chemicals
None
Air pollutant
Acute reaction
Discharged
to
Sewer
No
Unknown
Source: Adapted from information contained in Reference 28.
-------
TABLE VIII
WASTE TREATING PROCESSES BEING USED FOR SELECTED PETROCHEMICAL WASTES
Physical Treatment
Chemical
Treatment
Biological
Treatment
Ultimate Disposal
\o
B
O
0)
4J
B
Wastes from
Petrochemical Operations
B
O
fc.
CO
M
O
O
•H O
U 60
.3
B %
•H to
*J PQ
-H TJ
•H C
Q OJ
T3 to
q) Q
— « CO
i-( HI
Ob
P 4J
u en .
o o
u u
CO
0)
to
to
0)
u
eg
3
CO
TJ
O
3
pa.
(90
c
0.
-------
IP all cases, the exhaust gases from the incinerators have to
be scrubbed in high energy scrubbers with caustic soda or lime solutions.
to neutralize HC1 and other acids to salts.
D. The Potential for HCB and HCBD Contamination of Industrial Wastes,
By-Products and Products
t
On the basis of the best available technical information col-
i > •• • • . -i
lected, estimates were'prepared to quantify the probable extent of HCB and
HCBD formation which occurs in products, by-products and waste materials
during normal operation of chemical industries of interest to this study.
The results of this study serve to identify the major and minor
industries in respect to possible HCB and HCBD contamination of the envi-
ronment and to indicate the appropriate priorities for the scheduled EPA
monitoring of suspect industries in a separate program following the com-
pletion of Task I. These Estimates were made for those industries, in the
field of 23, which appeared to have a substantial potential for the genera-
tion of HCB or HCBD.
The supporting assumptions and calculations made in this study
are shown in Section IV, Part C, along with a brief description of the
probable contaminated materials (e.g., products, by-products or waste
streams). The results of this study are presented in Tables IX and X.
The estimates in Table IX show that three related chemical in-
dustries, carbon tetrachloride, perchloroethylene, and trichloroethylene
account for about 89% of the HCB and more than 99% of the HCBD.
For the chemical processes considered in Table IX, the total gen-
erated HCB was estimated to be in the range of 2.4 to 4.9 million pounds
in 1972. The estimated total HCBD ranged from 7.3 million to 14.5 million
pounds.
Table X shows the estimated quantities of HCB and HCBD generated
per ton of product. These data can be conveniently used to obtain an esti-
mate of the HCB and HCED generated at any individual chemical production
site.
95
-------
TABLE IX :. ' •
ESTIMATED TOTAL QUANTITIES OF HCB AND HCBD PRESENT IN
INDUSTRIAL WASTES. BY-PRODUCTS AND PRODUCTS IN 1972
• ' • -.,v U.S. '• '.-••••;•
Production
in 1972 HCB (OOP Ib)!/ HCBD (OQO lb)~
. Product (OOP Ib) High Low High Low
Perchloroethylene 734,800 3,500 1,750 8,670 4,340
Trichloroethylene 427,000 450 230 3,000 .1,500
Carbon Tetrachloride 997,000 400 200 2,790 1,400
Chlorine 19,076,000 390 160 70 40
Dacthal® 2,000 100 80 .0 0
Vinyl Chloride 4,494,000 27- o 0 0
Atrazine, Propazine, 112,000 9 5 0 0
Simazine
Pentachloro- 3,000 6 3 0 0
nitrobenzene
Mirex 1,000 2_ 1 _0 0
4,884 2,429 14,530 7,280
a/ Rounded to nearest 10,000 lb--except for vinyl chloride, atrazine,
propazine, simazine, pentachloronitrobenzene, and mirex.
_b/ Preliminary estimate—see Section IV-C.
96
-------
TABLE X
ESTIMATED QUANTITIES OF RGB AND HCBD
Product
Perchloroethylene
Trichloroethylene
Carbon Tetrachloride
Chlorine
Dacthal®
Vinyl Chloride
Atrazine, Propazine,
Simazine
Pentachloro-
nitrobenzene
Mirex
GENERATED PER TON OF
U.S.
Production
in 1972
Short Tons
.e 367,400
.e 213,500
>ride 498,500
9,538,000
1,000
2,545,000
ine, 56,000
PRODUCT IN
HCB (lb/
of produ
High
9.5
2.1
0.8
0.04
100.00
0.01
0.16
1972i/
ton
£t)
Low
4.8
1.1
0.4
0.02
80.00
-
0.09
HCBD (lb/ton
of product)
High
23.6
14.1
5.6
Low
11.8
7.1
2.8
0.007 0.004
0.0
0.0
0.0
0.0
0.0
0.0
1,500
500
4.0
4.0
2.0
2.0
0.0
0.0
0.0
0.0
A/ See Section VI-C (p. 73) for a description of assumptions and calcu-
lations used in estimating these values.
97
-------
USES FOR CHEMICAL PRODUCTS
This section provides a listing and brief discussion which out-
lines the major and minor uses of the 23 selected;chemicals which were
studied. Uses as raw materials or as intermediate? in other major manu-
facturing processes are indicated, and other-commercial applications are
also noted. '
•• t • ' ' • '
To the extent possible, use patterns are presented in terms of
the estimated percentage utilized for each area of application. For some
chemicals, where percentage usage data-could not be obtained, a general
description of uses is given. •
Since most of the chemical processes of interest in this study
involve production of chlorine or various chlorinated hydrocarbons, MRI
prepared a detailed materials flow diagram showing chlorine consumption
patterns in the U.S. This diagram, presented in Figure 28, indicates the
major chlorine compounds, products of special interest, production data,
and use patterns for all chlorinated products.
A . Hexachlorcbenzene
In 1972, the principle use was reported i'to be as a fungicide to
control wheat bunt and smut fungi of other grains. The technical grade
used in agriculture is reported to contain 98% hexachlorobenzene, 1.8%
pentachlorobenzene, and 0.2% of 1, 2,4,5-tetrachlorobenzene. Commercial
formulations applied as dusts contain 10 to 40% hexachlorobenzene ..!'
Other applications in 1972 included additives for pyrotechnic
compositions for the military, a porosity controller in the manufacture of
electrodes, a chemical intermediate in dye manufacture and organic syn-
thesis, and use as a wood preservative.
In 1974, a spokesman for the Stauffer Chemical Company reported
that Stauffer's entire HCB production capacity (the largest in the industry)
had been committed on a multi-year contract basis for use only as a rubber
peptizing agent in nitroso and styrene type rubber manufacture for automo-
bile tire plants.—
E. Hexachlorobutadien
HCBD was not produced in the U.S. as of June 1974; it is imported
from Germany by Dynamit Nobel America who is the. only supplier of HCBD in
the U.S. Approximately 200,000 to 500,000 Ib of HCBD are sold annually in
the U.S.
98
-------
Figure 28 - Chlorine Consumption Pattern (major chlorine
compound.) and compounds of special interest)
-------
The largest domestic use of HCBD is for recovery of "snift"
(chlorine-containing) gas in chlorine plants. This "snift" gas, which oc-
curs at the liquification unit, is cleaned by passing it through HCBD or
carbon tetrachloride. Many chlorine producers have changed to the use cf
HCBD in recent years. Dow Chemical Company is a major consumer of HCED
for this purpose.
The Kalocarbon Company, a firm manufacturing high-temperature
lubricants, has used HCBD as a fluid for gyroscopes and as a chemical
intermediate to produce lubricants. Halocarbon now uses very little HCBD
because of the decline in aerospace business. ".'•'•
HCBD is also used as a chemical intermediate in the manufacture
of rubber compounds. Mallinckrodt Chemical Works at Raleigh, North Carolina,
is a major user of HCBD for this application.
The technical literature indicates that HCBD has been used in
Russia as a fumigant to treat grape phylloxera. Industry sources indicate
that Russia is one of the major HCBD-cohsuming countries and uses 600 to
800 metric tons per year. Most of this material is routed to herbicidal
use, primarily for grape phylloxera in the Ukraine.
C. Chlorine^
The percentage distribution of major chlorine uses is shown below.
Percent of
Total Use
1. Manufacture of Chlorinated Hydrocarbons 59
2. Pulp and Paper Manufacturing . 18
3. Water Treatment 4 . .
4. Miscellaneous 19
100
4,127
D. Sodium Chlorat
Percent of
Total Use
1. Pulp Bleaching
2. Herbicide and Defoliant
3. Other Chlorates and Perchlorates
4. Miscellaneous
101
Preceding page blank
-------
4/
E. Sodium Metal"
Metallic sodium is primarily used in the manufacture of tetra-
ethyl and tetramethyl lead. Minor uses include.reduction of metal halides
tc the metals (e.g., titanium tetrachloride to titanium metal). .
4/
F. Carbon Tetrachloride""
'.;•'•'.' .-;;. ;'{: ; • .•. j • ' •• ' ' Percent of
' Total Use
1. Fluorocarbons 85
2. Grain Fumigants 8
3. Solvents 5
4. Miscellaneous (includes use as reaction
intermediate for other organic compounds) 2
100
4/
G. Perchloroethylene~
Percent of
Total Use
1. Textile Industry 58
2. Exports 17
3. Metal Cleaning 15
4. Chemical Intermediate 9
5. Miscellaneous ' 1
100
4/
H. Trichloroethylener"
Percent of
Total Use
1. Metal Degreasing . 87
2. Extraction Solvent (e.g., drycleaning) 3
3. Miscellaneous Uses 2
4. Exports 8
100
Miscellaneous applications include use as a low-temperature heat
transfer medium and as a component of various rust-prevention formulations
102
-------
4/
I. Vinyl Chloride Monomer~
Vinyl chloride is a starting material for production of poly-
vinyl chloride and its copolymers, and for methyl chloroform.
121
J. Pentachlorophenol-"- :
Percent of
' Total Use
1. Wood Preservative (penta) 78
2. Manufacture of Sodium Pentachlorophetiolate 17
3. Home and Garden Applications 3
4. Herbicide 2
100
K. Pentachlorobenzene
This chemical is produced largely as a captive intermediate for
the synthesis of specialty chemicals. The total domestic sales in 1972
are estimated to be less than 1 ton.15/
4/
L. Hexachloroethane~
This product is used in a wide variety of applications; these
uses are listed below.
1. As an additive in smoke-producing mixtures. This is one of
the principle applications. .
2. A mixture of hexachloroethane and sodium silicofluoride (20%
by weight) has been patented for use in degassing magnesium.
3, As an additive for extreme pressure lubricants.
4. To reduce ignitability of combustible liquids.
5. Fungicidal and insecticidal components.
6. Veterinary medicine—used for treatment of liver flukes of
cattle and sheep., -
7. Moth repellent.
8. . Plasticizer for cellulose esters.
103
-------
9. As;rubber vulcanizing accelerator.
10. Retardant in fermentation processes.
11. Component of submarine paints.
12. Fire-extinguishing fluids additive.
4/
M. Synthetic Rubber (chloroprene)""
Chloroprene is used primarily in polymerization processes for
.tion of neoprene elastomers.
the production of neoprene elastomers
121
N. Atrazim
Atrazine is a selective herbicide. The major use is on corn and
some is used on sorghum. Very little is used by industry (less than 10%).
0. Propazine
Propazine is a preemergence herbicide used for control of broad-
leaved and grassy weeds in millet, sorghum, and umbel liferrous crops.
T, .
P. Simazine —
Simazine is a widely used selective herbicide for control of
broadleaf and grassy weeds in corn, citrus, deciduous fruits and nuts,
established alfalfa, perennial grasses, and nursery plantings. It is also
used as a nonselective herbicide for vegetation control in noncropland.
Q. Pentachloronitrobenzene (PCNB)—
Pentachloronitrobenzene is used as a soil fungicide to control
diseases of cotton, potatoes, tomatoes and peppers. Use of 20% PCNB in
dust also gives satisfactory results as a seed disinfectant against smut.
R. Dacthal®^
Dacthal® is a preemergence herbicide used for cotton, peanuts,
and a variety of vegetables.
104
-------
Mirex is used for the control of some species of ants, and most
widely in the USDA's fire ant program in the southeastern states. It has
also been used for the control of cotton pests, and some Hawaiian pine-
apple growers have used it for control of mealy bugs and ants. It is gen-
erally used as a bait now. '
kl
T. Maleic Hydrazidg-
This product is used as a herbicide and plant growth inhibitor.
For example, it is used to control suckering of tobacco and for sprout
control on potatoes and onions. Another application involves the treat-
ment of turf or lawns to limit the number of mowings required. It may be
used to delay the flowering of fruit trees or the growth of shrubbery and
nursery plants until frost danger is past. It is marketed in the form of
the sodium or diethanolamine salts; the former contains 50% of the hydra -
zide and the latter 30%.
. •
U. Hexachlorocyclopentadiene (HOP)—
•'••'.,• Percent of
Total Use
1. Chlorendic Anhydride 28
1 2. Chlordane 33
! 3. Other Pesticides 39
100 .
Chlorendic anhydride is an intermediate for the production of
f lame-retardant plasticizers, fire-resistant polyester resins and paints,
and as a dye intermediate. HCP is a key intermediate in the manufacture
of the cyclodiene group of chlorinated insecticides. For example, HCP is
the starting material for the preparation of an estimated 45 to 50 million
pounds per year of pesticides including mi rex, dieldrin, endrin, aldrin,
chlordane, heptachlor, and others.
ryf I ' . '
V. Chlorinated Naphthalenes- —
The major uses for chlorinated naphthalenes are as a dielectric
for electronic components, as an additive in gear oils and cutting oils,
and as a flame-resistant component of plastics.
105
-------
•- •" A 1Q 147
W. Chlorinated Biphenylb ' '—
Polychlorinated biphenyls (PCBs) have been used in the U.S. and
elsewhere over thejpast 40 years for many industrial and consumer applica-
tions, i
Prior to 1971, about 40% of PCS products sold in the U.S. was
used in applications where containment was difficult and losses into the
environment were probable. These uses included plasticizers, hydraulic
fluids and lubricants, surface coatings, inks, adhesives, pesticide ex-
tenders and encapsulated dyes for carbonless duplicating paper. The re-
maining 60% of domestic sales was used 'primarily in electrical applica-
tions (transformers and capacitors).
During the period of 1969 to :1971, scientific evidence was ac-
cumulated which indicated that the PCBs were widely dispersed throughout
the environment and that they can have adverse ecological and toxicologi-
cal effects. PCBs which enter the environment can be stored in animal lip-
ids. These biphenyls resist metabolic changes and tend to be concentrated
at succeedingly higher levels in animals higher in the food chain. The
identification of PCBs as a potential food contaminant was first reported
in 1966. Subsequent investigations established several sources from which
foods may become contaminated with PCBs. The acute toxicities of PCBs in
animals is reported to be low. Alterations in the functioning of the liver
have been observed in a number of animal species and these alterations are
attributed to PCBs.13*14/
Because of these developments, the Monsanto Company undertook
certain voluntary restrictions in 1971 on the distribution of PCBs to
various industries. Under these restrictions, PCBs were sold only for elec-
trical applications in which the PCB is confined inside sealed containers.
In 1971, this type of electrical application represented 907o of the total
use. .
106
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IX. ENVIRONMENTAL AND HEALTH ASPECTS
This section describes and briefly discusses the environmental
and health aspects of the production of the two chemicals of primary inter-
est, HCB and HCBD, and also of the three related chemicals first identified
as of special interest to this study, i.e., pentachlorophenol, hexachloro-
ethane, and pentachlorobenzene. The information includes data taken from
Chemical Abstracts and miscellaneous technical publications. The follow-
ing outline describes the toxic hazard ratings used:
32/
Toxic Hazard Rating Code—
i . .
0 NONE: (a) No harm under any conditions; (b) harmful only
under unusual conditions or overwhelming dosage.
1 SLIGHT: Causes readily reversible changes which disappear
after end of exposure.
2 MODERATE: May involve both irreversible and reversible changes,
not severe enough to .cause death or permanent
injury.
3 HIGH: May cause death or permanent injury after very short
exposure to small quantities.
• t - -
U UNKNOWN: No information on humans considered valid by authors.
A.' Hexachlorobenzene
32/
General Information: —
Synonym: Perchlorobenzene
Description: Monoclinic prisms
Formula:
Constants: Mol wt: 284.80; m.p.: 230°C; b.p.: 326°C;
flash p.: 242°F; d: 1.5; vap. press.: 1.089
x 10"5 mm Hg at 20°C, 1 mm Hg at 114. 4°C; vap.
d.: 9.8
HCB is a very stable, unreactive compound. It is not hydrolized
in aqueous solutions and there is no evidence that it is broken down by
physical or chemical processes in the environment. Since HCB is volatile
107
-------
in water vapor even at low temperatures,, co-distillation is a mechanism .
for dispersal. HCB sublimes readily and will evaporate if exposed.to air
under conditions of adequate ventilation. The literature^' indicates that
aerial dispersion may be the major pathway for HCB entering the marine
environment.
;*••>'
The results of model ecosystem.studies conducted at the University
of Illinois on the environmental fate of hexachlorobenzene and five other
organochlorine pesticides (aldrin, dieldrin, endrin, mirex, and DDT) were.
OQ / ' ' -
reported in 1973^=i' A summary of these reported results is given in the
following paragraphs..
The basic model ecosystem methodology utilized radiotracer tech-
niques. The model ecosystem evaluation was conducted in a small glass aquar-
ium with a terrestrial-aquatic interface of pure sand. A measured portion
of radiolabeled pesticide was applied to sorghum seedlings grown on the
terrestrial portion. Salt-marsh caterpillars were fed on the leaves and
their fecal products and the larvae themselves contaminated the aquatic
portion of the system. The radiolabeled products were transferred through
several food chains, e.g., alga, snail, plankton, water flea, mosquito,
and fish. After 33 days in an environmental plant growth chamber at 80°F
and a 12-hr photo period, the experiment was terminated, and the amount
and nature of the ^C determined by homogenization of the organisms, ex-
traction with acetonitrile, TLC autoradiography, and liquid scintillation
counting. Wherever possible, identity of degradation products was deter-
mined by chromatography with known standards. The results for hexachloro-
benzene and its degradation products expressed as equivalent ppm values
are shown in Table XI.
108
-------
TABLE XI
DISTRIBUTION OF HEXACHLOROBENZENE AND DEGRADATION PRODUCTS
Hexachlorobenzene Equivalents (ppm)
1&
Total ^C
Hexachlorobenzene
(Rf = 0.80)*/
Pentachlorophenol
(Rf = 0.50)
Unknown I
(Rf = 0.10)
Unknown II
(Rf = 0.05)
Polar (Rf = 0.0)
Unextractable
H20
0.00644
0.00298
0.00034
0.00023
0.00143
0.00197
Alga
(oedogonium)
1.827
1.556
*—
—
0.271
Snail
(physa)
4.099
3.72
. "•
—
0.378
Mosquito
(culex)
0.737
0.429
••~
•
0.269
Water flea
(daphnia)
0.696
0.598
~ —
'
0.098
Fish
(gambusia)
-3,154
,0,.857
• — -
0.446
0.857
. 0:.995
§_/ TLC with benzene:acetone, 1:1.
Source: Adapted from information contained in Reference 33.
-------
Hexachlorobenzene was found in substantial quantities in the
various organisms with little evidence of degradation products except highly
polar materials,and conjugates. Hexachlorobenzene comprised 85.1% of the
total radioactivity in alga, 90.8% in the snail, 87.2% in the water flea,
58.3% in the mosquito, and 27.2% in the fish. The water phase contained an
appreciable quantity of pentachlorophenol. This compound was not found in
free form in any of the organisms of the system. Hydrolysis of polar prod-
ucts in the water showed a family of related compounds.which are other
chlorinated phenols. The reported information indicates that another investi-
gator has tenatively identified 2,4,5-trichlorophenol, along with penta-
chlorophenol, as urinary degradation products of hexachlorobenzene in the
rat.
The biodegradability index (BI) -values for hexachlorobenzene
were 0.46 in fish and 0.10 in snail, and ecological magnification values
(EM) were 287 in fish and 1,247 in snail as shown in Table XII.
TABLE XII
QUANTITATIVE VALUES FOR ECOLOGICAL MAGNIFICATION (EM) AND BIODEGRADABILITY
INDEX (BI) FOR EIGHT ORGANOCHLORINE PESTICIDES IN FISH AND SNAIL
Hexachlorobenzene
Aldrin
As Aldrin
As Dieldrin
Dieldrin
Endrin
Mirex
Lin dan e
DDT
DDE
ODD or TDE
Solubility
(ppm)
0.006
Fish (gambusia)
EM BI
_Snail (physa)
EM BI
287
0.46
1,247
0.10
ca.
0 . 20
0.25
0.23
0.085
7.3
0.0012
0.0013
0.002
3,140
5,957
2,700
1,335
• 219
560
84,545
27,358
83,500
0.00014
0.00013
0.0018
0.009
0.0145
0.091
0.015
0.032
0.054
44,600
11,149
61,657
49,218
1,165
456
34,545
19,529
8,250
0.0017
0.00016
0.0009
0.0124
0.006
0.052
0.044
0.017
0.024
Source: Adapted from information contained in Reference 33. .
i
These data show that hexachlorobenzene accumulated in the tissues of fish
and snail to levels much greater than .that in the water of the model systems.
110
-------
Toxicity
The results of a hazard rating for HCB reported in the technical
literature^' are presented below.
Toxic Hazard Rating '
Acute Local: Irritant 1
Acute Systemic: Ingestion 1
Chronic Local: Irritant 1
Chronic Systemic: U
Toxicology: Limited animal experiments suggest low toxicity
Fire Hazard: Slight, when exposed to heat or flame
Disaster Hazard: Dangerous, when heated to decomposition, it
emits highly toxic fumes of chlorides'
Other pertinent findings in the toxicological literature on HCB
are summarized in the following paragraphs.
There are few data (see Table XIII) on the single dose acute
toxicity of HCB. For single dose administration, HCB has a very low toxicity--
500 mg/kg interperitoneal is nonlethal in rats, and the oral lethal dose
of a 15% suspension of HCB in the female Japanese quail is greater than
1 g/kg*!' On the other hand, the subacute or chronic toxicity of HCB can
be significant, as shown in Table XIV..2/ The most pronounced effect of
chronic exposure appears to be dysfunction of the liver. Neurotoxic symp-
toms were observed in several of these studies.
347
F. DeMarteis— and co-workers have reported on the nervous and
biochemical disturbances resulting from oral administration of HCB to rats
o c o£ /
and other test animals. R. K. Ockner and R. Schmid > ' have reported on .
acquired porphyria in man and rat caused by HCB intoxications. H. Ehrlicher—
has discussed industrial observations of the toxicity of vaporous HCB; he
reports that no serious illnesses or changes of liver function in the blood
compound were noted by medical monitoring of production workers exposed t°_ft.
HCB vapors over a 40-year period. Finally, in a review by I. V. Sairtskii,—
it was found that an HCB concentration of 0.1 mg/liter could be assumed to
represent the threshold toxicity value, and that 1/100 of that value may
then represent the limit of permissible concentration of HCB in air for
workers.
Ill
-------
TABLE XIII
ACUTE TOXICITY OF HEXACHLOROBENZENE FOLLOWING SINGLE DOSE ADMINISTRATION
Species
Mice
Rats
Rabbits
Cats
Guinea Pigs
Guinea Pigs
Guinea Pigs
Bluegill Fish
Flathead Minnows
Rainbow Trout
Channel Garfish
Rats
Method of Minimum
Administration Toxic Dose
Oral 400
Oral 500
Oral
Oral
Oral
Oral
Oral
Water
Water
Water
Water
Interperitoneal
Average
Lethal
Dose
(ppm) .',
4,000
. 3,500
2,600
1,700
> 1,000
> 3,000
3,000
> 100
> 100
> 100
> 100
> 500
Total
Lethal Dose
7 ,500
6,000
-
Source: Adapted from information contained in Reference 3.
112
-------
TABLE XIV
. SUBACUTE AND CHRONIC TOXICITY OF HEXACHLOROBENZENE
Route
Species
Oral (in feed) Rats
Oral (in feed) Rats
Oral (in feed) Rats
Number
of
Animals
5
5
4
4
4
4
Dose
Test
Duration
2 mg/kg/day 13 days
6 mg/kg/day 13 days
20 mg/kg/day 13 days
60 mg/kg/day 13 days
200 mg/kg/day 13 days
10 mg/kg/day 30 days
30 mg/kg/day 30 days
65 mg/kg/day 30 days
100 mg/kg/day 30 days
Effects Observed
No toxic effects.
Very light skin twitching and
nervousness. Significant in-
corporation into-liver.
Neurotoxic symptoms. Increase in
liver weight.
Neurotoxic symptoms. Increase in
liver and kidney weight.
Neurotoxic symptoms. Increase in
liver and kidney weight.
No toxic effects.
Increase in food consumption and
body weight gains, increase in
coproporphyrin excretion in
urine; liver weight and liver:
body weight ratio increased.
Same as at 30 mg/kg/day.
Same as 30 mg/kg/day plus eleva-
tion in excretion of uroporphyrim.
-------
TABLE XIV (Continued)
Route
Species
Oral (in feed) Rats
Oral (in feed) Rats
Oral (in water) Rats
Oral (in feed) Japanese
Quail
Number
of
Animals
33
10
10
10
13
15
15
15
15
Dose
Test
Duration
100 mg/kg/day 51 days
300 mg/kg/day 10 days
150 mg/kg/day 30 days
50 mg/kg/day 30 days
Effects Observed
13 deaths in 1 month; neurotoxic
symptoms; increased liver weight;
porphyria.
30% mortality.
60% mortality.
30% mortality.
0.025 mg/kg/day 4-8 months No toxic symptoms. Possible effect
on conditioned reflexes.
1 ppm
5 ppm
20 ppm
80 ppm
90 days No toxic effects.
90 days Slight increase in liver weight;
minimal porphyria.
90 days. Increased liver weight, decreased
egg production; .porphyria; liver
and kidney pathological changes.
90 days 5 deaths (18- to 62-day period);
neurotoxic'symptoms; porphyria;
increased liver weight; decreased
egg production and hatchability;
liver and kidney pathological
changes.
-------
TABLE XIV (Concluded)
Route
Species
Oral (in feed) Japanese
Quail
Oral (in feed) Chickens
Oral (in feed) Guinea Pig
Mice
Oral (in feed) Rabbits
Oral (in feed) Male Rats
Number
of
Animals
12
12
12
26
Dose
2,500 ppm
500 ppm
100 ppm
Test
Duration
Effects Observed
30 days All died in 30 days. (4 died in
7 days).
30 days All died within a month.
3 months Mortality (l-20th day; 10 within
7 weeks; 1-10 weeks). Surviving
cock showed marked loss of weight.
Necrosis of liver cells; porphyria.
120-480 ppm in 3 months No toxic effects.
diet
0.5%
0.5%
0.5%
0.5%
0.2%
8-10 days Marked neurological symptoms.
8-10 days Marked neurological symptoms.
6 weeks Increase in urinary porphyrins.
8-12 weeks Death occurred.
12 weeks Retardation in weight gain; porphyria;
degenerative changes in the liver.
Source: Adapted from information contained in Reference 3.
-------
B. HexachlorobU'tadiene
39/
General Information —
Formula: C. Cl,
4 o
Constants: Mol wt: 260.7; melting range: -19 to 22°C; boiling
•; f 'range: 210 to 220°C; d: 1-675; vap. press.: 1.5
• •" '•• •'..'•' :mi Hg at 40°C \ : . . '
Toxicity
HCBD toxicity tests conducted by the Hazelton Laboratories of
' • 2 9/ '
Washington, D.(3., for the Diamond Shamrock Corporation^-:-' are discussed
in the following paragraphs.
The acute oral 0)50 of HCBD for male albino rats is 178
of body weight. At a dosage level of 100 ill/kg none of a group of five ani-
mals succumbed. At a level of 316 (il/kg, all of a group of five animals
succumbed within 2 days.
The acute dermal LD5Q of HCED for albino rabbits of either sex
is 1,780 lil/kg of body weight. After an exposure period of 24-hr none of
a group of four rabbits succumbed at a dosage level of 1,000 yl/kg. At a
dosage level of 3,160 p,l/kg, all of a group of five rabbits succumbed
within a period of 5 days. The exposed skins of all animals showed a mild
to moderate degree of erythema. This completely subsided by the secoriH
or third day and thereafter showed no gross signs of dermal irritation.
A single application of 0.05 HCBD to the eyes of a group of three.
albino rabbits of either sex produced a mild degree of eye irritation which
completely subsided within 24 hr. . There was no evidence of systemic toxicity
from mucous membrane absorption.
The acute inhalation Lt,-Q for varying species is:
95% Confidence
- (min) Limits - (min)
Mice 3LO 270 to 357
Rats 275 229 to 330
Guinea Pigs 200 165 to 242
116
-------
Ten mice, 10 rats, and 10 guinea pigs were exposed for 6 hr to
the aerosol of HCBD under dynamic conditions in a chamber. Normal concentra-
tion of the compound in 'the experimental atmosphere was 6,800 ppm (72,750
mg/m3). Direct comparison between compounds from the above data are only
permissible if the concentration in each case were the same. However, a
rough comparison of the toxicities of two other compounds, trichlorofluoro-
ethylene (TCFE), and perchloroethylene (PCE), can be made, if it is assumed
that the same quantitative response of the organism may be expected for
various values of C and t, provided (Ct) is a constant,
these three compounds is given below:
The L(Ct)50 for
Mean Concentration
Of Available Data
Compound (ppm) (mg/nr)
HCBD
PCE
TCFE
6,800
2,750
4,120
72 , 750
18,600
25,100
22.6
9.0
23.0
20.00
10.00
36.00
14.6
16.0
39.0
L(Ct)5o x 10"6 (mg-min/m3).
Guinea
Mice Rats Pigs Average
19.1
11.7
32.6
Other pertinent findings in the technical literature on HCBD
toxicity are summarized in the following paragraphs.
407
In 1967, V. F. Chernokan— observed in skin intake toxicity
studies, that HCBD caused skin irritation and hypermia in rats, with ex-
treme toxicological effects at concentrations approaching the LD5Q of 4.33
g/kg (165 mg/kg, oral). At 3.0 to 3.5 g/kg the animals displayed increased
motibility and agression, followed by paralysis of the extremities.
41 /
John C. Gage— conducted a study in 1970 of the subacute tox-
icity of 109 industrial chemicals. He found major kidney damage in.rats
exposed for periods of about 3 weeks to known concentrations of HCBD. The
results indicated degeneration of the protein, fat, and carbohydrate rela-
tions in cells and impared cell function.
42/
Stroganov and Kolosova— found that HCBD is toxic to some aquatic
organisms (e.g., Daphnia magma, Leucaspius delineatus, and fish) at concentra-
tions of 3 mg/liter of water.
4° /
F. G. Murzakaev—- conducted toxicity studies in which rats were
fed 20 mg/kg doses of HCBD. The results indicated degeneration of the protein,
fat, and carbohydrate relations in cells and impared cell function.
117
-------
C. Pentachloropheno1 .
32/
General Information—
Description: Dark-colored flakes and sublimed needle crystals
with a characteristic odor -..• .
Formula: Cl C.OH .
Constants: Mol wt: 266.4; mp: 191 C; b.p.: 310°C (decomposes);
d: 1.978; vap. press.: 40 mm at 211.2°C
The results of a hazard ratings for this chemical reported in
the technical literature^!/ are shown below.
•. i ,• •. • • " '.
Toxic Hazard.Rating
Acute Local: Irritant 3, Ingestion 3, Inhalation 3
Acute Systemic: Ingestion 3, Inhalation 3, Skin Absorption 3
Chronic Local: Irritant 2
Chronic Systemic: Ingestion 2, Inhalation 2, Skin Absorption 2
Toxicology: Acute poisoning is marked by weakness, convulsions,
and collapse. Chronic exposure can cause liver
and kidney injury.
Disaster Hazard: Dangerous, when heated to decomposition it
emits highly toxic, fumes of chlorides.
D. Hexachloroethane
32/
General Information—
Synonyms: Carbon trichloride; carbon hexachloride
Description: Rohmbic, triclinic or cubic crystals, colorless;
camphor-like odor
Formula: CC1 CC13
Constants: Mol wt: 236.76; m.p.: 186.6°C (sublimes); d: 2.091;
vap. press.: .1 mm at 32.7°C
118
-------
33/
The result of hazard ratings reported in the technical literature—
are given below.
327
Toxic Hazard Rating—
Acute Local: Irritant 2, Ingestion 2, Inhalation 2
Acute Systemic: Inhalation 2 .
Chronic Local: Irritant 2
Chronic Systemic: Ingestion 2
Toxicology: Liver injury has been described from exposure to
this material.
Explosion Hazard: Slight, by spontaneous chemical reaction.
Dehalogenation of this .material by reaction
with alkalies, metals, etc., will produce
spontaneously explosive chloroacetylenes.
Disaster Hazard: Dangerous, when heated to decomppsition, it
emits highly toxic fumes of phosgene.
32/
E. Pentachlorobenzene—
Toxicology: Very little data concerning toxic properties of .
this chemical are available in the technical literature. The literature—
indicates that the toxicity of this product is usually no greater, and
frequently is less than that of corresponding aromatic hydrocarbons.
Fire Hazard: Unknown
Explosion Hazard: Unknown
Disaster Hazard: Moderately dangerous, when heated to decomposi-
tion, toxic .fumes may be emitted. .
119
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X. SELECTION OF MONITORING SITES
An important objective in this study was to identify those chemi-
cal plant sites that appear to be most likely to produce significant amounts
of HCB and HCBD as by-products, wastes, etc., and therefore pose a potential
threat of environmental contamination. Criteria were therefore developed
!•.••'• ' • •': . ' •'(''
and then applied to all of the 'pertinent chemicals and processes to select
those specific plant sites which should be tested for HCB and HCBD emissions
in a subsequent EPA program. . ' Vi
The major selection criteria developed and applied by MRI in
this evaluation were:
• . ' Y .'..,'•'•" . ' ' ' • !!"'•
' ' . ; •!
* total volumes of production of chemicals at each plant sitel
* Total volume of discharge of waste materials of all types
(liquids, solids, and gases). Emphasis is placed on volume
of liquids and solids since HCB and HCBD have low volatility
and, therefore, tend to collect in these types of waste.
*' The known application of advanced pollution control technology--
e.g., the degree of sophistication of waste treatment and
waste disposal method in use at specific plant sites.
* The age of manufacturing plants and facilities and the known
process improvements which minimize pollution.
* The toxicity of the product(s) being produced. ;
* Production of captive products of interest used on the plant
site as an intermediate, etc., as opposed to production for
marketing.
* The reputation of companies or specific plants for high
standards of safety and/or pollution control in production
operations.
To the extent possible, these criteria were applied to each of
the identified chemical industries of interest to Task I. In some instances,
as noted, the available collected information for a given industry was
insufficient to support an evaluation of this type. The principal task in-
volved narrowing the field of plant sites in the chlorine industries because
of the large number of chlorine plants (65) and the wide geographic distri-
bution of these plants. A detailed discussion of the evaluation methodology
for the chlorine plants and other industries is presented in Appendix C.
120
-------
A brief discussion of the evaluation methods and results for
each of the chemical industries of interes.t is given below under subhead-
ings.
Chlorine plants; In 1973 there were 65 chlorine producing plants
in the U.S. Twenty-nine plants used diaphragm cells, 23 plants employed
mercury cells, and 13 plants used miscellaneous cell types or combinations
of cells. The 32 plants which use dimensionally stable anodes (DSAs) do
not form HCB or HCBD. The other 33 (nonDSAs) plants are considered to be
potential emitters of both of these chemicals.
Following application of the MRI criteria to the 33 nonDSA
chlorine plants (see Appendix C), the field was narrowed to the plant sites
shown in Table XV.
TABLE XV
CHLORINE PLANTS RECOMMENDED AS MONITORING TEST SITES
type Plant Plant Site Producer
Diaphragm cell 1. Houston, Texas Champion International
Corporation
2. Cramercy, Louisiana Kaiser Aluminum and Chem-
ical Corporation
Mercury cell 3. Linden, New Jersey Linden Chlorine Products,
Inc.
4. Mclntosh, Alabama Olin Corporation
It is suggested that initial monitoring tests be made only at
Sites (2) and (4). If these tests show substantial HCB and HCBD contam-
ination problems then it is recommended that follow-up testing be conducted
at Sites (1) and (3).
Sodium chlorate plants; This\chemical industry is not considered
to be a source of HCB and HCBD contamination. No evidence of such contam-
ination was obtained by inquiries made to producers of this chemical. All
domestic sodium chlorate producers are in the process of converting from
graphite electrodes to the more efficient metallized anodes (DSAs). The use
of these new electrodes eliminates the formation of chlorinated hydrocar-
bon wastes resulting from the deterioration of the graphite electrode.
121
-------
Carbon tetrachloride plants: As of 1973, carbon tetrachloride
was produced at 11 plant sites. The evaluation results (see Appendix.C)
are a recommendation that the following carbon tetrachloride plant sites
be monitored: (
*' E. I. du Pont de Nemours, Corpus Christi, Texas
* Vulcan Materials Company, Geismar, Louisiana ;.-!;''. '
- ' ' •!.•'•
•! ;
*• Vulcan Materials Company, Wichita, Kansas ' ' :! .
Perchloroethylene plants; Perchloroethylene was produced at
10 production sites in 1973. The results of the.MRI evaluation (see
Appendix C) indicate that the following perchloroethylene plants should
be recommended as monitoring test sites:,
* PPG Industry, Inc., Lake Charles, Louisiana
* Vulcan Materials Company, Geismar, Louisiana
* Vulcan Materials Company* Wichita, Kansas
Trichloroethylene plants: Trichloroethylene was produced at
five plant sites in 1973. Each of these plants is operated in conjunction
with perchloroethylene operations at a common site. The results of the
MRI evaluation warrant that the trichloroethylene plant of PPG Industry,
Inc., at Lake Charles, Louisiana, be recommended as a monitoring site.
Vinyl chloride monomer plants: In 1973, very .large quantities
(5,089 x 10" Ib/year) of vinyl chloride monomer were being produced in
the United States. The total number of operating plant sites during that
year was 16. On the basis of the MRI evaluation (see Appendix .C) one repre-
sentative vinyl chloride monomer plant was selected for inclusion in the
list of recommended monitoring test sites. The recommended site is the
Lake Charles, Louisiana, facility of PPG Industry, Inc.
Pentachlorophenol plants; Information on the technology of this
chemical industry indicates that the potential for environmental contamina-
tion by HCB or HCBD is very low or nonexistent. The Dow Chemical Company
claims no HCB is formed in their pentachlorophenol process and Monsanto
also reports that it has no problem with the formation of HCB in its penta-
chlorophenol production operations. For these reasons, no monitoring test
site is recommended. , .
122
-------
Hexachlorobenzene plants! Based on information obtained in Task
I, this chemical is produced largely as a by-product of the manufacture of
other chemicals such as perchloroethylene, etc. The actual processes used
are proprietary. The Stauffer Chemical Company, the only domestic producer
of HCB in 1974, produces a by-product HCB in their perchloroethylene (PCE)
manufacturing operations at Louisville, Kentucky. The tarry residue from
PCE operations is reported by an industry spokesman to contain about 80%
HCB and 10 HCBD. The HCB is recovered and sold and the remainder of the
tar is recycled to the process reactor. Therefore, the possibility of HCB
or HCBD entering the environment is considered to be very slight. This
plant is, therefore, not recommended for inclusion in the EPA site moni-
toring program.
Pentachlorobenzenet An industry spokesman— has reported that
this chemical is produced largely as a captive by-product (e.g., it is
used as an intermediate or disposed as waste on the plant site), by the
manufacturers of tetrachlorobenzene who are as follows:
Dover Chemical Corporation, Dover Ohio
Dow Chemical Company, USA, Midland, Michigan
Hooker Chemical Corporation, subsidiary of
Occidental Petroleum Corporation, Niagara Falls, New York
Solvent Chemical Company, Inc., Maiden, Massachusetts
Two specialty chemical companies are reported to produce and
sell pentachlorobenzene in very small quantities (i.e., less than 2,000
Ib/year) for both companies. These companies are: Aceto Chemical Company,
Inci, of Flushing, New York, and Chemical Procurement Labs, Inc., of College
Point, New York. The estimated total domestic production in 1972 was 1,000
to 2,000 tons. Since some HCB is formed as a by-product in the production
process, there is some risk of HCB pollution. Because this chemical is
produced principally as a captive product, which is consumed or disposed
of on the plant site, it is not recommended that any of these production
sites be included in the EPA site monitoring program.
Hexachloroethane; This chemical is manufactured domestically
by only one producer, Hummel Chemical Company, at South Plainfield, New
Jersey. In 1972, the production amounted to only 200 tons, which combined
with the low process operating temperature (100 to 140°C), makes it very
unlikely that this process poses any problem in regard to HCB or HGBD con-
tamination. Therefore, this production plant is not recommended for inclusion
in the list of EPA monitoring sites.
123
-------
i
-\
Hexachlor.obutadiene; Within recent years (i.e., during the 1960's)
HCBD was produced and sold as a by-product of the manufacture of perchloro-
ethylene and trichloroethylene. In 1974, however, no HCBD was produced do-
mestically and;all U.S. supplies, amounting to 200,OQO to 500,000 Ib, were
obtained by imports from Dynamit Nobel in Germany. Thus, it is not appro-
priate to consider site monitoring of HCBD plants in the U.S.
Synthetic rubber (chloroprene)t In 1974, chloroprene (the only
synthetic rubber deemed of interest to Task I) was being produced at six
manufacturing sites in the U.S. The total domestic production capacity in
1974 was 198,000 tons. Waste disposal information for the chloroprene manu-
facturing process was obtained from a Du Pont spokesman Ji?.' A sizable quan-
tity of solid waste consisting largely (90%) of reject rubber in the form
of "coagulum," a nondegradable, insoluble and nonflammable material, is
disposed of by landfill operations at the Du Pont facility. Du Pont inciner-
ates certain liquid chlorinated hydrocarbon wastes formed in chloroprene
processing. The hydrogen chloride produced in the waste-burning operation
is absorbed by water scrubbing and the hydrochloric acid solution formed
is then injected into a deep well operated by Du Pont. This spokesman re-
ported that neither HCB nor HCBD are present in the wastes from this in-
dustry. Because this spokesman's report concerned over two-thirds of the
total chloroprene production, no chloroprene plants are recommended for
monitoring.
Atrazine, propazine, and simazinet Ciba-Geigy Corporation pro- .
duces all of these pesticide products at its St. Gabriel, Louisiana, facility.
This plant is designed primarily for atrazine, but is used also for the
other two triazines. MRI studies show that significant quantities of HCB
can be formed in the manufacture of this group of pesticides. On the basis
of these studies, i't is recommended that the St. Gabriel, Louisiana, facility
of Ciba-Geigy be included in the group of plant sites for test monitoring.
> -
Pentachloronitrobenzene (PCNB); The chemical is produced domes-
tically solely by the Olin Corporation at Mclntosh, Alabama. The total 1972
production amounted to about 1,500 tons. Because HCB can be formed as a
by-product in the manufacture of PCNB, it is recommended that this plant
be included in the EPA site monitoring program. (It should be noted that
Mclntosh, Alabama, is also the location of a mercury cell chlorine plant,
which has been recommended for site monitoring.)
Dacthal®: This pesticide is produced only by Diamond Shamrock
Corporation at Greens Bayou, Texas. The total production in 1972 was esti-
mated to be 1,000 tons. In response to a written inquiry, this corporation
reported that the product now contains 0.3% by weight of HCB as a contaminant
and that the production waste material contains about 84% HCB. All of the
waste material is drummed or transferred to tank trucks and hauled to Rollins
International, Inc., Deer Park, Texas, for incineration. Because production
of Dacthal® increased from about 1,000 to 2,000 tons from 1972 to 1974, and
124.
-------
the concentration of HCB in the waste is near 847°, this plant site is recom-
mended for inclusion in the EPA site monitoring program.
Mirex; This pesticide is produced at only one site (Niagara
Falls, New York, Hooker Chemical Corporation). The total annual produc-
tion is estimated to be less than 500 tons. MRI has estimated relatively
small quantities of HCB (from 1,000 to 2,000 Ib/year) are formed in the
production of mirex. Because this chemical is produced in very small quan-
tities and at only one site, this plant is not recommended for the initial
EPA site monitoring program. It is recommended, however, that representa-
tive samples of mirex products be obtained, and analyzed for HCB content
to establish the extent of contamination. If substantial contamination is
established, then it is recommended that the mirex production site be mon-
itored.
Maleic hydrazidet In 1972, four plants produced a total of 2,000
tons of this chemical. No evidence was found in the Task I study to estab-
lish that any HCB or HCBD pollution problems are involved in the manufacture
of this chemical. Because of the low production, and the lack of evidence
concerning HCB or HCBD emissions during manufacture, none of these plants
are recommended for site monitoring.
Hexachlorocyclopentadiene (HCP); In 1971, four manufacturing
plants accounted for an estimated total production of 25,000 tons of HCP.
Some evidence was found that HCB and HCBD may be formed in the production
processes used*—' The current producers employ advanced waste disposal
technology including waste incineration. None of these production plants
are recommended for inclusion in the initial EPA monitoring program, but
a follow-up surveillance program involving analysis of plant products is
recommended.
Chlorinated naphthalene; Only one company (The Koppers Company,
Inc.) produces this chemical. The total sales volume for these products in
1974 amounted to less than 2,500 tons. A relatively low reaction temper-
ature (maximum of about 200°C) is used in production of these products.
The plant is reportedrJL*j£/ to use advanced pollution control equipment
to prevent atmospheric emissions. Small amounts of inert distillation resi-
due are hauled to a plant landfill. For these reasons, this plant is not
recommended as a monitoring site.
Chlorinated biphenyls (PCS); Monsanto Chemical Company, the
sole domestic producer of this type of product, has production facilities
at Anniston, Alabama, and Sauget, Illinois. In response to a written inquiry
(see Appendix B), the Monsanto Company has reported that in their production
of PCBs no detectable concentrations of HCB or HCBD occur in the products
or in process waste materials, and that no by-products are produced. On
the basis of this information and an analysis of the process and product
usage conditions, we conclude that the current production and use of PCBs •
does not create any HCB or HCBD pollution problems.
125
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! r . ' ' ' •
In summary, .the recommended plant locations and chemical opera-
tions for the initial EPA monitoring program are:
1. Lake Charles, Louisiana - perchloroethylene, trichloroethylene,
and vinyl chloride monomer.
2. Geismar, Louisiana - perchloroethylene, carbon tetrachloride.
! i . ' . - . ' ' I •• • ' ,
3. Gramercy, Louisiana - chlorine by diaphragm cell process.
4. Corpus Christi, Texas - carbon tetrachloride.
5. Wichita, Kansas - perchloroethylene and carbon tetrachloride.
i ' j
6. Mclntosh, Alabama - chlorine by mercury cell process and
pentachloronitrobenzene.
7. St. Gabriel, Louisiana - atrazine, simazine, propazine.
8. Greens Bayou, Texas - Dacthal®.
126
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APPENDIX A
PLANT CAPACITIES, PRODUCTION AND IMPORT DATA
FOR SELECTED CHEMICALS
127
-------
TABLE A-Ia
SUMMARY DATA FOR THE CHLOR-ALKALI INDUSTRY
i' " •
1. Salt consumption for Chlor-Alkali Production (1971)
* . - ; : . . _'. ' •;•..
Sodium Chloride: 19,621,000 tons .
Potassium Chloride: 282,000 tons (est)
2. Chlor-Alkali Production:
1971
(OOP tons)
9,352
9,667
198
1972
(000 tons)
. 9,868
10,266
178
Chlorine
Sodium hydroxide
Potassium hydroxide
Hydrogen 156 . . 161
(56 x 109 scf) (58 x 109 scf)
Source: Adapted from information contained in Reference 17.
128
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10
v£>
Allied Chemical Corporation
Industrial Chemicals Division
Aluminum Company of America
American Mageslum Company
BASF Wyandotte Corporation
Industrial Chemicals Group
Brunswick Pulp and Paper Company
Brunswick Chemical Company, Subsidiary
Champion International
Corporation
Detrex Chemical Industry, Inc.
Diamond Shamrock Corporation
Diamond Shamrock Chemical Company
Electro Chemicals Division
Dow Chemical Company USA
E. I. du Pont de Nemours and Company,.Inc.
Electrochemicals Department
TABLE A-Ib
CHLOR-ALKALI PRODUCTION —
Annual
Production
Capacity
i Production Site . (103 tons)
Acme,.North Carolina
Baton'Rouge, Louisiana
•Brunswick, Georgia
Moundsville, West Virginia
Syracuse (Solvay), New York
Point Comfort, Texas 150.0
Snyder, Texas . 26.0
Geismar, Louisiana 300.0
Port Edwards, Wisconsin . 55.0
Wyandotte, Michigan 120.0
Brunswick, Georgia 30.0
Canton, North Carolina . 13.0
Houston, Texas 14.4
Ashtabula, Ohio 22.0
Deer Park; Texas 440.0
Deer Park, Texas
Delaware City, Delaware
Mobile, Alabama 720.0
. Muscle Shoals, Alabama
Palnesville, Ohio
Dallesport, Washington ", Unknown
Freepo'rt, Texas _, 1,700.0
Midland, Michigan
Oyster Creek, Texas 1,576.0
Plttsburg, California
Plaquemine, Louisiana
Corpus Chrlsti, Texas 366.0
Memphis,' Tennessee |
Niagara Falls, New York I 122-4
Remarks
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells. Not operating.
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
New plant construction
Chlorine-caustic cells . .
New plant construction
Also magnesium cells
Chlorine-caustic cells
New.plant construction
By-product of metallic sodiura
manufacturing
-------
U)
O
Producer
Ethyl Corporation
Industrial Chemicals Division
FMC Corporation
Inorganic Chemicals Division
Fort Howard Paper Company
Georgia-Pacific Corporation
Bellingham Division
TABLE A-Ib (Continued)
Production Site
Baton Rouge, Louisiana ~]
Houston, Texas —I
South Charleston, West Virginia
Green Bay, Wisconsin
Bellingham, Washington
Plaquemine, Louisiana
The B. F. Goodrich Company
B. F. Goodrich Chemical Company, Division
Hercules, Inc.
Coatings and Specialty Products Department
Jefferson Chemical Company, Inc.
Kaiser Aluminum and Chemical Corporation
Kaiser Chemicals Division
Linden Chlorine Products, Inc
Mobay Chemical Company,
Division of Baychem Corporation
Monsanto Company
Monsanto Industrial Chemicals Company
N L Industry, Inc.
H-K, Inc., Subsidiary
Magnesium Division
Northwest Industry, Inc.
Velsicol Chemical Corporation, Subsidiary
Occidental Petroleum Corporation
Hooker Chemical Corporation, Subsidiary
Industrial Chemicals Division
Calvert City, Kentucky
Hopewell, Virginia
Port Neches, Texas
Cramercy, Louisiana
Linden, New Jersey
Cedar Bayou, Texas
Sauget, Illinois
Rowley, Utah
Memphis, Tennessee
Montague, Michigan
Niagara Falls, New York
Tacoma, Washington
Taft, Louisiana
Annua1
Production
Capacity
(IP3 tons)
230.4
277.2
Unknown
48.0
440.0
108.0
18.0
54.0
160.0
180.0
Remarks
By-product of metallic sodium
manufacturing
Chlorine-caustic cells
Chlorine-caustic cells
New plant construction
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
72.0 Electrolysis
94.0 Chlorine-caustic cells
80.0 New plant .construction
24.8 Chlorine-caustic cells
630.0 Chlorine-caustic cells
-------
01In Corporation
Chemicals Division
Pemwalt Corporation
Chemical Division
PPG Industry, Inc.
Chemical Division
Industrial Chemicals Division
BMI Company
Shell Chemical Company
Industrial Chemicals Division
Sobln Chemicals, Inc.
Stauffer Chemical Company
Industrial Chemical Division
Vicksburg Chemical Company
TABLE A-Ib (Concluded)
Production. Site
Augusta, Georgia
Charleston, Tennessee
Mclntosh, Alabama
Niagara Falls, New York _
Saltville, Virginia
Calvert City, Kentucky
Portland, Oregon
Tacoma, Washington
Wyandotte, Michigan
Guayanilla, Puerto Rico
Barberton, Ohio
Corpus Christ!, Texas
Lake Charles, Louisiana
New Martlnsvllle, West Virginia
Ashtabula, Ohio
Deer Park, Texas
Niagara Falls, New York
Orrlngton, Maine
Henderson, Nevada
Le Moyne, Alabama
St. Gabriel, Louisiana
Vicksburg, Mississippi
Annual
Production
Caoaci ty
(103tons)
524.2
342.0
185.0
1,638.0
Unknown
135.0
Unknown
72.0
270.0
33.6
Remarks
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic eelIs
Chlorine-caustic cells
By-product of metallic sodium
manufacturing
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cells
Chlorine-caustic cecils
Oxidation -of. HC1 -via NO
2
Vulcan Materials Company
Chemicals Division
Weyerhaeuser Company
Denver City, Texas
Newark, New Jersey
Wichita, Kansas
Longview, Washington
Unknown
153.0—
. 100.0
.Chlorine-caustic cells
. .Chlorine-caustic cells
Note: Several pulp and paper companies not listed are believed to have some captive production. Much of the above capacity is
produced for captive use only.
Source: Adapted from information contained in Reference 17,
-------
TABLE A-Ic
111
DOMESTIC CHLORINE PRODUCERS BY EPA REGION—'
Company
Location
Products
Region I
Sobin Chlor-Alkali
Region II
Hooker
01 in
DuPont
Hooker, Sobin
Allied
Vulcan
Linden Chlorine
Region III
Orrington, Maine
Niagara Falls^ New York
Niagara Falls, New York
Niagara Falls, New York
Niagara Falls, New York
Syracuse, New York
Newark, New Jersey
Linden, New Jersey
C12, NaOH
C12, NaOH
C12, NaOH
C12, Na metal
C12, KOH
C12, NaOH, Na2C03
C12, NaOH
C12, NaOH
Diamond
Hercules
Allied
PPG
PMC Corporation
Delaware City, Delaware
Hopewell, Virginia
Mouhdsvillei West Virginia
New Martinsville,
West Virginia
South Charleston,
West Virginia
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
Region IV
Goodrich
Pennwalt
Velsicol
DuPont
Olin
Vicksburg Chemical
Diamond
Olin
Diamond
Stauffer
Champion
Allied
Calvert City, Kentucky
CaIvert Ci ty, Kentucky
Memphis, Tennessee
Memphis, Tennessee
Charleston, Tennessee
Vicksburg, Mississippi
Muscle Shoals, Alabama
Mclntosh, Alabama
Mobile, Alabama
LeMoyne, Alabama
Canton, North Carolina
Acme, North Carolina
C12,
C12,
C12,
C12,
C12,
C12
C12,
C12,
C12,
ci2,
ci2,
C12,
NaOH
NaOH
NaOH
Na metal
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
132
-------
Company
Region IV (Concluded)
TABLE A-Ic (Continued)
Location
Product
Olin
Allied
Brunswick Chemical
Region V
Detrex
RMI Company
Diamond
PPG
BASF Wyandotte
Pennwalt
Dow
Hooker
Monsanto
Ft. Howard Paper
BASF Wyandotte
>
Region VI
Hooker
Kaiser Aluminum
BASF Wyandotte
Stauffer
Dow
Allied
Ethyl
PPG
Jefferson
Mobay
Dow
Alcoa
PPG
Champion
Diamond
Shell
Ethyl
Vulcan
Augusta, Georgia
Brunswick, Georgia
Brunswick, Georgia
Ashtabula, Ohio
Ashtabula, Ohio
Painesville, Ohio
Barberton, Ohio
Wyandotte, Michigan
Wyandotte, Michigan
Midland, Michigan
Montague, Michigan
East St. Louis, Illinois
Green Bay, Wisconsin
Port Edwards, Wisconsin
Taft, Louisiana
Cramercy, Louisiana
Geismar, Louisiana
St. Gabriel, Louisiana
Plaquemine, Louisiana
Baton Rouge, Louisiana
Baton Rouge, Louisiana
Lake Charles, Louisiana
Port Neches, Texas
Cedar Bayou, Texas
Freeport, Texas
Point Comfort, Texas
Corpus Christi, Texas
Houston, Texas
Deer Park, Texas
Deer Park, Texas
Houston, Texas
Denver City, Texas
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
C12, Na metal
C12, NaOH, Na2C03
C12, NaOH, Na2C03
C12, NaQH, Na2C03
Cl2j NaOH
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
C12,
C12,
C12,
ci2.
ci2,
C12,
C12,
ci2,
C12,
C12
ci2,
C12,
C12,
C12,
C12,
C12,
C12,
C12,
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
Na metal, Na
NaOH
NaOH
NaOH
NaOH
NaOH, Na2C03
NaOH
NaOH
NaOH
Na metal
NaOH
133
-------
Company
Region VII
Vulcan
Region IX
Dow
Stauffer
Region X
Georgia-Pacific
Hooker
Pennwalt
Weyerhaeuser
Pennwalt
TABLE A-Ic (Concluded)
Location
Wichita, Kansas
Pittsburg, California
Henderson, Nevada
Billingham, Washington
Tacoma, Washington
Tacoraa, Washington
Longview, Washington
Portland, Oregon
Product
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
C12, NaOH
,C12, NaOH
134
-------
TABLE A-II
LIST OF U.S. PRODUCERS OF SELECTED CHEMICALS^'
Producers
Sodium Chlorate
Brunswick Pulp and Paper Company
Brunswick Chemical Company, Subsidiary
Huron Chemicals
Georgia-Pacific Corporation
Belllngham Division
Kerr-McGee Chemical Corporation,
Subsidiary
Occidental Petroleum Corporation
Booker Chemical Corporation, Subsidiary
Industrial Chemicals Division
Pacific Engineering and Production
Company of Nevada
Penn-Olln Chemical Company
Pennwalt Corporation, Chemical Division
PPG Industry, Inc.
. Industrial Chemical Division
Rlegel Paper Corporation
Sodium Metal •
E. I. du Pont de Nemours and Company, Inc.
Production Site
Brunswick, Georgia
Butler, Alabama
Bellingham, Washington
Hamilton, Mississippi
Henderson, Nevada
Columbus, Mississippi
Niagara Palls, New York
Taft, Louisiana
Henderson, Nevada
Calyert City, Kentucky
Portland, Oregon
Wyandotte, Michigan
Lake Charles, Louisiana
Naheo la , Alabama
Riegelwood, North Carolina
Niagara Falls, New York
Monmh 4 c T«»no*»co**^
EPA
Region
IV
IV
X
IV
IV
II
IX
IV
X
' v . •
VI
IV
IV
II
IV
Annual
Production
Capacity
(103 tons)^'
7
4
4
33
62
16
45
•6
31
16
29
15
.4
7
42
35
Remarks
Captive product
Captive product
Captive product
MRI estimate
On standby in 1973
Captive product
Chlorine is produced as a
co-product in these plants
-------
TABLE A-II (Continued)
OJ-
Producers
Sodium Metal (Concluded)
Ethyl Corporation
Reactive Metals, Inc.
Carbon Tetrachloride
Allied Chemical Corporation
Specialty Chemicals Division
Dow Chemical Compnay
E. I. du Pont de Nemours and Company, Inc.
FMC Corporation
Inorganic Chemicals Division
Stauffer Chemical Company
Industrial Chemical Division
Vulcan Materials Company
Chemicals Division
Perchloroethylene
Diamond Shamrock.Corporation
. Diamond Shamrock Chemical Company
Electro Chemicals Division
Dow Chemical Company
Ethyl Corporation
Industrial Chemicals Division
Occidental Petroleum Corporation
Hooker Chemical Corporation, Subsidiary
Industrial Chemicals Division
Production Site
Baton Rouge, Louisiana
Pa sade na, Texa s
Ashtabula, Ohio
Moundsville, West Virginia
Freeport, Texas
Pittsburg, California
Plaquemlne, Louisiana
Corpus Christ!, Texas
South' Charleston, West Virginia
LeMoyne, Alabama
Louisville, Kentucky
Niagara Falls, New York
Gelsmar, Louisiana
Wichita, Kansas
Deer Park, Texas
Freeport, Texas
Pittsburg, California
Plaquemlne, Louisiana
Baton Rouge, Louisiana
Taft, Louisiana
EPA
Region
VI
VI
V
III
VI
IX
VI
VI
III
IV
IV.
II
VI
VII
VI
VI
IX
VI
Annual
Production
Capacity
(103 tons)-
45
30
37
4
65
22.5
50
250
150
100
35
75
17.5
20
80
60
10
75
Remarks
VI
VI
25
25
From CH4
From CH^
From CH^, 03^4 co-product
co-product
co-product
CS2 method
CS2 method
From CH^, C
CS2 method
co-product
From CH^, C2C14 co-product
From CH,, C2C1^ co-product
-------
TABLE A-II (Continued
LJ
Producers
Perchloroethylene (Concluded)
PPG Industry, Inc.'
• Industrial Chemical Division
Stauffer Chemical Company
Industrial Chemical Division
Vulcan Materials Company
Chemicals Division
Trlchloroethylene
Diamond Shamrock Chemical Company
Electro Chemicals Division
Dow Chemical, USA
)
Ethyl Corporation
Industrial Chemical Division
Hooker Chemical Corporation :
Industrial Chemicals Division
PPG Industry, Inc.
Industrial Chemical Division
'Vinyl Chloride Monomer
Allied Chemical Corporation
Industrial Chemicals Division
American Chemical Corporation
Continental Oil Company
Conoco Chemicals Division
Dow Chemical Company
Production Site
Lake Charles, Louisiana
Louisville, Kentucky
Baton Rouge, Louisiana
Taft, Louisiana
Lake Charles, Louistana
Baton Rouge, Louisiana
Long Beach, California
Westlake, Louisiana
Freeport, Texas
Oyster Creek, Texas
Plaquemine,'Louisiana
EPA
Region
VI
IV
VI
VI
VI
VI
IX
VI
VI
VI
VI
Annua1
Production
Capacity
(10 tons)-
100
35
Remarks
Geismar, Louisiana
Wichita, Kansas
Deer Park, Texas
Freeport, Texas
VI
VII
VI
VI
75
25
50
75
25
20
140
150
87.5
325
100
350
195
Ethylene as raw material
Ethylene as raw material
Ethylene as raw material
Acetylene as raw material
Ethylene as raw material
Ethylene-oxychlorlnation process
Ethylene-oxychlorination process
Ethylene process
Ethylene-oxychlorination process
Ethylene-oxychlorination process
Ethylene-oxychlorination process
-------
TABLE A-II (Continued)
0°
Producers
Vinyl Chloride Monomer (Concluded)
Ethyl Corporation .
Industrial Chemicals Division
The B. F. Goodrich Company
B. F. Goodrich Chemical Company, Division
Honochem, Inc.
PPG Industry, Inc.
Industrial Chemical Division
Shell Chemical Company
Industrial Chemicals Division
Tenneco, Inc.
Tenneco Chemicals, Inc.
Tenneco Intermediates Division
Union Carbide Corporation
Chemicals and Plastics Division
Uniroyal, Inc.
Uniroyal Chemical Division
Pentachlorophenol
Dow Chemical Company
Monsanto Industrial Chemical Company
Reichhold Chemicals, Inc.
Vulcan Materials.Company
Chemicals Division
Hexachlorobemene (HCB)
Hummel Chemical Company, Inc.
Production Site
Baton Rouge, Louisiana
Pasadena, Texas
Calver City, Kentucky
Gelsmar, Louisiana
Lake Charles, Louisiana
Deer Park, Texas
Nor co, Louisiana
Houston, Texas •-.
Texas City, Texas
Painesville, Ohio
Midland, Michigan
Sauget, Illinois
Tacoma, Washington
Wichita, Kansas
South Plalnfield, New Jersey
EPA
Region
VI
VI
IV
VI
VI
VI
VI
VI
V
V
X
VII
. II
Annual
:Production
Capacity
(IP3 tons)-
KO
75.
500 .
150 ...-,-
200
420
350
'
Remarks
' -ethylene-oxychlorination process
Ethylene-oxychlorination process
Ethylene—oxychlorlnation process
Acetylene process
Ethylene-oxychlorination
Ethylene process
112.5 "';-: . VAcetylene-process
75
350
7.5
13.
6
3.5
0.25
On standby. "Balanced ethylene
and acetylene
MRI estimate
Estimated capacity. Not in operation in
1974.
-------
TABLE A-II (Continued)
vO
Producers
Bexachlorobenzene (HCB) (Concluded)
Dover Chemical Corporation
Stauffer Chemical Company
Industrial.Chemical Division
Pentachlorobentene
Aceto Chemical Company, Inc.
Chemical Procurement Labs, Inc.
Dover Chemical Corporation
Dow Chemical Company
Occidental Petroleum Corporation
Hooker Chemical Corporation, Subsidiary
industrial Chemicals Division
Solvent Chemical Company, Inc.
Hexachloroethane
Hummel Chemical Company, Inc.
Hexachlorobutadiene (HCBD)
Diamond Shamrock Corporation
Diamond Shamrock Chemical Company
.Electro,Chemicals Division
Semi (forks
Ethyl Corporation .
Synthetic Rubber - Chloroprene .
b/
E. I. du Pont'de Nemours and Company,. Inc.—
Elastomer Chemicals Department
Petro-Tex Chemical Corporation —'
Production Site
'Dover, Ohio
Louisville,. Kentucky
Flushing, New York
College Point, New York
Dover, Ohio
Midland, Michigan
Niagara Falls, New York
Maiden, Massachusetts
South Plalnfleld, New Jersey
Deer Park, Texas
Ashtabula, Ohio
Baton Rouge, Louisiana
Laplace,. Louisiana
Louisville, Kentucky
Houston, Texas
EPA
Region
IV
ii
V
V
II
3
II
VI-
V
VI.
VI
IV
VI
Annual
Production
Capacity
(103
0.25
0.50
0.001
NA
NA
NA .
0.25
37.5
137.5
22.5
Remarks
Not in operation in 1974.
Estimated value
Specialty chemical companies,
MRI estimate
Produced as captive by-product;
None sold commercially.
MRI estimate
HCBD Is not currently produced for
. commercial marketing in the U.S.
A new plant at Victoria, Texas, was re-
ported to be under construction in 1974.
-------
TABLE A-II (Continued)
Producers
Production Site
EPA
Region
Annual
Production
Capacity
(103 tons)-/
Remarks
O
Atraztne
Ctba-Geigy Corporation
Gelgy Agricultural Chemicals Division
Propazine
Ciba-Geigy Corporation
Geigy Agricultural Chemicals Division
Ciba-Geigy Corporation
Geigy Agricultural Chemicals Division
Mclntosh, Alabama
St. Gabriel, Louisiana
St. Gabriel, Louisiana
IV -
VI
IV
St. Gabriel, Louisiana
IV _
75
Plant designed primarily for Atrazine,
but can be used for other triazines.
Capacity given is total for atrazine,
propazine and simazine.
Pentachloronitrobenzene
Olin Corporation
Chemicals Division
Custom Chemicals
Dacthal
Diamond Shamrock Corporation
Diamond Shamrock Chemical Company
Biochemicals Division
Mirex
Occidental Petroleum Corporation
.Hooker Chemical Corporation, Subsidiary
Industrial Chemicals Division
Mclntosh, Alabama
Rochester, New York
Green Bayou, Texas
Niagara Falls, New York
II
VI
II
2.0
. 2.5
0.2
MRI estimate
MRI estimate
MRI estimate .
-------
TABLE A-II (Concluded)
Producers
Production Site
EPA
Region
Annual
Production
• Capacity
(103 tons)!/
Remarks
Halelc Hydraside
The Ansul Company
Chemical Division
Chem Formulators, Inc.
Chemical Division
Fairmount Chemical Company, Inc.
Unlroyal, Inc.
Unlroyal Chemical IHvisIon
Hexachlorocvclooentadlene
Marinette, Wisconsin
Nltro, West Virginia
Newark, New Jersey
Geismar, Louisiana
V—1
III
II
VI —'
MRI estimate
Occidental Petroleum Corporation
Booker Chemical Corporation, Subsidiary
Electrochemical and Specialties Division
Northwest Industries, Inc.
Velslcol Chemical Corporation, Subsidiary
Chlorinated Naphthalenes
Koppers Company, Inc.
Chlorinated Blphenyls
Monsanto Company
Montague, Michigan V
Niagara Falls, New York II
Memphis, Tennessee IV
Marshall, Illinois (captive V —'
use)
Bridgeville, Pennsylvania III
Sauget, Illinois
30
3.0
.20-25
Pentane .chlorination
Pentane chlorination .
MRI estimate for 1972
Pentane chlorination
NaOCl chlorination of cyclopentadiene
from naphtha
MRI estimate, process is
" proprietary.
Molten biphenyl Is chlorinated with
gaseous chlorine in presence of iron
catalyst.
a/ NA indication, data were not available.
b/ Data from Chemical Week. September 22, 1971.
-------
TABLE A-III
Chemical
Chlorine
Sodium Chlorate
Sodium Metal
Carbon tetrachloride
(CC14)
Perchloroethylene
Production Production Capacity
i
Year
1963
1964
1965
1966
1967
1968
1969
'1970
1971
1972
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1971
1968
1969
1970
1971
1972
1973
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
for all U.S.
Producers
(103 tons)
5,464
5,945
6,517
7,204
7,680
8,444
9,376
9i764
9,352
9,868
124.3
136.3
134.3
154.2
155.5
167.4
187.2
197.7
. 196.6
214
230
0.075
380
425
465
505
498.5
525
162.5
182.9
214.7
231.3
266.5
318.3
317.7
353.4
351.7
367.4
for all U.S.
Producers
(103 tons)
7,765
8,505
' -
10,349
10,662
-.-.'
157
-
170
170.5
170.5
201.5
214.0
230.5
230.5
230.5
312
0.095
789
540
U.S. Imports
CIO3 tons)
35.10
3.92 '••
2.42
2.38
3.23
. 4.48
6.06
11.54
.13.55
16.25
_
25.17 '
- ..,••.
'
. 28.75
35.00
25.05
33.95
25 .00
22.15
17.35.
20.10
22.20
NA
22.34
Remarks
Source: Chlorine
Institute
Growth per year
. 1972-1980 estimated
: at +6%
MRI estimate of produ
rate for 1972
Projections indicate I
total demand for CC
will increase from
500,000 to 675,000 I
from 1972 to 1977
Estimated consumption
growth for 1972 to
' 1980 is + 6.57.
142
-------
TABLE A-III (Continued)
Chemical
Trichloroethylene
Vinyl Chloride Monomer
Pentachlorophenol (PCP)
Hexa'chlorobenzehe
Pentachlorobenzene
Hexachloroethane
Year
1960
1962
1964
1966
1968
1971
1972
1973
1969
1970
' 1971
1972
1973
1975
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
1958
1959
1960
1973
Production
for all U.S.
Producers
UO3 tons)
0.175
0.180
265
213.5
236
2,000
2,050
2,544.5
'
2,800
16.96
18.45
19.98
21.63
22.12
24.30
23.00
23.60
25.45
24.5
23.30
28.6
0.38
0.36
0.22
0.35
Production Capacity
for all U.S.
Producers U.S. Imports
(103 tons) (103 tons) Remarks
29.6
32.5
... • 37.8
59.5
29.3
.4.6
• . . Estimated consumption
240 .23.72 "growth 1972-1975 =.
+9.5%, 1975-1980 = "
. •." +6.5%.
2.000
; . .
2,500 .
2,863 0.927 Estimated production
3,600 - . growth from 1973 to
. . 1975 is +13.5%.
These figures may include
some double reporting of
the 13 to 14 million Ib
of sodium pentachloro-
. phenate made from PCP.
26. ' None ;
34.5
NA. . NA
NA ' . . ."NA ' ' • ' . ' • . '
NA . NA . •
0.75-1.0 None
1972
1972
Hexachlorobutadiene (HCBD) 1972
Synthetic Rubber,
Chloroprene
Atrazine
1971
1972
1973
1972
< 0.001
0.2
None
178
45-55
0.001
0.25
NA
198
>75
NA
0.077
None
0.1-;25
7.3
None
MRI estimate of sales
volume. There is also
captive production.
MRI production and
capacity estimates.
HCBD is not currently
produced for commercial
marketing.
MRI production .estimate
143
-------
TABLE A-III. (Concluded)
Chemical
Propazine
Simazine
Pentachloronitrobenzene
Dae thai
Mirex
Maleic Hydrazlde
Hexachloro-
cyclopentadiene
Chlorinated
Naphthalenes
Chlorinated
Biphenyls
Production Production Capacity
l :
Year
1972
1972
1967
1968
1969
1972
1972
1974
for all U.S.
Producers
(103 tons)
2
4
-
-
.'
1.5
1
2
for All U.S.
Producers
(103 tons)
'.."-'
- .'..
„ .
-
- . ' ...
2.0
1.3
2.5
U.S. Imports .
(103 tons)
None
None
0.015
:o.oio
0.066 .
'• . - .
.•"-. .- MR:
1972
< 0.5
Remarks
< 0.6
1967
1968
1969
1972
1971
1972
1969
1970
1971
1972
1973
1967
1968
1969
1970
1971
1972
1973
1974
-
. -
-
4
25.0
25.0
< 2.5
< 2.5
< 2.5
< 2.5
< 2.5
37.7
42.4
38.2
42.5
20.2
19.3
20
20
-'
' -•
•
. V .5
30
30
_
_•
•
i.
3.
48
48
48
48
48
24
24
24
0
'0
0.0017
MRI estimate for
1972 capacity
MRI estimate
.MRI estimate
MRI estimates
MRI estimates
Only 1 domestic
producer
MRI estimate of
capacity
Only 1 domestic
producer
144 .
-------
Basis for MRI estimates shown in this appendix; Estimated values for an-
nual production rates and for annual production capacities were prepared
by MRI on the basis of information developed by one or more of the follow-
ing methods.
* Estimates provided by MRI consultants or in-house advisors.
* Extrapolation of available data which apply for.different
operating years.
* Calculation and application of the average production rate
or capacity per plant for a given chemical industry.
* Use of applicable data for a similar product and production
operation.
* Use of information provided in personal communications with
company spokesmen.
145
-------
APPENDIX B
RESULTS OF A WRITTEN INQUIRY TO CHEMICAL MANUFACTURERS
146
-------
MRI developed a five-page questionnaire for use in more intensive
industrial surveys. This questionnaire requested detailed information con-
cerning production, use, and release into the environment of'HCB and. HCBD
in all physical forms and as a constituent of any type-of processed material.
Following review and approval of this questionnaire by the U.S. Environmental
Protection Agency, copies of the questionnaire, accqmp.air.Les by a coyer letter,
were mailed to hi rip Selected chemical, .companies (coqpor;.il;c .office address)
as follows: :•:'.•'•••' • • ' : " ••' . •'.-''.- '•.'.• .•' • • .'• •
.• ' "•'•' Dow Cl.ir.micn.I Company • , . • • :' ' .
' '•'• Occidovita I. 'lYl'.rolfimi (lo.rpo'ra'lioii.-l'lr'ok'-r' (.lliei'ijYcfll Corporation-
''•' Vulcan Mal.eri.ali; Comapiiy-Chcui'Lca.!.:; Di vi. y'ion '• .-• • : •
Stauffer-'Chemical Coinpany-Industria-J. 'Chemical".-Division.'
-v Diamond-Shamrock .Corporation , : • .
* Ciba-Geigy Corporation . ... .
« PPG Industry, Inc.-Industrial Chemical Division
* E. I. du Pont de Nemours and Company, Inc.. .
* Monsanto Company •• . .
A sample copy of the entire questionnaire, including the one-
page introduction, follows.
147
-------
SURVEY. OF INDUSTRIAL PROCESSING DATA
Midwest Research institute is presently conducting a program for
the Office of Toxic Substances of the U. S. Environmental Protection Agency
under contract No. 68-01-2105. The primary purpose of this program is to
collect information on product ion/formation, use and release into the en-
vironment of two toxic substances, namely, hexachlorobenzerie (HCB) and
hexachlorobutadiene (HCBD). .
In addition to industries that directly produce or use HCB and
HCBD, we have identified the following chemicals as materials whose manufacture
may produce small amounts of either HCB or HCBD as a by-product, waste
material, or impurity in a product.
Carbon Tetrachloride Dacthal
Perchloroethylene Pentachloronitrobenzene
Chlorine Synthetic rubber (chloroprenei
Trichloroethylene Sodium chlorate
Atrazine Mirex
Propazine
Simazine Hexachlorocyclopentadiene
Vinyl chloride Chlorinated napthalene
Chlorinated biphenyl
The MRI study is based on available information in the literature
aud private communications with industry personnel, via telephone, letters
and questionnaire. We have completed searching the literature and contacting
some of the chemical industries by telephone and letter inquiries. In order
to get a statistically reliable overview of the indusLrial situation on the
subject, it is important that we contact as many industries as possible.
The enclosed questionnaire attempts to do just this. We, therefore,
solict your co-operation in filling out the questionnaire; your early
response (within 6 weeks) will be sincerely appreciated.
If your department cannot supply the requested information
please forward to other departments which can respond to this questionnaire.
If you have any questions concerning this questionnnaire, please call Mr.
Charles Mununa at (816) 561-0202 (Extension 415).
148
-------
QUESTIONNAIRE PREPARED FOR ' . .
OFFICE OF TOXIC SUBSTANCES
U.S. ENVIRONMENTAL PROTECTION AGENCY
(Please fill in the details and check the appropriate blanks)
1. Parent Corporation Name:
Mailing Address:
2. Person to contact regarding information supplied in questionnaire
Mr/Mrs/Miss
Address:
Phone
3. Tf your company manufactures any of the chemicals listed in the
cover letter please complete the following form
Listed
Chemical Production site-city or town and state
a.
b.
c.
d. .
e.
f. .
g. .
h, _
.1- .
i.
k.
•1.
m.
n.
o.
*If additional space is needed, please use the back of this sheet,
149
-------
Listed . , .
Chemical (con't.) Production site-city or Mown and state (con't.)
P.
q-
r.
s.
t.
u.
v.
w.
X.
4a. Has any chemical analysis ever been made on any of your products,
by-products*, or process waste materials to determine the presence
of HCB or HCBD? "..*'
HCB . HCBD
yes no yes no
4b. If the answers are "no", then based on your experience, do you think
that any HCB or HCBD may be contained in any of your products, by-products*
or process waste materials?
Any HCB Any HCBD / .'. •
yes no yes ' '. no
If any of your answers to question 4 are "yes", please complete
the remaincr . of questionnaire; otherwise return questionnaire as completed
to this point.
5. Where would the HCB or HCBD occur?
a. In product(s)? b. In by-product(s)? c. In process waste
.. .' . materials?
yes no yes no yes no
By-products are also referred to as co-products.
150
-------
6. For each "yes" answer to any category in question 5 please identify
compound(s) by name(s) and form(s) (i.e., solid, liquid or gas). Also
indicate approximate concentration level(s) and plant location(s).
a. In products
Name(s) and form(s) and plant location(s):
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Approximate concentrations levels of HCB and/or HCBD (specify wt. % or ppm)
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
HCB
it
it
n
n
it
ii
n
n
it
n
it
HCBD
it
n
n
it
b. In by-products
Name(s) and form(s) and plant location(s):
/' 1. ; __
2. .
3. ' '
4. ' ' .
5. __ ; ._ ;
6.
7. '
8.
9. '
10. '
11.
12. . ' ••
151
-------
6b.-continued
.Approximate concentration levels of IK'B and/or HCBD (specify wt. % or ppm)
1 - HCB HCBD •'.-.•- ,'• .
2. " ; ." .'•-...-
3. " "' . .• " . • .'.-'.
; 4. " • . • ; . ; " . - ..
5ii - 11 .
• ' . ^ . __
6, " ' '.. " .
7. " . " •....-. ;
'8. " . " •_____ ' '• '
' 9. ". " '•. ' ' - '•• ..•
10. " ". .
11. " ; " . .• • • . •
12.
c. In process waste materials
Name(s) and form(s) and plant location(s):
1.
2. ,
3. ,
4.
.
7.
8.
9.
10.
11.
12.
Approximate concentration levels of HCB and/or HCBD (specify wt. 7, or ppm)
Before waste disposal treatment After treatment (if any)
HCB HCBD '
1. HCB
2,
3.
4.
5. "
6.
7.
HCBD
n
n
n
it
ti
ii
8. " "
9. " "
10.
n
11. " "
12. "
n
n
n
n
it
it
n
it
152
-------
7. What waste disposal techniques do you use?
. /
Please describe techniques briefly and also comment on their effectiveness
in preventing the release into the environment of HCB and HCBD. (e.g.,
land fill, waste pond, deep .jell injection, incineraf. i.on). If
incineration is used please indicate operoiting conditions such as .
temperature, retention time, gas scrubbing procedure, etc. .
8. Please estimate the total amount (Ibs/day or Ibs/yr) of HCB or HCBD that
actually leaves your plant(s):
a. Tn liquid, gaseous and solid waste streams . ' '
b. As impurities in products • ". • . . '
C: As a component of by-products •• '' .
9. 1- the extent possible within the constraints of proprietary considerations,
for each product identified in part 6a please describe briefly the
production process used and the approximate annual production:
Process description (e.g. major Approximate
reactions carried out, or U. S. Annual Production
Product Patent Number) Tons
153
-------
A discussion and- summary of the replies to this written inquiry
is presented in the following paragraphs. .
1. Monsanto Company; Monsanto indicated that in their production
of chlorinated biphenyl (Monsanto1s only chemical operation of interest to
Task I), no detectable-concentrations of HCB or HCBD occur in the product
or in process waste materials, anq} that no by-products are produced. In
Monsanto's waste disposal operation, scrap liquids containing chlorinated
biphenyl are incinerated at about 2700°F for .a 1.5 sec retention'period ••
and the off-gases are scrubbed to remove hydrogen chloride.
2. Dpw Chemical Company; Dow reported that none of their chemi-
cal operations posq any HCB or HCBD pollution problems. Dow stated that
these toxic materials appear only in their process waste materials and that
the total amount of HCB or HCBD emitted from their plants in the form of '
liquid, gaseous, and solid wastes is too low "for an accurate estimate. The
process waste materials, principally tars from manufacture of chlorinated
solvents, are reported by Dow to be disposed of by a highly effective in-
cineration system.
3. Vulcan Materials Company; Vulcan indicated that HCB and
HCBD are contained in their "hex residue" solid waste formed during pro-
duction of carbon tetrachloride and perchloroethylene, and that all of
this waste is impounded in an earth-covered groundfill. Vulcan reported
that no HCB or HCBD actually leaves their plant sites.
4. Diamond Shamrock Company: Diamond reported that one of their
products, Dacthal®, contains 0.3% HCB and that HCB and/or HCBD occur also
in process waste materials from the manufacture of Dacthal®, perchloro-
ethylene, and trichloroethylene. The Dacthal® waste contains about 84% HCB. "
The company stated that all of the waste materials containing HCB and HCBD
are placed in sealed containers and hauled to Rollins International, Inc.,
in Houston, Texas, for incineration. . .
5. Ciba-Geigy Corporation; This corporation produces atrazine,
propazine and simizine at St. Gabriel, Louisiana (the only domestic pro-
duction site). Geigy reports that no. HCBD is formed, but that HCB occurs
in the products and in the waste materials (still bottoms, a liquid residue)
and in trace amounts in vent scrubber emissions. .
The other four companies .did not respond to this written inquiry,
even after repeated follow-up requests. .
.154
-------
APPENDIX C
PROCEDURE FOR SELECTING MONITORING SITES
155
-------
Chlorine Plants
There are 65 plants (1973) in the United States which produce.
chlorine.. Some use dimensionally stable anodes (DSAs), some • do not. The
plants are categorized by the types of cells they employ, and a list showr
ing the 65 plants by cell type is given below. .
Number Number Number Not
of Using ' Using
: Plants DSAs DSAs
Diaphragm cell plants . 29 '••.'.11 18
Mercury cell plants 23 16 :1 ' .
Diaphragm and mercury cell plants 5. 5 0
Fused salt cell plants 4 .0 . 4.
HC1 electrolysis plants 1'. 0 1
Diaphragm and fused salt cell plants 1. 0 1 .
Diaphragm and magnesium cell plants 1 0 .1
Nonelectrolytic plants 1 _0 1
Total • . .65 32 ' 33 :
Tables C-I through C-V, which follow, show data which were uti-
lized in selecting monitoring sites from the. group of chlorine plants which
do not use DSAs. The plants using DSAs do not form HCB or HCBD. The others
are considered to be potential emitters of both of these chemicals.
Criteria and Assumptions for Selection of Sampling Sites
(A) Production: Where production figures are grouped, assume
each plant produces the same amount of chlorine.
(B) Age of plant: Given—newer is assumed to be cleaner.
(C) Age of cells: Given—newer is assumed to be cleaner..
(D) Types of cells: All Hooker cells have about the same graphite
consumption and are considered..equal to
each other in pollution potential. Dow
cells have the same graphite anodes as
Hooker cells. The difference is that Dow
cells incorporate a multiplicity of unit
cells which reduce floor space and invest-
ment costs. Columbia cells also have a
graphite anode, the difference being that
the fingers of the anode extend all the
way across the cell..5_l/
. . 156 ...
-------
TABLE C-I
NON-PSA PLANTS
(Diaphragm Cells)
State and City
(1) Baton Rouge,
Louisiana
(2) Syracuse,
New York
(3) Wyandotte,
. Michigan .
.(4) Houston,
Texas
(5) P.ittsburg-,-
•...," California,
(6) Plaquemine,
. : Louisiana
(7) Midland,
Michigan
Producer
Allied Chemical
Corporation
BASF Wyandotte .
Corporation
Champion International
• Corporation
Dow Chemical Company
Dow Chemical Company
Dow Chemical Company
Year
Built
1937
1927
1938
1936
1917
1958
1897
Cells Production
(Year Installed) (tons/day)
Hooker S-4 (1968)
Hooker S-4 (1968)
Hooker S-3B
Hooker S
Dow
Dow
Dow
594. , .
(in 5 plants)
120
Unknown
: 1,576
-------
TABLE C-I (Concluded)
Oi
oo
State and City
(8) Freeport,
Texas
(9) Green Bay,
Wisconsin
(10) Port Neches,
Texas
(11) Gramercy,
Louisiana
(12) Taft,
Louisiana
(13) Tacoma,
Washington
(14) Barberton,
Ohio
(15) Corpus Christi,
••'•.• Texas
(16) Henderson,
. Nevada
(17) Newark,
New Jersey'-
(18) Denver City,
Texas
Year
Producer Built
Dow Chemical Company 1940
Fort Howard Paper 1968
Company
Jefferson Chemical 1959
Company, Incorporated
Kaiser Aluminum and 1958
Chemical Corporation
Hooker Chemical 1966
.Corporation
Hooker Chemical 1929
Corporation
PPG Industries, 1936
Incorporated
PPG Industries, 1938
. . Incorporated
Stauffer Chemical Company 1942
of Nevada, Incorporated
Vulcan Materials 1961
Company
Vulcan Materials 1947
Company
Cells
(Year Installed)
Dow,
(Magnesium)
Hooker S-4
Hooker S-3B
Hooker S-3B
Hooker S-4
Hooker S-3
Columbia'
Columbia N-l, N-3
Hooker S
Hooker S-4 (1968)
Hooker S
Production
(tons/day)
1,700
Unknown
54
160
630
(in 5 plants)
1,638
[(in 5 plants)
.270
(in:3 plants)
153
(in 3 plants)
-------
TABLE C-II
a/
Plant No.-
RECOMMENDATIONS AFTER APPLICATION OF CRITERIA, BY TYPE OF CELLS
Hooker Cells Recommendation: Based on Criteria
Select: high volume
Eliminate: newer same company as (1)
Select: high volume
Select: old, unknown volume
Eliminate: newer
Eliminate: low volume
Select: high volume
Eliminate: new, same company as (13)
Select: high volume
Select: high volume '
Eliminate: low volume
Eliminate: low volume
1
2 '< -
3
4
9
10
11
12
13
16
17
18
Plant No.
5
6
7
8
Plant No.
14
15
S-4
S-4
S-3B
s .
S-4
S-3B
, . S-3B
S-4
S-3
S
S-4
S
Dow Cells
Columbia Cells
Eliminate: same as (7)
Eliminate: same as (7)
Select: older
Select: higher volume
but newer
but newer
Select: older, high volume
Select: older, high volume
a/ Referenced to Table C-I.
159
-------
TABLE C-III
NON-PSA PLANTS
(mercury cells)
State and City
Producer
Year Cells
Built (year installed)
(1) Brunswick, Georgia Allied Chemical Corporation 1957
(2) Acme, North Carolina Allied Chemical Corporation 1963
(3) Linden, New Jersey Linden Chlorine Products, Inc. 1956
Solvay V-100 -
Solvay V-200
BASF-Krebs(1969)
Production
(tons/day)
594
(in 5 plants)
- - 180
(4) Mclntosh, Alabama
(5) Augusta, Georgia
(6) Niagara Falls,
New York
(7) Charleston,
Tennessee
Olin Corporation
Olin Corporation
Olin Corporation
Olin Corporation
1952 Olin E-8
1965 Olin E-llF
1897 Olin E-11F(1960)
1962 Olin E-llF, E-812
524
Recommendations Regarding Sampling Sites:
Criteria: (A) Production; (B) age of plant; (C) age of cells; and (D) type'of cells.
(A) Production is similar for all plants (i.e., 100-200 tons/day).
(B) Only plant built before 1950 was (6).
(C) All cells built after 1950.
(D) Cell types determine the selection. Graphite loss in each type of cell (see Table C-4) :is
ranked below with the highest graphite consumption cell given first. Higher graphite loss
increases the potential for HCB and HCBD formation. - .-.'..
Eliminate; (1), (2), (5), (6), (7) due to ceLL type. ••:;".»-_'v
Recommend: (3) Linden Chlorine Products, Inc., Linden, New Jersey, since it has highest
graphite loss and relatively high production, and (4) Olin Corporation,
. Mclntosh, Alabama, second highest graphite loss and oldest, cells of group.
-------
State and City
(1) Niagara Falls,
New York
(2) Memphis,
Tennessee
(3) Baton Rouge,
Louisiana .
(4) Houston, Texas
(5) Cedar Bayou,
Texas
(7) Vicksburg,
Mississippi
TABLE C-IV
NON-DSA PLANTS
(miscellaneous cell types)
Producer
E.. 1. du Pont de
Nemours and Company,
Incorporated
E. I. du Pont de
Nemours and Company,
Incorporated
Ethyl Corporation
Ethyl Corporation
Mobay Chemical Company
(6) Ashtabula, Ohio RMI Company
Vicksburg Chemical
Company
(8) Freeport, Texas Dow Chemical Company
Recommendations Regarding Sampling Sites
Year
Built
1898
1958
1952
1972
1949
1962
1940
Cells
(year installed)
Downs (fused salt)
Downs (fused salt)
Downs
Hooker S-3D (diaph.)
Downs (fused salt)
Uhde (HC1)
Downs (fused salt)
None
Fused magnesium chlo-
ride yields Cl~ and
magnesium
Production
(tons/day)
.122
230
. 7.2
Unknown
33
Unknown
(A) Eliminate (5) since it ia new, has a low production, and involves HC1 electrolysis.
(B) Eliminate (7) since it has no cells (noneiectrolytic) and has a very low production.
(C) The'remaining six plants are fused salt processes which do not involve carbon.
Therefore, eliminate these plants from consideration. Also, they have low pro-
duction volumes of Clo.
Recommended Sample Sites : None
-------
TABLE C-V
GRAPHITE CONSUMPTION/TON Gig FOR DIFFERENT . '
TYPES OF CELLSJffi
Graphite Consumed/
Type of Cell Ton Chlorine (lb)
.;!.;,!,-• .; ; •;.']..: ~~: ••:!";•.'•.'• •
Diaphragm cells: ' '' ' ' Hooker S-3B ' . 5.3'-7.0
Hooker S 6.7
Mercury cells: Solvay V-100 or V-200 : .3-4
• Olin E-11F 4.8
Olin E-8F . . 5.3 .
BASF-Krebs 5-6
162
-------
It appears that the potential for HCB generation is similar for
all cells with graphite anodes; but no operating data were found for Dow
cells and Columbia cells.
Plants are most conveniently grouped by cell type for compari-
son. The comparison of plants with similar cells.eliminates one variable;
cell type. ' '
Production quantity and age of the cells are compared for each
plant against the others first, with age of plant considered only if the
other two factors are about equal. Production quantity is more important
than cell age in this comparison.
Below is a summary of the non-DSA diaphragm cell plants listed
in Table C-II that are recommended for further consideration as monitoring
test sites.
Cell Type
at Hooker S-4
b. Hooker S-3B
c. Hooker S
e.
f,.
g-
h.
i 1
j-
Plant Site
Baton Rouge, Louisiana
Wyandotte, Michigan
Houston, Texas
d. Hooker S-3B Grammercy, Louisiana
Hooker S-3
Hooker S
Dow
Dow
Columbia
Columbia
Tacoma, Washington
Henderson, Nevada
Midland, Michigan
Freeport, Texas
Barberton, Ohio
Corpus Christi, Texas
Producer
Allied Chemical Corporation
BASF Wyandotte Corporation
Champion International
Corporation
Kaiser Aluminum and Chemical
Corporation
Hooker Chemical Corporation
Stauffer Chemical Company of
Nevada, Inc.
Dow Chemical Company
Dow Chemical Company
PPG Industries, Inc.
PPG Industries, Inc.
Final evaluation of recommended diaphragm cell plants: Because
of the producers experience in manufacture of toxic chemicals, eliminate:
a, b, e, f, g, h, i and j.
Recommended;
Sites c and d.
Plant site monitoring should be considered for
163
-------
Carbon Tetrachloride Plants
In 1973, carbon tetrachloride was manufactured at the following
plant sites: .
1
2
3
4
5
7
8
9
10
11
Plant Site
Moundsville, West Virginia
Freeport, Texas
Pittsburg, California
Plaquemine, Louisiana
Corpus Christi, Texas
South Charleston, West
Virginia
Le Moyne, Alabama
Louisville, Kentucky
Niagara Falls, New York
Geismar, Louisiana
Wichita, Kansas
Producer
Allied Chemical Corporation
Dow Chemical Company
Dow Chemical Company
Dow Chemical Company
E. I. du Pont de Nemours and
Company, Inc.
FMC Corporation
Stauffer Chemical Company
Stauffer Chemical Company
Stauffer Chemical Company
Vulcan Materials Company
Vulcan Materials Company
Production
•;';' Capacity
'(103 tons/
year )
4
65
22.5
50
250
150
100
35
75
17.5
20
Eliminate: Plant 1 because of the very low production capacity.
Plants 2, 3, and 4 because Dow incinerates hex wastes in an incinerator
which is reported to be highly effective (99.9470 destruction of HCB .and
HCBD). .
Plants 6, 7, and 9 because the low temperature (30°C) carbon
disulfide process used is not amenable to the formation of either HCB or
HCBD. Plant 8 because Stauffer produces HCB and is well aware of the po-
tential hazards of HCB and HCBD.
Recommended monitoring test sites; Plant 5 because it has, by
far, the highest production capacity, and it is a new and uhproven plant
(on-stream since late 1973). Perchloroethylene is a by-product at this
-Du Pont plant.
Plants 10 and 11 because Vulcan uses landfill operationsr-with
questionable safety—in disposing of hex wastes. Perchloroethylene is also
produced at these two Vulcan plants. .
164
-------
Perchloroethylene Plants
sites:
In 1973, perchloroethylene was produced at the; following plant
2
3
4
5
6
.7
8
9
10
Plant Site
Deer Park, Texas
Freeport, Texas
Pittsburg, California
Plaquemine, Louisiana
Baton Rouge, Louisiana
Taft, Louisiana
Lake Charles, Louisiana
Louisville, Kentucky
Geismar, Louisiana
Wichita, Kansas
Producer
Diamond Shamrock Chemical
Company
Dow Chemical Company
Dow Chemical Company
Dow Chemical Company
Ethyl Corporation
Hooker Chemical Corporation
PPG Industries, Inc.
Stauffer Chemical Company
Vulcan Materials Company
Vulcan Materials Company
Production
Capacity
(103 tons/
year)
80
60
10
75
25
25
100
35 '
75
25
Eliminate; Plant 1 because all wastes containing HCB and HCBD
are drummed and hauled off-site to Rollins International, Inc., in Houston,
Texas, and incinerated.
Plants 2, 3, and 4 because Dow incinerates the hex wastes in a
special incinerator which is claimed to be highly effective (i.e., 99.9+%
destruction).
Plant 5 because the production capacity is low and Ethyl has a
good plant safety reputation. ;
Plant 6 because the production capacity is small, and Hooker .has
experience with toxic chemicals.
Plant 8 because this is a relatively small production capacity,
and Stauffer is reported to recover all by-product HCB for sale and to
recycle the remainder of the hex material, to the process. Therefore, the
possibility of HCB or HCBD entering the environment is slight.
Recommended monitoring test sites; Plants 7, 9, and 10. •
165
-------
Plant 7 is recommended because it has the highest production
capacity and was reported to have used a landfill operation (which is not
considered to be a safe method for disposal) until completion of an in-
cinerator in 1973.
Plants 9 and 10 are recommended because landfill operations are
used for disposal of hex wastes. : , • : ,' '
Trichloroethylene Plants . . '.•'''
In 1973, trichloroethylene was produced at the following plant
sites: .'...• !
Production
: . Capacity
(103 tons/
Plant Site Producer year)
Deer Park, Texas Diamond Shamrock Chemical 50
Company
Freeport, Texas Dow Chemical Company 75
Baton Rouge, Louisiana Ethyl Corporation 25
Taft, Louisiana Hooker Chemical Corporation .20
Lake Charles, Louisiana PPG Industries, Inc* 140
The hex wastes from trichloroethylene production are disposed
of in the same manner as the hex wastes from perchloroethylene production.
In each case, the trichloroethylene plants are operated in conjunction
with a perchloroethylene operation at a common plant facility. The Lake
Charles, Louisiana, site of PPG Industries, Inc., is recommended for on-.
site monitoring because of the very large production capacity.
166
-------
Vinyl Chloride Monomer ^
Vinyl chloride monomer was,produced in 1973 at the following
plant sites:
Plant Site
Baton Ecuge, Louisiana
Long Beach, California
Westlake, Louisiana
Freeport, Texas
Oyster Creek, Texas
Plaquemine, Louisiana
Baton Rouge, Louisiana
Pasadena, Texas
Calvert City, Kentucky
Geismar, Louisiana
Lake Charles, Louisiana
Deer Park, Texas
Norco, Louisiana
Houston, Texas
Texas City, Texas
Painesville, Ohio
Producer
Allied Chemical Corporation
American Chemical Corporation
Continental Oil Company
Dow Chemical Company
Dow Chemical Company
Dow Chemical Company
Ethyl Corporation
Ethyl Corporation
B. F. Goodrich
Monochem, Inc.
PPG Industries, Inc.
Shell Chemical Company
Shell Chemical Company
Tenneco, Inc.
Union Carbide Corporation
Uniroyal, Inc.
Production
• Capacity
(lO3 tons/
year)
150
87.5
325
100
350
195
150
75 .
500
150
200
420
350
112.5
75
NA
The technical literature and inquiries to industry spokesmen
indicate a potential for the formation of HCB. Spokesmen from Dow Chemical
Company and from Ethyl Corporation have indicated that no HCBD is formed
in the manufacture of vinyl chloride. Vinyl chloride is commonly produced
from ethylene dichloride, which in turn is made from ethylene.
Based on the limited data collected concerning the composition
of the tarry wastes in this industry, MRI has estimated that significant
quantities of HCB could be formed in the manufacturing operations and con-
tained in these tarry residues.
On the basis of this evaluation one representative vinyl chloride
monomer plant was selected for inclusion in the list of recommended monitor-
ing test sites. The selected site is the Lake Charles, Louisiana, facility
of PPG Industries. This is a large production capacity plant (200 x 103
tons/year).
167
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LITERATURE REFERENCES
1. Coniglio, W. M., Hexachlorobenzene Presentation to EPA Hazardous Mate-
rial Advisory Committee, 6 August 1973. ' .
2. Personal Communication with Mr. Ronald Steinkoenig, Vice-President
of International Marketing for Sobin Chemicals Company, June 1974.
3. National Academy of Sciences, "Assessing Potential Ocean Pollutants:
A Report of the Study Panel on Assessing Potential Ocean Pollutants,"
Ocean Affairs Board, Commission on Natural Resources, National Re-
search Council, Washington, D.C. (1975).
4. Kirk-Othmer Encyclopedia of Chemical Technology, Kirk, R. E., and
D. F. Othmer, eds., Second edition supplement, all volumes, Inter-
science Publishers, Division of John Wiley and Sons, Inc. (1972).
5. Personal Communication with Ms. Doris J. Ruopp, U.S. Environmental
Protection Agency, Office of Categorical Programs, Washington, D.C.,
18 September 1973.
6. Residue Rev., Gunther, F. A., ed., 3j6:55 (1971).
7. McBee, E. T., and R. E. Hatton, "Production of Hexachlorobutadiene,"
In.d. Eng. Chem., 41(4);809 (1949).
8. Environmental Protection Agency, "Development Document for Proposed
Effluent Limitations Guidelines and New Source Performance Standards
for the Major Inorganic Products Segment of the Inorganic Chemicals
Manufacturing Point Source Category, EPA 440/1-73-007, Washington,
D.C., August 1973.
9. Faith W. L., D. B. Keyes, and R. L. Clark, Industrial Chemicals,
Third edition, John Wiley and Sons, Inc., New York, New York (1965).
10. Personal Communication with Mr. W. R. Taylor, Diamond Shamrock Chem-
ical Company, Cleveland, Ohio, August 1974.
11. .Lawless, E. W., T. L. Ferguson, and R. von RUmker, "Pollution Poten-
tial in Pesticide Manufacturing," Final Report by Midwest Research
Institute on Contract No. 68-01-0142 for the Environmental Protec-
tion Agency, June 1972. (NTIS Nos PB-213 and 782/3.)
12. von RUmker, R., E. W. Lawless, and A. F. Meiners, "Production, Distri-
bution, Use and Environmental Impact Potential of Selected Pesti-
cides," Final Report by Midwest Research Institute on Contract No.
EQC-311 for Council on Environmental Quality, March 1974.
168
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13. Environmental Health Perspectives} Experimental Issue No. 1, p. 1,
April 1972.
1.4. Interdepartmental Task Force on PCB's, "Polychlorinated Biphenyls
and the Environment," Com-72-10419, Washington, D.C., May 1972.
15. Personal Communication with Mr. R.;J. Moolenaar of the Dow Chemical
Company, Midland, Michigan, July 1974.
16. Personal Communication with Mr. H. A. Campbell of Vulcan Materials
Company, Chemicals Division, Wichita, Kansas, August 1974.
17. Chlorine Institute, Inc. North American Chlor-Alkali Industry Plants
and Production Data Book, C. I. Pamphlet No. 10, New York, New York
(1974).
18. Matthews, F. W., and G. G. Warren, "A Distillation Method for, the
Separation of Impurities in Commercial Chlorine," Can. J. Techno1.,
3.2:193-198 (1954).
19. Personal Communication with Mr. Dick Hall of Diamond Shamrock Cor-
poration, Cleveland, Ohio, June 1974.
20. Personal Communication with Mr. W. R. Taylor, Diamond Shamrock Cor-
poration, Cleveland, Ohio, July 1974. .
21. Personal Communication with Mr. Frank Conrad, Director of Industrial
Chemicals Research, Ethyl Corporation, Baton Rouge, Louisiana, August
1973.
22. Personal Communication with Mr. H. R. Deutsch of E. I. du Pont de
Nemours at Louisville, Kentucky, September 1974.
23. Personal Communication with M*r. Sam Gilford, Research Department,
Hooker Chemical Corporation, Niagara Falls, New York, April 1974.
24. Personal Communication with an MRI Consultant, April 1974.
25. Personal Communication with Mr. Dave Eynon, Vice-President in charge
of Pollution Abatement, Koppers Company, Inc., Pittsburgh, Pennsylvania,
June 1974.
26. Personal Communication with Mr. Kenneth Hoy, Marketing Manager, Coating
Resins, Koppers Company, Inc., Pittsburgh, Pennsylvania, June 1974.
27. Personal Communication with Mr. W. B. Papageorge, Monsanto Industrial
Chemical Company, St. Louis, Missouri, April 1975.
169
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28. Booz-Allen Applied Research, Inc., "A Study of Hazardous Waste Mate-
rials, Hazardous Effects and Disposal Methods," Vols. I, II, and
III, Environmental Protection Agency (PB-221-465, PB-221-466, and
PB-221-467), Springfield, Virginia, July 1973.
29. Personal Communication With Mr. E.'Hall, Regional Environmental Man-
ager, Diamond Shamrock Corporation, Deer Park, Texas, 9 April 1974.
. t • • _ , ''{''
• • - t- ' .'•
30. Personal Communication with Mr. L. H. Meyers, Marketing Manager, Stauffer
Chemical Company, Westport, Connecticut, June 1974.
31. Personal Communication with Mr. Ronald Gagnon, Solvent Sales Manager,
Occidental Petroleum Corporation, May 1974.
32. Sax, N. I, Dangerous Properties of Industrial Materials, Second edi-
tion, Reinhold Publishing Corporation, New York, New York (1963).
33. Metcalf, R. L., I. P. Kapoor, P. Y. Lu, C. K. Schuth, and P. Sherman,
"Model Ecosystem Studies of the Environmental Fate of Six Organo-
chlorine Pesticides," Environmental Health Perspectives, May 1963.
34. DeMarteis, F., B. E. Prior, and C. Rimington, Nature, .19U363-366
(1961); Chem. Abstr.. 55j26249c (1961).
35. Ockner, R. K., and R. Schmid, "Acquired Porphyria in Man and Rat Due
to Hexachlorobenzene Intoxication," Nature, 189(4763): 499 (1961);
Biol. Abstr.. 36:55376 (1961).
36. Ockner, R. K., and R. Schmid, "Acquired Cutaneous Porphyria Due to
Hexachlorobenzene Intoxication," Fed. PrOc.. .20(1, part 1):376 (1961);
Biol. Abstr.. 3(5:80553 (1961). . >• /
37. Ehrlicher, H., "Industrial Observations of, and Experience with the
Toxicity of Vaporous Chlorinated Benzenes (mono- to hexachloro-
benzene), Zentralbl. Arbeitsmed. Arbeitsschutz. 18/7):204-205 (1968);
Chem. Abstr.. 69:9304 (1968).
38. Sairtskii, I. V., "The Basis for Determining Safe Permissible Con-
centrations of Hexachlorobenzene and Pentachloronitrobenzene in
the Air," 'Vopr. Prom, i Sel'skokhoz. Toksikol. Kievsk. Med. Inst.,
1518.: 173 (1964); Chem. Abstr.. 63;8952d (1965).
39. Diamond Alkali Company, "Hexachlorobutadiene," Diamond Chemicals Tech-
nical Bulletin Ol-B-310, Cleveland, Ohio (undated).
40. Chernokan, V. F.y.Vop.' Gig. Toksikol. Pestits., Tr. Nauch. Sess, Akad.
Med. Nauk SSR (1967 (published 1970)); Chem. Abstr.. 74:97218r (1971).
170
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41. Gage, J. C., "Substitute Inhalation Toxicity of 109 Industrial Chem-
icals," Brijt.^J^Ind.^Medi, ,221(1); 1-18 (1970); Chem. Abstr.. 73_: 183
(1970).
42. Stroganov, N. S., and L. V. Kolosova, "Effects of Small Concentrations
of Hexachlorobutadiene on Aquatic Organisms," Tr. Morsk. Obshehest,
Ispyt. Prir.. 3J): 126-138 (1968); Chem. Abstr.. T2:113 (1970).
43. Murzakaev, F. G., "Changes in the Absorption Properties of Rat Tissue
and Organs Due to Hexachlorobutadiene,11 Farmako 1. i Toksiko 1., ,2£(6):
712-714 (1966); Chem. Abstr.. 6^6:4324 (1967).
44. Stanford Research Institute, Directory of Chemical Producers» SRI
Chemical Information Services, Menlo Park, California (1974).
45. Stanford Research Institute, Chemical Economics Handbook. SRI Chemical
Information Services, Menlo Park, California, 1973 and 1974.
46. Predicasts, 1973 and 1974, Annual Cumulative Editions, Cleveland:
Predicasts, Inc.
4^4 U.Si Tariff Commission, Synthetic Organic Chemicals. U.S. P'fbdUihfcib'n
and Sales, 1970, T.C. Publication 479, U.S. Government Printing
Office, Washington, D.C. (1972).
48. McCurdy, P. P., "Facts and Figures for the Chemical Industry," ACS
Official Report No. 55, Chem. and Eng. News. 51.(23):9-46 (1973).
49. U.S. Department of Commerce, "U.S. Imports for Consumption and Gen-
eral Imports," Social and Economic Statistics Administration, Bureau
of Census, FT246/Annual (1973).
50. Sconce, J. S., Chlorine: Its Manufacture, Properties and Uses, Reinhold
Publishing Corporation, New York, New York (1962).
171
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SUBJECT INPEX FOR THE CHEMICALS STUDIED
Atrazine ....
Production Sites and Volumes ............ ... . , . ; . 25
Manufacturing Methods, By-Products, Contamination and Risks. ..•'.-. 52
Waste Disposal . -.,.•..;..•..•. ,, . ... 87
Uses for the Chemical Products . . .-. ..'.,.. ... . ....'. . 104
Selection of Monitoring Sites 124
t
.- •. , t
Carbon Tetrachlorlde . . • . ' '
Production Sites and Volumes ............ 19
Manufacturing Methods, By-Products, Contamination and Risks. ... 37
Waste Disposal 86
Uses for the Chemical Products , . . . . .... . . . .... . . .. . . 102
Selection of Monitoring Sites . 122
Biphenyls :". : '
Production Sites and Volumes ................... 27
Manufacturing Methods, By-Products, Contamination and Risks. ... 72
Waste Disposal . .;.... 91
Uses for the Chemical Products . . . . . . . . . ; . . . . . . . . 106
Selection of Monitoring Sites. . . .... . . . . . . . . . . . . 125
Chlorinated Naphthalenes ; .
Production Sites and Volumes ........ 27
Manufacturing Methods, By-Products, Contamination arid Risks. ... 71
Waste Disposal ............." 89
Uses for the Chemical Products •. . . . .... . . .. . 105-
Selection of Monitoring Sites. .................. 125
Chlorine
Production Sites and Volumes ............ . 15
Manufacturing Methods, By-Products, Contamination and Risks. . . . 33
Waste Disposal 85
Uses for the Chemical Products . . . . . . . . . ... . . ... . 101
Selection of Monitoring Sites. ...... 121
172
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SUBJECT INDEX FOR THE CHEMICALS STUDIED (Continued)
Dacthai®'
Production Sites and Volumes • . 25
Manufacturing Methods, By-Products, Contamination and Risks. ... 50
Waste Disposal . 87
Uses for the Chemical Products 104
Selection of Monitoring Sites. . 124
Hexachlorobenzene . •
Production Sites and Volumes 15
Manufacturing Methods, By-Products, Contamination and Risks. ... 28
Waste Disposal 85
Uses for the Chemical Products 98
Environmental and Health Aspects ...... 107
Selection of Monitoring Sitea. ..-..' 123
Hexachlorobutadiene
Production Sites and Volumes .... 15
Manufacturing Methods, By-Products, Contamination and Risks. . . . 32
Waste Disposal . . . 85
Uses for the Chemical Products 98
Environmental and Health Aspects . . . . . . . ... ... . . . . 116
Selection of Monitoring Sites 124
Hexachlorocyclopentadiene
Production Sites and Volumes . 25
Manufacturing Methods, By-Products, Contamination and Risks. ... 71
Waste Disposal . 89
Uses for the Chemical Products •. •. 105
Selection of Monitoring Sites. . 125
Hexachloroethane
Production Sites and Volumes .............. 22
Manufacturing Methods, By-Products, Contamination and Risks... . .68
Waste Disposal 89
Uses for the Chemical Products ... .\. 103
Environmental and Health Aspects . . ,\. . . . . 118
Selection of Monitoring Sites. .... X ...... .123
\
173
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SUBJECT INDEX FOR THE CHEMICALS STUDIED (Continued)
Maleic Hydrazide
Production Sites and Volumes . 25
Manufacturing Methods, By-Products, Contamination and Risks. ... 70
Waste Disposal . . . . ." 89
Uses for the Chemical Products 105
Selection of Monitoring Sites 125
Mirex
Production Sites and Volumes . 25
Manufacturing Methods, By-Products, Contamination and Risks. . . . 58
Waste Disposal 88
Uses for the Chemical Products 105
Selection of Monitoring Sites 125
Pentachlorobenzene
Production Sites and Volumes 22
Manufacturing Methods, By-Products, Contamination and Risks. ... 55
Waste Disposal 87
Uses for the Chemical Products 103
Environmental and Health Aspects ..... 119
Selection of Monitoring Sites * • 123
Pentachloronitrobenzene
Production Sites and Volumes ..... 25
Manufacturing Methods, By-Products, Contamination and Risks. ... 58
Waste Disposal 87
Uses for the Chemical Products 104
Selection of Monitoring Sites 124
Pentachlorophenol
Production Sites and Volumes 22
Manufacturing Methods, By-Products, Contamination and Risks. ... 66
Waste Disposal 89
Uses for the Chemical Products 103
Environmental and Health Aspects ..... 118
Selection of Monitoring Sites 122
174
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SUBJECT INDEX FOR THE CHEMICALS STUDIED (Continued)
Perchloroethylene
Production Sites and Volumes . i. ; . i . . '. . . i . . . , .... 19
Manufacturing Methods, By-Products, Contamination and Risks. ... 40
Waste Disposal . . . . . . . .• ; . . ..... ..' ... 86
Uses for the Chemical Products . . . . ; ... .<..'... .... 102
Selection of Monitoring Sites 122
Propazine
Production Sites and Volumes . . . . . . . . . . . . .'-'. ... . . 25
Manufacturing Methods, By-Products, Contamination and Risks. ... 55
Waste Disposal ...... . . ......... . 8?
Uses for the Chemical Products ..... . . . . . . . . . . ... 104
Selection of Monitoring Sites '. * 124
Simazine
Production Sites :and Volumes .... . ' * . ... . ; . .25
Manufacturing Methods, By-Products, Contamination and Risks. . . . 55
Waste Disposal . ... . . ; . . . . . . • '• • • • ••'•'"•"• • • • • 87
Uses for the Chemical Products ...... ; . . . . . . . . . . . 104
Selection of Monitoring Sites. .......... .r. .... . . 124
Sodium Chlorate
Production Sites and Volumes ....... 19
Manufacturing Methods, By-Products, Contamination and Risks. ... 59
Waste Disposal . . 88
Uses for the Chemical Products . . . . 101
Selection of Monitoring Sites. ^ ..... .'.'... . . . 121
Sodium Metal
Production Sites and Volumes . 19
Manufacturing Methods, By-Products, Contamination and Risks. ... 61
Waste Disposal .......................... 88
Uses for the Chemical Products . . . ... . . ..'. . 102
175
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SUBJECT INDEX FOR THE CHEMICALS STUDIED (Concluded)
Synthetic Rubber (Chlproprene)
Production Sites and Volumes ..... .............. 22
Manufacturing Methods, By-Products, Contamination and Risks. . . . 70
Waste Disposal ... ........ ............... 89
Uses for the Chemical Products ......... . . . ...... 104
Selection of Monitoring Sites. .................. 124
Trichloroethylene
''
Production Sites and Volumes ... . ..... 19
Manufacturing Methods, By-Products, Contamination and Risks. . . . 46
Waste Disposal , 87
Uses for the Chemical Products .................. 102
Selection of Monitoring Sites r ............. 122
Vinyl Chloride Monomer
Production Sites and Volumes ........... . . 22
Manufacturing Methods, By-Products, Contamination and Risks. . . . 63
Waste Disposal * . . . . .... . . . . .88
Uses for the Chemical Products 103
Selection of Monitoring Sites. 122
176
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