450484007m
September 1986
Locating And Estimating Air Emissions
From Sources Of Chlorobenzenes
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office Of Air And Radiation
Office Of Air Quality Planning And Standards
Research Triangle Park, North Carolina 27711
SM-Xl
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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental
Protection Agency, and has been approved for publication as received from the contractor. Approval does
not signify that the contents necessarily reflect the views and policies of the Agency, neither does mention
of trade names or commercial products constitute endorsement or recommendation for use.
EPA-450/4-84-007m
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CONTENTS
Figures v
Tables vil
1. Purpose of Document 1
2. Overview of Document Contents 3
3. Background ...... 5
Nature of Pollutant 5
Overview of Production and Uses H
4. Emission Sources of Chlorobenzenes 19
Chlorobenzene Production 19
Use of Chlorobenzenes in the Production
of Dyes and Pigments 3S
Use of Chlorobenzenes as Solvents in
Organic Solvent Cleaning Operations 53
Use of Monochlorobenzene and o-Dichlorobenzene
as Dye Carriers in Textile Dyeing. . .- 61
Manufacture of Chloronitrobenzenes from
Monochlorobenzene. 64
Manufacture of Diphenyl Oxide from
Monochlorobenzene 70
Use of Monochlorobenzene in the Manufacture of DDT. . 72
Manufacture of 3,4-Dichloroaniline from
o-Dichlorobenzene 75
Use of Chlorobenzenes in the Manufacture of
Toluene Diisocyanate 80
Use of o-Dichlorobenzene as a Solvent in
Pharmaceutical Manufacturing 85
Use of p-Dichlorobenzene as a Space Deodorant .... 88
Use of p-Dichlorobenzene in Moth Control 89
Use of p-Dichlorobenzene in the Production of
Polyphenylene Sulfide 90
Use of Dichlorobenzenes in Pesticides 93
Use of Chlorobenzenes in Bonded Abrasive
Products Manufacture 95
Use of Chlorobenzenes in Wood
Preservatives 96
Use of 1,2, 4-Trichlorobenzene as a Dye Carrier
in the Textile Dyeing Industry 97
Use of 1,2,4-Trichlorobenzene in the
Manufacture of Pesticide Intermediates 100
Use of 1,2,4-Trichlorobenzene in Functional
Fluids 104
Hexachlorobenzene Generation during Chlorinated
Solvent Production 107
Hexachlorobenzene Generation during Pesticide,
Herbicide, and Fungicide Production 116
111
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Contents (continued)
Use of Fungicides and Herbicides Containing
Hexachlorobenzene 118
Volatilization of Chlorobenzenes from
Wastewater Treatment Operations 120
Burning of Waste Oil 122
Miscellaneous Uses of Chlorobenzenes 123
5. Source Test Procedures 126
References 129
IV
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FIGURES
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Basic operations that may be used in continuous
Basic operations that may be used in
DCB and TCB production
Production schematic for hexachlorobenzene from
Production schematic for hexachlorobenzene by
Dye intermediates derived from 1,2,4-trichlorobenzene. . .
Pollution control equipment - dye carriers ........
Synthesis of various intermediates for dye and
Basic operations that may be used in DDT production. . . .
Basic operations that may be used in toluene diisocyanate
Basic operations that may be used in pharmaceutical
Process flow diagram of PPS manufacture
Page
. 14
, 18
. 35
. 36
. 39
. 40
. 41
. 42
. 55
. 57
. 63
. 65
. 73
. 91
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Figures (continued)
Number Page
19 Process flow diagram for the production of carbon
tetrachloride and perchloroethylene by
hydrocarbon chlorinolysis . .108
20 Process flow diagram for the production of
perchloroethyleneand trichloroethylene
by chlorination 109
21 Process flow diagram for the production of
perchloroethylene and trichloroethylene
by oxychlorination 110
22 Method 23 Sampling Train 127
vi
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TABLES
Number
1 Synonyms and Trade Names for Chlorinated Benzenes 7
2 Properties of Industrially Significant Chlorobenzenes ... 8
3 Emission Factors for a Hypothetical
Monochloxobenzene Production Plant 25
4 Chemical Producers of Monochlorobenzene - 1984
26
5 Emission Factors for a Hypothetical
o-Dichlorobenzene Production Plant .......... 29
6 Emission Factors for a Hypothetical
p-Dichlorobenzene Production Plant .......... 30
7 Chemical Producers of o-Dichlorobenzene and
p-Dichlorobenzene - 1984 ............... 32
8 Chemical Producers of Trichlorobenzenes - 1984 ....... 34
9 Dyes and Pigments Utilizing Chlorobenzene Solvents ..... 44
10 Emission Factors for o-Dichlorobenzene in Dye
Synthesis ....................... 48
11 Dye and Pigment Manufacturing Companies - 1-984
49
12 Properties of Halogenated Solvents Used in Organic
Solvent Cleaners . .
13 Organic Solvent Degreaser Control Equipment ..... ... 59
14 Principal Industrial Users of Organic Solvent
Cleaners - 1980 ................... 60
15 Chemical Producers of o- and p-Chloronitrobenzenes - 1984 . 69
16 Pesticides using 3, 4-Dichloraniline as an
Intermediate - 1984 .................. 76
17 Emissions Factors for the Production of
3, 4-Dichloroaniline ........... • ...... 77
18 Chemical Producers of 3, 4-Dichloroaniline - 1984 ...... 79
vii
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Tables (continued)
Number page
19 Chemical Producers of Toluene Diisocyanate - 1984 84
20 1978 Regional Dichlorobenzene Emissions Estimates
from Pesticide Formulation 94
21 1,2', 4-Trichlorobenzene Emissions from Specific Water
Treatment Processes in Wet Processing Textile
Mills - 1979 98
22 Chemical Producers of Trichlorobenzene-derived
Pesticides - 1977 103
23 Summary of Disposal Practices for Hexachlorobenzene
Wastes - 1984 112
24 Chemical Producers of Carbon Tetrachloride - 1984 113
25 Chemical Producers of Trichloroethylene - 1984 114
26 Chemical Producers of Perchloroethylene - 1984 115
27 Previously Registered Seed Treatment Formulations
Containing Hexachlorobenzene 119
viii
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SECTION 1
PURPOSE OF DOCUMENT
EPA, States and local air pollution control agencies are becoming
increasingly aware of the presence of substances in the ambient air that
may be toxic at certain concentrations. This awareness, in turn, has
led to attempts to identify source/receptor relationships for these
substances and to develop control programs to regulate emissions.
Unfortunately, very little information is available on the ambient air
concentrations of these substances or on the sources that may be
discharging them to the atmosphere.
To assist groups interested in inventorying air emission's of
various potentially toxic substances, EPA is preparing a series of
documents such as this that compiles available information on sources
and emissions of these substances. This document specifically deals
with chlorobenzenes, namely, monochlorobenzene, dichlorobenzenes,
trichlorobenzenes, and hexachlorobenzene. Its intended audience
includes Federal, State and local air pollution personnel and others who
are interested in locating potential emitters of chlorobenzenes and
making preliminary estimates of air emissions therefrom.
Because of the limited amounts of data available on chlorobenzene
emissions, and since the configuration of many sources will not be the
same as those described herein, this document is best used as a primer
to inform air pollution personnel about 1) the types of sources that may
emit chlorobenzenes, 2) process variations and release points that may
be expected within these sources, and 3) available emissions information
indicating the potential for chlorobenzenes to be released into the air
from each operation.
The reader is strongly cautioned against using the emissions
information contained in this document to try to develop an exact
assessment of emissions from any particular facility. Since
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insufficient data are available to develop statistical estimates of the
accuracy of these emission factors, no estimate can be made of the error
that could result when these factors are used to calculate emissions
from any given facility. It is possible, in some extreme cases, that
orders-of-magnitude differences could result between actual and
calculated emissions, depending on differences in source configurations,
control equipment and operating practices. Thus, in situations where an
accurate assessment of chlorobenzene emissions is necessary, source-
specific information should be obtained to confirm the existence of
particular emitting operations, the types and effectiveness of control
measures, and the impact of operating practices. A source test and/or
material balance should be considered as the best means to determine air
emissions directly from an operation.
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SECTION 2
OVERVIEW OF DOCUMENT CONTENTS
As noted in Section 1, the purpose of this document is to assist
Federal, State and local air pollution agencies and others who are
interested in locating potential air emitters of chlorobenzenes and
making gross estimates of air emissions therefrom. Because of the
limited background data available, the information summarized in this
document does not and should not be assumed to represent the source
configuration or emissions associated with any particular facility.
This section provides an overview of the contents of this document.
It briefly outlines the nature, extent and format of the material
presented in the remaining sections of this report.
Section 3 of this document provides a brief summary of the physical
and chemical characteristics of chlorobenzenes, commonly occurring forms
and an overview of their production and uses. A chemical use tree
summarizes the quantities of chlorobenzenes consumed in various end use
categories in the United States. This background section may be useful
to someone who needs to develop a general perspective on the nature of
the substances and where they are manufactured and consumed.
Section 4 of this document focuses on major industrial source
categories that may discharge air emissions containing chlorobenzenes.
This section discusses the manufacture of chlorobenzenes, their use as
industrial feedstocks, and their use as individual commercial products.
For each major industrial source category described in Section 4,
example process descriptions and flow diagrams are given, potential
emission points are identified, and available emission factor estimates
are presented that show the potential for chlorobenzene emissions before
and after controls employed by industry. Individual companies are named
that are reported to be involved with either the production or use of
chlorobenzenes, based primarily on trade publications.
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The final section of this document summarizes available procedures
for source sampling and analysis of chlorobenzenes. Details are not
prescribed nor is any EPA endorsement given or implied to any of these
sampling and analysis procedures. At this time, EPA generally has not
evaluated these methods. Consequently, this document merely provides an
overview of applicable source sampling procedures, citing references for
those interested in conducting source tests.
This document does not contain any discussion of health or other
environmental effects of chlorobenzenes, nor does it include any
discussion of ambient air levels or ambient air monitoring techniques.
Comments on the contents or usefulness of this document are
welcomed, as is any information on process descriptions, operating
practices, control measures and emissions information that would enable
EPA to improve its contents. All comments should be sent'to:
Chief, Noncriteria Emissions Section (MD-14)
Air Management Technology Branch
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
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SECTION 3
BACKGROUND
NATURE OF POLLUTANT
The chlorinated derivatives of benzene, c6H(g_x) Clx, form a group
of stable, colorless, pleasant smelling compounds. The six hydrogen
atoms of the benzene ring can be substituted by chlorine, forming twelve
chlorine compounds:
monochlorobenzene
o-dichlorobenzene
p-dichlorobenzene
m-dichlorobenzene
1,2,3-trichlorobenzene
1,2,4-trichlorobenzene
1,2,5-trichlorobenzene
1,2,3,4-tetrachlorobenzene
1,3,4,5-tetrachlorobenzene
1,2,4,5-tetrachlorobenzene
pentachlorobenzene
hexachlorobenzene
Only the mono-, di-, and trichlorobenzenes have important
industrial applications. Thus, this report deals with air emissions of
the following chlorinated derivatives of benzene:
monochlorobenzene ortho-dichlorobenzene
Cl
para-dichlorobenzene meta-dichlorobenzene
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1,2,3-trichlorobenzene
Cl
1,2,4-trichlorobenzene
Cl
1,3,5-trichlorobenzene
hexachlorobenzene
Although it has no current commercial applications, hexachlorobenzene is
also included due to toxicity considerations, its past usage, and
generation as a byproduct in other manufacturing processes. Synonyms
and trade names for these chlorinated benzenes are given in Table 1.
The physical properties of the industrially significant chloro-
benzenes are listed in Table 2. Vapor pressure as a function of
temperature is correlated by the Antoine equation:
Iog10 P (kPa) = A - B/(T+C) - 0.875097,
where T is the temperature in °C and A, B, and C are the Antoine
constants. Antoine constants found in the literature are listed in
Table 2.
Monochlorobenzene is almost insoluble in water. If it accumulates
in raw water systems, it tends to sink. Because of its comparatively
high volatility, there may be a greater tendency for monochlorobenzene
to accumulate in still lake waters rather than fast moving streams and
rivers.
Monochlorobenzene has a high solubility in nonpolar solvents, and
all chlorinated derivatives of benzene are soluble in lipids. Partition
coefficient data for chlorinated benzenes show an increase in partition
coefficient with an increase in the degree of chlorination. In general,
a positive correlation exists between partition coefficient and degree
of bioaccumulation.
Ortho- and meta-dichlorobenzene are neutral, mobile, colorless
liquids with similar and characteristic odors. Para-dichlorobenzene is
a pleasant smelling white crystalline solid. The crystals readily
sublime at room temperature. Solubilities of the dichlorobenzenes are
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TABLE 1: SYNONYMS AND TRADE NAMES FOR CHLORINATED BENZENES1'2
Monochlorobenzene:
benzene chloride; chlorobenzene;
chlorobenzol; phenyl chloride; MCB;
NCI-C54886
o-Dichlorobenzene:
orthodichlorobenzene; ortho-dichlorobenzene;
ortho-dichlorobenzol; 1,2-dichlorobenzene;
ODB; ODCB; Dizene*; Chloroben*; Dowtherm* E;
"Special termite fluid"; Termitekil;
Dilatin DB
p-Dichlorobenzene:
paradichlorobenzene; para-dichlorobenzene;
para-dichlorobenzo1; 1,4-dichlorobenzene;
PDB; PDCB; Di-chloricide*; Paracide*;
Paradi*; Paradow*; Paramoth*; Santochlor*;
Parazene; Paranuggets; paraCrystals; p-
chlorophenyl chloride; Evola; Persia-Perazol
m-Dichlorobenzene:
metadich lor obenzene; meta-dich lorobenzo 1;
meta-dichlorobenzene; 1,3-dichlorobenzene;
m-phenylenedichloride
1,2,3-Trichlorobenzene:
1,2,3-trichlorobenzol; 1,2,3-TCB; 1,2,6-
trichlorobenzene; vic-trichlorobenzene
1,2,4-Tr ichlorobenz ene:
1,2,4-trichlorobenzol; 1,2,4-TCB; asym-
trichlorobenzene; Hostetex L-Pec
1,3,5-Trichlorobenzene:
1,3,5-trichlorobenzol; 1,3,5-TCB; sym-
trichlorobenzene; s-trichlorobenzene; TCBA
Hexachlorobenzene:
Amatin; Anticarie; Bunt-Cure; Bunt-No-More;
Co-op Hexa; Granox NM; HCB; HEXA C.B.;
Julin's Carbon Chloride; No Bunt; No Bunt
40; No Bunt 80; No Bunt Liquid; pentachloro-
phenyl chloride; perchlorobenzene; phenyl-
perchloryl; Sanocide; Smut-Go; Snieciotox
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TABLE 2. PROPERTIES OF INDUSTRIALLY SIGNIFICANT CHLOROBENZENES1'3'4'5
00
Chemical Abstract Service
Registry Number
Chemical Formula
Molecular Weight
Molecular Formula
Physical Properties
Physical State at STP
Boiling Point (at 760mm)
Melting Point
Density (g/ml)
(at 20°C/4°C)
Vapor Pressure
(mm llg at 25°C)
Antolne Constants
A
B
C
Vapor Density
Solubility in Water
Log Partition Coefficient
(Octanol/H 0)
Atmospheric Reactivity
Transformation Products
Reactivity Toward Oil
Reactivity Toward 0
MCD
108-90-7
112.56
C6H5C1
liquid
-colorless
131. 7°C
-45.5°C
1.1058
11.8
16.0676
3295.12
-55.60
3.88
insoluble
2.84
1/3 Butane
No reaction
o-DCB
95-50- 1
147.0
C6H4C12
liquid
-colorless
180. 5°C
-17.0°C
1.305
1.28
16.2799
3798.23
-59.84
5.05
slightly
(0.145g/l H 0)
3.38 2
1/2 Butane
5% Propylene
p-DCB
106-46-7
147.0
C H Cl
64 2
monocllnlc
crystals
(volatile)
174.12°C
53.5°C
1.288
1.89
16.1135
3626.83
-64.64
-_..
nearly Inaol.
(0.079g/l 11 0)
3.39 2
1/2 Butane
5% Propylene
m-DCB 1,2,4-TCB
541-73-1 120-82-1
147.0 181.5
W12 C6H3C13
liquid liquid
-colorless
173. 0°C 213. 0°C
-24.7°C 16.6°C
1.288 1.46
0.4 0.29
16.8173
4104.13
-43.15
insoluble Insoluble
---
•
«• — — H o. •.
---
1,3,5-TCB 1,2,3-TCB HCB
108-70-3 87-61-6 118-74-1
181.5 181.5 284.76
C H Cl C H Cl C Cl
633 633 66
solid solid solid
crystalline crystalline crystalline
208. 0°C 218. 0°C 3229°C
63.0°C 52.4°C 230°C
1.69 1.57 (at 23°C)
0-15 --- 1.68 x 10~5
Insoluble insoluble insoluble
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similar to those of monochlorobenzene, and the dichlorobenzenes also
form a number of azeotropes. All three dichlorinated compounds are
combustible.
The trichlorinated benzenes are white crystalline solids except for
1,2,4-trichlorobenzene which is a colorless liquid. Solubilities are
similar, with insolubility in water, generally good solubility in
alcohol, ether, benzene, and chloroform, and relatively high lipid
solubility.
Hexachlorobenzene is a colorless crystalline solid at normal
temperatures shown to degrade slowly in the environment. Although
insoluble in water, it is slightly soluble in cold alcohol and soluble
in benzene, chloroform, and ethyl ether. Rapid sublimation of the
crystals occurs in the temperature range of 0° to 30°C.
As a group, chlorobenzenes are much less reactive than the
corresponding chlorinated derivatives of alkyl compounds and are similar
in reactivity to the vinyl chlorides. They are very stable to nucleo-
philic attack due to resonance in the molecule resulting in a shortening
of the carbon chlorine bond distance and an increase in bond strength.
At room temperature and pressure, chlorobenzenes are not attacked
by air, moisture, or light. They are not affected by steam, prolonged
boiling with aqueous or alcoholic ammonia, other alkalis, hydrochloric
acid, or dilute sulfuric acid. Hydrolysis takes place at elevated
temperatures in the presence of a catalyst to form phenols.
Chlorobenzenes are subject to attack by hot concentrated sulfuric
acid to form a chlorobenzene-p-sulfonic acid. Nitric acid will react
with chlorobenzenes at the meta and para positions on the ring to form
chloronitrobenzenes at -30° to 0°C. At higher temperatures, the nitra-
tion will either proceed further to form a dinitrochloro compound,
chloronitrophenol, or a nitrophenol.
Chlorobenzenes are attacked by electrophilic agents. Substitution
for monochlorobenzene is predominantly para; with some ortho substitu-
tion. The higher chlorinated benzenes tend to resist electrophilic
substitution but can be substituted under extreme conditions.
Chlorobenzenes also undergo some free radical reactions. Formation
of organometal lie compounds (originals, ary 1-lithium compounds) provides
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a useful route to many organic intermediates. Photochemical transforma-
tions occur on irradiation of chlorinated benzenes, which are much less
stable to radiation than benzene. On ultraviolet irradiation or pulse
hydrolysis in solution, chlorobenzenes may polymerize to biphenyls,
chloronaphtha1enes, or other more complex products.
Because of the wide variety of chemical reactions that
chlorobenzenes can undergo, chlorinated benzenes can be used as
reactants in numerous commercial processes to produce a wide variety of
products.
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OVERVIEW OF PRODUCTION AND USES
Twelve chlorinated benzenes can be formed by replacing some or all
of the hydrogen atoms of benzene with chlorine atoms. With the
exceptions of 1,3-dichlorobenzene, 1,3,5-trichlorobenzene, and 1,2,3,5-
tetrachlorobenzene, they are produced readily by chlorinating benzene in
the presence of a Friedel-Crafts catalyst. The usual catalyst is ferric
chloride, either as such or generated in situ by exposing a large
surface of iron to the liquid being chlorinated. Each compound, except
hexachlorobenzene, can be chlorinated further; hence, the product is
always a mixture of chlorinated benzenes. Pure compounds are obtained
by distillation and crystallization.
Chlorobenzenes were synthesized first in the middle of the
nineteenth century. The first direct chlorination of benzene was
reported in 1905. Commercial production was initiated in 1909 by the
former United Alkali Company in England. In 1915, the Hooker Electro-
chemical Company began operation*of its first chlorobenzenes plant in
the United States at Niagara Falls. The Dow Chemical Company also
started its U.S. production of chlorobenzenes in 1915.
Currently, there are five domestic producers of chlorobenzenes at
the same number of locations. In 1984, production capacity for mono-
chlorobenzene was 157 x 103 Mg, for o-dichlorobenzene it was 35 x
103 Mg, and for p-dichlorobenzene, 54 x 103 Mg.7'8'9 Few data are
available on production of more highly chlorinated benzenes.
Processes for the manufacture of chlorobenzenes have developed over
a long period of time, with various chemistry and product separation
methods being used. The process currently used by industry is direct
chlorination of benzene in the presence of FeCl3 catalyst to produce
monochlorobenzene. The monochlorobenzene reacts with the remaining
chlorine to form dichlorobenzenes. Hydrogen chloride is a by-product in
both reactions. Along with the two major isomers of dichlorobenzene,
ortho- and para-, a very small amount of the meta-isomer is formed. As
chlorination is continued, tri-, tetra-, penta-, and hexachlorobenzenes
are formed. Usually, trichlorobenzene is the only one of the more
highly chlorinated products found in significant amounts. The degree of
chlorination of benzene can be controlled by the choice of the catalyst,
11
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temperature, and benzenecchlorine ratio in the reactor feed. Hydrogen
chloride, a byproduct of the reaction, is processed under anhydrous
conditions before it is absorbed in water. The reaction and the
recovery operations, in most cases, are continuous.
Chlorobenzene production plants vary in capacity from 10 million to
160 million kg/year. In general, with the decreasing use of monochloro-
benzene, the thrust of commercial Chlorobenzene producers has been
toward maximizing dichlorobenzene and trichlorobenzene capacity.
Demand for monochlorobenzene as a feedstock comes mostly from the
synthetic organic chemical industry. Accordingly, since the manufactur-
ing process is simple, it is often manufactured in the same plant in
which it is consumed. The two major markets for monochlorobenzene have
been in the manufacture of phenol and o- and p- nitrochlorobenzenes.
Continued growth in these markets is doubtful, since cumene is now
primarily used as a raw material for phenol manufacture. ^ Other feed-
stock uses include use^ in the manufacture of diphenyl oxide, rubber
intermediates, and DDT.
o-Dichlorobenzene is used primarily in organic synthesis of 3,4-
dichloroaniline which is used as an intermediate in the production of
pesticides. Demand for o-dichlorobenzene as a solvent carrier in the
manufacture of toluene diisocyanate for polyurethane manufacture has
increased, and is expected to grow faster than any other use. It also
is used as a solvent in paint removers and engine cleaners, in de-inking
12
solvents, and in dye manufacture.
p-Dichlorobenzene is used extensively as a moth repellent. Its
vapor pressure and pleasant odor make it very suitable for this applica-
tion. It is predicted that this use will hold steady, in addition to
its use as a space odorant. Moderate growth is expected for its use in
the manufacture of polyphenylene sulfide resins. It is also used in
the production of dye intermediates, insecticides, Pharmaceuticals, and
as an extreme pressure lubricant.
1,2,4-Trichlorobenzene is primarily used in textile dyeing
operations as a dye carrier but also finds uses in production of
herbicides and dyes. It has also been employed as a high melting point
12
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product solvent, degreasing agent, termite control agent, synthetic
transformer oil, lubricant, heat transfer medium and dielectric fluid.
m-DCB, 1,2,3-TCB, and 1,3,5-TCB, and all three tetrachlorobenzenes
are not discussed here due to their limited production and use.
Hexachlorobenzene is no longer produced or imported into the United
States for commercial usage. Formerly, hexachlorobenzene was used as an
active ingredient in fungicidal preparations, but this use has been
nearly eliminated due to the cancellation of registry of HCB-containing
fungicides. Currently, hexachlorobenzene is formed as a process waste
byproduct during the manufacture of specific chlorinated solvents and
pesticides.1^'15
A summary of current uses of each of the industrially significant
chlorobenzenes is presented in Figure 1, along with the percentage of
total product devoted to each use. Since hexachlorobenzene has no
current uses, a summary of past uses is presented in Figure 2.
13
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Benzene + Chlorine
•> Monochlorobenzene >
Production of
chloronitrobenzene
(32 percent)
Use as solvent in
toluene diisocyanate
manufacture, pesticide
formulation, and as
a degreasing agent
(42 percent)
Production of dipheny 1
oxide and phenyl
phenols
(15 percent)
Other uses
(11 percent)
Figure 1. Uses of chlorinated benzenes.
10
14
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Benzene + Chlorine
-> o-Dichlorobenzene
Production of 3,4-
dichloroaniline
(65 percent)
Use as toluene
diisocyanate process
solvent
(15 percent)
Other solvent uses
(10 percent)
Dyestuff manufacture
(5 percent)
Other uses
(5 percent)
Figure 1. (continued) Uses of chlorinated benzenes.
12
15
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Benzene + Chlorine
-> p-Dichlorobenzene
_ Space deodorant
(44 percent)
_ Moth repellant
(23 percent)
_ Polyphenylene sulfide
resin
(23 percent)
'-Other uses
(10 percent)
Figure 1. (continued) Uses of chlorinated benzenes.
16
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_ Use as a dye carrier
| (46 percent)
I
Benzene + Chlorine > 1,2,4-Trichlorobenzene > l_ Production of
I herbicides, including
I dicamba
| (29 percent)
I
|_ Other uses
- (25 percent)
Figure 1. (continued) Uses of chlorinated benzenes.
17
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Benzene + Chlorine > Hexachlorobenzene >
_ Agricultural seed
treatments
Pyrotechnic and
ordnance materials
production
Synthetic rubber
production
Primary aluminum
production
_ Wood preservation
Graphite electrode
production
Figure 2. Past uses of hexachlorobenzene.
16
18
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SECTION 4
EMISSION SOURCES OF CHLOROBENZENES
This section discusses chlorobenzene emissions from direct sources
such as the production of monochlorobenzene, dichlorobenzenes, tri-
chlorobenzenes, and hexachlorobenzene; production of chemicals which use
chlorobenzenes as feedstocks; and direct use of the chemicals. Genera-
tion of hexachlorobenzene as a byproduct in other manufacturing pro-
cesses is also discussed. Process descriptions, uses, and related
emissions are discussed for the following chlorobenzenes:
• Monochlorobenzene
• o-dichlorobenzene
• p-dichlorobenzene
• m-dichlorobenzene
• 1,2,3-trichlorobenzene
• 1,2,4-trichlorobenzene
• 1,3,5-trichlorobenzene
• hexachlorobenzene
Due to limited current uses, tetrachlorobenzenes and pentachloro-
benzenes are considered industrially insignificant and are not
discussed.
CHLOROBENZENE PRODUCTION
The general process by which chlorobenzenes are manufactured is
direct chlorination of the benzene ring in the presence of a catalyst to
form monochlorobenzene (MCB) and o- and p-dich lorobenz enes. By the
manipulation of process controls such as choice of catalyst, tempera-
ture, and the benzene-chlorine ratio, it is possible to maximize the
production of specific chlorobenzenes; however, coproduction of higher
19
-------
chlorobenzenes cannot be eliminated. Further chlorination of the mono-
and dichlorobenzene (DCB) forms produces higher chlorobenzenes including
trichlorobenzenes, tetrachlorobenzenes, pentachlorobenzenes, and hexa-
chlorobenzenes of which only the trichlorobenzene isomers are formed in
significant amounts.
The following sections detail production processes by which
monochlorobenzene, m-, o-, and p-dichlorobenzenes, isomers of tri-
chlorobenzenes (TCBs), and hexachlorobenzene are isolated and processed.
It is important to note that all processes presented are general in
nature. Contact should be made with individual plants for specific
processes used at their facilities. Emissions data are discussed
following each process.
Process Descriptions: Monochlorobenzene
• In general, the most widely used process by which benzene is
chlorinated to form MCB is by passing dry chlorine into benzene gas in
the presence of a catalyst in the following reaction:
Cl
FeCl
2
3
Benzene Monochlorobenzene
The catalyst most often used is ferric chloride; catalysts employed to
a lesser extent are anhydrous aluminum chloride, stannic chloride,
molybdenum chloride, Fuller's earth, and metallic iron or aluminum
filings. Specific processes, including the continuous, batch, and
Raschig methods of benzene chlorination, are most often used in produc-
tion of MCB. A purification process is then used to further separate
the crude MCB from other chlorobenzene forms and impurities. Prior to
the reaction for all of the above methods, benzene gas is dried either
by azeotropic distillation or with silica gel, caustic soda, or alumina.
Chlorine gas is prepared by scrubbing with concentrated sulfuric acid to
remove moisture and impurities.^ The chlorination then proceeds by one
of the above-mentioned methods.
The continuous process is most often used because it produces high
yields containing up to 95 percent MCB and small amounts of DCB isomers.
20
-------
It is not possible by selecting catalyst conditions or by modifying
process parameters to prevent the formation of DCBs. Basic operations
that may be used in the continuous production of MCB are shown in
Figure 3. The process begins with a series of small, externally cooled
cast iron or steel vessels containing the catalyst (which may consist of
Raschig rings of iron or iron wire). Chlorine is supplied into each
vessel through suitably disposed inlets to maintain a large benzene to
chlorine ratio at all points along the reaction stream. The temperature
is held between 20 to 40°C to minimize the production of DCBs which form
at higher temperatures. Dry benzene (Stream 1) and dried recycled
benzene (Stream 2) are introduced into the reactor, which produces an
overhead gas (Stream 3) and crude reaction liquid product (Stream 4).
The overhead gas (Stream 3), containing HC1, unreacted chlorine, inert
gases from the chlorine feed, benzene and other VOCs, is sent to an
organic absorber where benzene and other VOCs are removed. The bottoms
from the organic absorber (Stream 6) flow to the HC1 stripper for
recovery of HC1.18 The overhead gas (Stream 5) is sent to HC1
absorption. Byproduct hydrogen chloride is then removed in the HC1
absorber, where it is saturated by washing with a refrigerated solvent
(e.g., o-dichlorobenzene) or low vapor pressure oil, and then recovered
18 19
in wash towers as commercially usable hydrochloric acid. »
Crude reaction liquid product (Stream 4) enters the crude
chlorobenzene distillation column which produces overheads (Stream 7),
containing most of the chlorobenzenes, unreacted benzene, and some HC1,
and a bottom stream from which catalyst and other byproducts are
separated (Stream 8) and processed for reuse. The overheads (Stream 7)
pass through a HC1 stripper and then into a benzene recovery column
(Stream 9). Part of the subsequent benzene-free stream (Stream 10) is
returned to the organic absorber while the remainder (Stream 11) enters
the MCB distillation column. The overhead MCB distillation product
(Stream 12) is then stored while the bottom stream containing DCB and
TCB isomers is processed. In most cases, isomer separation processing
is conducted simultaneously with MCB production but is discussed
separately in subsequent sections.
21
-------
tAll-GAS IREAIMOKir
CIUOMIMAIION
KEACIOK
CRUI*.
CIIIOROIICN2EME
DISFItlAIION
IICI
SIRIITER
K>
f
4
VENF
<^
HEAVY- tHUS
IHCX'ESSIMCi:
^lEUIRALIMIIOM
RCCOVfRY.
DRYING
0
WAS IE
>
NCI/IRAU7ED
CAIAIYSF
L
I
WAIIR
WASH:
BEIIZFIIE
EiRYII IO
DISFUIAFION
BEMZFtlE
RECOVC-KY
MCO
DISIItlAIION
IO
ISOMIR
FRACIIOIIAIIOM
(See Figure 4)
FUGITIVE
EMISSIONS
OVERALL
PLANT
NOTE: The numbers in tills figure refer to process streams, as discussed iit the text,
and Llie letters
-------
Under some circumstances, a batch process is used. In the batch
process benzene is contained in a deep, iron or mild steel vessel lined
with lead cooling coils. The catalyst, usually sublimed FeCl3, is added
in a benzene solution. Chlorine is fed into the bottom of the
chlorinator through a lead covered pipe at a rate to maintain the
temperature below 45°C in order to minimize production of DCBs. The
crude chlorobenzene stream and HC1 waste stream are collected and
treated as in the purification and recovery processes described above.
Faith, Keyes, and Clark describe a higher temperature batch
process where chlorine is bubbled into a cast iron or steel tank con-
• 19
taining dry benzene with 1 percent its own weight of iron filings.
Temperature is maintained at 40 to 60°C until density studies indicate
that all benzene is chlorinated. The temperature is then raised to 55°
to 60°C for six hours until the density rises to 1.280 g/cm3. The same
methods of chlorobenzene purification and HC1 recovery in batch form are
then employed. At 100 percent chlorination, the products are 80 percent
monochlorobenzene, 15 percent p-dichlorobenzene, and 5 percent
o-dichlorobenzene.
Another method of MCB production is the vapor phase chlorination of
benzene by the Raschig process. Chlorine produced by the catalytic
oxidation of hydrogen chloride is introduced into a preheated mixture of
benzene vapor, air and steam. The mixture is then brought into contact
at 220 to 260°C with a mixed catalyst of copper oxide and oxides of
Group III and VIII metals on a silica gel. To control the temperature,
the catalyst is packed in small diameter tubes. To reduce DCB forma-
tion, only 10 percent of the benzene is reacted at a time. Purification
and recovery proceed as indicated previously.
Emissions
The primary emissions from the production of MCB result from the
tailgas treatment vent (A), where inert gases originally contained in
the chlorine feed are vented (Figure 3). The vent stream also contains
benzene and chlorobenzenes. Normal practice in the industry is not to
20
provide an emission control device on this vent.
23
-------
Other sources of chlorobenzene emissions include: benzene
drying (B), heavy-ends processing (C), benzene recovery (D), MCB
distillation (E), emissions due to storage (F) and handling (G),
volatilization of MCB from waste water (H), fugitive emissions during
solid waste handling (I) and fugitive emissions from valves, flanges,
seals, etc. (J).2^ (Note: All above letters in parenthesis refer to
potential emission release points in Figure 3.)
Emission factors for the production of monochlorobenzene are given
in Table 3.
Source Locations
Major producers of MCB are listed in Table 4.
Process Descriptions; Dichlorobenzenes
Mixtures of dichlorobenzenes can be produced at similar or the same
facilities as MCB by chlorinating MCB or benzene at 150 to 190°C in the
presence of ferric chloride, as shown below.
Cl
monochlorobenzene o-dichlorobenzene p-dichlorobenzene
o- and p-Dichlorobenzene—
The residue from distillation of crude chlorobenzene, consisting
mainly of o- and p-DCB, is the principal source of these isomers.
Figure 4 presents basic operations that may be used to produce o- and p-
DCB and TCB. In a continuation of the production of MCB, o- and p-DCB
can be separated by fractional distillation. Isomer fractionation
yields p-DCB (with traces of o-DCB and m-DCB) which enters the overhead
(Stream 1) while the o-DCB enters the bottoms (Stream 2). The o-DCB
bottoms (Stream 2) undergoes fractional distillation and produces an o-
DCB overhead (Stream 3), which is sent to storage, and bottoms
18
(Stream 4), which is further processed to yield TCBs.
The crude p-DCB with other trace isomers (Stream 5) is purified by
batch crystallization. Part of the purified p-DCB (Stream 6) is sent to
liquid storage while the remainder (Stream 7) undergoes freezing,
24
-------
TABLE 3. EMISSION FACTORS FOR A HYPOTHETICAL MONOCHLOROBENZENE
PRODUCTION PLANT21
Emission category kg MCB emitted per Mg MCB produced
Process 2.06
Storage • 0.45
Fugitive 0.69
TOTAL 3.20
Note: The above emission factors are only general estimates derived from
site visit measurements. No specific information was available on
particular emission points included in each of the above emission
categories or on the type of production processes used (batch or
continuous) or on specific control technologies employed, if any.
Another reference estimates that total VOC emissions for a model
plant (producing MCB, DCBs and TCBs by the continuous process shown
in Figures 3 and 4) are 4.13 kg VOC per Mg of chlorobenzene
products, of which approximately 50 percent, or 2.07 kg/Mg, is
benzene. From this, it can be inferred that the MCB emission
factors may be considerably less than shown in the above table.
Of course, any given monochlorobenzene production plant may vary in
configuration and level of control from this hypothetical facility.
The reader is encouraged to contact plant personnel to confirm the
existence of emitting operations and control technology at a
particular facility prior to estimating emissions therefrom.
25
-------
TABLE 4. CHEMICAL PRODUCERS OF MONOCHLOROBENZENE - 19847
Monsanto Company
Monsanto Industrial Chemicals Company
Sauget, Illinois
PPG Industries, Inc.
Chemicals Group
Industrial Chemical Division
Natrium, West Virginia
Standard Chlorine Chemical Company, Inc.
Delaware City, Delaware
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
26
-------
(From
Figure 3)
SOlVENf-GRADE
1KB
FRACflONAriON
o-IXB
DtSriLLAIOI
f-Kt
CRYSIAl
PACKAGING
FUGITIVE
EMISSIONS
OVERALL
PLANT
NOTE: The numbers in tlilH figure refer to process at reruns, an dismissed In the text.
nnd the letters designate process vents. The heavy lines represent final product
streams through the process.
Figure 4. Basic operations that may be used in DCS and TCB production.
18
-------
crushing, screening, and packaging of p-DCB crystals. The mother liquor
from crystallization (Stream 8) is sent to DCB solvent grade fraction-
al ization where it is separated into solvent grade o-DCB (Stream 9) and
18
p-DCB (Stream 10) and stored. °
m-Dichlorobenzene—
Usually, m-DCB is obtained by subjecting o- and p-DCB to an
isomerization process. The isomers are heated to 120°C under 650. psig
pressure in the presence of aluminum chloride together with either
hydrogen chloride or a small amount of water, or alternatively at a
higher temperature in the presence of aluminum chloride alone.
As an option, higher chlorinated benzenes can be reduced with hydrogen
at 350 to 500°C in the presence of cuprous halide on alumina. TCB
mixtures have also been reduced with hydrogen in the presence of
catalysts such as molybdenum oxide, chromium oxide, or nickel chloride.
Also, 100 percent m-DCB can be formed by catalytically reducing 1,3,5-
TCB for 7 hours at 205°C. Excess hydrogen and by-product hydrogen
chloride are removed through a reflux condenser. .
Crowder and Gilbert (1958) patented a vapor-phase dehalogenation of
1,3,5-TCB using platinum on activated charcoal as a catalyst at 375°C
and 1 psig pressure. Distillation of products by this method yields 65
percent m-DCB.
Emissions
Emissions from the continuous process (Figure 4) are primarily from
the batch p-DCB crystallization vent (A). An exhaust fan (B) releases
sublimation losses from freezing, crushing, and the p-DCB crystal
packaging hoods to the atmosphere. Some emissions are also expected
from liquid product storage (C), handling (D), and the vacuum system (E)
rt f\
which services the vacuum stills. Fugitive emissions may be expected
from certain valves, pumps, etc. (F). Data are not available to esti-
mate emissions from the production of m-DCB. Emission factors for o-
and p-DCBs are shown in Tables 5 and 6.
28
-------
TABLE 5. EMISSION FACTORS FOR A HYPOTHETICAL 0-DICHLOROBENZENE
PRODUCTION PLANT22
Emission category kg o-DCB emitted per Mg o-DCB produced
Process 2.32
Storage 0.47
Fugitive 0.76
TOTAL 3.55
Note: The above emission factors are only general estimates derived from
site visit measurements. No specific information was available on
particular emission points included in each of the above emission
categories or on the type of production processes used (batch or
continuous) or on specific control technologies employed, if any.
Another reference estimates that total VOC emissions for a model
plant (producing MCB, DCBs and TCBs by the continuous process shown
in Figures 3 and 4) are 4.13 kg VOC per Mg of chlorobenzene
products, of which approximately 50 percent, or 2.07 kg/Mg, is
benzene. From this, it can be inferred that the o-DCB emission
factors may be considerably less than shown in the above table.
Of course, any given o-dichlorobenzene production plant may vary in
configuration and level of control from this hypothetical facility.
The reader is encouraged to contact plant personnel to confirm the
existence of emitting operations and control technology at a
particular facility prior to estimating emissions therefrom.
29
-------
TABLE 6. EMISSION FACTORS FOR A HYPOTHETICAL P-DICHLOROBENZENE
PRODUCTION PLANT22
Emission category kg p-DCB emitted per Mg p-DCB produced
Process 5.81
Storage 0.41
Fugitive 1.02
TOTAL 7.24
Note: The above emission factors are only general estimates derived from
site visit measurements. No specific information was available on
particular emission points included in each of the above emission
categories or on the type of production processes used (batch or
continuous) or on specific control technologies employed, if any.
Another reference estimates that total VOC emissions for a model
plant (producing MCB, DCBs, and TCBs by the continuous process shown
in Figures 3 and 4) are 4.13 kg VOC per Mg of chlorobenzene
products, of which approximately 50 percent, or 2.07 kg/Mg, is
benzene. From this, it can be inferred that the p-DCB emission
factors may be considerably less than shown in the above table.
Of course, any given p-dichlorobenzene production plant may vary in
configuration and level of control from this hypothetical facility.
The reader is encouraged to contact plant personnel to confirm the
existence of emitting operations and control technology at a
particular facility prior to estimating emissions therefrom.
30
-------
Source Locations
Major producers and processors of o- and p-DCB are listed in
Table 7. No information concerning producers of m-DCB is available.
Process Descriptions; Trichlorobenzenes
The most common process by which trichlorobenzenes are formed is
the catalytic chlorination of o- and p-DCB at 20 to 30°C in the presence
of ferric chloride. The reaction is allowed to proceed until a density
of 1.4 at 15°C is obtained, at which time the acid is neutralized and
the products are fractionally distilled to yield 1,2,4- and 1,2,3-
isomers.
1,2-DCB
Cl
FeClo
Cl
1,2,3-TCB
Cl
O
ci
1,4-DCB
1,2, 4-TCB
Similarly, 1,3,5-TCB can be obtained by the chlorination of m-DCB.
Cl
FeCl,
1,3-DCB
1,3,5-TCB
Most TCBs are produced at the same location as the lower chlorinated
benzenes where the TCBs are fractionally separated from DCBs.6 It is
assumed that most TCBs are produced by the batch method due to the low
volume of domestic production.*
Other trichlorobenzene production processes mentioned in the
literature include: (1) the reaction of a, p, or ybenzene
hexachloride with alcoholic potash at 100°C to produce all three TCB
isomers; (2) the dehalogenation of a-benzene hexachloride with pyridine
to form all three TCB isomers; and (3) the reaction of a-benzene hexa-
chloride with calcium hydroxide to form primarily 1,2,4-TCB.6 Further
31
-------
TABLE 7. CHEMICAL PRODUCERS OF 0-DICHLOROBENZENE AND P-DICHLOROBENZEHE
19848'9
Monsanto Company
Monsanto Industrial Chemicals Company
Sauget, Illinois
PPG Industries, Inc.
Chemicals Group
Industrial Chemical Division
Natrium, West Virginia
Specialty Organics Inc. -
Irwindale, California processor - (see note)
Standard Chlorine Chemical Company, Inc.
Delaware City, Delaware
Note: Producers manufacture a variety of chlorinated benzenes;
processors purchase a mixture of chlorobenzenes and
isolate specific dichlorobenzene isomers. 'This listing is
subject to change as market conditions.change, facility
ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by
consulting current listings and/or the plants themselves.
The level of chlorobenzene emissions from any given
facility is a function of variables such as capacity,
throughput and control measures, and should be determined
through direct contacts with plant personnel.
32
-------
process details are not available. Contact should be made with specific
plants to determine manufacturing processes used on site.
Emissions
Trichlorobenzene emissions released during the continuous product
process (Figure 4) result from storage (C) and handling (D) of tri-
chlorobenzene products. Fugitive emissions of TCBs may also occur when
leaks develop in valves, pump seals, and major equipment (F). Secondary
emissions from MCB production (Figure 3) are also possible from vola-
tilization of TCB from waste water stream (H) containing dissolved
benzene and other VOCs, and the catalyst waste stream (l).2^ No infor-
mation was available concerning identification of specific TCB isomers.
Source Locations
Table 8 summarizes the locations of plants which manufacture
• specific isomers of TCB.
Process Description; Hexachlorobenzene
Although hexachlorobenzene production has been discontinued in the
United States, literature cites two basic direct synthesis methods
available for HCB production which are: (1) the reaction of hexachloro-
cyclohexane isomers with sulfuryl chloride or chlorosulfonic acid and
(2) the reaction of benzene with chlorine in the presence of ferric
chloride.24
HCB is produced by refluxing hexachlorocyclohexane (CgHgClg)
isomers with sulfuryl chloride (S02C12) or chlorosulfonic acid (HCISO-J
in the presence of a ferric chloride or aluminum chloride catalyst
(Figure 5). After refluxing for several hours at 130 to 2008C, the
product stream is cooled to promote crystallization. HCB crystals are
then separated by filtration or centrifugation and then washed and dried
for packaging.
HCB is also produced by reacting benzene with excess chlorine in
the presence of ferric chloride at 150 to 200°C (Figure 6). The
product stream is scrubbed to remove hydrogen chloride. Gaseous chloro-
benzenes in the stream are returned to the reactor, while the remaining
reaction products are cooled to less than 100°C to crystallize HCB. The
HCB is then separated by centrifugation, washed, dried, and packaged.24
33
-------
TABLE 8. CHEMICAL PRODUCERS OF TRICHLOROBENZENE - 198423
1.2.3-Trichlorobenzene
Standard Chlorine Chemical Company, Inc.
Delaware City, Delaware
1.2.4-Trichlorobenzene
Standard Chlorine Chemical Company, Inc.
Delaware City, Delaware
1.3.5-Trichlorobenzene
Southland Corporation
Chemical Division
Great Meadows, New Jersey
Mixed Isomers
PPG Industries, Inc.
Chemicals Group
Industrial Chemical Division
Natrium, West Virginia
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
34
-------
LO
t_n
C6H6C16
Isomers
Chlorosulfonic Acid
or Sulfuryl Chloride
Reflux-
Condenser-
Reactor with FeCl
as Catalyst
Drying
Packaging
Shipment of
Hexachlbrobenzene
Figure 5. Production schematic for hexachlorobenzene from hexachlorocyclohexane.2^
-------
GJ
a\
Cl,
C6H6
Primary Reactor
with Fed-
as Catalyst
Separation
Drying
Packaging
Shipment of
Less Chlorinated
Benzenes
Byproduct
HC1
Scrubber
Crystallizer
Partially Chlorinated Benzenes
Centrifuge
Drying
and
Packaging
Shipment of
Hexachlorobenzene
Figure 6. Production schematic for hexachlorobenzene by chlorination
of benzene.
-------
No information was found in the literature to suggest that either
of these reactions has been used commercially to produce HCB. The most
common method of HCB generation is by recovering it from the waste
byproduct streams in chlorinated solvents production. Recovery of HCB
as a byproduct of chlorinated solvent production is discussed in the
section entitled "HCB Generation during Chlorinated Solvent
Production."
Emissions
No information is available concerning emissions from either method
of direct production of HCB.
Source Locations
Commercial production of HCB in the United States was discontinued
around 1975. In the literature, three companies at three'locations were
identified to be producing HCB at some time as a product chemical.
These companies were Dover Chemical, Dover, Ohio; Hummel Chemical, South
Plainfield, New Jersey; and Stauffer Chemical, Louisville, Kentucky.
Reportedly, Hummel Chemical only repackaged and distributed HCB produced
by Dover Chemical. Regardless of the exact number of producers, it is
known that all companies manufactured HCB by recovering it from waste
byproduct streams generated by chlorinated solvents production. *
According to information received from HCB users, there is little
HCB still produced worldwide. One HCB fungicide manufacturer in Canada
reported that he had only been able to locate one supplier of HCB
anywhere and this was located in Spain.
37
-------
USE OF CHLOROBENZENES IN THE PRODUCTION OF DYES AND PIGMENTS
The uses of chlorobenzenes in the dye and pigment industry are two-
fold: (1) to synthesize other intermediates which are subsequently
utilized in the formation of specific dyes and pigments; and (2) as
inert process solvents in dye and pigment manufacturing. The following
describes the use of chlorobenzenes in each of the above applications.
The Ecological and Toxicological Associates of the Dyestuffs Manufactur-
ing Industry indicates that the process information mentioned below is
outdated; however no new information was provided.
Use of Chlorobenzenes in the Synthesis of Intermediates
The chlorobenzene group is one of many classes of compounds used to
synthesize intermediates in the dye and pigment industry. Chloroben-
zenes are normally purchased outside of the industry, converted into
more complex intermediates and ultimately into dyes and pigments. Some
of the intermediates may be dyes themselves so that the distinction
between them and dyes and pigments is somewhat arbitrary. Figures 7
through 10 show the various reactions involving chlorobenzenes.
Process Description—
In the dye and pigment industry, reactions for the production of
intermediate dyes are generally carried out in kettles made from cast
iron, stainless steel, or steel lined with rubber, glass (enamel),
brick, or carbon blocks. The kettles have capacities of 500 to 10,000
gallons and are equipped with mechanical agitators, thermometers or
temperature recorders, condensers, pH probes, etc., depending on the
nature of operation. Jackets or coils serve to heat by circulation of
high-boiling fluids (hot oil, Dowtherm*), steam or hot water. The
kettles may be cooled with chilled brine. Unjacketed kettles are often
used for aqueous reactions where heating is effected by direct introduc-
tion of steam and cooling is effected by addition of ice or by the use
27
of heat exchangers.
Products are transferred from one piece of equipment to another by
gravity flow, pumping, or by blowing with air or inert gas. Solids are
separated by either centrifuges, filter boxes, continuous belt filters,
and either plate-and-frame or recessed plate filter presses.
38
-------
Chlorobenzene
LO
VO
C1S03H
MeS03H
HNOo
HS0
24
HNOo
H2S04
4-Chlorobenzene- -
sulfonyl chloride
1-Chlorobenzene-
4-methy leuIfone
l-Chloro-2-
nitrobenzene
l-Chloro-4-
nitrobenzene
l-Chloro-2,4-
dinitrobenzene
Zn,
NH,
HNO
o
4-Chlorobenzene-
sulfinic acid
4-Chlorobenzene-
sulfonamide
4-Chloro-2-nitro-
benzenesulfonyl chloride
Figure 7. Dye intermediates derived from monochlorobenzene.
26
-------
Oleum HN03 Red'n
o-Dichlorobenzene 3,4-Dichloro- 4,5-Dichloro-2-nitro- 2-Amino-4-5-dichloro-
benzeneaulfonic benzenesulfonic acid benzenesulfonic acid
acid
Figure 8. Dye intermediate derived from o-dichlorobenzene
-------
COC1,,
p-Dichlorobenzene•
2,5-Dichlorobenzoic
acid
UNO,
Red'n
Oleum
UNO,
-2, 5-Dichloronitro-
benzene
2, 5-Dicliloroaniline ^- 2, 5-Dichlorosulf-
anilic acid Red'n
Diketene
2,5-Dichloro-4-hydra-
zinobenzeneBulfonic
acid
JleOH
HaDH
NaOH
Nil,
4-Chloro-2-nitro-
anisole
4-Chloro-2-nitro-
phenol
-4-Cliloro-2-nitro
aniline
l-(2, 5-Dichloro-4-
sulfopheny D-3-
metliy 1-5-pyrnzolone
Red'n
BON
•3-Chloro-o-
anisidine
5'-Chloro-3-hydroxy-
2-naphtho-o-anisidide
ONII,
Red'n
4-Anilino-2-nitro-
anisole
3-Anilino-o-anisidine
HNOo
Red'n
-^-4-Chloro-2,6-
dinitrophenol
2-Amino-4-chloro-6
nitrophenol
Red'n
2-Amino-4-chloro-
phenol
' *• 2-Amino-4-chloro-
phenol-S-sulfonic
acid
Red'n
— ^- 4-Chloro-o-phenyl-
enediamine
PJguvu 0. nyc Intermediates derived Prom p-diclilorohonzcnc.26
-------
1,2, 4-Trichloro--
benzene
2,4,5-Trichloro-
nitrobenzene
Red'n
2, 4, 5-Trichloroaniline
-_Mefi!L
NaOIl
-4,5-Dichloro-2-methoxy-
nitro-benzene
HeOIL
NaOH
•5-Chloro-2,4 Dimethoxy-
nitrobenzene
Red1
• 5-Chloro-2,4-di *-5'-Chloro-3-hydroxy-2'-,
methoxyaniline 4'-dimethoxy-2-
naphthanilide
Figure 10. Synthesis of various intermediates for dye and pigment .production from 1,2,4-trichlorobenzene.26
-------
When possible, intermediates are taken for subsequent manufacture
without drying. When drying is required, air or vacuum ovens, rotary
dryers, or spray dryers are used. Drum dryers (flakers) may also be
used, although less commonly: -Dyestuffs which require wet grinding,
especially disperse dyes, are often spray dried with solid diluents to
achieve standardization.
Small tonnages of numerous intermediates needed exclusively by the
dye industry have made continuous processes impractical. Batch pro-
cesses remain the rule but progress in computer and electronic technolo-
27
gies has led to a growing use of automatic process control.
Use of Chlorobenzenes as Process Solvents
Chlorobenzenes find uses as inert process solvents in the
production of a number of dyes and pigments. In Table 9, dyes and
pigments which use specific chlorinated benzenes as solvents are
categorized into dye or pigment classes according to the nature of their
chemical structure. Individual dyes and pigments within a class are
produced by the same processes as described below.
Description of Process Using MCB—
MCB is used as a process solvent in the manufacture of seven
indigoid dyes and pigments. Of these, six are thioindigoid colors and
one is a hybrid of indigo (C.I. 73000) and a specially made intermediate
structurally related to the thioindigo colors. Due to the corrosive
nature of the reactants involved in these processes, glass-lined vessels
28
and efficient stirring are required.
The manufacture of the thioindigoid colors involves two process
steps, one of which is a diazotization. Because low temperatures are
required, ice is used in substantial quantities. Temperature conditions
range from 0 to 70°C.28 Information regarding these processes is some-
what limited.
In the production of the hybrid dye, one of the reaction steps is
exothermic and must be maintained below 17°C to obtain a high yield.
Another reaction requires a temperature of 125°C, using MCB as the
28
process solvent.
43
-------
TABLE 9. DYES AND PIGMENTS UTILIZING CHLOROBENZENE SOLVENTS
Chlorobenzene
Solvent
Monochlorobenzene
.
o-Dichlorobenzene
1 , 2, 4-Trichlorobenzene
Dye or
Pigment Class
Thioindigoid
Thioindigoid
Thioindigoid
Thioindigoid
Thioindigoid
Thioindigoid
Indigoid
Xanthene
Oxaz ine
Oxazine
Pyranthrone
Anthraquinone
Anthraquinone
Anthraquinone
Anthraquinone
Anthraquinone
(oxazole)
Benzanthrone
Antraquinone
Anthraquinone
Anthraquinone
Anthraquinone
Color
Index
(C.I.)
73310
73312
73335
73360
73385
73390
73670
45180
51300
51319
59700
61725
63365
65049
68420
67000
59825
61725
63365
65049
68420
Dye or
Pigment Name
Pigment Red 87
Pigment Red 88
Vat Orange 5
Vat Red 1,
Pigment Red 181,
D+C Red 30,
Vat Violet 2
Pigment Violet 36
Pigment Red 198
Vat Black 1
Mordant Red 27
Direct Blue 106
Pigment Violet 23
Vat Orange 9
Vat Yellow 3
Vat Violet 17
Pigment Yellow 123
Pigment Yellow 108
Vat Red 10
Vat Green 1
Vat Yellow 3
Vat Violet 17
Pigment Yellow 123
Pigment Yellow 108
44
-------
Description of Process Using o-DCB—
o-DCB is used as a process solvent in the production of one
xanthene dye, one oxazine dye, one oxazine pigment, one pyranthrone dye,
and five anthraquinone dyes. In addition, these dyes may be used to
produce other related dyes and pigments by halogenation.
As many as three process steps may be required in the production of
xanthene dyes.29 The required reactions are carried out in glass-lined
batch reactor vessels with continuous stirring under atmospheric pres-
sure. o-DCB is used as a process solvent to make the xanthene dye with
a color index of 45180 (Mordant Red 27). The initial condensation
reaction is carried out with a 100 percent stoichiometric excess of
sulfuric acid which is later recovered.
The initial condensation reaction in zanthene dye production is
carried out with 5-hydroxytrimellitic acid and a 100 percent stiochio-
metric excess of sulfuric acid which is later recovered. m-Diethyl-
aminophenol is added gradually to the other reactants over a period of 3
hours at 150 to 180°C. Cyclization of the intermediate product is
accomplished with 78 percent sulfuric acid at 175-to 180°C for 3 hours.
The manufacture of oxazine dyes and pigments involves the
condensation of a substituted aniline compound with a substituted
phenolic compound (or a phenol ether), followed by an oxidative reaction
which forms the oxazine ring system.30 Stirred batch reactors with
glass linings are required for most of the reactions involved in making
these products. The oxazine pigment (C.I. 51319) is produced by con-
densing chloranil with 3-amino-9-ethyIcarbazole using sodium acetate as
catalyst. o-DCB is used as the process solvent in the reaction which
requires 7 hours at 60 to 115°C. The condensation product is cyclized
(refers to ring formation) to the pigment with benzenesulfony1 chloride
at 180°C. The crude pigment is subsequently washed and filtered. o-DCB
is also used as a process solvent in the manufacture of an oxazine
pigment (C.I. 51300); however, no specific process information was
available.
Pyranthrone (C.I. 59700) can be made from either l-chloro-2-
methylanthraquinone or pyrene as the principal organic starting
material.3* Glass-lined, stirred reaction vessels are required due to
45
-------
the corrosive nature of the reactants. o-DCB is used as a process
solvent in this process. The dimerization of the l-chloro-2-methy 1-
anthraquinone takes place at 150 to 160°C in 6 hours while cyclization
to the dye requires a further 3 hours at the same temperature.
Of the five anthraquinone dyes which use o-DCB as a process
o f%
solvent, four are amides of aminoanthraquinone compounds. The amides
are made by the reaction of an aromatic carboxylic acid chloride with
the selected amino compound at temperatures between 50 and 160°C.
Glass-lined reactor vessels are required along with good stirring.
Cooling of the exothermic reacting mixture may be necessary as the
starting materials are combined. An inert organic solvent is required
for this process which dissolves the starting materials well and has a
high boiling point. o-DCB and TCB are typically used here.
The other anthraquinone dye which uses o-DCB as a pro.cess solvent
is an oxazole compound (with C.I. 67000) and is made from 2-amino-3-
hydroxy anthraquinone. ' Batch type reaction vessels made of iron and
with good stirrers are typically used. In addition, the reactor must
have a cooling coil to remove heat generated by the moderately exo-
thermic first reaction between the aminoanthraquinone and the acid
chloride. The cyclization of the resulting amide to the desired oxazole
is carried out in o-DCB at 140°C in 5 hours.
Description of Process Using TCB—
TCB is used as a process solvent in the halogenation of dyes and in
the production of benzanthrone dyes. The halogenated product is
obtained by treating the simple dye itself with a halogen or a halogen
carrying compound. These reactions can usually be carried out in iron
equipment provided that moisture is rigorously excluded; however, glass-
lined equipment is often used. Water scrubbers are generally used to
trap the effluent hydrogen halide which is formed in most cases. Of the
halogen used, only half appears in the product with the remainder being
converted to the hydrogen halide. A compound which typically functions
as a halogen source is sulfuryl chloride. When this compound is used,
both sulfur dioxide and hydrogen chloride are by-products. Halogena-
tions are generally carried out at temperatures in the range of 40 to
55°C although some cases require temperatures as high as 155 to 190°C.
46
-------
TCB is known to be used as a process solvent in the production of a
o e
benzanthrone dye commonly called Vat Green 1 (C.I. 59825). Iron
vessels with good stirring may be used. The manufacture of benzanthrone
dyes depends on the modification of the primary intermediate,
benzanthrone. In order to make Vat Green 1, three process steps are
required. The alkali treatment of benzanthrone to make dibenzanthrony1
takes place at 112°C for 1 to 4 hours. The dibenzanthrony 1 is then
oxidized to the diketo compound at 25 to 30°C for 4 hours. The methyla-
tion of the dihydroxy compound is achieved by reducing the diketo com-
pound with boiling sodium bisulfite at 210°C for 4 hours.
As noted in the discussion on the amide production of anthraquinone
dyes, TCB is often used as a process solvent.
Emissions
Emission factors for the use of o-DCB in dye synthesis appear in
Table 10. Literature information does not distinguish between emissions
resulting from the synthesis of intermediates or process solvent usage.
Information regarding the nature and quantities of air emissions of
other chlorobenzenes produced during dye and pigment manufacture was not
available. The reader is advised to seek emissions data through contact
with specific plant personnel.
Source Locations
A list of dye and pigment manufacturers which may utilize chloro-
benzenes in certain processes is contained in Table 11. The Ecological
and Toxicological Association of Dyestuffs Manufacturing Industry indi-
cates that this list is outdated and does not reflect the major restruc-
25
turing which has occurred in the industry during recent years. No new
information was provided, however. Ciba Geigy of Greensboro, North
Carolina, reports to have used chlorobenzenes as process solvents but
has discontinued the production of vat dyes (anthraquinone type) which
utilized them.-*7
47
-------
TABLE 10. EMISSION FACTORS FOR 0-DICHLOROBENZENE IN DYE SYNTHESIS22
Emission category kg o-DCB emitted per Mg dye produced
Process 0.40
Storage 0.05
Fugitive 0.05
TOTAL 0.50
Note: These emission factors are only general estimates. No
information is available on specific emission points
included in each emission category, the type of production
processes used, or specific control technologies employed,
if any. Any given dye synthesis plant may vary in con-
figuration and level of control from this hypothetical
facility. The reader is encouraged to contact plant per-
sonnel to confirm the existence of emitting operations and
control technology at a particular facility prior to esti-
mating emissions therefrom.
48
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TABLE 11. DYE AND PIGMENT MANUFACTURING COMPANIES - 198436
New Jersey
1. American Cyanamid Company
Organic Chemicals Division
Wayne, New Jersey
2. Atlantic Industries
Nutley, New Jersey
3. BASF Wyandotte Corporation
Paper Colors and Chemicals Department
Parsippany, New Jersey
Pigments Division
Parsippany, New Jersey
4. Buffalo Color Corporation
West Paterson, New Jersey
5. Cplor-Chem International Corporation
Glen Rock, New Jersey
6. Chem-Mark, Inc.
Bound Brook, New Jersey
7. Dye Specialties Inc.
Secaucus, New Jersey
8. Fabricolor Inc.
Paterson, New Jersey
9. Eeubach Inc.
Newark, New Jersey
10. Indol Color Company, Inc.
Elizabeth, New Jersey
11. International Dyestuffs Corporation
Clifton, New Jersey
12. Leeben Color
Division of Tricon Colors, Inc.
Elmwood Park, New Jersey
(continued)
49
-------
TABLE 11. (continued)
New Jersey (continued)
13. Mobay Chemical Corporation
Dyes and Figments Division
Union, New Jersey
Dyes and Pigments Division
Pigments Department
Hawthorne, New Jersey
14. Passaic Color and Chemical Company
Paterson, New Jersey
15. Pfister Chemical Inc.
Ridgefield, New Jersey
16. Pope Chemical Corporation
Paterson, New Jersey
North Carolina - South Carolina
1. American Hoechst Corporation
Specialty Products Group
Dyes and Textile Chemicals Department
Charlotte, North Carolina
2. BASF Wyandotte Corporation
Colors and Auxilaries Division
Charlotte, North Carolina
3. Carolina Color & Chemical Corporation
Charlotte, North Carolina
4. Ciba-Geigy Corporation
Greensboro, North Carolina
5. Crompton & Knowles Corporation
Charlotte, North Carolina
6. Crown Metro Inc.
Greenville, South Carolina
7. C.H. Patrick & Company, Inc.
Greenville, South Carolina
(continued)
50
-------
TABLE 11. (continued)
North Carolina - South Carolina (continued)
8. Sandoz Colors and Chemicals
Charlotte, North Carolina
9. Sodyeco Inc.
Charlotte, North Carolina
10. Synalloy Corporation
Blackman Uhler Chemical Division
Spartanburg, South Carolina
Ohio
1. Day-Glo Color Corporation
Cleveland, Ohio
2. Sterling Drug Inc.
Hilton-Davis Chemical Group
Cincinnati, Ohio
3. Sun Chemical Corporation
Cincinnati, Ohio
New York
1. Bern Colors - Poughkeepsie Inc.
Poughkeepsie, New York
2. Chemische Fabric Rohner AG
Hauppauge, New York
3. Pylam Products Company, Inc.
Garden City, New York
Pennsylvania
1. Allegheny Chemical Corporation
Ridgeway, Pennsylvania
2. John Campbell & Company, Inc.
Perkasie, Pennsylvania
(continued)
51
-------
TABLE 11. (continued)
Pennsylvania (continued)
3. C. Lever Company, Inc.
Bensalem, Pennsylvania
Miscellaneous
1. Carroll Products Inc.
Wood River Junction, Rhode Island
2. Carey Industries Inc.
Danbury, Connecticut
3. Eastman Chemical Product, Inc.
Kingsport, Tennessee
4. GCA Corporation
Stamford, Connecticut
5. ICI Americas Inc.
Wilmington, Delaware
6. Morton Thiokol, Inc.
Morton Chemical Division
Chicago, Illinois
7. Organic Chemical Corporation
East Providence, Rhode Island
8. Warner-Jenkinson Company
St. Louis, Missouri
Note: This listing is subject to change as market conditions
change, facility ownership changes, plants are closed,
etc. The reader should verify the existence of particular
facilities by consulting current listings and/or the
plants themselves. The level of chlorobenzene emissions
from any given facility is a function of variables such as
capacity, throughput and control measures, and should be
determined through direct contacts with plant personnel.
52
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USE OF CHLOROBENZENES AS SOLVENTS IN ORGANIC SOLVENT CLEANING OPERATIONS
Chlorobenzenes are employed as cleaning and degreasing agents in
solvent cleaning operations to remove water-insoluble soils from metal,
plastic, fiberglass or other surfaces. o-DCB is contained in automobile
cleaners; carburetor cleaners; in formulations to remove paints, inks,
varnishes, lacquers, resins, gums, waxes, heavy greases, acetylcellu-
lose, sulfur and organic sulfur compounds, and tarry substances in
stills and processing equipment; shoe polish; metal polish; rust pre-
•J Q
ventatives; and other cleaning/polishing formulations. ° 1,2,4-TCB is
used in degreasing formulations for electronic wafer stripping in the
electronic components industry and engine cleaning.
Many cleaning processes are performed in organic solvent cleaners
using solvent formulations which include chlorobenzenes. Table 12 com-
pares properties of known solvents used in degreasing with properties of
chlorobenzenes. Organic solvent cleaning (degreasing) is used in manu-
facturing processes in preparation for painting, plating, inspection,
repair, assembly, heat treatment or machining. Types of organic solvent
cleaners which may utilize chlorobenzenes include cold cleaners and
conveyorized degreasers.
The simplest and least expensive organic solvent cleaners are cold
cleaners which use solvents at room temperature. A cold cleaner usually
consists of a tank containing non-boiling solvent and a draining surface
or basket. Typical operations are spraying, flushing and immersion
using room temperature or slightly heated solvent solution made up of a
petroleum-derived solvent, halogenated solvent or a solvent blend. A
blended solvent used in carburetor and automobile parts marketed by
Safety-Kleen Corporation contains methylene chloride, o-DCB, and
cresylic acid, covered by an aqueous soap solution. Two basic cold
cleaner designs are the conventional cold cleaner (dipping tank) shown
in Figure 11 and the remote reservoir cold cleaner. In the remote
reservoir cold cleaner, parts are sprayed in a work space which drains
to an enclosed reservoir, preventing evaporative loss. Agitation by
means of pumping, compressed air, vertical agitation or ultrasound
increases cleaning efficiencies of dip tanks.
53
-------
TABLE 12. PROPERTIES OF HALOGENATED SOLVENTS USED IN ORGANIC SOLVENT CLEANERS^0
Ln
Solvents
Most widely used
Trichloroethylene
Perchloroethylene
1,1, 1-Trichloroethane
Methylene Chloride
Trichlordtrif luoroethane
Boiling
point
(°C)
86.7
120.8
74.1
39.8
47.6
Vapor Vapor
pressure density
(nunHg @ 25°C) (Air = 1.0)
75.0 4.5
18.6 5.7
123.0 4.6
438.0 2.9
796.0 6.5
Molecular
weight
131.40
165.85
133.42
84.94
187.0
Weight
density
(kg/1)
1.45
1.61
1.31
1.32
1.58
Water
solubility
(g/lOOg)
0.107 (20°C)
0.015 (25°C)
0.095 (20°C)
1.32 (20°C)
0.017 (25°C)
Chlorobenzenes*
o-Dichlorobenzene
1, 2,4-Trichlorobenzene
1,3, 5-Trichlorobenzene
1 , 2, 3-Trichlorobenzene
180.5
213.0
208.0
218.0
1.45 5.1
0.29
0.15
0.07 .
147.0
181.5
181.5
181.5
1.31
1.46
1.45 (20°C)
insol.
insol.
insol.
*Note: MCB is not used as a cleaning solvent.
-------
Cover
Basket
Solvent
Cleaner
Pump
Figure 11. Cold cleaner.
41
55
-------
Conveyorized degreasers are continuous or batch loading units which
employ a cold cleaner. The units are enclosed to prevent solvent losses
due to air movement in the plant. Seven types include monorail, cross-
rod, vibra, ferris wheel, belt, strip, and circuit board cleaners.
The circuit board degreaser is similar to the belt degreaser shown
in Figure 12, which is designed to clean long and thin parts. The
three types of cleaners used in production of circuit boards are
developers, strippers and def luxers. In the process, ultraviolet light
in the pattern of an electrical circuit is projected onto a copper sheet
covered with resist (a photosensitive material with special properties).
The image of the circuit pattern exposes the resist causing it to bond
to the surface of the metal. A developer degreaser is employed to
dissolve the unexposed resist; unexposed copper is removed by etching in
an acid bath. At this time, the stripper (containing 1,2,4-TCB) dis-
solves the developed resist and a wave of solder passes over the bare
circuit bonding to it. The defluxer removes flux left after the solder
hardens. Depending on the nature of the materials cleaned, circuit
board cleaners use either room temperature solvents or vapors.
No further information exists on the actual quantities of
chlorobenzenes used or specific processes or equipment which are
employed for the uses of chlorobenzenes as cleaning solvents.
Emissions
Types of emissions produced by cold cleaning include those gen-
erated by bath evaporation to surrounding air, solvent carry-out of
cleaned parts, agitation, waste solvent evaporation and spray
evaporation. Emissions associated with conveyorized degreasers result
from the same processes but to a lesser degree because of the nearly
complete enclosure of the conveyorized system. Some emissions are also
expected from evaporation of blended cleaning solvents during mixing and
handling.
Uncontrolled emissions from degreasers can be approximated by
material balance by assuming that the quantity of makeup solvent is
equal to the amount of solvent evaporated from the process, over the
long term. To estimate emissions after controls by material balance,
the quantity of solvent collected or destroyed in control devices, and
56
-------
Conveyor
Path
Ul
Mesh
Belt
Figure 12. Mesh belt conveyorized degreaser.
41
-------
not recycled to the process, must be subtracted from the quantity of
makeup solvent. One source estimates the average emission rate for a
cold cleaner unit is 289 kg per year assuming 2250 hours per year.^
Emission control technologies and practices employed by organic solvent
degreasing and their removal efficiencies are listed in Table 13.
Although chlorobenzenes are expected to contribute to degreaser
emissions, it should be noted that significant use of chlorobenzenes as
primary degreasing solvents has not been documented. Chlorobenzenes, by
themselves, are not used as solvents, but rather, probably only occur in
solvent mixtures. Moreover, the quantities of chlorobenzenes used in
solvent mixtures are not likely to be very large. ^ The reader is
encouraged to contact local plant personnel for information on specific
processes, solvent formulations emissions and control technologies.
Source Locations
Organic solvent cleaners which use halogenated solvents are
utilized in the production and maintenance of nearly all metal-based
commodities. The five principal industries which employ the use of each
organic solvent cleaner type are listed in Table 14.
58
-------
TABLE 13. ORGANIC SOLVENT DEGREASER CONTROL EQUIPMENT
,a,44
VOC Emissions During
Operation
Percent of Total
Source VUG Emissions
Cold Cleaner Bath evaporation
Solvent carry-out
20
25
Control Equipment
Demonstrated
Device Efficiency (%)
Cover 92b
Drain racks 50
Ventilation exhaust 60-90
Waste solvent
disposal
55
system to carbon
adsorber
Holding tank
Still
Suitable disposal
>85Z by volume
vo
Cold Conveyorized
Degreaser
Bath evaporation
Solvent carry-out
Waste solvent
disposal
85
15
Entrance & exit area covers
Water separator
Drying racks
Drying tunnel
Ventilation exhaust
system (including above
devices) to carbon
adsorber
Still (built-in or external)
60
aChlorobenzenes, by themselves, are not used as solvents, but rather, probably only occur in solvent
mixtures. Moreover, the quantities of chlorobenzenes used in solvent mixtures are not likely to be very
large. Tims, the percent of VOC emissions represented by chlorobenzenes will not be very large.
With cover in place all but 2 hours per day for 5 days per week.
-------
TABLE 14. PRINCIPAL INDUSTRIAL USERS OF ORGANIC SOLVENT CLEANERS - 1980a>40
Standard
industrial
classification
I. Cold Cleaners0
753 Auto repair
359 Misc. machinery, except electrical
354 Metalworking machinery
458 Air transport - maintenance
356 General industrial machinery
Subtotal
Overall total
II. Convevorized Degreasersc
356 General industrial machinery
372 Aircraft and parts
366 Communication equipment
364 Electric lighting and wiring
339 Misc. primary metal products
Subtotal
Overall total
Estimated
no. of
cleaners
(1980)
557,300
92,200
45,500
45, 500
35,900
776,400
1,077,400
470
430
370
330
290
1,890
4,990
Percentage
of overall
total
51.7
8.5
4.2
4.2
3.3
72.1
100.0
9.4
8.6
7.4
6.6
5.8
37.9
100.0
Chlorobenzenes, by themselves, are not used as solvents, but rather, probably only occur in solvent
mixtures. Moreover, the quantities of chlorobenzenes used in solvent mixtures are not likely to be very
large. 5
''Each industry group is preceded by a 3 digit SIC code which represents that group.
"Includes cold cleaners using both halogenated and non-halogenated solvents.
-------
USE OF MONOCHLOROBENZENE AND 0-DICHLOROBENZENE AS DYE CARRIERS IN
TEXTILE DYEING
Monochlorobenzene (MCB) and o-dichlorobenzene (o-DCB) are effective
dye carriers in the coloring of textile products.11'46 Dye carriers, or
dyeing accelerants, are used to promote dye migration and transfer to
produce even and satisfactory dyeings. They may be used on cellulose
triacetate fibers but are typically used on polyester. The choice of a
particular dye carrier often may be based on availability, cost,
toxicity, ease of handling, and so on.
Carrier selection is governed primarily by the carrier's boiling
point. It must be high enough so that evaporation or steam distillation
of the carrier does not occur at the dyeing temperatures, and low
enough so that it may be removed from the fabric under plant drying
conditions. Since dye carriers have little or no solubility in water,
emulsifiers are needed to disperse the carrier in the dye bath. Many
carriers are available in the pre-emulsified form. As a general rule,
stronger carriers, including phenolic and chlorinated aromatic com-
pounds, are used in open equipment, at a boil, while weaker carriers are
used in high temperature dyeing.
Process Description
Dyeing procedures vary with the textile fiber content and the
equipment used.46 Two carrier dyeing procedures for 100 percent
polyester fabrics are described below.
Procedure 1 — The dyebath is prepared by adding water conditioning
chemicals for proper water hardness. Dyes are combined with cold water
to form a paste which is diluted with warm water (70°C), and then added
to the bath containing the fabric. Mixing is initiated for 10 minutes
and 5 to 10 grams per liter of carrier are added according to manu-
facturers instructions. The pH is adjusted to 5 with acetic acid. The
bath is brought to a boil over 30 to 45 minutes, boiled for 1 hour, and
then cooled slowly. After cooling, the materials are rinsed completely
and further processed to remove residual carrier and unfixed dye.
61
-------
Procedure 2 — The dye bath is prepared in a similar manner to that
presented in procedure 1. After adjusting the pH, both dye dispersant
and 1 to 3 grams of carrier per liter of dye bath are added. The
temperature is then raised from 50 to 88°C at the rate of 2°C per
minute. The equipment is then pressure sealed, and the temperature is
raised at the rate of 1°C per minute until it reaches ,130°C. This
temperature is maintained for 1/2 to 1 hour, depending on the desired
shade, and then cooled to 82°C at 1 to 2°C per minute. After depr.es-
surization the material is processed as in procedure 1.
Emissions
Possible sources of pollution and control methods for dye carriers
are shown in Figure 13. No quantitative emissions data for the textile
dyeing industry are available. The reader is encouraged to contact
plant personnel to confirm the existence qf emissions and control tech-
nology to estimate emissions for a specific source.
Source Locations
A listing of the plants involved in the dyeing of cellulose
triacetate fibers and polyesters was not available. The Standard
Industrial Classification (SIC) codes for establishments engaged in the
dyeing of man-made fibers are listed below:
• Broad woven fabrics of man-made fiber - 2262
• Raw stock and narrow fabrics of man-made fiber - 2269.
62
-------
CARRIER ACTIVE INGREDIENT
o\
CO
EFFLUENT
COLLECTION
AIR POLLUTION
CONTROL EQUIPMENT
DRYER
HEATSETTING
CHEMICAL and /or BIOLOGICAL
DEGRADATION
Figure 13. Pollution control equipment' - dye carriers.
-------
MANUFACTURE OF CHLORONITROBENZENES FROM MONOCHLOROBENZENE
The largest consumption of MCB in the U.S. is in the production of
chloronitrobenzenes. Major uses of chloronitrobenzenes are as inter-
mediates in the manufacture of dyes, pigments, and pesticides.
Small amounts of chloronitrobenzenes are used directly as starting
materials in dye and pigment production. More often, chloronitro-
benzenes are used to produce further dye intermediates, including
nitroaniline and phenylenediamine. The o-chloronitrobenzene-derived
intermediates shown in Figure 14 are used in the manufacture of specific
nitro and thioindigo dyes and pigments and others which could not be
identified.
Chloronitrobenzenes also are used in pesticide manufacture to
produce other intermediate forms including p-nitroaniline and p-
nitrophenol. p-Nitrophenol is necessary in the manufacture of organo-
phosphate pesticides, parathion, and methylparathion.
Parathion Methylparathion
Process Description
Chloronitrobenzenes are manufactured by the nitration of
monochlorobenzene using a mixed acid solution of nitric acid and
sulfuric acid at 40 to 70°C for 12 hours.47
HN03
H2S04
N02
monochlorobenzene l-chloro-2-nitrobenzene l-chloro-4-nitrobenzene
Input materials to produce 1 metric ton of combined chloronitrobenzenes
include 4536 kg of MCB and 9570 kg of combined 30 to 35 percent nitric
acid and 52 to 55 percent sulfuric acid. The product mixture at the end
of 12 hours is comprised of (34%) ortho- and (65%) para-chloronitro-
benzenes.
64
-------
l-Chloro-2-nitro-
benzene
Zn
Ui
NaOll
C1S03H
_Na2S2.
-NaOH-
MeS03H
3,3'-Dichlorobenzi-
dine dihydrochloride
4-Chloro-3-nltrobenzene
.sulfonyl chloride —
4-Chloro-3-nitro-
•benzenesulfon—
amide
4-Chloro-3-nitrobenzene-
.sulfonanilide
4-Chloro-H-methyl-3-
nitrobenzenesulCon-
amide
4-Chloro-N, ^l-dilnethyl-
3-nitrobenzene8ul£on-
amide
bis-(2-Nitrobenzene)
'disulfide
H20
2-Nj trobenzene-
"aulfonic acid
Red'n
2-Aminobenzene-
eulfonic acid
.o-Nitrophenol
4-Chloro-3-nitro-
• plieny Imethy 1—
sulfone
•Continued (Figure 14b)
-Continued (Figure 14c)
Figure I4a. Synthesis of various intermediates for dye and pigment production from o-cbloronitrobenzene.
26
-------
l-Chloro-2-
nitrobenzene
(from Figure Ua)
HaOII
HeOH
• 2-Methoxynitro-
beosene
Oleum
O\
O\
t I
4-Hathoxy-3-nltro-
benzeneaulfonic
acid
Red'n
o-Anliidine
3-A»lno-4-»ethoxy-
benteneaulfonic
acid
CH
UNO,
4,4'-Cyclohexyl-
idenedi-o-
aniaidine
4-Hitro-o-
•nitidin*
5-NUro-o-
•nisidinc
Aceto-o-—
•nUididc
UNO,
«. 4-Nitro-2-«ceto«nl«ide
4 S-nitro-2-ecetoani«idide
CIUO
MaUSO
o-Anlaid inome thane-
aulfonic acid
3-A»ino-4-»ethoxy-
benceneaulfonic acid
S-Amino-4-Bethoxy-
2-nitrobenEene-
lulfonic acid
COC1.
5,5'-UreylenebU
(4-Bethoxy-2-nltrobenzene-
aulfonic acid)
Red'n
5.5'-Uteyl-
enebia-(2-
amino-4-
methoxy-
benzene-
•ulfonic
acid)
Diketene
Acetoacet-o-
aniaidld*
4-"itro-o-aniaidlne
24
2.4-Dlanlno-
dianlnoaniaole
Alk
4|ll?__^o-Dl.ni.idin.
Zn.NaOII diliydroclilotide
* „ 3,3"-Dlhydroxy-4'.41"-
13 bi-2-naphtho-o-aniaidide
Figure 14b. Synthesis of various intermediates for dye and pigment production from o-chloronitrobenzene
26
-------
l-Chloro-2-
nitrobenzene
(from Figure
Ua)
Red'n
2-Chloroaniline
2-Nitroaniline
4-Chloro-3-nitro-
benzenesulfonic
acid
Diketene
2-Chloroaceta-
nilide
*• Acetoacet-2-
chloroanilide
o-Fhenylenediamine
2-Chloro-4-nitro
acetanilide
NaOH
2-Chloro-4-nitroaniline
1,2,3-Benzo-
triazole
Figure 14c. Synthesis of various intermediates for dye and pigment production from
o-chloronitrobenzene. °
-------
In the separation process the para- isomer is isolated from the
isoiner mixture by recrystallization, while the o-chloronitrobenzene is
purified by rectification. No further information is available on the
manufacturing process.
Emissions
No emissions data are available on the use of MCB in the production
of chloronitrobenzenes. The reader is advised to contact plant per-
sonnel to identify control technology and emissions for a specific plant
process.
Source Locations
p-Chloronitrobenzenes are primarily manufactured by pesticide
companies for use as intermediates in their own processes. Table 15
lists producers of o- and p-chloronitrobenzene in the U.S.
68
-------
TABIJE 15. CHEMICAL PRODUCERS OF 0- AND P-CHLORONITROB ENZ ENES - 198448
E.I. duPont de Nemours & Company, Inc.
Chemicals and Pigments Department
Deepwater, New Jersey
Monsanto Company
Monsanto Industrial Chemicals Company
Sauget, Illinois
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
69
-------
MANUFACTURE OF DIPHENYL OXIDE FROM MONOCHLOROBENZENE
Due to its geranium-like odor, diphenyl oxide (also known as phenyl
ether) finds its major use in the manufacture of perfumed products,
particularly soaps. Other uses are as heat transfer fluids; medicines;
resins for laminated electrical insulation; chemical intermediates for
such reactions as halogenation, acylation, and a Iky lation; and dye
carriers.
Process Description
Diphenyl oxide is typically produced in a continuous flow tubular
reaction system. ^ Chlorobenzene is reacted with aqueous sodium
hydroxide (NaOH), and recycled products (containing phenol and sodium
phenoxide). These reactants are heated to between 275 and 300°C by
passing through a nickel-lined heat exchanger. The reaction temperature
of 400°C is achieved electrically and the reactants are allowed to flow
through the system for 10 to 30 minutes. The reaction must be main-
tained at sufficient pressure (>_ 26.2 MPa (258.6 atm)) to prevent
vaporization which would allow NaCl, NaOH, or phenoxide to be deposited
on the tube walls causing hot spots and excessive corrosion. The re-
sulting two layers from the reaction are: (1) aqueous phenoxide, and
(2) an oily layer consisting mainly of diphenyl oxide and unreacted
Chlorobenzene. Diphenyl oxide is recovered by distillation of this oily
layer.
Emissions
Although quantitative estimates are unavailable, only small
quantities of MCB are believed to be emitted during the diphenyl oxide
manufacturing process. The reader is advised to contact plant personnel
for information concerning emissions and control technology employed for
specific processes.
Source locations
Facilities which are reported in the SRI Directory of Chemical
Producers for 1984 as producers of diphenyl oxide are Dow Chemical,
U.S.A. of Midland, Michigan and Monsanto Industrial Chemicals Company of
Chocolate Bayou, Texas. Monsanto reports that their diphenyl oxide
70
-------
process does not utilize monochlorobenzene. This listing is subject
to change as market conditions change, facility ownership changes,
plants are closed, etc. The reader should verify the existence of
particular facilities by consulting current listings and/or the plants
themselves. The level of chlorobenzene emissions from any given
facility is a function of variables such as capacity, throughput and
control measures, and should be determined through direct contacts with
plant personnel.
71
-------
USE OF MONOCHLOROBENZENE IN THE MANUFACTURE OF DDT
MCB is used in the production of the insecticide dichlorodipheny 1-
trichloroethane (DDT).
Process Description
DDT is produced by the reaction of chloral (or chloral hydrate) and
52
MCB in the presence of
C1 - ^ + CH(OH), + ^ Cl
I 2
cci3
MCB chloral hydrate MCB DDT
The process illustrated in Figure 15 consists of four basic stages:
reaction, separation, processing, and waste control and recovery.
In the "two-stage" reactor, two moles of MCB are reacted with one
mole of chloral (with ^SO^ as a catalyst) to form DDT. Unprocessed
DDT, excess MCB and spent H2SO^ (Stream 1) are extracted from the
reactor and sent to the DDT separator. DDT (Stream 2) is then washed
with sodium hydroxide and water. Final processing of the washed DDT
(Stream 3) includes crystallization, drying, or flaking. It is then
either packaged (Stream 4) or enters a formulation process (Stream 5).
The DDT process contains three waste recovery steps. One step
removes the MCB from the separating and processing streams and recycles
it (Stream 6) to the reaction step. The second step removes acid from
the separator stream, recycles it (Stream 7) to an acid recovery plant
and returns the recovered acid (Stream 8) to the initial reaction step.
Waste acid (Stream 9) is combined with dilute caustic from the DDT
washer (Stream 10) in a neutralized stage. The final step is recovery
C ty
of waste from the clean-up operations (Stream 11).
Emissions
Greatest emissions of MCB during DDT production are from the
recycling vent (A).*1 Due to the insolubility of MCB in water, emis-
sions are also possible from the evaporator and recycling pond (B).
72
-------
VENT
i
VENT
NaOH-
H2O
FLOOR AND
LABS AND WASH-UP DRAINS
MCB-
CHLORAL-
H2S04
CO
EVAPORATOR
AND RECYCLE
WATER POND
BAGHOUSE
LIQUID WASTES
NOTE: The numbers in tills figure refer Co process stremns, as discussed in the text,
and Clio letters designate process vents'. The heavy lines represent final product
streams through the process.
Figure 15. Basic operations that may be used in DDT production.
11
-------
DDT is known to contain monochlorobenzene as an impurity which will
be emitted during shipping, handling, and use. Since all DDT produced
in the U.S. is exported, DDT-related MCB emissions would only be
expected from shipping and handling of DDT. No information was avail-
able concerning actual emission rates from these sources.
Source Locations
No current information is available on the production sites of DDT
in the United States.
74
-------
MANUFACTURE OF 3,4-DICHLOROANILINE FROM 0-DICHLOROBENZENE
An important compound derived from o-DCB is 3,4-dichloroaniline
which is used as an intermediate in the production of an anilide
pesticide and two substituted urea pesticides. Common names for these
pesticides are propanil, diuron, and linuron, respectively. Dow
Chemical also cited usage of 3,4-dichloroaniline as an intermediate for
polyethers and as a cross-linkage agent in epoxy tar products.
Pesticides and production locations are listed in Table 16.
56
Process Description
Commercially, 3,4-dichloroaniline is prepared by the nitration of
o-DCB followed by reduction of the resulting 3,4-dichloronitrobenzene.
In many cases, the nitration operation produces two immiscible layers.
For safety reasons and ease of operation, atmospheric pressures and
temperatures from 0 to 120°C are used. At higher temperatures, com-
peting oxidation reactions become important. Reaction residence times
for nitration range from 1 to 60 minutes. The nitration reaction may be
written as:
Cl
HNO,
H2S04
o-dichlorobenzene
3,4-dichloronitrobenzene
The reduction of 3,4-dichloronitrobenzene may be achieved in two
ways: (1) by employing iron and HC1; and (2) by using hydrogen and a
catalyst with some heating, Other operating parameters are not known.
The reduction reaction may be written as:
HNO,
H2S04
3,4-dichloronitrobenzene
3,4-dichloroaniline
Emissions
Process, storage, and fugitive emission factors for the production
of 3,4-dichloroaniline are given in Table 17. The reader is encouraged
75
-------
TABLE 16. PESTICIDES USING 3,4-DICHLOROANILINE AS AN INTERMEDIATE - 198453»54»55
Scientific Name
Common/Registered
Brand Names
Produceri
Location
Anilide Pesticide
3,4-Dichloropropionanilide
I, I
Propanil
Rohm and Haas Stan
Blue Spruce Company
Rohm and Haas Company
Rohm and Haas Tennessee, Inc.
Vertac Chemical
Bound Brook, NJ
Knoxville, TN
West Helena, AR
Ol
Substituted Urea
Pesticide
3-[3,4-Dichlorophenyl]-l,
1 -dimethyl urea
3-[3, 4-Dichloropheny 1]-1
methoxy-1-methylurea
Diuron
DCMU
PHC
. DuPont Karmex*
Linuron
Afalon
DuPont Lorox*
E.I. DuPont de Nemours & Co., Inc.
Biochemical* Department LaPorte, Tx
E.I. DuPont de Nemours & Co., Inc.
Biochemical* Department LaPorte, TX
East Chicago, IN
Note: This listing is subject to change as market conditions change, facility ownership changes, plants are closed, etc. The
reader should verify the existence of particular facilities by consulting current listings and/or the plants themselves.
The level of chlorobenzene emissions from any given facility is a function of variables such as capacity, throughput and
control measures, and should be determined through direct contacts with plant personnel.
-------
TABLE 17. EMISSION FACTORS FOR THE PRODUCTION
OF 3,4-DICELOROANILINE22
Emission category
kg o-DCB emitted per Mg
3,4-Dichloroaniline produced
Process 1.05
Storage 0.15
Fugitive 0.30
TOTAL 1.50
Note: These emission factors are only general estimates. No
information is available on specific emission points
included in each emission category, the type of production
processes used, or specific control technologies employed,
if any. Any given dichloroaniline production plant may
vary in configuration and level of control from this
hypothetical facility. The reader is encouraged to con-
tact plant personnel to confirm the existence of emitting
operations and control technology at a particular facility
prior to estimating emissions therefrom.
77
-------
-------
to contact plant personnel for information regarding actual emissions
and control technologies employed at specific locations.
Source Locations
Producers of 3,4-dichloroaniline and their locations are given in
Table 18.
78
-------
TABLE 18. CHEMICAL PRODUCERS OF 3,4-DICHLOROANILINE - 19848
Blue Spruce Company
Bound Brook, New Jersey
E.I. duPont de Nemours & Company, Inc.
Chemicals and Pigments Department
Deep Water, New Jersey
Monsanto Company
Monsanto Industrial Chemicals Company
Luling, Louisiana
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
79
-------
USE OF CHLOROBENZENES IN THE MANUFACTURE OF TOLUENE DIISOCYANATE
o-DCB and MCB are used in the manufacture of 2,4-toluene
diisocyanate (TDI) which is primarily used in the production of
urethane.^7 Urethane components derived from TDI are used to
manufacture flexible or semi-flexible foams in furniture, bedding, and
automotive products and rigid polyurethane foams for use as insulation
58
materials in refrigerators, freezers, and water heaters.
In the TDI manufacturing process described below, o-DCB is used as
an inert process solvent. Alternatively, TDI may be produced by a
process which utilizes monochlorobenzene; however, no details are
available concerning this method.
Process Description
TDI is produced by the nitration of toluene followed by the
reduction of dinitrotoluene to form 2,4-toluenediamine which is then
phosgenated to form TDI.^9 The reaction steps are illustrated below:
+ 2 HNO,
H2S04
2H20
toluene
Reaction 2:
N02
2,4-dinitrotoluene
'2 + 6 H,
Catalyst
4H20
dinitrotoluene
2,4-toluenediamine
toluene
diamine
2COC1
phosgene
Heat
4HC1
NCO
2,4-toluene-
diisocyanate
80
-------
A typical TDI plant operates continuously and is integrated with
the production of dinitrotoluene and toluenediamine. The process flow
diagram shown in Figure 16 represents a continuous process using
toluene, nitric acid, hydrogen, and phosgene as input materials. Only
the phosgenation reaction (reaction 3) will be discussed here since it
is the only reaction in the TDI process which involves o-DCB.
Purified toluene diamine (TDA) (Stream 1) is reacted with phosgene
(Stream 2) in the presence of o-DCB solvent (Stream 3) to form crude TDI
(Stream 4). Phosgene is condensed out of the by-product HC1 and subse-
quently recycled to the reactor. The HC1 that goes overhead from the
condenser (Stream 5) may contain trace amounts of phosgene and is there-
fore sent to the phosgene absorber. The crude TDI mixture from the
phosgenation reactor is sent to a distillation column for removal of
phosgene. The phosgene overhead (Stream 6) from this distillation and
the HC1 and trace-phosgene stream (Stream 5) from the reactor condenser
are combined (Stream 7) and sent to a column that absorbs phosgene with
the o-DCB solvent. The solvent is then stripped of phosgene in a
distillation column and recycled to the absorber.
The TDI-DCB solvent mixture (Stream 8) from the phosgene removal
distillation column is sent to a vacuum distillation column to recover
the DCB solvent overhead, which is then recycled to the phosgenation
reactor. The crude TDI (Stream 9) from the bottom of the solvent
recovery distillation column is vaporized by flash distillation to
separate TDI from any polymeric isocyanates that might have been
CQ
formed.
The bulk of commercially used TDI is a mixture of 80 percent 2,4-
toluene diisocyanate and 20 percent 2,6-toluene diisocyanate. However,
a 65:35 mixture and pure 2,4-isomer are also available.
Emissions
Possible o-DCB emissions include the residue separation vacuum jet
vent (A) and the vacuum jet vents (B) associated with solvent recovery
distillation, TDI f lash distil lation, and TDI purification distil la-
tion.59 It is estimated that only a small fraction of o-DCB utilized is
released into the atmosphere. Allied Chemical reported that in 1978
approximately 1 percent or less of the o-DCB purchased was released.
81
-------
CD
PHOSPHOGENATION <8
REACTORIS)
HCI BY-PRODUCT
TO STORAGE
MCI PHOSGENE , PHOSGENE
ABSORPTION STRIPPER ABSORPTION
DISMUAIION
NO'l'E: The numbers in tliia figure refer to process streams, ns discussed In the text,
;uul thu Jottcru duali'iiatu IHUCCJUH venLu.
Figure 16. Basic operations that may be used in toluene diisocyanate production.
59
-------
Source Locations
Producers of TDI used are listed in Table 19. It is not known
whether the producers actually utilize o-DCB or MCB as described above.
01 in reports that MCB is used in their TDI production process, a major
portion of which is incinerated.^2 BASF reports that "MCB emissions
should not be assumed to necessarily result from [its Geismar, IA] TDI
Qrt
operations."*
83
-------
TABLE 19. CHEMICAL PRODUCERS OF TOLUENE DIISOCYANATE - 198461
BASF Wyandotte Corp.
Polymers Group
Urethanes Chemicals Business
Geismar, LA
Dow Chemical U.S.A.
Freeport, IX
ICI Americas Inc.
Performance Resin Division
Rubicon Chemicals, Inc.
Geismar, LA
Mobay Chemical Corporation
Polyurethane Division
Cedar Bayou, TX
New Martinsville, WV
Olin Corporation
Olin Chemicals Group
Lake Charles, LA
Moundsville, WV
This listing is subject to change as market conditions change, facility
ownership changes, plants are closed, etc. The reader should verify the
existence of particular facilities by consulting current listings and/or
the plants themselves. The level of chlorobenzene emissions from any
given facility is a function of variables such as capacity, throughput and
control measures, and should be determined through direct contacts with
plant personnel.
84
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USE OF 0-DICHLOROBENZENE AS A SOLVENT IN PHARMACEUTICAL MANUFACTURING
0-DCB is used as a solvent in the manufacturing of pharmaceutical
products by chemical synthesis.
Process Description
Synthetic Pharmaceuticals are normally manufactured in a series of
batch operations, many of which involve the use of solvents.
Figure 17 presents basic operations that may be used in a batch
synthesis process. To begin a production cycle, the reactor is washed
with water and dried with a solvent. Air or nitrogen is usually used to
purge the tank after it is cleaned. Solid reactants and solvent are
then charged to the reactor. After the reaction is complete, remaining
unreacted volatile compounds and solvents may be distilled off, typi-
cally using a water cooled condenser. The pharmaceutical product is
then transferred to a holding tank. In the holding tank," the product
may be washed three to four times with water or solvent to remove any
remaining reactants and byproducts. The solvent used in washing gen-
erally is distilled from the reaction product. The crude product may
then be dissolved in another solvent and transferred to a crystal lizer
for purification. After crystallization, the solid material is sepa-
rated from the remaining solvent by centrifuging. While in the cen-
trifuge, the product cake may be washed several times with water or
solvent. Tray, rotary, or fluid-bed dryers are employed for final
63
product finishing.
Emissions
Where o-DCB is used as a solvent in the manufacture of a pharma-
ceutical product, each step of the manufacturing process may be a source
of o-DCB emissions. The magnitude of emissions varies widely within and
among operations; therefore, it is impossible to cite typical emission
rates for various operations. Based on an industry-wide mass balance,
140 grams of o-DCB per megagram used are emitted directly to the air.
Also, 8,300 g/Mg used are estimated to be released as sewage. Some of
this o-DCB will volatilize subsequent to discharge creating a secondary
source of emissions.
85
-------
VENT
VENT
SOLIDS
SOLVENT
H2O
SOLVENT VENT
VENT
oo
a\
PRODUCT
SOLVENT
DISTILLATION
Figure 17. Basic operations that may be used in pharmaceutical manufacturing.
-------
An approximate ranking of emission sources has been established and
is presented below in order of decreasing emission significance. The
first four sources typically account for the majority of emissions from
a plant.63
• Dryers
• Reactors
• Distillation units
• Storage and transfer
• Filters
• Extractors
• Centrifuges
• Crystallizers
Condensers, scrubbers, and carbon adsorbers can be used to control
emissions from all of the above emission sources. Storage and transfer
emissions can also be controlled by the use of vapor return lines,
conservation vents, vent scrubbers, pressurized storage tanks, and
floating roof storage tanks.
Source Locations
The Standard Industrial Classification (SIC) code for
pharmaceutical preparations is 2834. There are approximately 800
pharmaceutical plants producing drugs in the United States and its
territories. Host of the plants are small and have less than 25
employees. Nearly 50 percent of the plants are located in 5 states: 12
percent in New York, 12 percent in California, 10 percent in New Jersey,
5 percent in Illinois, and 6 percent in Pennsylvania. These states also
contain the largest plants in the industry. Puerto Rico has the
greatest growth in the past 15 years, during which 40 plants have
located there. Puerto Rico now contains 90 plants or about 7.5 percent
of the total.63
87
-------
USE OF P-DICHLOROBENZENE AS A SPACE DEODORANT
The majority of p-DCB produced in the United States has a non-
intermediate dispersive use in space, toilet bowl, and garbage
deodorants. Due to its volatility, density, pleasant odor, and solid
nature at room temperature, it is used alone or in combination with
disinfectant substances to produce deodorants in a variety of continuous
evaporation forms, most commonly solid air deodorizers and toilet
blocks.
Process Description
p-DCB derived deodorant products contain up to 100 percent p-DCB
with the addition of a perfume in some cases. Limited information was
available detailing the processes by which the deodorant types are
manufactured. However, most solid block deodorants are formed by
combining the active ingredients such as p-DCB with a carrier sub-
stance.65 The most common carrier for all types of deodorants is water;
however, other carriers such as process oils, solvents, and various
petroleum products are also employed depending on the form of the
deodorant. In solid and semisolid products, active ingredients are
incorporated into sublimable water based gels, waxy solids, or powder
form. The process by which active substances are incorporated into
toilet blocks is assumed to be similar in nature.
Emissions
It is estimated that all p-DCB incorporated into solid space and
garbage deodorants will enter the atmosphere by sublimation during
production or use. Use of toilet bowl deodorizers is expected to
contribute only minor amounts of p-DCB, the balance entering the
3 8
sewerage.
Source Locations
For 1984, 33 percent of U. S. p-DCB production is expected to be
used in the manufacture of space deodorants. Information concerning
specific manufacturers was not available. Users of p-DCB-based
deodorant products include the industrial, commercial, and consumer
sectors.
88
-------
USE OF P-DICHLOROBENZENE IN MOTH CONTROL
p-DCB is used in consumer, commercial, and industrial sectors in
different applications for moth control. p-DCB formulated into cakes,
blocks and balls contain greater than 99 percent p-DCB.38 Information
on manufacture of these products is not available.
Commercial applications of moth control products include preserva-
tion of glycerin treated dried flowers during storage and handling and
moth proofing of textiles during production. ° p-DCB is applied to the
textiles during the dyeing operation and then may be fixed in the fibers
by chemical reactions with a protein. " It may also be sprayed onto
fabric combined with a volatile solvent.
Emissions
All p-DCB used in moth control products and applications is expected
to be emitted to the atmosphere by sublimation during production or
use.38
Source Location
Uses of moth control agents are too widespread to categorize.
Manufacturers of moth control agents containing p-DCB were not identi-
fiable due to limited information.
89
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USE OF P-DICHLOROBENZENE IN THE PRODUCTION OF POLYFHENYLENE SULFIDE
p-DCB is used in the production of polyphenylene sulfide, a
commercial polymer with many industrial applications. Characteristics
of polypheny 1 sulfide, also named polythio-l,4-pheny lene, or PPS,
include: good thermal stability, retention of mechanical properties at
elevated temperatures, excellent chemical resistance, and an affinity
for a variety of fillers.67 It is also in a class of polymers with high
dielectric strength useful for insulation applications. PPS has a
variety of industrial applications for molded parts including non-
lubricated bearings, seals, pistons, impellers, pump vanes and elec-
tronic components. ' It can also be applied as a coating to metals and
ceramics as a protective and corrosion resistant medium for equipment in
the chemical and petroleum industries. When mixed with small amounts of
polytetrafluoroethylene, it provides a non-stick surface in cookware and
other industrial applications.
Process Description
PPS is formed by the following reaction of p-DCB and sodium sulfide
in a polar solvent.
r^r\
+ 2NaCl
- X
PPS
Steps involved in the manufacture of PPS shown in Figure 18 are:
(1) preparation of sodium sulfide from aqueous caustic and aqueous
sodium hydrosulfide in a polar solvent, (2) dehydration by distillation
of the above feedstock, (3) polymer formation from the reaction of the
sodium sulfide stream and p-DCB at an elevated temperature in a polar
solvent, (4) polymer recovery, (5) removal of by-product sodium chloride
by washing, (6) drying and (7) packaging.68 The product of the above
process can be used in coating applications by slurry-coating
procedures; however, most often it is used as a feedstock in the
production of molding-grade resins.
Molding-grade resins are produced by a curing process in which the
virgin polymer is exposed to a small amount of air at a high
90
-------
NaSH
L_
P-DICHLOROBENZENE
NaOH
I
t
PREPARATION
DEHYDRATION
I
POLYMERIZATION
POLYMER RECOVERY
POLYMER WASHING
POLYMER DRYING
POLAR SOLVENT
H2O
PACKAGING (VIRGIN POLYMER)/CURING (MOLDING RESIN)
Figure 18. Process flow diagram of PPS manufacture.1
68
91
-------
temperature. At this point, a higher molecular weight resin is produced
while lower molecular weight oligomers are volatilized. Residence time,
reaction temperature, and melt viscosity are important in the formation
of various grades of PPS. The cured polymer is cooled, combined with
fillers (such as glass fibers, if desired), pelletized, and then
68
packaged. °
Emissions
No emissions data are available for the production of polypheny lene
sulfide. To determine actual emissions from particular processes,
specific plants should be contacted.
Source Locations
Polyphenylene sulfide is produced by Phillips Petroleum at
facilities in Borger and Pasedena, Texas.69 This listing is subject to
change as market conditions change, facility ownership changes, plants
are closed, etc. The reader should verify the existence of particular
facilities by consulting current listings and/or the plants themselves.
The level of chlorobenzene emissions from any given facility is a
function of variables such as capacity, throughput and control measures,
and should be determined through direct contacts with plant personnel.
92
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USE OF DICHLOROBENZENES IN PESTICIDES
Both o- and p-DCB are listed in the Farm Chemicals Handbook for
agricultural application.70 In addition to moth control, p-DCB is used
in tobacco seed beds for blue mold control, peach tree borer control and
to prevent mildew and mold on leather and fabrics. o-DCB has more
widespread use as an herbicide, insecticide and soil fumigant effective
in control of peach tree borers, bark beetles and grubs, mites, termites
and insects in poultry houses and animal sleeping quarters.
Pesticides are most commonly used in the forms of dusts, water
dispersion, emulsions, and solutions depending on the type of control
required. Active ingredients are combined with accessory agents (such
as dust carriers, solvents, emulsifiers, wetting and dispersing agents,
deodorants or masking agents) to form dusts, wettable powders, granu-
lars, emulsives, baits and slow release formulations. The above formu-
lations are generally applied by three methods determined by the type of
carrier used: (1) spraying (with a water or volatile oil carrier),
(2) dusting (with a fine powder carrier), or (3) fumigation (in which
the formulation is applied as a gas).'* Information was not available
for specific application procedures or formulation processes of DCBs.
Emissions
No information was available concerning emissions from formulation
processes or application of specific pesticide formulations. It is
assumed that all DCBs used in pesticide applications are released to the
atmosphere at a rate depending on volatility and application form. An
estimate of emissions for regional pesticide formulation sites is given
in Table 20.
Source Locations
Information on formulators of pesticides containing DCBs was not
available. Limited information was available on the current location of
DCBs pesticide use.
93
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TABLE 20. 1978 REGIONAL DICHLOROBENZENE EMISSIONS
ESTIMATES FROM PESTICIDE FORMULATION (kg/yr)
Region
New England
Mid Atlantic
East North Central
West North Central
South Atlantic
East South Atlantic
West South Atlantic
Mountain
Pacific
Sites •
4
37
19
15
17
14
15
5
13
1978 Emissions
o-DCB p-DCB
(kg/yr) (kg/yr)
20
181
92
72
84
68
73
25
64
36
331
170
134
152
125
134
45
116
Total
139
680
635
94
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USE OF CHLOROBENZENES IN BONDED ABRASIVE PRODUCTS MANUFACTURE
The abrasives industry employs small amounts of p-DCB and 1,2,4-TCB
in the production of ceramic- and resinoid-bonded products in the shape
of wheels, discs, sticks, blocks and segments.
Process Description
The first step in bonded abrasives manufacture is the combining of
abrasive grain materials (such as aluminum oxide, silicon carbide,
and/or diamond grains), wetting agents (of which some or all consist of
1,2,4-TCB) and bonding materials in large kettle type machines
resembling bakery dough mixers. ' Ceramic bonding materials include
feldspar, frit and clays selected for their fusibility. After mixing,
measured amounts are poured into slightly oversized molds, compressed in
hydraulic presses, and then dried under constant humidity. The forms
are then fired in bell, periodic, or continuous kilns for several days
at temperatures up to 1260°C.
The same process is used in making resinoid-bonded wheels; however,
lower curing temperatures of 150 to 200°C are used. If a more porous
structure is desired, p-DCB is added during mixing. p-DCB is used as an
additive because as a solid it can be crushed into definable grit size.
During the curing process, the p-DCB volatilizes, leaving pores and wide
grain spacing.
Emissions
Small amounts of p-DCB and TCB are released in the formulation and
mixing of process constituents in abrasives manufacture; however, most
of these substances volatilizes during the curing process. As a result,
39
emissions from the use of the finished products are negligible.
Source Locations
No information was available on abrasive or grinding wheel
producers which use p-DCB or 1,2,4-TCB in the manufacturing process.
95
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USE OF CHLOROBENZENES IN WOOD PRESERVATIVES
DCB and TCB isomers are used as repellents and wood preservatives
against termites, powder-post beetles, and carpenter ants. The chloro-
benzene products are applied on surfaces or injected into standing wood
buildings.^^ The DCB technical wood preservative product contains a
mixture of 75 to 85 percent o-DCB and 15 to 25 percent dissolved p-DCB.
The technical product of TCB contains 1,2,4-TCB and a small amount
of the 1,2,3-TCB isomer. No information was found on the formulation
process or application practices.
Emissions
Approximately 1 percent of 1,2,4-TCB is estimated to be emitted to
the atmosphere during application and handling, the balance remaining in
the wood. 39 Emissions factors for DCBs and 1,2,3-TCB have not been
reported.
Source Locations
The formulations and users of wood preservatives and products
containing chlorinated benzenes are not identified in the literature.
96
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USE OF 1,2,4-TRICHLOROBENZENE AS A DYE CARRIER IN THE TEXTILE DYEING
INDUSTRY
The most widely known use of 1,2,4-TCB is that of a dye carrier in
textile dyeing operations. Textile mill operations which USB 1,2,4-TCB
include wool scouring, woven fabric finishing (simple and complex
processing with desizing), and knit fabric finishing. In most cases
1,2,4-TCB dye carrier is used only when specific (usually darker)
hues are required in man-made fibers.
Process Description
When used as a dye carrier, 1,2,4-TCB is combined with a disperse
dye and a leveling agent, and then applied to the material at 100°C for
several hours.^9 Typically, the amount of TCB contained in the dye
carrier formulation ranges from 10 percent to 90 percent of the total
formulation or from less than 2 percent to 10 percent by weight, once
added to the bath. At this point, excess carrier is removed by either
(a) alkaline scour at 70° to 80°C with sulfated fatty alcohol, or
(b) rinsing the material followed by heating to 1908C for one minute.
General process and equipment for use of dye carriers are described in
the section entitled Use of Monochlorobenzene and o-Dichlorobenzene as
Dye Carriers in Textile Dyeing.
Emissions
It is estimated that all of the 1,2,4-TCB contained in the dyeing
solutions is released to the environment. A small quantity is emitted
to the atmosphere during the removal of excess solution from the
material by evaporation. The majority of 1,2,4-TCB is discharged to the
waste water stream in the release of spent dye solution and alkaline
scouring wastes. Due to the volatility of 1,2,4-TCB in water, secondary
emissions from the waste water stream are possible.
Wet processing textile mills employ various levels of available
control technologies which may remove TCBs from the waste water. In
Table 21, levels of control technology are shown with the estimates of
quantities of TCB emitted for wool scouring, woven fabric finishing and
knit fabric finishing processes. Preliminary waste water treatments
include neutralization, screening, equalization, heat exchange,
97
-------
TABLE 21. 1,2,4-TCB EMISSIONS FROM SPECIFIC WATER TREATMENT PROCESSES '
IN WET PROCESSING TEXTILE MILLS - 1979 (MEGAGRAMS)39
Textile
Operation
Vlool Scouring
Z of
TCB-
Quantity Releaaed (Me)*
total TCB- containing
Type of
Treatment
containing
waatea
wactes
(Mg)
Water"
Direct Indirect Airc Land
Woven Fabric Finishing
Z of
TCB-
total TCB- containing
containing
waatea
wactea
(Mg)
Quantity Releaaed (Ha)*
Waterb
Direct Indirect Airc Land
Knit Fabric Finishing
Quantity Released (MR)"
Z of
TCB-
total TCB- containing
containing
waatea
waatea
(Mg)
Water0
Direct Indirect
Airc Land
None 35
Preliminary 29
37 6 31
30 12 18
41 615 41 574
22 330 34 296
51 961 66 895
21 396 — 396
lO
Biological
or
Equivalent
Advanced
Unknown
TOTAL
35
0
0
99
38
0
0
105
3 1 17d 17d 25
— __ _« __ 1
__ __ 11
21 SO 17 17 100
375
15
165
1501
28 10 169d 169d 20
— 15 2
132 33 -- — 6
235 913 169 184 100
377
38
113
'1885
21 17 169d 169d
— 38
92 21 — ~
283 1225 169 207
Quantities releaaed to each media are added to equal the number in the previous "TCB-containing waatea" columna.
After treatment waate water ia discharged directly into surface water or entera a publicly-owned treatment work (indirect)*
cDoea not include emissions due to volatilization from waate water aubaequent to discharge. <
Assumes that 1,2,4-TCB removed during waate water treatment when aent to land waa equally divided between air and land.
-------
disinfection, primary sedimentation, and/or floatation. Further treat-
ment in wet mills may include the use of aerated and unaerated lagoons,
biological filtration, activated sludge, and chemical coagulation/f loc-
culation. Advanced treatment refers to the use of activated carbon,
chemical coagulation, ozonation, filtration, ion exchange and membrane
processes. These waste water treatment processes may result in the
release of 1,2,4-TCB into the atmosphere.
In a 1979 EPA survey, it was estimated that 3,490 Mg of 1,2,4-TCB
were used by domestic textile mills. ' Assuming that the survey is
representative of the entire textile industry (which is estimated to
consist of 2,000 wet processing mills), and that each operation used a
proportional quantity, then it is calculated that 3, 43, and 54 percent
of the total 3,490 Mg of TCB, or 105, 1501, and 1885 Mg, were used by
wool scouring, woven fabric finishing, and knit operations, respec-
tively.
Source Locations
A listing of the plants involved in the dyeing of man-made fibers
was not available. The Standard Industrial Classification (SIC) codes
for these establishments are listed below:
• Broad woven fabrics of man-made fiber - 2262
• Raw stock and narrow fabrics of man-made fiber - 2269.
99
-------
USE OF 1,2,4-TRICHLOROBENZENE IN THE MANUFACTURE OF PESTICIDE
INTERMEDIATES
TCB is used as an intermediate in the production of dicamba
(herbicide), stirofos (insecticide), trichloro-nitrobenzene
(fungicide), and 2,5-dichlorobenzoic acid (herbicide).39 It is also
possible to produce the herbicide chloramben from 2,5-dichlorobenzoic
acid.
Process Descriptions
1,2,4-TCB is used to produce dicamba (3,6-dichlorolo-anisic acid,
3,6-dichloro-2-methoxybenzoic acid) by what is known as the dicamfaa
39
process. '
Cl .
_ Dimethyl
Sulfate
dicamba
In the process, TCB and sodium hydroxide are dissolved in methanol in
the presence of carbon dioxide and dimethyl sulfate and heated to 190°C
for 4 hours in a bomb. The resultant mixture is cooled, filtered,
dryed, and further processed to make dicamba.
Stirofos, or 2-chloro-l-(2,4,5-trichloropheny 1) ethenyl dimethyl
39
phosphate, is produced by reacting 1,2,4-TCB with aluminum chloride.
Dichloroacetyl chloride is stirred into the mixture, heated slowly to
90°C and maintained for 4 hours. The reaction mixture is then poured
into an ice and hydrochloric acid solution and extracted with ether.
The organic layer is washed successively with diluted hydrochloric acid,
water, sodium bicarbonate solution, and saturated sodium chloride solu-
tion. Solvent is separated by evaporation and residue is distilled to
produce 2,2,2',4l,5'-pentachloroacetophenone, which is reacted with
trimethyl chloride to yield the herbicide stirofos.
100
-------
Dichloro
acetyl
chloride
CH3C=0
trimethvl
imi
ohi
phosphate
Cl CH3
HC=C-P04
Cl
1,2,4-TCB ' ' pentachloroacetophenone stirofos
Trichloronitrobenzene is produced by the nitration of TCB with a
nitrating solution of 18 percent nitric acid, 73 percent sulfuric acid
and 9 percent sulfur trioxide.3^ Initially, the nitrating agent is
heated to 35°C and then added to the TCB while stirring. The reaction
temperature is held at 110°C for 6.5 hours after which time the reaction
mixture is poured into water. Immediate precipitation produces a yield
of 90.5 percent of l,2,4-trichloro-3,5-dinitrobenzene.
01
Cl
1,2,4-TCB
1,2,4-tricoloro-3,5-dinitrobenzene
1,2,4-TCB also reacts with cuprous cyanide to form 2,4-dichloro-
phenyl nitrile which undergoes hydrolysis to produce the herbicide, 2,5-
dichlorobenzoic acid.3^ 2, 5-Dichlorobenzene may also be used as an
intermediate to produce the herbicide, Chloramben, using the Chloramben
CQOH
Chloramben
Cl
1,2,4 TCB
process
2,5-dichlorobenzoic acid
Chloramben
No further information is available on the Chloramben process.
Emissions
An estimated 33 percent of the total quantity of the TCB used by
the pesticide industry was converted or consumed during the manufac-
turing process. Furthermore, based on process descriptions, approxi-
mately 1 percent of the TCB used was released into the environment, of
which two-thirds was discharged to air.3^
In the first step of dicamba manufacture, 90 percent of 1,2,4-TCB
is consumed in production of 2,4-dichloropheny 1. The remaining 10
101
-------
percent is assumed to be released into the environment, most of which is
probably converted to other compounds by side reactions. Less than
1 percent used for dicamba production was released to the air in the
39
form of fugitive and handling emissions.
Stirofos production incorporates 77 percent of the TCB into the end
product, leaving a possibility of 23 percent being released into the
environment. However, much of this 23 percent further undergoes side
reactions while some is recycled, resulting in less than 1 percent of
39
TCB being released into the air by fugitive and handling emissions.
In trichloronitrobenzene formulation, 91 percent of TCB is consumed
into the end product, and a negligible proportion is discharged to
air.3*
No information was available on emissions from the production of
2,5-dinitrobenzoic acid or chloramben. For actual emissions and control
technologies used at a specific plant, contact with appropriate plant
personnel is advised.
Source Locations
Producers of TCB-derived pesticides and their locations are shown
in Table 22 where information was available. Production information was
not obtained for trichloronitrobenzene. The Standard Industrial
Classification (SIC) code for pesticide production is 2879.
102
-------
TABLE 22. CHEMICAL PRODUCERS OF TCB-DERIVED PESTICIDES - 197774
Dicamba aka 3,6-Dichloro-o-anisic Acid
3,6-Dichloro-2-methoxybenzoic Acid
Banvel* D
Northwest Industries Inc.
Vesicol Chemical Corporation Subsidiary
Chattanooga, Tennessee
Trimec*
FBI-Gordon Corporation
Kansas City, Kansas
Stirofos aka 2-chloro-l-(2,4,5-trichlorophenyl)-viny 1 dimethyl sulfate
2-chloro-l-(2,4,5-trichlorophenyl)-ethenyl dimethyl sulfate
Gardona*
Shell Chemical Company
Agricultural Division
Mobile, Alabama
Chloromben aka 3-amino-2,5-dichlorobenzoic acid
Verbigen*
GAP Corporation
Chemical Division
Texas City, Texas
Amiben*
Rorer/Amchem
Amchem Products Incorporated
Ambler, Pennsylvania
Piedmont, California
St. Joseph, Missouri
Union Carbide Corporation75
Agricultural Products Group
Clinton, Iowa
Texas City, Texas
Woodbine, New Jersey
Note: This listing is subject to change as market conditions
change, facility ownership changes, plants are closed,
etc. The reader should verify the existence of particular
facilities by consulting current listings and/or the
plants themselves. The level of chlorobenzene emissions
from any given facility is a function of variables such as
capacity, throughput and control measures, and should be
determined through direct contacts with plant personnel.
103
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USE OF 1,2,4-TRICHLOROBENZENE IN FUNCTIONAL FLUIDS
Approximately 18 percent of 1,2,4-TCB production is used in formu-
lations of functional fluids such as dielectric liquids and transformer
oils. The fluids are standardized mixtures of TCB and polychlorinated
biphenyls (PCBs) primarily used in electrical apparatus such as capaci-
tors and transformers. Functional fluids, also called askarels, differ
slightly in composition depending on the type of electrical equipment in
which they are used.39 Addition of TCB to PCB lowers the viscosity of
the mixture. Askarels are used in electrical equipment because they are
non-flammable, chemically stable, have a low vapor pressure and a high
dielectric constant. Capacitors use an askarel mixture with a dielec-
tric constant similar to the capacitor paper in order to create a homo-
geneous electric field. Use of these fluids has been phasing out due to
the voluntary halt in production of their PCB constituents in October
1977.
Process Description
During the manufacture of electrical apparatus, liquid dielectric
with TCB concentrations ranging from 0.3 to 20 percent by weight is
39
injected through small seal holes in the casings.-*7
Emissions
Very limited amounts of trichlorobenzene are believed to be lost
during manufacture of electrical apparatus. One estimate suggests that
less than 1 percent of the total 1,2,4-TCB impregnated into the appa-
ratus is introduced to the environment, half of which is emitted into
the air as fugitive emissions. Fluids contained within electrical
equipment in use are isolated from the environment; however, emissions
may occur upon leakage or rupture of the equipment.
Due to the past use of TCBs in transformer fluid mixtures, TCB
emissions are possible from the disposal or destruction of PCB-
contaminated materials. Contaminated materials include: PCB fluids,
PCB,articles (items which contain PCBs and whose surface(s) have been in
direct contact with PCBs) and PCB containers (barrels, drums,
containers, etc., that contain PCBs and whose surfaces have been in
104
-------
direct contact with PCBs).76 Under current regulations, PCB contaminated
equipment and fluids are required to be disposed of by incinerator, high
efficiency boiler, chemical waste landfill, or other approved disposal
methods. Selection of disposal/destruction method is determined by the
concentration of FCBs contained in the materials.
At one electrical wire insulation incinerator, trichlorobenzene and
tetrachlorobenzene emissions have been measured to be less than
0.5 mg/hr and 0.3 mg/hr, respectively, during normal operation.77 The
facility utilized waste transformer oil containing less than 50 ppm PCBs
as fuel, and burned off the insulation from aluminum and copper windings
of non-rebuildable transformers. The incinerator employed both primary
and secondary combustion chambers and an afterburner.
No specific information was available detailing emissions from high
efficiency boilers, landfills or other disposal technologies. However,
negligible amounts of TCB are expected to volatilize over time as a
result of landfilling of PCB contaminated apparatus.
For data on specific source emissions and control technologies,
contact should be made with personnel at individual plants.
Source locations
Approximately 18 percent of the total 1,2,4-TCB production is used
in synthetic transformer oil and dielectric fluids. ? No information
concerning locations of transformer oil and dielectric fluids producers
was available.
As of July 1984, four commercial incinerators, eight industrial
incinerators and two mobile incinerators have been approved for the
destruction of PCB materials. The commercial units include those
operated by Rollins Environmental Services in Deer Park, Texas; Energy
Systems Company (ENSCO) in El Dorado, Arkansas; General Electric Company
in Pittsfield, Massachusetts; and SCA in Chicago, Illinois. The
industrial PCB incinerators are operated by the General Electric Company
in Waterford, New York; by Dow Chemical in Freeport, Texas; Oyster Creek,
Texas; and Plaquemine, Louisiana; by Vulcan Materials in Geismar,
Louisiana; by PPG in Lake Charles, Louisiana; by LaPort Chemical
Corporation in Pasadena, Texas; and by Los Alamos Scientific in Los
105
-------
Alamos, New Mexico. The mobile incineration systems are operated by
78 79
EPA, Edison, New Jersey; and Pyro-Magnetics, Tullahoma, Tennessee. '
Specific locations of other incinerators which may be used for
destruction of electrical apparatus containing TCB or PCS fluids, were
not identified in the literature. However, the source classification
code (SCC) for incineration of industrial wastes in EPA's National
Emissions Data System is 5-03-001-xx.80 The reader should verify the
existence of particular facilities by consulting the plants themselves.
106
-------
HEXACHLOROBENZENE GENERATION DURING CHLORINATED SOLVENT PRODUCTION
Approximately 60 percent of the total national HCB waste load is
attributable to chlorinated solvent production, primarily from the pro-
duction of carbon tetrachloride, trichloroethylene, and perchloro-
ethylene. Of these, perchloroethylene production is expected to produce
the greatest quantity. The production of several other chlorinated
solvents, such as ethylene dichloride and 1,1,1-trichloroethane, also
have the potential to produce HCB at trace levels.
Process Description
During the production of carbon tetrachloride, trichloroethylene,
and perchloroethylene, HCB is formed as a reaction byproduct from
chlorination, oxychlorination, and cracking operations. Flow diagrams
illustrating the main processes for producing carbon tetrachloride,
trichloroethylene, and perchloroethylene are presented in Figures 19,
20, and 21. Potential HCB-containing waste streams are indicated in
these figures. Hexachlorobenzene is usually found as a residue in the
heavy ends or still bottoms during distillation or purification. The
heavy, tarry residue also contains other chlorinated hydrocarbons in
addition to HCB. Generally, these wastes are removed and stored in
containers prior to their ultimate disposal by incineration. ^
The HCB levels in production wastes vary greatly by chemical and by
plant. This variability in the HCB concentration is related to the
processes and feedstock materials used. Wastes generated by trichloro-
ethy lene production appear to contain the lowest levels of HCB. In
general, it is difficult to quantify a typical HCB concentration in the
14
process wastes.
Emissions
The HCB generated by the production of the chlorinated solvents
occurs as bottoms from distillation processes. When the HCB-containing
waste is removed from the distillation unit, the HCB portion is
essentially solid. Considering its physical state and. the low vapor
pressure of HCB at ambient temperatures (i.e., 20°C), the potential for
fugitive HCB volatilization during waste generation and waste handling
107
-------
CATALYST
CARBON
fUO
O
00
OlORINOLVSIS
REACTOR
iici i ei,
REMOVAL '
COLUHN
CARBON mRACIHORlOE
FROH HnilANOL
MYDROCMLORINATION
AND METIIVLCHLORIDE
CULMINATION PROCESS
CONTAINING
HASTE
CRUDE CARBON
STORAGE TETRACMORIOE
DISTILLATION
CARBON
TETRACIIORIDE
STORAGE
PERCHLORO-
ETIIYLCNE
STORAGE
PERCHLOROETHYLEHE
DISTILLATION
CAUSTIC
SCRUBBER
CHLORINE
ABSORPIION
CfHIIHN
IICI
ABSORBER
BY-PRODUCT
IICI
STORAGE
Figure 19. Process flow diagram for the production of carbon tfttrachloride
and perchloroethylene by hydrocarbon chlorinolysis.
-------
HYDROGEN fill OR I DC
TO OTHER PROCESSES
CHLORINE <
PEROIIORO-
tTHYIENE/
IRKIIIOHO-
ETHYUNE
COLIIHM
O
VO
ETHYLENE
DICHLORIOE
STORAGE
UASTEWATER
TO TRFATHENT
RECYCLE
ORGANIC
STORAGE
C. CHLORINATED
OROANICS FROM
OIIIEH PROCESSES
LOADING
> LOADING
PERCHLORO-
ETIIV1EHE
COLUMN
PERCHLOROETIIAHE
STORAGE
IICD-CONTAINING
WASTE
Figure 20. Process flow diagram for the production of perchloroethylene
and trichloroethylene by chlorination.14
-------
AQtirnus WASTE
I TO WAIIt
. I WATHINT
HYOROTIIIORIC ACID
(BY-PNOMICI)
BOILER FEED I
WATER
OXYGEN
CHORINE OR
HYDROGEN
CHLORIDE
ETHYLENE
DICIHORIOE
STORAGE
1 .-,
1
D BED
C10R
AQUEOUS
WASTE
DRV
cot
FINES 10 WASTE
TREATMENT
UJ
RECYCIE
ORGANIC
STORAGE
C? CHLORINATED ORGANIC*
FROH OTHER PROCESSES
ORGANIC
RECVCIE
SYSTEM
HCB-CONTAINING
WAS IE
PFRCIIIORO-
IIHYIENE/
TRICIIIORO-
COIUHN
Figure 21. Process flow diagram for the production of perchloroethylene-
and trichloroethylene by oxychlorination.^
-------
operations is minimal. Actual tests at a perchloroethylene plant have
indicated that HCB waste handling operations are not a source of HCB air
emissions. In these tests, neither uncontrolled air emissions
associated with handling HCB-containing waste nor air emissions from
01
waste storage tanks were found to contain HCB.
In the past, waste storage piles at plants indirectly generating
HCB may have been fugitive HCB emission sources due to slow evaporative
losses. More recently, however, with the advent of the management and
control of hazardous wastes under the Resource Conservation and Recovery
Act (RCRA), the use of waste storage piles has greatly declined because
of the stringent site containment and monitoring requirements in place
for open piles. Most HCB waste generators currently store their wastes
01
in containers prior to final disposal in incinerators or landfills.
The majority of chlorinated solvent plants known to generate HCB
wastes use incineration as a means of ultimate disposal, while a few
utilize off site landfill facilities (Table 23). Of the plants known to
be incinerating their wastes, all but one, Diamotiti Shamrock, incinerate
their wastes on the plant site. The plants operate RCRA approved
incinerators which must be at least 99.99 percent efficient at destroy-
ing HCB. The offsite incinerator must meet the same RCRA requirements
to be allowed to burn HCB. The ultimate HCB emission point from incine-
rating these wastes will not necessarily be the incinerator stack, but
will probably be the stack on the caustic wet scrubber used to control
81
hydrochloric acid (HC1) emissions from the incinerator.
Source Locations
Currently known producers of carbon tetrachloride, trichloro-
ethylene, and perchloroethy lene and their methods of production are
shown in Tables 24, 25, and 26. Most of the listed facilities reported
HCB-containing wastes on their Resource Conservation and Recovery Act
(RCRA) Fart A applications on file with the EFA and State hazardous
81
waste agencies.
Ill
-------
TABLE 23. SUMMARY OF DISPOSAL PRACTICES FOR HEXACHLOROBENZEHE WASTES -
81
1984s1
Plant
Location
HCB Waste Disposal Method
Dow Chemical
E.I. EuPont
de Nemours
Diamond Shamrock
LCP Chemicals
and Plastics
Stauffer Chemical
PPG Industries
Vulcan Materials
Olin Corporation
SDS Biotech
Velsicol Chemical
Freeport, TX
Plaquemine, LA
Pittsburg, CA
Corpus Christi, TX
Deer Park, TX
Moundsville, WV
Louisville, KY,
Lake Charles, LA
Geismar, LA
Wichita, KS
Leland, MS
Greens Bayou, TX
Memphis, TN
Marshall, IL
On-site Incineration
On-site Incineration
On-site Incineration
Unknown
Off-site Incineration
Off-site Landfill
Unknown3
On-site Incineration
On-site Incineration
On-site Incineration
Off-site Landfill
Off-site Landfill
Off-site LandfiM
Off-site Landfill
a
It is known that the plant does not have on-site landfilling or
incineration.
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
112
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TABLE 24. CHEMICAL PRODUCERS OF CARBON TETRACHLORIDE - 198482
Company
Location
Method of Production
Dow Chemical
Freeport, Texas
Pittsburg, California
Plaquemine, Louisiana
E.I. DuPont de Nemours
Ingleside, Texas
LCP Chemicals and Plastics
Moundsvilie, West Virginia
Stauffer Chemical
Louisville, Kentucky
— LeMoyne, Alabama
Vulan Materials
Geismar, Louisiana
Wichita, Kansas
Methane chlorination and
chlorine lysis of mixed hydrocarbons
with perchloroethylene co-product
Methane chlorination and
chlorinolysis of mixed hydrocarbons
with perchloroethylene co-product
Chlorinolysis of mixed hydrocarbons
with perchloroethylene co-product
Methane and ethylene chlorination
with perchloroethylene co-product
Methyl chloride chlorination and
methane chlorination
Methane chlorination
Carbon disulfide chlorination
Chlorinolysis of mixed hydrocarbons
with perchloroethylene co-product
Methyl chloride and methane
chlorination, chlorinplysis of
mixed hydrocarbons with perchloro-
ethylene co-product
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
113
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TABLE 25. CHEMICAL PRODUCERS OF TRICHLOROETHYLENE - 198483
Company
Location Method of Production
Dow Chemical Chlorination of ethylene dichloride
Freeport, Texas
PPG Industries, Inc. Oxychlorination of ethylene
Lake Charles, Louisiana dichloride
Note: This listing^is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
114
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TABLE 26. CHEMICAL PRODUCERS OF PERCHLOROETHYLENE - 198484
Company
Location
Method of Production
Diamond Shamrock
Deer Park, Texas
Dow Chemical
Freeport, Texas3
Fittsburg, California
Plaquemine, Louisiana
E.I. DuPont de Nemours
Corpus Christi, Texas
PPG Industries, Inc.
Lake Charles, Louisiana
Stauffer Chemical
Louisville, Kentucky3
Vulcan Materials
Geismar, Louisiana
Wichita, Kansas
Chlorination of ethylene dichloride
Chlorinolysis of mixed hydrocarbons
producing carbon tetrachloride as a
co-product
Chlorinolysis of mixed hydrocarbons
producing carbon tetrachloride as
a co-product
Chlorinolysis of mixed hydrocarbons
producing carbon tetrachloride as
a co-product
Not available
Chlorination of ethylene dichloride
Chlorinolysis of mixed hydrocarbons
producing carbon tetrachloride as
a co-product
Chlorinolysis of mixed hydrocarbons
producing carbon tetrachloride as
a co-product
Chlorinolysis of mixed hydrocarbons
producing carbon tetrachloride as a
co-product
Plants on standby.
Note: This listing is subject to change as market conditions change,
facility ownership changes, plants are closed, etc. The reader
should verify the existence of particular facilities by consulting
current listings and/or the plants themselves. The level of
chlorobenzene emissions from any given facility is a function of
variables such as capacity, throughput and control measures, and
should be determined through direct contacts with plant personnel.
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HEXACHLOROBENZENE GENERATION DURING PESTICIDE, HERBICIDE, AND FUNGICIDE
PRODUCTION
The production of aromatic chlorinated hydrocarbon pesticides,
herbicides, and fungicides has been indicated in the literature to
generate HCB wastes. In total, pesticide production accounts for about
40 percent of the HCB generated in the United States. The bulk of HCB
from pesticide production is associated with two compounds: the fungi-
cide pentachloronitrobenzene (PCNB) and the herbicide dimethyl tetra-
chloroterephthalate (DCTA), or Dacthal*. The production of another
pesticide, chlorothalonil or Daconil*, is also expected to generate HCB
wastes. ^
Process Descriptions
Pentachloronitrobenzene (C^Cl^SO^) is produced by chlorinating
various chloronitrobenzenes in the presence of an iron-iodine catalyst.
As with other HCB-generating processes, HCB from PCNB production is
expected to occur in distillation bottoms. No further information is
available concerning the production process.
The production of Dacthal* involves the reaction of hexachloro-p-
xylene with terephthalic acid, followed by the chlorination of the crude
reaction product to form tetrachloroterephthaloy1 dichloride. Reactions
during the chlorination process form HCB. The chlorination product then
undergoes esterification to produce Dacthal*. HCB is a component of the
solid waste streams generated by this process. In 1975, HCB was
reported to constitute 84 percent of wastes from Dacthal* production;
however, no information is available concerning current levels of HCB in
production wastes.
All data relating to the production of Daconil* and quantities of
HCB generated are confidential because there is only a single producer
of the compound. However, the production of this chemical has not been
discussed in the literature as being an HCB source, and it is believed
that the quantities of HCB generated are small in comparison to those
from PCNB and Dacthal*.
116
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Emissions
HCB air emissions from pesticide production result primarily from
the final waste disposal activities used to treat the HCB wastes. HCB
wastes from pesticide production are disposed of in off-site landfills.
As a result, HCB emissions from landfills can occur from volatilization
and windblown and physical displacement of soil particles containing
adsorbed HCB.81 Current waste practices for HCB waste-producing plants
appear in Table 23.
The above pesticides contain HCB as a contaminant and will be
81
released upon use.
Source Locations
The only facility currently producing PCNB is Olin Corporation in
Leiand, Mississippi. Dacthal* and Daconil* are manufactured by SDS
Biotech (formerly Diamond Shamrock) in Green Bayou, Texas.1* This
listing is subject to change as market conditions change, facility
ownership changes, plants are closed, etc. The reader should verify the
existence of particular facilities by consulting current listings and/or
the plants themselves. The level of HCB emissions from any given
facility is a function of variables such as capacity, throughput and
control measures, and should be determined through direct contacts with
plant personnel.
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USE OF FUNGICIDES AND HERBICIDES CONTAINING HEXACHLOROBENZENE
HCB will be released to the environment through the use of an HCB
product or the use of a material containing HCB as a contaminant.
The only product line in use in the United States containing HCB as
an active ingredient is a group of fungicides used as seed treatments
(Table 27). Since these seed treatments are applied as liquids, some
potential for fugitive HCB volatilization exists during application.
Subsequent volatilization of HCB from the treated seeds may also be a
source of HCB emissions. Due to recent EPA cancellation of the regis-
tration of these HCB treatment fungicides, their use should cease after
QI
existing inventories are depleted.
The most important source of HCB air emissions appears to be the
use of PCNB, Dacthal*, and Daconil*, which contain HCB as a trace con-
taminant. PCNB is a fungicide mainly used as a soil and seed treatment
for cotton, peanuts, and turf. Dacthal* is a herbicide treatment for
soils used to grow vegetables, field crops, strawberries, nursery stock
and turf. No specific uses of Daconil* were found in the literature.
These compounds are used in much greater quantities and on a much wider
variety of materials than the chemicals containing HCB as an active
ingredient. No effort has been made to reduce or ban the use of PCNB,
Dacthal*, or Daconil*. Fugitive HCB air emissions could potentially
occur from the application of these chemicals due to volatilization and
windblown displacement of soil containing adsorbed HCB. HCB emissions
of this type could occur in any region of the country because PCNB,
81
Dacthal*, and Daconil* are applied in agricultural areas nationwide.
118
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TABLE 27: PREVIOUSLY REGISTERED SEED TREATMENT FORMULATIONS
CONTAINING HEXACHLOROBENZENE16'*
Ortho Wheat Seed Protectant (Slurry)
Ortho Drill Box Wheat Seed Protectant
Ortho HCB 4 Flowable Seed Protectant
No Bunt "40"
Rhodia No Bunt Liquid
Hexachlorobenzene (Technical Grade)
Captan-Hexachlorobenzene 40-40 Seed Protectant
Captan-Hexachlorobenzene 20-20 Seed Protectant
Captan-HCB-Maneb 20-20-20 Seed Protectant
Captan-Hexachlorobenzene 40-10 Seed Protectant
Agsco DB-Yellow-A Seed Disinfectant
Miller's Smut-Go
Res-Q Seed Disinfectant Powder
Dual Purpose Res-Q
Res-Q-100 Seed Disinfectant and Protectant Dust or Slurry
Res-Q-200 Seed Disinfectant and Protectant Dust or Slurry
Parsons Seed Saver-DB
Granox N-M Fungicide Seed Treatment
Granox Flowable Seed Treatment
Seed Shield Maneb/HCB Flowable
Seed Shield Maneb-HCB Planter Box Seed Treater
Thihex
Sowmatic I
Clean Crop M50-H10 Seed Protectant for Small Grains
Seed-Treat JJrill Box & Slurry #40
Clean Crop HCB Seed Treater
Maneb-HCB Planter Box Seed Treater
Registrations for these compounds have been cancelled by EPA as of
1984." Upon cancellation it is a violation of FIFRA to further
produce or use the compounds after existing inventories are depleted.
119
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VOLITILIZATION OF CHLOROBENZENES FROM WASTEWATER TREATMENT OPERATIONS
Chlorobenzenes may be emitted when wastes containing chlorobenzenes
are present in surface impoundments for treatment and storage of waste-
water or in open treatment and storage tanks. Treatment and storage
facilities may be located at the site of generation of the waste, or at
a separate commercial waste treatment plant. In addition, publicly
owned treatment works (POTWs) may emit chlorobenzenes if they receive
wastewaster from plants producing chlorobenzenes either as a main
product or as a byproduct, or from plants using chlorobenzenes as an
intermediate. For example; at one 42 million gallon per day (MGD) POTW,
93, 61 and 100 percent, respectively, of the influent contributions of
1,2,4-TCB, m-DCB, and p-DCB were found to have originated as byproducts
of industrial processes. Moreover, at this plant, approximately 54
percent of the volatile organics (including MCB) were attributed to
industrial origins.
A typical secondary treatment facility sequence utilized by many
existing wastewater treatment facilities consists of screening, grit
removal, primary clarification, conventional activated sludge with aera-
tion, and chlorination. Due to the volatile nature of chlorobenzenes,
air emissions are expected mainly from clarification and aeration pro-
cesses. Measurements of the chlorobenzenes concentrations in the
effluent of the 42 MGD POTW discussed above suggest that the overall
treatment process removes 40 to 90 percent of the incoming chloro-
benzenes, primarily during activated sludge aeration. Partitioning of
1,2,4-TCB, m-DCB, and p-DCB to the primary clarifier sludge and
activated sludge indicates that some fraction of these pollutants may
accumulate onto settleable or floatable solids. However, the remainder
is expected to be removed by either air stripping or by biodegrada-
86
tion. Air stripping would result in air emissions of chlorobenzenes.
Testing of the aeration basins at a small municipal treatment plant
(handling 40 percent industrial and 60 percent municipal sewage) result-
ed in the measurement of emissions of o-DCB and m-DCB ranging from
levels of 148 to 478 grams/hour and 155 to 609 grams/hour, respective-
0*7
ly. Monochlorobenzene was measured only at trace quantities. No data
120
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were collected for other chlorobenzenes. Too little data are available
to extrapolate these test results to other wastewater treatment plants.
Source Locations
Specific locations of POTWs that treat wastewater containing VDC were
not identified, therefore the reader should contact particular facilities
to determine if such wastes are treated. For the locations of industrial
facilities handling VDC wastes, refer to separate sections on production
processes where VDC is produced or used as a feedstock.
121
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BURNING OF WASTE OIL
Monochlorobenzene and o-dichlorobenzene have been identified as
contaminants of potential concern in waste crankcase oils used as fuel.
Approximately 1.2 billion gallons of used automotive and industrial oils
are generated annually of which 35 percent is collected and used as
fuel.8** Studies of waste oil composition show that waste industrial
oils are contaminated with chlorinated solvents. It has also been
suggested that chlorinated hydrocarbons in the oils are formed chemical-
ly during oil use or may result from contamination by solvents in hold-
ing tanks. Observed concentration ranges for MCB and o-DCB in waste
88
oils are 4 to 500 ug/1 and 60 to 160 ug/1, respectively.
Emissions
It is uncertain how much MCB and o-DCB are released into the
atmosphere during the burning of waste oil as fuel. Emissions are
related to initial concentrations of chlorobenzene in the waste oil as
well as boiler operating parameters and control devices. No information
was available concerning actual emission rates.
Source Locations
Locations of boilers which use waste oils for fuel have not been
identified in the literature.
122
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MISCELLANEOUS OSES OF CHLOROBENZENES
The following section discusses miscellaneous uses of chloroben-
zenes in production for which no detailed information is available.
Also included are possible uses and emission sources for less commonly
used chlorobenzenes not previously discussed, namely, m-DCB, 1,2,3-TCB
and 1,3,5-TCB.
Monochlorobenzene
MCB is used consumptively as an inert process solvent in the pro-
duction of rubber intermediate and during diisocyanate manufacture. As
an inert process solvent, MCB is the medium in which the process
reaction occurs and is later separated for recovery and recycling.
Nonrecoverable solvent and impurities are released primarily in water
discharges, with a small quantity emitted to the atmosphere.*1
MCB is employed as a solvent in the production of adhesives,
paints, polishes, and waxes. The exact function of solvent use is not
known, however, it is estimated that a majority of MCB is retained in
the product and will be released through subsequent use.11
Until recently, Monsanto Company utilized large quantities of
monochlorobenzene in its popular pesticide, Lasso*. Since then,
Monsanto has reformulated the pesticide from a liquid to a new encap-
sulated version which will ultimately lower Monsanto's MCB use by
80 percent. No information was available concerning processes or
QQ >
emissions. * '
o-Dichlorobenzene
Like p-DCB, o-DCB is also used as a deodorant; however, due to its
liquid form it is distributed in a different manner. Literature cites
its use in wastewater treatment for this purpose, although details were
not disclosed for actual usage.
p-Dichlorobenzene
Lesser known uses of p-DCB include its use in the manufacture of
Pharmaceuticals, floor waxes and finishes, as a chemical intermediate,
and as an extreme pressure lubricant.11 Para-dichlorobenzene is present
123
-------
as a contaminant in the above substances and may be released through
subsequent use.
m-Dichlorobenzene
The use of m-DCB is not extensive, although it has been used as a
fumigant and insecticide. Due to its limited use, emissions contributed
by these sources are negligible. 1
1.2.4-Trichlorobenzene
1,2,4-TCB is used as a solvent for crystallization of high melting
point products, in termite control, in septic tank and drain cleaner
preparations, and as a lubricant. Further information on the above uses
is not available. Emissions are given off during production and use of
secondary products. *
1.3.5-Trichlorobenzenes
1,3,5-TCB is also used as a solvent for high temperature melting
point products in addition to uses as a coolant in electrical installa-
tions and glass tempering, heat transfer medium, lubricant, and syn-
thetic transformer oil. It is used in termite preparations, the manu-
facture of 2,5-dichlorophenol, polyester dyeing and insecticides. It is
estimated that emissions are released during the production and use of
these products.11'39
1.2.3-Trichlorobenzenes
The limited uses of 1,2,3-TCB include its use as an organic inter-
mediate, termite control agent, agricultural insecticide, and synthetic
transformer oil. Emissions are expected from termite control opera-
tions, agricultural runoff, general laboratory usage and from its use as
a transformer oil.
Hexachlorobenzene
HCB solid wastes are generated during the synthesis of hexachloro-
cyclopentadiene (HCCPD), a chemical intermediate used to make pesticides
and flame retardants. Currently, Velsicol Chemical operates two HCCPD-
generating facilities located in Marshall, Illinois, and Memphis,
Tennessee (subject to change as market conditions change, facility
ownership changes, plants are closed, etc.).1" Wastes generated in the
124
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distillation bottoms contain 2 to 6 percent HCB, and are landfilled,
81
potentially resulting in volatilization during waste handling.
HCB wastes are also known to have been generated during past elec-
trolytic chlorine production and sodium chlorate production processes
which used graphite anodes containing coal tar pitch binder. Since then
almost all graphite anodes have been replaced with metal anodes in
these operations.
Industrial uses of HCB have declined in recent years. Currently no
HCB is produced domestically or imported into the United States. Of
importance only from a historical standpoint, past uses of HCB include
(1) as a porosity agent in the manufacture of industrial graphite
anodes; (2) as a fluxing agent in smelting operations of primary alumi-
num production; (3) as a peptizing agent in the manufacture of nitros
and styrene rubbers, and (4) as a feedstock in pxoduction of pyrotechnic
(e.g., signal flares) and ordnance (e.g., tracer bullets) materials for
military and civilian applications.
125
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-------
SECTION 5
SOURCE TEST PROCEDURES
Chlorobenzene emissions can be measured using EPA Reference
Method 23, which was proposed in the Federal Register on June 11,
1980.90 The method has not been validated by EPA for chlorobenzenes but
a similar analytical procedure has been used to measure occupational
exposures to chlorobenzenes.
In Method 23, a sample of the exhaust gas to be analyzed is drawn
• • •
into a Tedlar or aluminized Mylar bag as shown in Figure 22. Tedlar
is considered a more reliable bag material than Mylar for chloroben-
zenes. The bag is placed inside a rigid leak proof container and evac-
uated. The bag is then connected by a Teflon sampling line to sampling
probe (stainless steel, Pyrex* glass, or Teflon ) at the center of the
stack. Sample is drawn into the bag by pumping air out of the rigid
container.
The sample is then analyzed by gas chromatography (GC) coupled with
flame ionization detection (FID). Analysis should be conducted within
one day of sample collection. The recommended GC column is 3.05 m by
3.2 mm stainless steel, filled with 20 percent SP-2100/0.1 percent
Carbowax 1500 on 100/120 Supelcoport. This column normally provides an
adequate resolution of halogenated organics. (Where resolution
interferences are encountered, the GC operator should select the column
best suited to the analysis.) The column temperature should be set at
100°C. Zero helium or nitrogen should be used as the carrier gas at a
flow rate of approximately 20 ml/min.
The peak area corresponding to the retention time of chlorobenzenes
is measured and compared to peak areas for a set of standard gas
mixtures to determine the chlorobenzene concentration. The range of the
method is 0.1 to 200 ppm; however, the upper limit can be extended by
extending the calibration range or diluting the sample. To avoid
126
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FILTER
(GLASS WOOL)
SAMPLING
BAG
RIGID
LEAKPROOF
CONTAINER
FLOW
METER
CHARCOAL
TUBE
Figure 22. Method 23 Sampling Train.
9Q
127
-------
absorption of chlorobenzenes by the Tedlar bag, the sample should be
analyzed as soon as possible after collection, preferably on the same
day. The method does not apply when chlorobenzenes are contained in
particulate matter.
128
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-------
REFERENCES
1. Investigation of Selected Potential Environmental Contaminants:
Halogenated Benzenes. EPA-560/2-77-004, U.S. Environmental
Protection Agency, Office of Toxic Substances, Washington, D.C.,
July 1977. pp. 6-43.
2. Health Assessment Document for Chlorinated Benzenes. EPA-600/8-84-
015A. U.S. Environmental Protection Agency, Office of Research and
Development, Cincinnati, Ohio, April 1984. p. 3-6.
3. Reid, R.C., Prausnitz, J.M., and T.K. Sherwood. The Properties of
Gases and Liquids, Third Edition. McGraw-Hill Book Company, New
York, New York, 1977. p. 184.
4. Windholz, M. ed. The Merck Index Tenth Edition. Merck and
Company, Rahway, New Jersey, 1984. pp. 298, 444, 677, 1377.
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153, 157, 171.
6. Kirk-Othmer Encyclopedia of Chemical Technology. Volume 5. Third
Edition: Wiley-Interscience Publication, New York, New York, 1980.
pp. 797-808.
7. 1984 Directory of Chemical Producers, United States of America.
SRI International, Menlo Park, California, 1984. p. 493.
8. Reference 7, p. 525.
9. Reference 7, p. 526.
10. Chemical Profile: Monochlorobenzene. Chemical Marketing Reporter,
Volume 226, Number 13, September 24, 1984. p. 74.
11. Slimak, K. et al. Materials Balance for Chlorobenzenes. EPA-560/
13-80-001, U.S. Environmental Protection Agency, Office of Toxic
Substances, Washington, D.C., January 1980. pp. 3-1 to 3-19.
12. Chemical Profile: o-Dichlorobenzene. Chemical Marketing Reporter,
Volume 226, Number 12, September 17, 1984. p. 58.
13. Chemical Profile: p-Dichlorobenzene. Chemical Marketing Reporter,
Volume 226, Number 11, September 10, 1984. p. 62.
14. Brooks, G.W. and G.E. Hunt. Source Assessment for
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129
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,
15. Reference 14, pp. 19-22.
16. Reference 14, pp. 22-29.
17. Liepins, R. and F. Nixon. Industrial Process Profiles for
Environmental Use: Chapter 6.' The Industrial Organic Chemicals
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February 1977. pp. 6-55 to 6-56.
18. Organic Chemical Manufacturing. Volume 6: Selected Processes.
EPA-450/3-80-028a, U.S. Environmental Protection Agency Office of
Air Quality Planning and Standards, Research Triangle Park, North
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19. Lowenheim, F.A. and, M.K. Moran. Faith, Keyes, and Clark's
Industrial Chemicals. Fourth Edition. John Wiley and Sons, New
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20. Reference 18, pp. IV-1 to IV-5.
21. Human Exposure to Atmospheric Concentrations of Selected Chemicals,
Volume II: A Summary of Data on Chlorobenzenes. U.S. Environ-
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Standards, Research Triangle Park, North Carolina. PB83-265249,
February 1982. p. 7-16.
22. An Exposure and Risk Assessment for Dichlorobenzenes. Final Draft.
U.S. Environmental Protection Agency, Office of Water Regulations
and Standards, Washington, D.C., 1981. p. A-l.
23. Reference 7, p. 941.
24. Reference 14, pp. 2-9.
25. Clarke, Eric A., Ecological and lexicological Association of
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Quality Planning and Standards, Durham, North Carolina, March 13,
1985.
26. Steadman, T.R. et al. Industrial Process Profiles for
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EPA-600/2-77-023g, U.S. Environmental Agency, Cincinnati, Ohio,
February 1977. pp. 15-63.
27. Kirk-Othmer Encyclopedia of Chemical Technology. Volume 8. Third
Edition. John Wiley and Sons, New York, New York, 1979. pp. 175-
176.
28. Reference 26, pp. 152-153.
130
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29. Reference 26, pp. 89-91.
30. Reference 26, pp. 108-110.
31. Reference 26, p. 119.
32. Reference 26, p. 130-132.
33. Reference 26, pp. 139-140.
34. Reference 26, pp. 92-93.
35. Reference 26, pp. 120-122.
36. 1984 Buyers Guide. Textile Chemist and Colorist. Volume 16,
Number 7, July 1984. p. 7.
37. Telephone Conversation between E. Bolin, Ciba-Geigy Corporation,
Greensboro, North Carolina, and Janice L. Demmy, GCA Corporation,
Chapel Hill, North Carolina, June 3, 1985.
38. Reference 22, pp. 3-1 to 3-13.
39. McNamara, F.W. et al. An Exposure and Risk Assessment for 1,2,4-
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Agency, Office of Water Regulations and Standards, Washington,
D.C., June 1981. pp. 3-10 to 3-15.
40. Guidelines for Control of Trichloroethylene, Perchloroethylene,
1,1,1-Trichloroethane, Methylene Chloride, and Trichlorofluoro-
ethane from Existing Organic Cleaners. Working Group Draft. U.S.
Environmental Protection Agency, Office of Air Quality and Planning
Standards, Research Triangle Park, North Carolina, July 1981.
pp. 2-2 to 2-8.
41. Reference 40, pp. 3-2 to 3-20.
42. Reference 40, pp. 4-1 to 4-7.
43. Reference 21, p. 7-20.
44. Organic Solvent Cleaners-Background Information for Proposed
Standards. EPA-450/2-78-045a, U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Research
Triangle Park, North Carolina, October 1979. p. 7-4.
45. Rosensteel, R.E., U.S. Environmental Protection Agency, Chemicals
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131
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46. Reference 27, pp. 150-157.
47. Reference 17, pp. 6-61 to 6-62.
48. Reference 7, p. 497.
49. Reference 17, p. 6-153.
50. Reference 7, p. 782.
51. Mai loch, C.D., Monsanto Company, St. Louis, Missouri. Letter to
D.R. Patrick, Pollutant Assessment Branch, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina, July 16,
1982.
52. Honea, F.I., Industrial Process Profiles for Environmental Use:
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Environmental Protection Agency, Office of Energy, Minerals and
Industry, Research Triangle Park, North Carolina, January 1977.
pp. 21-22.
53. Reference 52, p. 163.
54. Reference 7, p. 771.
55. Reference 7, p. 772.
56. Reference 17, pp. 6-68 to 6-70.
57. Parr, J., Parsons, T.B. and N.P. Phillips. Industrial Process
Profiles for Environmental Use: Chapter 9. The Synthetic Rubber
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Industrial Environmental Research Laboratory, Cincinnati, Ohio,
February 1977. p. 60.
58. Chemical Week Buyer's Guide '84 (Dow Chemical), McGraw-Hill Inc.,
New York, New York, 1982. p. 14.
59. Organic Chemical Manufacturing. Volume 7: Selected Processes.
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Air Quality Planning and Standards. Research Triangle Park, North
Carolina, December 1980. pp. 3-II-1 to 3-III-7.
60. Turetsky, W.S., Allied Chemical, Morristown, New Jersey. Letter to
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61. Reference 7, p. 661.
132
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62. Norwood, V.M., Olin Chemicals Group, Charleston, Tennessee. Letter
to D.R. Patrick, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, July 24, 1980.
63. Control of Volatile Organic Emissions from Manufacture of
Synthesized Pharmaceuticals Products. EPA-450/2-78-029, U.S.
Environmental Protection Agency, Research Triangle Park, North
Carolina, December 1978. p. 1-2 to 4-1.
64. Reference 63, p. A-3.
65. Kirk-Othmer Encyclopedia of Chemical Technology. Volume 16. John
Wiley and Sons, New York, New York, 1982. pp. 297-306.
66. Kirk-Othmer Encyclopedia of Chemical Technology, Volume 13. John
Wiley and Sons, New York, New York, 1981. pp. 478-479.
67. Boscato, J.F. et al. Synthesis of Polyphenylene Sulfur. Polymer
Bulletin (Berlin) 4(7):357-359, 1981.
68. Kirk-Othmer Encyclopedia of Chemical Technology, Volume 18. John
Wiley and Sons, New York, New York, 1982. pp. 802-808.
69. Deitsch, M. and V. Kollonitsch, eds. The Kline Guide to the
Plastic Industry. Charles Kline and Company, Fairfield, New
Jersey, 1983. p. 318.
70. Berg, G.L., ed. Farm Chemicals Handbook. Meister Publishing
Company, Willoughby, Ohio, 1984. pp. C168, C172.
71. Reference 66, pp. 416-417.
72. Reference 21, p. 7-22.
73. Kirk-Othmer Encyclopedia of Chemical Technology. Volume 1. John
Wiley and Sons, New York, New York, 1982. pp. 43-45.
74. Reference 52, pp. 134-216.
75. Reference 7, p. 765.
76. Polychlorinated Biphenyls (PCBs), Manufacturing, Processing and
Distribution in Commerce and Use Prohibitions, 40 CFR Part 761.
Federal Register, Volume 44, No. 106, May 31, 1979. pp. 31514-
31568.
77. Source Test Report: Summary of Emissions to the Atmosphere for
Ross Electric of Washington, Inc., State of Washington Department
of Ecology, February 6, 1985. p. 2.
133
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78. Mclnnes, R.G., and R.C. Adams. Provision of Technical Assistance
to Support Implementation of the PCS Regulations (January -
December 1983), U.S. Environmental Protection Agency, Office of
Research and Development, Washington, D.C.
79. Cohen, E., U.S. Environmental Protection Agency, Region III,
Hazardous Waste Management Division, Philadelphia, Pennsylvania.
Letter to Tom Lahre, U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Research Triangle Park,
North Carolina, February 7, 1985.
80. Supplement No. 12 for Compilation of Air Pollutant Emission
Factors, Third Edition. AP-42, U.S. Environmental Protection
Agency, Office of Air, Noise, and Radiation, Office of Air Quality
Planning and Standards, Research Triangle Park, North Carolina,
April 1981. p. C-ll.
81. Reference 14, pp. 29-46.
82. Smith, M. Preliminary Study of Sources of Carbon Tetrachloride.
EPA-450/5-83-007, U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards, Research Triangle Park, North
Carolina, June 1984. p. 3-2.
83. Chemical Product Synopsis: Trichloroethylene. Mannsville Chemical
Products, Cortland, New York, April 1984.
84. Chemical Product Synopsis: Perchloroethylene. Mannsvil le Chemical
Products, Cortland, New York, April 1984.
85. Certain Pesticide Products; Intent to Cancel Registrations.
Federal Register, Volume 49, No. 110, June 6, 1984. pp. 23440-
23441.
86. Fate of Priority Toxic Pollutants in POTW's - 30-Day Study. EPA-
440/1-82-302, U.S. Environmental Protection Agency, Effluent
Guidelines Division, August 1982. pp. 1-65.
87. Pellizzari, E.D. Volatile Organics in Aeration Gases of Municipal
Treatment Plants: Project Summary. EPA-600/52-82-056, U.S.
Environmental Protection Agency, Office of Research and
Development, Municipal Environmental Research Laboratory,
Cincinnati, Ohio, August 1982. pp. 3-4.
88. Liquid Fuel Sample Analysis. Eureka Laboratories, Inc.,
Sacramento, California, November 10, 1984. pp. 1-3.
89. Reference 10, p. 3.
90. Method 23. Determination of Halogenated Organics from Stationary
Sources. Federal Register, Volume 45, No. 114, June 11, 1980.
pp. 39776-39784.
134
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91. Chemical Product Synopsis: Dichlorobenzene. Mannsville Chemical
Products, Courtland, New York, March 1983.
92. Letter from L.N. Medaugh of BASF Wyandotte Corp. to T. Lahre of
U.S. Environmental Proection Agency. March 7, 1985.
93. Grome, T.G. and G.E. Wilkins. Source Assessment for para-
Dichlorobenzene. Prepared for U.S. Environmental Protection Agency
under Contract 68-02-3889 by Radian Corp. Research Triangle Park,
N.C., September 5, 1985.
135
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-450/4-84-007m
2.
3. RECIPIENT'S ACCESSION NO.
TITLE AND SUBTITLE
LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES
OF CHLOROBENZENES
EPORT DATE ,„„.
September 1986
S. PERFORMING ORGANIZATION CODE
AUTHOR(S)
GCA Technology
Bedford, MA 01730
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EPA Project Officer: Thomas F. Lahre
16. ABSTRACT
To assist groups interested in inventorying air emissions of various potentially
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available information on sources and emissions of these substances. This document
deals specifically with Chlorobenzenes. Its intended audience includes Federal,
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emitters of Chlorobenzenes and in making gross estimates of air emissions therefrom.
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Chlorobenzenes
Sources
Locating Emissions Sources
Toxic Substances
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