-------
TABLE 2.4 OTHER PRODUCERS OF CHLORINATED BENZENES (continued)
Ni
I
•-J
Company
Hummel Chemical Co., Inc.
(Blackwood and Sipes,
1977)
Kennedy and Klein, Inc.
(Comer et al., 1979)
Hontrose Chemical Corp.
of California (Investiga-
tion of Selected Poten-
tial Environmental Con-
taminants, 1977)
Stauffer Chemical Co.
(Blackwood and Sipes,
1977)
Rhodia, Inc.
(Blackwood and Sipes,
1977)
PPG Industries, Inc.
(Investigation of Selec-
ted Potential Environ-
mental Contaminants, 1977)
Specialty Organlcs '
(Investigation of Selec-
ted Potential Environ-
mental Contaminants, 1977)
01 o> oi i in c c 01
ot c c c o i i
X X
-------
TABLE 2.4 OTHER PRODUCERS OF CHLORINATED BENZENES (continued)
OO
Company
Eastman Kodak
(Investigation of Selec-
ted Potential Environ-
mental Contaminants, 1977)
Guardian Chemical Co.
(Investigation of Selec-
ted Potential Environ-
mental Contaminants, 1977)
Transvaal, Inc.
(Investigation of Selec-
ted Potential Environ-
mental Contaminants, 1977)
Aceto Chemical Co.
(Investigation of Selec-
ted Potential Environ-
mental Contaminants, 1977)
Chemical Procurement
Labs, Inc.
(Investigation of Selec-
ted Potential Environ-
mental Contaminants, 1977)
o> a
a a a i in c e
ft* c c coii^Qja) a* a)
C 41 0 OKOO-CC UN
«i N N NoaiuubfoirMiuai i i i c c
N C C C rH C OC OC • N N ^\ 10 V (001 <0 01 Q)s~v a)
» -0 ^1
u ^ ^ ^ ON .CN f tf aj ato 4-i^ M^ w.a caw U-H tu 14) id] r- *j i^ t^i JZ xo.nw *jn nw OJQ. co
O-H*H 03 -H • » . *u Ou) »o " O » O UI/1U
C'O'O *Org (S CO (M-H-rtCCNl-(CMt-(eNr-t*JeC
o i.i i i . « . »i4 Ki3 *j: »^: -.c a>B o)
B O S O 0.rH rH ^H ,_|U U%^ rHti ^U ^IO U ^ O.
X
X
X X
X
X
0)
c
a)
N
C
0
o
o
X
f.
1. Hooker Chemicals and Plastics no longer produces chlorobenzenes (Journal of Commerce, 1976).
2. 1,3,5-trichlorobenzene is produced as a specialty chemical (Comer et al., 1979).
3. Pentachlorobenzene is produced as a captive byproduct (Investigation of Selected Potential Environmental Contaminants, 1977).
A. Specialty Organics Is a processor rather than a manufacturer (Investigation of Selected Potential Environmental Contaminants, 1977).
5. Transvaal, Inc. imports rather than produces chlorobenzenes (Investigation of Selected Potential Environmental Contaminants f 1977).
-------
FIGURE 2.1 LOCATION OF PLANTS MANUFACTURING CHLOROBENZENES
(1) Allied Chemical Corp., Solvay, New York
(2) Dover Chemical Corp., Dover, Ohio
(3) Dow Chemical Co., Midland, Michigan
(4) Hummel Chemical Co., Inc., South Plainfield, New Jersey
(5) ICC Industries, Niagara Falls, New York
(6) Kennedy and Klein, Inc., Red Bank, New Jersey
(7) Monsanto Co., Sauget, Illinois
(8) Montrose Chemical Corp. of California, Henderson, Nevada
(9) PPG Industries, Inc., New Martinsville, West Virginia
(10) Standard Chlorine of Delaware, Inc., Delaware City, Delaware
(11) Stauffer Chemical Co., Louisville, Kentucky
2-9
-------
2.3 IMPORTS AND EXPORTS
Table 2.5 summarizes the imports of chlorobenzene compounds from 1972
through 1978. The quantities imported vary from year to year. No information
was readily available for those chlorobenzenes that are produced in small
quantities and have limited uses (e.g., 1,2,3-trichlorobenzene, 1,2,3,4-tetra-
chlorobenzene, etc.).
Belgium, France, and West Germany are major exporters of chlorobenzenes to
the United States (Investigation of Selected Potential Environmental Contaminants,
1977). However, the majority of the chlorobenzene imports in 1975 came from
Poland (SRI, 1977). Only one importer, Transvaal, Inc., is known. This company
ceased production of tetrachlorobenzene in favor of its importation from West
Germany (Investigation of Selected Potential Environmental Contaminants, 1977).
Dichlorobenzene exports amounted to 500 kkg in 1975 and 1200. kkg in 1976
(SRI, 1977). It is estimated that 17,400 kkg of dichlorobenzene will be exported
in 1979 (U.S. Exports, 1979). No information regarding the exports of other
chlorobenzene compounds was readily available.
2.4 PRODUCTION METHODS AND PROCESS
The higher chlorinated benzenes are produced with chlorobenzene during the
catalytic chlorination of benzene but the amounts are small. Changes in the
reaction conditions can maximize or minimize the production of specific chloro-
benzenes (Investigation of Selected Potential Environmental Contaminants,
1977). In general, the higher chlorinated isomers are produced via the chlorination
of the lesser chlorinated isomers. However, the rate of chlorine substitution
will decrease with the degree of chlorination (Investigation of Selected Potential
Evnironmental Contaminants, 1977), so it is sometimes necessary to use less
direct routes for the production of the more highly chlorinated compounds (e.g.,
hexachlorobenzene from cyclohexane).
2-10
-------
TABLE 2.5 IMPORTS (kkg)
to
I
COMPOUND
monochlorobenzene
o-dich lorobenzene
m-dichlorobenzene
p-dlch lorobenzene
t r Ich lorobenzene-mixed
lanmpra
1,2,4-trichlorobenzene
1, 2, 5-trlchlorobenzene
1,2,4, 5-tetracholorobenzene
1972
6
1
1973
1
2
20
80
1974
700
700
10
400
1300
10
700
1975
3800
50
1976
2800
800
2
100
4
20
1977
500
500
10
3
10
20
1978
400
20
60
10
900
600
SOURCES: (Investigation of Selected Potential Environmental Contaminants, 1977; SRI, 1977; USITC, 1979, 1978b, 1977c, 1976b)
-------
3.0 RELEASES FROM USE
3.1 RELEASES FROM CHLOROBENZENE USAGE
The current usage of chlorobenzene is as follows: production of chloronitro-
benzenes (35%), use as a solvent (30%), production of diphenyl oxide (10%),
production of rubber intermediates (10%), and other uses (including DDT production)
(15%) (Hydroscience, 1978). Table 3.1 summarizes these usages and the losses of
chlorobenzene to the environment from these usages.
The greatest releases of chlorobenzene are from its use as a solvent.
Chlorobenzene is used as a solvent in the production of adhesives, paints,
polishes, and waxes; it is also used as an inert process solvent in the manufacture
of diisocyanates, Pharmaceuticals, and natural rubber, and as a dye carrier in
textile dyeing operations (Investigation of Selected Potential Environmental
Contaminants, 1977). Although some losses will occur during the production of
adhesives, paints, polishes, and waxes (see Table 3.1, footnote 3), we estimate
that the majority of the chlorobenzene will be retained in the products and
subsequently released to the air through their use. However, as an inert
process solvent, chlorobenzene serves as the medium in which a chemical reaction
occurs. The product is separated from the solvent, some of the solvent is
recovered and recycled, and the remainder is released to water and air. It is
estimated that all of the chlorobenzene used as an inert solvent during a year
will be released, with the majority (98%) entering the water.
In Table 3.1, footnote 5, it is estimated that 7% of the available chlo-
robenzene (10,400 kkg) is used in the production of the insecticide dichloro-
diphenyltrichloroethane (DDT). Montrose Chemical Corporation is the only producer
of DDT in the United States (Midwest Research Institute, 1972). All of the
chlorobenzene produced in Montrose's plant in Henderson, Nevada is captively
used in the production of DDT (Hydroscience, 1978); the DDT plant is located in
Torrance, California and some formulation is done there (Midwest Research Institute,
1972). Other formulators are Helena Chemical and Valley Chemical, Mississippi;
Micro Chemical, Louisiana; and Olin Corporation, Arkansas (Midwest Research
Institute, 1972). Essentially all the DDT produced in the United States is
exported (SRI, 1977).
3-1
-------
TABLE 3.1 RELEASES FROM USES OF CHLORINATED BENZENES
PROCESS
Monochloro-
benzene Use
Production of
chloronitro-
benzene
Production of
Adheslves, Paints,
Polishes, Waxes
Use of Adhesives
Paints, Polishes,
Waxes
Use as an inert
process solvent
Production of
Diphenyl Oxide
Production of
Rubber Inter-
mediates
AMOUNT
USED (kkg)
51,900*
13.4002
13.1003
stored in
products
31.2002
14.8001
14.8001
POINT SOURCES
OF
RELEASE
Spills
QUANTITIES
STORED
(kkg)
13.1003
stored in
products
RELEASES TO THE ENVIRONMENT
Air
Amt.
(kkg) Form
703
f!3,1003
<6004
Land
Amt.
(kkg) Form
Water
Amt.
(kkg) Form
2003
f30,6004
u>
N>
-------
TABLE 3.1 RELEASES FROM USES OF CHLORINATED BENZENES (Continued)
PROCESS
Production of
DDT
Export of DDT
Other uses
o-Dlchlorobenzene
Use
Production of
3,4-dichloro-
aniline
Use as TDI
process solvent
AMOUNT
USED (kkg)
10.4005
1007 as a
contaminant
11.9005
9,6009
2.2009
POINT SOURCES
OF
RELEASE
Reactor vent
Reactor scrubber
Recycling vents
Acid wastes
Crystallizer, dryer,
f laker liquid
Spills
Wash-up and lab
Formulation and Packaging
Spills
Vents
Scrubber on vents
Solvent disposal to water
Centrifuge residue
QUANTITIES
STORED
(kkg)
56
to landfill
10
0.6 U
in landfill
RELEASES TO THE ENVIRONMENT
Air
Amt.
(kkg) Form
26
1356
6
negligible
2io
Land
Amt.
(kkg) Form
I7
Water
Amt.
(kkg) Form
A
19b
6
3126
56
106
2°
20 10
in
<2,1771U
-------
TABLE 3,1 RELEASES FROM USES OF CHLORINATED BENZENES (Continued)
PROCESS
Other solvent
uses
Production of
Dyes, including
Mordant Red 27,
Direct Blue 108,
and Direct
Violet 54
Other uses,
including
use as a
pesticide and
deodorant
Exports
p-Dichloro-
benzene Use
Use as a
deodorant
Use for
moth control
AMOUNT
USED (kkg)
1.5006
7009
7009
7.3008
9.70012
7.80012
POINT SOURCES
OF
RELEASE
Spills
Toilet bowl
garbage
Moth balls
QUANTITIES
STORED
(kkg)
13
5200 J in
landfill
RELEASES TO THE ENVIRONMENT
Air
Amt.
(kkg) Form
I11
«1,700}*
13,700
£7,80014
Land
Amt.
(kkg) Form
711
Water
Amt.
(kkg) Form
6411
54,10013
w
-------
TABLE 3.1 RELEASES FROM USES OF CHLORINATED BENZENES (Continued)
•*
PROCESS
Other manu-
facturing
Exports
1,2,4-Tri-
chlorobenzene
Use
Use as a
dye carrier
Production
of herbicides,
including
dicamba and
2,5-dichloro-
benzoic acid
Other uses
including
functional
fluids
AMOUNT
USED (kkg)
1.90012
10.1008
6,20016
1 ft
3.90010
3>40016
POINT SOURCES
OF
RELEASE
Spills
Vats during dyeing
Waste water
Removal from fabric
Alkaline scour
Heating
QUANTITIES
STORED
(kkg)
RELEASES TO THE ENVIRONMENT
Air
Amt.
(kkg) Form
215
6017
17
160
Land
Amt.
(kkg) Form
io15
Water
Amt.
(kkg) Form
8915
17
60QO
1 7
30 '
OJ
Ul
-------
Table 3.1 footnotes:
1. Production of monochlocobenzene In 1977 was reported to be 147,700 kkg (U.S. International Trade Commission, 1978a). Imports
of this compound In 1977 were reported at 500 kkg (U.S. International Trade Commission, 1978b). Losses during Import were estimated
co be 6 kkg (page 2-22). No Information on exports of this compound were obtained, and exports are assumed to be 0 kkg. Therefore the
amounts of chlorobenzene available for use In this year would be 147,700 kkg + (500 kkg - 6kkg) - 148,200 kkg of monochlorobenzene.
Using the percentages of uses of monochlorobenzene stated by llydrosclence (1978), this available chlorobenzene can be broken
down Into the following amounts used:
Production of chloronltrobenzene 51,900 kkg (35Z)
Use as a solvent 44,500 kkg (30Z)
Production of dlphenyl oxide 14,800 kkg (101)
Production of rubber Intermediates 14,800 kkg (10Z)
Production of DDT and other uses 22,200 kkg (15Z)
2. Of the 44,500 kkg of monochlorobenzene used as a solvent, we estimated that the larger portion (70Z) muy be used an an Inert
process solvent. This estimation Is based on the fact that two of these processes, dllsocyanate production und textile
dyeing,are done on a large scale. The other 30Z of monochlorobenzenc use would Include the formulation of udheslves, paints,
polishes, and waxes.
Inert process solvent - (70Z)(44,500) - 31,200 kkg
Adhesive, paints, polishes, waxes - (30Z)(44,500) - 13,400 kkg
3. During the production of adhcslves, paints, polishes and waxes, we estimate that 2Z of the monochlorobenzune used will be
lost to spillage. Of this, we estimate a 1.5X loss to air through evaporation.
(0.015)(13,400 kkg) - 200 kkg
(0.005)(13,400 kkg) - 70 kkg
The remaining monochlorobenzene (13,400 kkg - 270 kkg - 13,100 kkg) Is retained In these compounds and will be released to air
through their use.
4. At a maximum, all of the chlorobenzene used as an Inert process solvent (31, 200 kkg) will be released to the environment
during use or disposal. Two percent might be expected to be lost to air through volatilization during uae. while 98Z Is
estimated to be discarded after use. We assume that the discarded amount Is released to water, since we have no other Information
on solvent disposal.
(0.02)(31.200 kkg) - 600 kkg
(0.98)(31.200 kkg) - 30, 600 kkg
-------
Table 3.1 footnotes (continued):
5. la 1973 and 1974, DDT production was estimated to account for 71 and 7.SI, respectively, of oonochlorobenzene use (Investigation
of Selected Potential Environmental Contaminants, 1977; SRI, 1977). Assuming that DDT production has remained at a similar
use level (7% of monochlorobenzene production), we estimated that (0.07)(148,200 kkg) or 10,400 kkg of monochlorobenzene Is
used In the production of DDT (see footnote 1). The remaining 81 of the category "DDT and other uses" (footnote 1) would be
attributed to "other uses" of monochlorobenzene. This amount Is (0.08)(148, 200 kkg) or 11,900 kkg.
6. From analysis of the DDT production process (Figure 3.1), we have estimated the following possible losses during DDT production.
These losses are based on knowledge of the high vapor pressure and low water solubility of chlorobcnzene.
a) reactor vent - (0.0002)(10,400 kkg) - 2 kkg to air
b) reactor vent scrubber - (0.0018)(10,400 kkg) - 19 kkg to recycling pond
c) vents from recycling - (0.013)(10,400 kkg) - 135 kkg to air
d) acid wastes - (0.0005)(10,400 kkg) - 5 kkg to landfill
e) liquid from crystallizer, dryer, flaker - (0.03)(10,400 kkg) - 312 kkg to recycling pond
f) spills - (0.0005)(10,400 kkg) - 5 kkg to recycling pond
g) washup and lab - (0.001)(10,400kkg) - 10 kkg to recycling pond
h) formulation and packaging - (0.0002)(10,400 kkg) - 2 kkg to recycling pond, negligible air release
7- All DDT produced In the U. S. la exported to other countries. If we estimate that II of the chlorobunzune uued In tliu
production of DDT remains as a contaminant (100 kkg) and that IX of DDT Is spilled during transport out of the country,
(10,400 kkg)(0.01)(0.01) or 1 kkg would be expected to be released to land during transport.
8. Exporta of dlchlorobunzenes from the first 6 months of 1979 were obtained from the U. S. Department of Commerce (September 1979).
This amount was 8, 700 kkg/6 months or 17,400 kkg/yr. Assuming:
a) 1979 Is comparable to 1977
b) no meta-dlchlorobenzene Is exported
c) amounts of o- and p-dlchlorobenzene are exported In the same proportions as they are made - 21,500 kkg o-dlchlorobenzene and
29, 500 kkg p-dlchlorobenzene or 421 ODCB and S8X PDCB (U.S. International Trade Commission, 1978a).
We would expect exports of o-dlchlorobenzene In 1977 to be (17, 400 kkg)(0.42) or 7300 kkg and exports of p-dlchlorobenzene In
1977 to be (17, 400kkg)(0.58) or 10,100 kkg.
9. Quantities of o-dlchlorobenzene available for use In 1977 were calculated from amounts produced, Imported and exported.
These amounts were 21, 500 kkg (U.S. International Trade Commission, 1978a), 500 kkg (U.S. International Trade Commission,
1978b) and 7300 kkg (footnote 8), respectively. In addition, 6 kkg of ODCB are lost during Import (pg. 2-22).
21,500 kkg + (500 kkg - 6 kkg) = 22,000 kkg - 7300 kkg - 14,700 kkg
-------
Table 3.1 footnotes (continued):
Using the percentage uses of o-dlchlorobenzene stated by Hydrosclences (1978) and SRI (1977), we estimate the following
amounts of o-dlchlorobenzene use:
Production of 3.4-dichloroanlllne 9600 kkg (65Z)
Use of TDI process solvent 2200 kkg (151)
Other solvent uses 1500 kkg (10X)
Dye manufacture 700 kkg (5Z)
Other uses (Including as pesticide 700 kkg (51)
and deodorant)
10. Amounts of OUCB released during use as a TDI process solvent were estimated using a process schematic for this process
(Figure 3.2). These estimates were based upon knowledge of the physical properties of ODCB (e.g. high vapor pressure, low
water solubility).
a) Vents from process - (.001)(2200 kkg) - 2 kkg to air
b) Scrubbers on vents - (.009)(2200 kkg) - 20 kkg to water
In addition to these estimates, an estimate of the amount of ODCB landfllled In the centrifuge residue was obtained. Processes
j_j Research (1977) reported that 558 kkg of centrifuge residue were produced each year per TDI plant. Since 10 plants are In operation
Co (Directory of Chemical Producers, 1977), we would expect 5580 kkg of centrifuge residue to be produced. Since It was stated that
less than several hundred ppra of this centrifuge residue Is ODCB (Investigation of Selected Potential Environmental Contaminants,
1977), we estimate (5580 kkg)(100 ppm) or 0.6 kkg of ODCB is released In this residue each year.
Finally, quantities of TDI solvent not released during use would be disposed of In some way after use. This solvent Is probably
released to water.
11. Amount of ODCB released during export were estimated at 1Z of the amount exported. Of the amount spilled, 88Z was estimated
to be cleaned up and, therefore, released In water. Ten percent of the spillage might be expected to remain on land, while
2Z was estimated to volatilize.
(7300 kkg)(0.01)(0.02) - 1 kkg to air
(7300 kkg)(0.01)(0.10) - 7 kkg to land
(7300 kkg)(0.01)(0.88) - 64 kkg to water
12. Quantities of p-dichlorobenzene available for use In 1977 were calculated from amounts produced and exported. These amounts were-
29,500 kkg (U. S. International Trade Commission. 1978). and 10,100 kkg (footnote 8). No Import data was obtained.
29,500 kkg - 10.100 kkg - 19,400 kkg
-------
Table 3.1 footnotes (continued):
Using the percentage uses of p-dlchlorobenzene stated by SRI (1977), we estimate the following amounts of p-dichlorobenzene
use:
Use as a deodorant 9700 kkg (50Z)
Use for moth control 7800 kkg (401)
Other manufacturing 1900 kkg (10Z)
13. PDCB Is used as a toilet bowl deodorant and a garbage deodorant. We estimated that the greater use (60Z) would be as a
toilet bowl deodorant.
Toilet bowl - (0.60) (9700 kkg) - 5800 kkg
Garbage - (0.40) (9700 kkg) - 3900 kkg
In Its use as a toilet bowl deodorant, we further estimated that 701 would be released to the water, whereas 301 would volatize
Into the air.
W . Water - (0.70) (5800 kkg) - 4100 kkg
VO
Air - (0.30) (5800 kkg) - 1700 kkg
In its use as a garbage deodorizer, we estimated that 951 would be released to the air, while 51 might be landfllled in the
garbage.
Air - (0.95) (3900 kkg) - 3700 kkg
Landfill - (0.05) (3900 kkg) - 200 kkg
14. It was estimated that release of p-dlchlorobenzene from mothball use would be entirely to air.
15. Releases during export of PDCB were estimated to be similar to releases during export of ODCB (footnote 11).
(10.100 kkg)(0.01)(0.88) - 89 kkg to water
(10,100 kkg)(0.01)(0.10) - 10 kkg to land
(10,100 kkg)(0.01)(0.02) - 2 kkg to air
16. A minimum production figure for 1.2,4-TCB Is shown in Table 2.2, footnote 1 (II,400 kkg). Since no import or export figures
could be obtained for 1,2,4-TCB, we assume that these quantities are 0 kkg. Therefore, the minimum amount of 1,2,4-TCB
available for use Is 13, 400 kkg.
Using the percentage uses of 1,2,4-TCB stated by Investigation of Selected Potential Environmental Contaminants (1977), the following
amounts of 1,2,4-TCB are used:
-------
Table 3.1 footnotes (continued):
Use as a dye carrier 6200 (461)
Production of herbicides 3900 (29Z)
Other uses 3400 (25Z)
17. During use of 1,2,4-TCB as a dye carrier, we estimated that IX of the amount used would be released to the air during the
dyeing process. In addition, It was estimated that as much as 31 of the 1,2,4-TCB used might be absorbed by the fiber. Two
processes are used to remove 1,2,4-TCB from the fiber - alkaline scour and heating (Schmldlln, 1963). Since heating Is used
preferably with dye carriers which are readily sublimed, we estimated that this process may remove up to 2.SZ of
1,2,4-TCB absorbed by treated fibers. The other 0.51 Is probably removed by the alkaline scour technique. Finally, 96Z of
the 1,2,4-TCB used Is estimated to be released In the wastewater from the dyeing operation.
Vats - (0.01)(6200 kkg) - 60 kkg to air
Heating - (0.025) (6200 kkg) - 160 kkg to air
Alkaline scour - (0.005)(6200 kkg) - 30 kkg to water
OJ
1 Uastewater - (0.9 6)(6200 kkg) - 6000 kkg to water
-------
Figure 3.1 illustrates the manufacturing process for DDT. The condensation
of chlorobenzene with chloral hydrate in the presence of sulfuric acid produces
DDT, as follows:
MCB
chloral
hydrate
MCB
DDT
The releases of chlorobenzene during the production of DDT are summarized in
Table 3.1 (see footnote 6). It is estimated that the greatest releases to the
atmosphere will be from the recycling vents while the greatest releases to the
water will be the waste stream from the crystallizer dryer flaker.
DDT is known to contain chlorobenzene as an impurity (Investigation of
Selected Potential Environmental Contaminants, 1977), but no information was
available regarding the amount of impurity. It is estimated (see Table 3.1,
footnote 7) that in one year, 100 kkg of chlorobenzene is retained as an impurity
in DDT. Since DDT is exported, the contaminants will only be released in the
United States from spills during transport to the port and these are estimated
to release 1 kkg of chlorobenzene to the land.
No information regarding the production processes for the manufacture of
chloronitrobenzenes, diphenyl oxides, or rubber intermediates from chlorobenzene
was readily available. Therefore, no estimates of releases from these processes
were made.
The largest area of consumption of chlorobenzene is in the production of
chloronitrobenzene. Du Pont and Monsanto have high yields of o- and p-chloro-
nitrobenzene from chlorobenzene (Investigation of Selected Potential Environmental
Contaminants, 1977); Monsanto captively uses much of the chlorobenzene it produces
to manufacture chloronitrobenzenes (Hydroscience, 1978). Chloronitrobenzenes
are intermediates in the production of phenylene diamine, nitroaniline, chloro-
aniline, and nitrophenol. These compounds are further used to produce dyes,
3-11
-------
FIGURE 3.1 PRODUCTION OF DDT . (Midwest Research Institute, 1972)
U)
M
Isi
NaOH
Floor and
Surface
Drains
Labs and
Wash-Up 1
C6H5CI
CCI3CHO
Evaporative
and Recycle
Water Pond
Crystal lizer
Dryer
F laker
Recycle
Acid
Acid
Recovery
Plant
Liquid
Waste
> (t>
Acid
Neutra-
lizer
Wastes
i
To Class 1
Dump
Formulation
Plant
-------
rubber chemicals, and pesticides (Stetcher, 1968; Hahn, 1970; Hancock, 1975).
Chlorobenzene may be a contaminant of chloronitrobenzene and would be released
during the manufacture of products from chloronitrobenzene or be carried through
as a contaminant of these secondary products.
Diphenyl oxide is used as a heat transfer medium, in perfuming soaps, and
in organic syntheses. Chlorobenzene will be released in the production of
diphenyl oxide, and in the manufacture and use of secondary products from
diphenyl oxide contaminated with Chlorobenzene.
3.2 RELEASES FROM DICHLOROBENZENE USAGE
3.2.1 o-Dichlorobenzene
The majority of the ODCB produced in the United States is consumed in the
production of 3,4-dichloroaniline (see Table 3.1, footnote 9). No information
on the production process was readily available so no estimates of ODCB release
during the process were made. 3,4-dichloroaniline is an intermediate in the
production of herbicides (propanil, diuron, neburon), dyes, polyethers, and
epoxy tar resins (SRI, 1977; Investigation of Selected Potential Environmental
Contaminants, 1977). Releases of ODCB will occur during the production of 3,4-
dichloroaniline and during the manufacture of products using 3,4-dichloroaniline
contaminated with ODCB.
ODCB is used as an inert process solvent in the manufacture of toluene
diisocyanate (TDI). During the synthesis of TDI, phosgene is reacted with 2,4-
diaminotoluene in an ODCB solution (Investigation of Selected Potential Environmental
Contaminants, 1977). Figure 3.2 illustrates the production process for TDI. In
the course of one year, all the ODCB used as a solvent will be released to the
environment. The majority of the ODCB will be released to the waste stream with
the remainder being released to air or landfilled (see Table 3.1. footnote 10).
Approximately 14% of the ODCB available is consumed in the production of
dyes and pesticides, and as a solvent. ODCB is an intermediate in the production
of the following dyes: Mordant Red 27, Direct Blue 108, and Direct Violet 54.
3-13
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FIGURE 3.2. TOLUENE DIISOCYANATE MANUFACTURE (Processes Research, 1977)
2 /.-DAT
Phosgene
I
I—1
4^
PHOSGCNE
BASIS: ) KG TOLUENE OIISOCYANATE
KGASSER
STEAM EJECTOR
P] TO WASTE WATER
— REFINED TOLUENE
OIISOCYANATE 1.0
TO
WASTE WATER
VENT
TO AIR
U-J WATtR
TO WASTE
WATER
CENTRIFUGE
RCSIOUE
STEAH EJECTOR
WASTE GAS SCRUBBER (HATTER)
HCI 0.0?S
i
W,XSTE WATER
CENTRIFUGE RESIDUE (LIQUID 4 SOL10I
POITM-RS WIO TARRY ^TTER 0.019
KfTRIC CriLOR!0£ O.OQI35
WAS IE ISOCtAHATES 0.00058
I
LA'ID
-------
Other compounds can be used to produce the two direct dyes but Mordant Red 27
can only be produced from ODCB. (SRI, 1977.) Solvent uses include paint formu-
lations, engine cleaning compounds, cleaning and polishing formulations, degreasing
agents, and wood-preserving compounds (World Health Organization, 1974). ODCB
is registered for use a pesticide against termites, beetles, bacteria, slime,
and fungi, however, little is believed to be used at present. ODCB is also used
to control the odor in industrial wastewater (Investigation of Selected Potential
Environmental Contaminants, 1977). No information on the processes involved in
the manufacture of these compounds from ODCB was available. However, ODCB
releases will occur during the production of these compounds and ODCB may be
present as a contaminant.
A large portion (33%) of the ODCB produced is exported (see Table 3.1,
footnote 8). ODCB is released to air, land, and water through spills associated
with exportation.
3.2.2 p-Dichlorobenzene
Much of PDCB is used directly as a deodorant for toilets and garbage, and
in moth control. The majority of PDCB used in this manner will enter the atmosphere
by sublimation (Investigation of Selected Potential Environmental Contaminants,
1977). In its use as a toilet deodorizer, some PDCB will enter the atmosphere
but the majority will enter the sewer system (see Table 3.1, footnote 13)
(Investigation of Selected Potential Environmental Contaminants, 1977).
Some PDCB is used in the manufacture of polyphenylene sulfide resins, dye
intermediates, insecticides, Pharmaceuticals, and as an extreme pressure lubricant
(World Health Organization, 1974; Investigation of Selected Potential Environ-
mental Contaminants, 1977). Little information on the processes utilized to
manufacture these compounds was available. Again, PDCB could be a contaminant
of these substances and will be released during their production.
It is estimated that 10,100 kkg of PDCB were exported in 1977 (see Table
3.1, footnote 8). During exportation, PDCB will be released to air, land, and
water (the majority to water) from spills (see Table 3.1, footnote 15).
3-15
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3.2.3 m-Dichlorobenzene
Very little information regarding MDCB is available. Hawley (1977) notes
that MDCB is used as a fumigant and an insecticide.
3.3 RELEASES FROM TRICHLOROBENZENE USAGE
3.3.1 1,2,4-Trichlorobenzene
The majority of the 1,2,4-TCB produced in the United States is used as a
dye carrier. 1,2,4-TCB is mixed with disperse dye and a leveling agent; this
mixture is then applied to the material at 100°C for several hours (Investigation
of Selected Potential Environmental Contaminants, 1977). It is estimated that
all of the 1,2,4-TCB will be released during this process but that the majority
of the releases will occur from the release of the dye solution into the waste
stream (see Table 3.1. footnote 17). The carrier that remains on the fabric
will be removed by heating or an alkali scour (Investigation of Selected Potential
Environmental Contaminants, 1977) and will be released to air and water (see
Table 3.1, footnote 17).
The remainder of the 1,2,4-TCB has a variety of uses. 1,2,4-TCB is used in
the production of several herbicides (dicamba, 2,5-dichlorobenzoic acid) but
little information is available on the manufacturing processes involved. Other
uses of 1,2,4-TCB include: a solvent for the crystallization of high melting
point products, degreasing agent, termite control ,agent, dye intermediate,
synthetic transformer oil, lubricant, heat transfer medium, and dielectric fluid
(Investigation of Selected Potential Environmental Contaminants, 1977; Comer
et al., 1979; Third Report of TSCA Interagency Testing Committee, 1979). Again,
the manufacturing processes are unknown; 1,2,4-TCB may be present as a contami-
nant in these products, and it will be released to the environment during the
production and use of these compounds.
3.3.2 1.2.3-Trichlorobenzene
1,2,3-TCB has a variety of uses and these are similar to those for 1,2,4-
TCB. These uses are: an organic intermediate, termite control agent, synthetic
transformer oil, and dye intermediate (Comer et al., 1979; Third Report of
TSCA Interagency Testing Committee, 1979). No quantitative information on the
3-16
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production and use of 1,2,3-TCB is available. However, the TSCA Interagency
Testing Committee Report (1979) noted that 1,2,3-TCB is released to air and
water through agricultural runoff, termite control operations, use as a transformer
oil, and its general use in the laboratory.
3.3.3 1,3,5-Trichlorobenzene
No quantitative information is available on the production and use of
1,3,5-TCB. This compound is used as a solvent for high-temperature melting
products, a coolant in electrical installations and glass tempering, a heat
transfer medium, a lubricant, synthetic transformer oil, in termite preparations,
in the manufacture of 2,5-dichlorophenol, in polyester dyeing, and in insecticides
(Identification of Organic Compounds, 1975).
3.4 RELEASES FROM TETRACHLOROBENZENE USAGE
3.4.1 1,2,4,S-Tetrachlorobenzene
1,2,4,5-TECB is an intermediate in the production of herbicides, defoliants,
insecticides and fungicides (Third Report of the TSCA Interagency Testing Committee,
1979; Investigation of Selected Potential Environmental Contaminants, 1977).
All the 1,2,4,5-TECB produced by Dow is reportedly captively consumed in the
manufacture of 2,4,5-trichlorophenol which has germicidal properties and is used
in the production of the herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T)
(Hydroscience, 1978; Investigation of Selected Potential Environmental Contaminants,
1977). 2,4,5-trichlorophenol is a fungicide and is used as a disinfectant, a
preservative for leather, textiles and wood, and as an intermediate in the
production of herbicides (other than 2,4,5-T) and insecticides (Investigation of
Selected Potential Environmental Contaminants, 1977).
The only quantitative information available is a 1973 break down of 1,2,4,5-
TECB usage. Since the end of the Vietnamese War, the demand for herbicides such
as 2,4,5-T has decreased so the 1973 break down is considered to no longer be
representative of the usage of 1,2,4,5-TECB.
1,2,4,5-TECB is also used in electrical insulation, as temporary fire-
retardant protection in packaging, as an impregnant for moisture resistance, and
as a dielectric fluid (Investigation of Selected Potential Environmental Contaminants,
1977; Third .Report of the TSCA Interagency Testing Committee, 1979).
3-17
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3.4.2 1,2,3,4-Tetrachlorobenzene and 1,2,3,5-Tetrachlorobenzene
1,2,3,4-TECB is a component of dielectric fluids and is used in chemical
syntheses (Comer et al., 1979; Third Report of the TSCA Interagency Testing
Committee, 1979). No quantitative information was available.
1,2,3,5-TECB may have uses similar to the other tetrachlorobenzene isomers
but no information was available regarding its actual use (Comer et al., 1979).
3.5 RELEASES FROM' PENTACHLOROBENZENE USAGE
Pentachlorobenzene is used as a chemical intermediate. Olin Corporation
uses the higher chlorinated benzenes to produce the soil fungicide pentachloro-
nitrobenzene and pentachlorobenzene is present as a contaminant (less than
0.2%). (Investigation of Selected Potential Environmental Contaminants, 1977.)
No quantitative information on pentachlorobenzene was available.
3.6 RELEASES FROM HEXACHLOROBENZENE USAGE
Hexachlorobenzene is used in the manufacture of wood preservatives, aromatic
fluorocarbons, dyes, and organic compounds. Other uses include: a grain fungicide,
a pyrotechnic compound, a peptizing agent in rubber manufacture, and a porosity
controller* (Identification of Organic .Compounds in Effluents., 1975; Blackwood.
and Sipes, 1977,) As a fungicide, hexachlorobenzene is used to control wheat
bunt and smut fungi of grains; hexachlorobenzene was used in Washington, Oregon,
and California as a fungicide in the early 1970's but there is no current infor-
mation on its use (Blackwood and Sipes, 1977).
Blackwood (1977) notes that the major source of pollution by hexachlorobenzene
is from the production of other chemicals (see section 4.0).
3.7 RELEASES FROM MIXED ISOMER USAGE
A mixture of tri-, tetra- and pentachlorobenzene has been used to reduce
the attack of gastropods such as snails and oyster drills on commercially important
clams and oysters. This product is called Polystream and consists of a minimum
of 95% total active tri-, tetra- and pentachlorobenzenes; it is mixed with sand,
and applied around oyster and clam beds in order to repel predators (MacKenzie,
3-18
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1970). Polystream acts by swelling the tissues of certain species of gastropods,
and eventually causes death in these organisms (Loosanoff et al., 1960). The
compound does not harm the shellfish it is designed to protect, although it has
been found that some of the compound remains in the tissues of clams and oysters
for a brief period of time following treatment (MacKenzie, 1970). No information
was available regarding current usage of Polystream.
There is also a mixture of trichlorobenzenes commercially available. This
mixture consists of 85% 1,2,4-TCB, 7.3% 1,2,3-TCB, and traces of di- and tetrachloro-
benzenes. This mixture is used as a solvent, a lubricant, and a dielectric
fluid (Investigation of Selected Potential Environmental Contaminants, 1977).
However, no other quantitative information was available.
3-19
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4.0 RELEASES FROM INDIRECT PRODUCTION
Several forms of indirect production have been elucidated for chlorinated
benzenes. These include the metabolism and degradation of insecticides, the
metabolism of chlorinated benzenes, the chlorination of water, the production of
tetrachlorobenzene by marsh grass, and the production of hexachlorobenzene as
a byproduct in the formation of chlorinated compounds.
The metabolism of the insecticide lindane (1,2,3,4,5,6-hexachlorocyclo-
hexane) has been the subject of several studies.. For example, when lindane was .
topically applied to houseflies, the following percentages of metabolites were
formed during metabolism: 0-0.1% 1,2,4-TCB; 0-0.1% 1,2,4,5-TECB; and trace
amounts of 1,2,3-TCB, 1,2,3,4-TECB, and PCB (Reed and Forgash, 1970). Rabbits
14
which were orally dosed with C-lindane produced 6% ODCB, 0.3% 1,2,4-TCB, and
traces of 1,2,3,4-TECB, 1,2,3,5 and/or 1,2,4,5-TECB, and PCB as ether-soluble
urinary metabolites (Karapally et al., 1973). In addition, tri and tetrachloro-
benzenes were reported as metabolites of lindane in pheasant eggs and chicks and
in carrot mold (Third Report of the TSCA Interagency Testing Committee, 1979).
Lettuce contained 1,2,3-TCB, 1,2,4-TCB, 1,2,3,4-TECB, PCB and HCB as metabolites
(Investigation of Selected Potential Environmental Contaminants, 1977). Since
lindane is produced in small quantities (<500 kkg/yr. estimated; Midwest Research
Institute, 1972), we do not feel that this would be a significant source of
chlorinated benzenes in the environment.
Another pesticide which has been shown to produce chlorinated benzenes as
metabolites is Terraclor (pentachloronitrobenzene), a soil fungicide. Beagles
and rats orally dosed with this pesticide contained low levels of PCB and HCB.
In addition, cotton plants grown in soil treated with Terraclor also were shown
to contain PCB and HCB (Kuchar et al., 1969). Since production of this compound
was also estimated to be low ( <1400 kkg/yr; Midwest Research Institute, .1972), the
production of chlorinated benzenes from this source also is apparently not
significant.
In addition to reports on lindane metabolism by biological organisms,
the degradation of lindane to trichlorobenzene is also of interest. It has been
4-1
-------
reported that residues of trichlorobenzene are produced during the baking of
bread and breakfast cereals (Third Report of the TSCA Interagency Testing
Committee, 1979).
The dehalogenation of higher chlorinated benzenes is a method of indirect
production of the lower chlorinated benzenes. For example, Jondorf et al. (1958)
reported the production of di- and trichlorobenzenes by the dechlorination of
tetrachlorobenzenes in rabbits. This metabolism appeared to be the result
of action by bacteria in the rabbit gut. Parke and Williams (1960), studying
the metabolism of 1,3,5-TCB, demonstrated that monochlorobenzene is formed
during this process. These researchers also found that 10-20% of an oral dose
of pentachlorobenzene was converted to lower chlorinated benzenes; however, HCB
appeared not to be metabolized. Since these compounds are formed through a
metabolic process, the amounts produced are probably small.
Another indirect source of chlorinated benzenes may be the chlorination
of water. Chlorination of benzene and chlorobenzene at pH 3 has been reported;
however, these compounds do not appear to be chlorinated at higher pHs. Since
most water treatment processes take place at pH 5-9, this is generally not
considered to be a significant source of chlorinated benzenes (unpublished data,
EPA Monitoring and Data Support Division).
An additional source of production of tetrachlorobenzenes appears to be
their production by marsh grass (Investigation of Selected Potential Environ-
mental Contaminants, 1977). This may be a significant natural source of chlo-
rinated benzenes.
A final indirect source of chlorinated benzenes is their production as a
waste or byproduct of other chemical reactions. Hexachlorobenzene is produced
in large amounts during the production of chlorinated solvents and pesticides
(Blackwood and Sipes, 1977). Residues from these processes are estimated at
1000 to 3900 kkg/yr. However, quantities of HCB released to the environment
are probably lower due to incineration of some wastes. Fourteen types of
industrial processes produce HCB as a waste or byproduct. In addition,
significant amounts of HCB are present in some products as a contaminant.
Table 4.1 shows the estimated amounts of HCB present in industrial wastes,
byproducts, and products in 1972. This appears to be a significant source of
hexachlorobenzene.
4-2
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TABLE 4.1 ESTIMATED TOTAL QUANTITY OF HEXACHLOROBENZENE
CONTAINED IN U.S. INDUSTRIAL WASTES, BYPRODUCTS,
AND PRODUCTS IN 1972 (Blackwood and Sipes, 1977)
Product
Perchloroethylene
Trichloroethylene
Carbon tetrachloride
Chlorine
Dacthal
Vinyl chloride
Atrazine, propazine,
simazine
Pentachloronitrobenzene
Mirex
TOTAL
U.S. production,
1,000 metric tons
334
194
453
8,660
0.9
2,040
51
1.4
0.4
_a
Estimated HCB
produced, metric tons
High
1,590
204
182
177
45
12
4
3
0.9
2,200
Low
794
104
90
73
36
0
2
1
0.4
1,100
applicable.
4-3
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5.0 RELEASE SOURCE EVALUATION
The total releases of chlorinated benzenes to the environment from their
production and use are at least 72,000 kkg (summation of releases from Tables
2.7 and 3.1). Based on the estimates in Tables 2.7 and 3.1, of the 72,000 kkg
released to the environment, 38% (27,000 kkg) enters the atmosphere, 1% (800 kkg
enters the land or is landfilled, and 61% (44,000 kkg) enters the water.
Monochlorobenzene is produced in the greatest quantities, and contributes 46,000
kkg to the total quantity released. Dichlorobenzenes and 1,2,4-trichlorobenzene
contribute 20,000 kkg and 6,(100 kkg respectively. Since very little quantitative
information was available for the production and usage of the other chlorinated
benzenes, it was not possible to estimate their releases.
Comparing the releases for production and use of chlorobenzene and the
dichlorobenzenes, it is apparent that the releases from usage are much larger
than the releases from production. For chlorobenzene, 700 kkg are released
during its production; this is only 2% of the chlorobenzene releases - usage
accounts for the remaining 98% (45,000 kkg). This estimate is primarily based
on the nonconsumptive (e.g., solvent) uses of chlorobenzene since data on
consumptive uses were lacking. However, any releases from consumptive use of
chlorobenzene will further increase the usage releases thus diminishing the
contribution of production releases. The results are similar for the dichloro-
benzenes - 3% (600 kkg) of the releases are from production while 97% (.20,000
kkg) of the releases are from nonconsumptive uses.
Since chlorinated benzenes have numerous solvent applications and are used
directly as pesticides (e.g., moth control), these are their major sources of
environmental release. The uses and releases of chlorinated benzenes in moth
control and as deodorizers are fairly widespread throughout the United States.
Releases from solvent uses, however, would be concentrated at the manufacturing
plants where they are used. Thus, areas where plants using chlorobenzenes as
solvents are clustered may be important sources of large environmental releases
of chlorobenzenes.
5-1
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The production sites for chlorinated benzenes may also be important sources
of release. Most of the plants that produce mono- and dichlorobenzenes produce
the higher chlorinated benzenes as well. These sites would be sources of release
for a variety of chlorinated benzenes, and the total quantities of chlorinated
benzenes released would be higher than has been estimated. More information on
the production of the higher chlorinated benzenes is needed in order to more
accurately assess their contribution.
In addition to releases of chlorinated benzenes during manufacture and use
of these compounds, releases of hexachlorobenzene as a by-product, contaminant
or waste of other organic syntheses appears to be significant. More information
on these processes is needed in order to more accurately assess the amounts of
hexachlorobenzene released to the environment.
5-2
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6..0 DATA GAPS
Numerous data gaps were encountered during the preparation of this report.
These data gaps were due to incomplete literature on pertinent subjects, the
fact that much of the industrial information is confidential, the lack of
research in various areas, and the lack of monitoring data within the industrial
facilities. Table 6.1 lists the major data gaps for each compound and recommen-
dations of methods for their solution.
The most important areas for which basic data was lacking were production
and uses of the chlorobenzene compounds. In the production area, the releases
can be better estimated when there is data available on the actual quantities
of each chlorobenzene compound produced by each process, what the release fac-
tors for each process are, and how the wastes are treated by each manufacturer.
For example, in the production of monochlorobenzene, both o-dichlorobenzene
and p-dichlorobenzene are produced; however, the quantities recovered and the
quantities released are not well-determined in the literature. An analysis of
the products from each manufacturing process would indicate which isomers are
present and the quantity since all the isomers are formed under similar condi-
tions.
Under the uses of the chlorobenzene compounds, the most serious lack of
data was the absence of actual breakdown of the uses as well as the lack of
qualitative information on each use. Basic information on the uses needs to
be obtained in order to determine the releases from.the uses. This information
includes specific data on how much of each chlorobenzene compound is used in
each area, the nature of each area (consumptive or honconsumptive), where the
products are manufactured, what the products are, and where the products are
used. In many cases, an analysis of consumer goods for chlorobenzene impurities
or content in indicated.
This study involved twelve compounds, and the data gaps are such that
original research and monitoring are indicated to fill them. For these reasons,
a Level III materials balance would be required to eliminate the data gaps and
to adequately determine the releases of chlorobenzenes to the environment.
Approximately 6,000 manhours (or 3 manyears) would be needed to find the data
through extensive literature searches, contacts with, industry and trade associa-
tions, and monitoring studies within the industrial sites.
6-1
-------
TABLE 6.1 DATA CAPS AND RECOMMENDATIONS
ho
DATA CAPS
Honochlorobenzene
A. Production
1. Complete list of 1977 producers
2. Chlorlnatlon of benzene
a. Which processes (batch or continuous) are used by
the various producers
b. What additives (e.g.,fuller's earth, aluminum
chloride) are used to vary amounts of mono- and
dlchlorobenzene made
c. Description of the continuous process and releases
which occur using the continuous process
d. Amounts of chlorinated benzenes present In
polychlorInated aromatic resinous waste
e. Percentage breakdown of o-, p-, and m-dlchlorobenzene
produced In dlchlorobenzene waste
3. Imports
a. Quantity Imported
b. Route of Importation
c. Releases during Import
ft. Amount produced during metabolism of higher chlorinated
benzenes
B.. Uses
RECOMMENDATIONS
TSCA non-confidential data on producers; contacts with Industry;
Chemical Economics Handbook
Industry contacts ; Chemical Economics Handbook
Industry contacts
Industry contacts; chemical engineering literature
Laboratory examination of waste; Industry contacts
Laboratory examination of waste; Industry contacts
Contacting import agents; detailed Information from USITC;
Chemical Economics Handbook
Contact with industries Importing; contact with Import agents
Industry importing; Dept. of Transportation; Coast Guard;
port authorities; American Association of Railroads
Laboratory research required to assess which organisms
metabolize higher chlorinated benzenes and at what rate
1. Specific rubber intermediates produced from MCB
2. Specific formulations of adhcslvea, paints, polishes and
waxes made from MCB
International Institute of Synthetic Rubber Manufacturers; Rubber
Manufacturers Association, Inc.; Manufacturing Chemists Association;
chlorobenzene manufacturers; American Chemical Society
Consumer Product Safety Commission; Effluent Guidelines
3. Knowledge of "other uses" of MCB
Survey of consumer products; Effluent Guidelines; extensive
literature search; Manufacturing Chemists Association;
American Chemical Society
-------
TABLE 6.1 (continued)
4. Production processes for:
a. Chloronltrobcnzcnc
b. Dlphenyl oxide
c. Rubber intermediates
d. Adhcslves, paints, polishes, waxes
e. Pharmaccutteals
f. Natural rubber
g. Dyeing
Faith, Kcyes and Clark's Industrial Chemicals; Kirk-Othmor
Faith, Keyes and Clark's Industrial Chemicals; Klrk-Othmer
International Institute of Synthetic Rubber Manufacturers; Rubber
Manufacturers Association; Inc.; Industrial Process Profiles: Synthetic
Rubber Manufacturers
Effluent Guidelines
HIM Computer Research and Technology Division
Rubber Manufacturing Association
Textile trade associations
I
U)
5. Further knowledge of production processes for:
a. DDT
- • b. Dlleocyanates
6. Releases of MCR which occur from processes in 4 and 5
7. Carry-over of MCB impurities in primary products Into:
a. Phcnylene dlamlne
b. Nitroanlline
c. Chloroanlllne
d. Nitrophenol
e. Heat transfer media
f. Soaps
g. Organic chemicals
h. DDT which is exported
1. Diisocyanates
j. Pharmaceuticals
k. Natural rubber
j. Fabrics
Montrose Chemical Corporation
Diisocyanate manufacturers
Contacts In t, ;)m| 5; industrial rant arts; Kf f 1 i.i'DI
Quality control office of manufacturers of chloronitrobenzcne
(Dupont, Monsanto) or its products; extensive literature search;
laboratory analysis
Quality control office of manufacturers of dlphenyl oxide or its
products; extensive literature search; laboratory analysis
Quality control office of Montrose Chemicals Corporation;
literature search; laboratory analysis
Quality control office at manufacturers of these products;
literature search; laboratory analysis
-------
TABLE 6.1 (continued)
9. MCB releases from production and/or use of above products
10. Export
a. Amounts exported
b. Export process
c. Releases during export
11. Storage
a. Amounts stored
l». Amount :i rrl riiMi-J tlurlil}', Hlor;i}',i*
ra - Dlclilorolionzcne
A. Production
1. Quantities produced
2. Producers
a. Locations
b. Capacities
3. Detailed production process
4. Associated releases
5. Imports
a. Origin of Imports
b. Companies that Import and from where
c. Ports of entry
d. Modes of transport and associated releases
6. Indirect Production
a. Metabolism of higher chlorinated benzenes
(1) quantity produced (amount Ingested, yield)
(2) where It goes
Determine production processes from Industry or literature and
obtain any release data
Contact with industries exporting; export agencies; Bureau of Census
files; Chemical Economics Handbook
Contact with industries exporting; contact with export agents
Contact with industry exporting; Uept. of Transportation; Coast Cu.inl
American Association of Railroads; port authorities
Contact with chlorobcnzcnu industry
Contact with chlorobenzcnc manufacturers; USITC;
TSCA nonconfidentlal data on producers
Chemical Economics Handbook; TSCA nonconfIdcntlal data on
producers; contacts with Industry
Contact with chlorobenzene Industry; Chemical Economics Handbook
Contact with chlorobenzene industry
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that Import; USITC
USITC; Import agents; Coast Guard
Contact with Industry Importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
Research needed to assess which organisms metabolize higher
chlorinated benzenes and the rate of metabolism
-------
TABLE 6.1 (continued)
I
01
B. Uses
1. Fumlgant and pesticide
a. Amount used In each
b. Where used
c. Associated rclcnnca
2. Other uses
3. Exports
a. Quantity exported
b. Destinations
c. Who exports and to where
d. Ports of exit
e. Modes of transportation and associated
releases
. Storage
Agricultural trade association; contact uith Industry
Contact with chlorobenzene Industry; extensive literature search
Bureau of Census; Chemical Economics Handbook
Chemical Economics Handbook; Bureau of the Census;
export agents; chlorobenzene industry
Contact with chlorobenzene industry
Bureau of the Census; export agents; chlorobenzene Industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Railroad Association;
port authorities; chlorobenzene industry
Contact with chlorobonzrne Industry
o- ltichloroln-1 iy. cm;
A. Production
1. List of actual producers and their capacities and locations
2. Quantity produced during production of chlorobenzene
3. Quantity produced directly
4. Releases during production (batch, continuous, direct)
5. Imports
a. Origin of Imports
b. Companies that Import (and from where)
c. Ports of entry
d. Modes of transfer and associated losses
TSCA non-confidential data on producers; Chemical Economics
Handbook; contacts with Industry
Contact with chlorobenzene manufncturers; extensive literature
search
Contact with chlorobcnzcne manufacturers
Contact with clilorobenzenc manufacturers; chemical engineering
literature
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that import; USITC
USITC; Import agents; Coast Guard
Contact with industry importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
-------
TABLE 6.1 (continued)
6. Indirect Production
a. Metabolism of higher chlorinated benzc.ies
(1) Quantity produced
(2) Where It goes
b. Metabolism of llndane
(1) Quantity produced
(2) Where It goes
Research needed to assess which organisms metabolize compounds
and rate of metabolism
n. linns
1. Production Processes and Locations
a. 3, 4-dlchloranlllne and its products
b. Dye production
- Mordant Red 27
- Direct Blue 108
- Direct Violet 54
c. Other solvent uses
- Cleaning and polishing formulations
- Paint formulations
- Engine cleaning compounds
- Dcgrcasing agents
- Wood-preserving compounds
Chemical Economics Handbook; Faith Kcycs and Clark's Industrial Clifiiili-;il •
Klrk-Ottimer; trade associations for pesticides and dyes; American
Chemical Society; industry contacts
Textile associations; literature search; industry contact
Effluent guidelines; literature search; Consumer Products Safety
Commission; industry contacts
2. Impurity
a. 3, 4-dlchloroanlllne and its products
b. TDI
c. Dyes
3. Method of disposal of solvent from TDI manufacture
4. Process using dyes contaminated with ODCB
Industry contacts; extensive literature search; laboratory analysis
Contacts with quality control office at Mobay Chemical Corporation
or Dow Chemical Company; laboratory analysis; extensive literature
search
Textile trade associations; laboratory analysis; extensive literature
search
Mobay Chemical Corporation, Dow Chemical Company, 01 in Corporation
Textile associations; literature-search
-------
TABLE 6.1 (continued)
5. Actual produces containing ODCB in formulations
("other solvent uses")
6. Quantity used as pesticide
a. What application
b. Where
Effluent Guidelines
Agricultural trade associations; extensive literature search;
Industry contacts
7. Quantity used as uastewater deodorant
where and how much
Contact with chlorobenzene manufacturers; Consumer Products
Safety Commission
8. Exports
a. Ooscinntions
b. Ports of exit
c. Mode of transportation and associated releases
d. Which companies export
9. Storage
Chemical Economics Handbook; Bureau of Census; export agents;
chlorobenzene industry
Bureau of Census; export agents; chlorobenzene Industry;
Coast Guard
Dept. of Transportation; Coast Guard; American Association of
Railroads; port authorities; chlorobenzene industry
Contact with chlorobenzene Industry
Contact vith chlorobenzene indstry
p- Plchlorobenzene
A. Production
1. List of actual producers and their capacities and
locat ions
2. Quantity produced during production of MCB
3. Quantity produced directly
^. Releases during production (batch vs. continuous vs.
direct)
5. Imports
a. Origin of imports
b. Companies that import and from where
c. Ports of entry
d. Modes of transport and associated rrlensen
TSCA nonconfIdentlal data on producers; Chemical Economics Handbook;
contacts with Industry
Contact with chlorobenzene manufacturers; extensive literature search
Contact with chlorobenzene manufacturers
Contact with chlorobenzene manufacturers; chemical engineering
literature
Import agents; US1TC; Chemical Economics Handbook
Import agents; contact with companies that Import; USITC
USITC; Import agents; Coast Guard
Contact with Industry importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
-------
TABLE 6.1 (continued)
6. Indirect Production
a. Metabolism of higher chlorinated benzenes
(1) Quantity produced
(2) Where it goes
Research needed to assess which organisms metabolize higher
chlorinated benzenes and the rate of metabolism
I). Duns
1. Production Processes and Locations
I
00
a. Polyphenylene sulflde resins
b. Dye intermediates
c. Insecticides
d. Pharmaceuticals
2. Quantities used In 01
3. Impurity in products from 01
4. What Insecticides produced and where used
5. What pharmaceutical products
6. What dye Intermediates
Klrk-Othmer; Faith, Keyes and Clark's Industrial Chemicals;
industry contacts; Chemical Economics Handbook
Textile associations; American Chemical Society; literature search;
Industry contacts
Agricultural trade associations; contact with chlorobenzene
Industry
NIH Computer Research and Technology Division; contact with
chlorobenzene Industry
Contact with chlorobenzene manufacturers and manufacturers of
specific products •
Industry contacts; extensive literature search; laboratory analysis
Agricultural trade associations; contact with chlorobenzene
Industry
NIII Computer Research and Technology Division; contact with
chlorobenzene Industry
Textile trade associations; contact with chlorobenzene industry
7. Quantity FCDB used as garbage deodorant and
which products contain it
Consumer product survey; contact with chlorobenzene industry;
Consumer Product Safety Commission
8. Toilet deodorant
a. Quantity used
b. Which products contain it
c. Releases - air vs. water
Contact with chlorobenzene Industry; Consumer Product Safety
Commission
.Consumer Product Safety Commission
Laboratory examination of releases from use
-------
TABLE 6.1 (continued)
9. Extreme pressure lubricant
s
a. Quantity used
b. Consumptive vs. nonconsunptIve use
c. Associated releases (production and uses)
10. Exports
a. Destinations
b. Who exports and to where
c. Ports of exit
d. Modes of transportation and associated releases
11. Storage
Contact with chlorobenzene Industry
Manufacturing Chemists Association; industry contacts
Industry contacts
Chemical Economics Handbook; Bureau of the Census; export agents;
chlorobenzene Industry
Contact with chlorobenzene industry
Bureau of the Census; export agents; chlorobenzene industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Association of Railroads,
port authorities; chlorobenzene Industry
Contact with chlorobenzene industry
A. Production
1. Actual production figure
2. Producers
a. All and locations
b. Capacities and which process
3. Quantity produced by ench method
a. Chlorlnation of ODCB
b. Hexachlorobenzene
c. Byproduct of PDCB
l>. Releases associated with each method
5. Imports
a. Quantity
b. Origin of Imports
USITC; TSCA nonconfidentlal data on producers
Contact with chlorobenzene manufacturers; Chemical Economics
Handbook; TSCA nonconfIdentlal data on producers
Chemical Economics Handbook; contact with chlorobenzene industry
Contact with industry
USITC; Chemical Economics Handbook
Import agents; USITC; Chemial Economics Handbook
-------
TABLE 6.1 (continued)
c. Companies Chat Import and from where
d. Ports of entry
e. Modes of transport and associated releases
Import agents; contact with companies that Import; USITC
USITC; Import agents; Coast Guard
Contact with Industry Importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
I
h—'
o
6. Indirect Production
a. Metabolism of higher chlorinated benzenes
(1) Quantity produced
(yield, amount ingested)
(2) Where It goes
(excreted vs. retained)
b. Metabolism of llndane
(1) Quantity produced
(2) Where It goes
Research needed to assess which organisms metabolize thesi-
compounds nnd the rate of metabolism
B. Uses
1. Production Processes and Locations
a. Herbicides
dlcamba
2,5-dlchlorobenzoic acid
2. Impurity In products from 11
3. Which herbicides are produced
4. Quantities TCB used for each
American Chemical Society; agricultural trade associations;
contact with pesticide industry
Quality control office of manufacturers; extensive literature
search; laboratory analysis -
Contact with chlorobenzene or pesticide manufacturers;
agricultural trade associations; American Chemical Society
Contact with chlorobenzene or pesticide manufacturers
5. Othrr uses
a. Quantity TCB used in each
b. Which are consumptive and which are nonconsumptlve
c. Production process for consumptive
d. Impurity In products
e. Which nonconsumptlve uses are products on the commercial
market
Contort with chlorohcnzene manufocturera; extensive literature
acarcli
f. Releases associated with each use
-------
TABLE 6.1 (continued)
6. Process for release of dye solution containing TCB
7. Exports
a. Quantity
b. Destinations
c. Who exports and to where
d. Ports of exit
e. Modes of transportation and associated releases
8. Storage
Textile trade associations; textile Industry contacts;
extensive literature search
Bureau of the Census; Chemical Economics Handbook
Chemical Economics Handbook; Bureau of the Census; export agents;
chlorobenzene Industry
Contact with chlorobenzene Industry
Bureau of the Census; export agents; chlorobenzene Industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Association of Railroads;
port authorities; chlorobenzene Industry
Contact with chlorobenzene industry
I ,2,3-Trlchlorobcnzcno
A. Production
1. Quantity produced
2. Companies - locations
capacities
process
3. Quantity produced by each process and process details
a. Chlorlnation of ODCB
b. Hexachlorobenzene dechlorlnatlon
4. Releases associated with each process
5. Imports
a. Quantity
b. Origin of imports
c. Companies that Import and from where
d. Ports of entry
e. Modes of transport and associated releases
TSCA nonconfidcntlal data on producers; USITC; Chemical Economics
Handbook; contacts with industry
TSCA nonconf1dent la1 data on producers; Chemlal Economics Handbook
Contacts with chlorobenzene industry; Chemical Economics Handbook
Contacts with Industry and extensive literature search
USITC; Chemical Economics Handbook; contact with chlorobenzene industry
Import agents;-USITC; Chemical Economics Handbook
Import agents; contact with companies that Import; USITC
USITC; Import agents; Coast Guard
Contact with industry importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
-------
TABLE 6.1 (continued)
6. Indirect Production
a. Metabolism of higher chlorinated benzenes
(1) Quantity Ingested
(2) Yield of reaction
(3) Where product goes
b. Metabolism of llndane
(1) Quantity produced
(2) Released or retained
Research needed to aaseaa which organisms metabolize these
compounds and the rates of metabolism
B. Uses
ON
I
1. What chemicals produced from 1,2,3-TCB and
quantity for each and where
2. Which dyes produced from 1,2,3-TCB and
quantity for each and where
3. Production processes
a. Organic chemicals identified In 01
b. Dyes identified in 02
4. Impurity
a. organic chemicals (from SI)
b. Dyea (from 62)
5. Quantity used as synthetic transformer oil
6. Quantity used in termite, control nnd where used
7. Identify other uses
a. Pesticide
b. Laboratory
8. Exports
a. Quantity
b. Destinations
c. Who exports and to where
Contacts with chlorobenzene industry; extensive literature search;
Chemical Economics Handbook
Textile trade associations; contacts with chlorobenzene Industry;
Chemical Economics Handbook; Colour Index
Klrk-Othmer; Faith, Keyes and Clark's Industrial Chemicals;
Chemical Economics Handbook
Extensive literature search; contacts with textile Industry
Quality control offices; laboratory analysis; extensive literature
search
Contact with chlorobenzene Industry; contact with electrical
industry
Contact with chlorobenzene Industry; contact with pesticide
industry
Contact with chlorobenzene and pesticide Industry;
extensive literature search; contact with laboratories
Bureau of the Census; Chemical Economics Handbook
Chemical Economics Handbook; Bureau of the Census; export agents;
chlorobenzene industry
Contact with chlorobenzene Industry
-------
TABLE 6.1 (continued)
d. Ports of exit
e. Modes of transportation
9. Storage
Bureau of the Census; export agents; chlorobenzene Industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Association of Railroads
port authorities; chlorobenzene Industry
Contact with chlorobenzene Industry
I
H-1
CO
1, 3, 5 - Trlchlorobenzene
A. Production
1. Quantity produced
2. Companies
a. Location
b. Capacities
3. Process description/schematic
4. Releases associated with production
S. Imports
a. Quantity
b. Origin of Imports
c. Companies that import and from where
d. Ports of entry
e. Modes of transport and associated releases
6. Indirect Production
a. Metabolism of higher chlorinated benzenes
(1) How much produced by this method
(quantity Ingested, yield of metabolism,
where goes)
B. UHCS
1. Production Processes and Locations
a. 2,5-dlchlorophcnol and products
b. Insecticides
TSCA nonconfidential data on producers; contact with industry;
USITC; Chemical Economics Handbook
TSCA nonconfIdential data on producers; Chemical Economics
Handbook; contact with industry
Contact with industry; extensive literature research
Contact with Industry; extensive literature search
USITC; Chemical Economics Handbook; contact with chlorobenzene industry
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that Import; USITC
USITC; Import agents; Coast Guard
Contact with industry importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
Research needed to assess which organisms metabolize higher
chlorinated benzenes and the rate of metabolism
Klrk-Othmer; Faith, Keyes and Clark's Industrial Chemicals;
Chemical Economics Handbook
Contact with pesticide and chlorobenzene industries
-------
TABLE 6.1 (continued)
2. Impurity
a. 2,5 - dichlorophnnol and products
b. Insecticides
3. Identify Insecticides produced from 1,3,5-TCB mid
where used
Quality control offices; laboratory analysis; contact with
manufacturers
Quality control offices; laboratory analysis; contact with
manufacturers
Contact with chlorobenzene Industry; Chemical Economics Handbor/K
It. Solvent uses
a. Process description
b. Products containing 1,3,5-TCB
c. Descriptions of applications
Contact with chlorobenzene industry; Consumer Product Safety
Commission; Textile trade associations; contacts with pesticide
industry; contacts with electrical Industry; extensive literature
search
I
t—•
*-
5. Exports
a. Quantity
b. Destinations
c. Who exports and to where
d. Ports of exit
e. Modes of transportation and associated releases
6. Storage
Bureau of the Census; Chemical Economics Handbook
Chemical Economics Handbook; Bureau of the Census; export agents
chlorobenzene Industry
Contact with chlorobenzene industry
Bureau of the Census; export agents; chlorobenzene industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Association of Railromls;
port authorities; chlorobenzene Industry
Contact with chlorobenzene Industry
1,2,A,5-Tctrachlorohen/enr
A. Production
1. 1977 producers
2. Amount of 1,2,4,5-TKCB produced by chlorlnatlon
of 1,2.4-TCB
3. Production process and releases from production
Chemical Economics Handbook; TSCA nonconfidentlal data on producers
contacts with Industry; USITC
Chemical Economics Handbook; contacts with industry
Contacts with Industry; extensive literature search;
Chemical Economics Handbook
-------
TABLE 6.1 (continued)
4. Imports
a. Quantity
b. Origin of imports
c. Companies that Import and from where
d. Forts of entry
e. Modes of transport and associated releases
5. Indirect production by:
a. Metabolism of Undone
b. Marsh grass
USITC, Chemical Economics Handbook, contacts with Industry
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that Import; USITC
USITC; Import agents; Coast Guard
Contact with Industry importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
Research needed to assess which organisms metabolize these compounds
and the rate of metabolism
B. Uses
1. Current breakdown of amounts used
2. Specific herbicides, defoliants, insecticides and
fungicides produced
3. Production processes for:
a. herbicides
b. defoliants
c. insecticides
d. fungicides
e. 2,4,5-trlclilorophenol
4. Releases from these processes
5. Impurities of 1,2,4,5-TECB in products carried
over into:
a. Use of herbicides, defoliants, insecticides and
fungicides
b. Production of 2.4,5-T, herbicides and
defoliants
Contact with chlorobenzcnc industry; Chemical Economics Handbook
Contact with chlorobenzene and pesticide industries;
extensive literature search
Contact with pesticide industry; extensive literature search
Contact manufacturers (Dow); Kirk-Othmer
Contact with pesticide Industry; contact 2,4,5-tricliloroulienol
manufacturers; extensive literature search
Contacts with pesticide industry; extensive literature search;
laboratory analysis
Quality control offices; contact with manufacturers (Dow);
laboratory analysis, extensive literature search
6. Releases from above processes
Contacts with industry; extensive literature search
-------
TABLE 6.1 (continued)
!
i—•
ON
7. Releases during the use of 2,4 ,5-trichlorophenol a a
fungicide, disinfectant, wood preservative, leather
textile preservative
8. Releases during use of 1,2,4,5-TECB as:
a. Electrical insulation
b. Fire retardant
c. Impregnant for moisture resistance
d. Dielectric fluid
9. Exports
a. Quantity
b. Destinations
c. Who exports and to where
d. Ports of exit
c. Modes of transportation and associated releases
10. Storage
a
and
Contacts with manufacturers and pesticide Industry;
extensive literature search
Contacts with Industry; extensive literature search; Consumer Produce
Safety Commission; contacts with electrical Industry
Bureau of the Census; Chemical Economics Handbook
Chemical Economics Handbook; Bureau of the Census; export ugentu;
chlorobenzene Industry
Contact with chlorobenzene industry
Bureau of the Census; export agent; chlorobenzene industry;
Coast Guard
Coast Guard, Dept. of Transportation; American Association of Railru;ul4
port authorities; chlorobenzene industry
Contact with chlorobenzene Industry
.1. '.' I ti-'!'••' r.-ii-liliiriilii'iiy.i'iii:
A. Production
1. 1977 producers of 1,2,3,4-TECB
2. Amount of 1,2,3,4-TECB produced from:
a. Chlorination of 1.2,3-TCB
b. Sandmeyer reaction on 1,2,3-TCB
3. Production processes for 1,2,3,4-TECB and releases
from these processes
4. Imports
a. Quantity
b. Origin of imports
c. Companies that Import and from where
TSCA nonconfIdential data on producers; Chemical Economics
Handbook; contacts with Industry
Chemical Economics Handbook; contacts with industry
Contacts with Industry; extensive literature search;
Chemical Economics Handbook
Chemical Economics Handbook; USITC; contacts with chlorobenzene
industry
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that Import; USITC
-------
TABLE 6.1 (continued)
d. Ports of entry
e. Modes of transport and associated releases
5. Indirect production of 1,2,3,4-TECB by:
a. Metabolism of llndane
b. Marsh grass
USITC; Import agents; Coast Guard
Contact with Industry Importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
Research required to assess which organisms metabolize llndane
and the rate of metabolism
Research needed to assess quantities of TECB produced by marsh
grass and amount of marsh grass present
cr>
!
11. Uses
1. Breakdown of amounts used
2. Specific chemicals produced from 1,2,3,4-TECB
3. Production processes for these chemicals and releases
during production
4. Carry-over of 1,2,3,4-TECB Impurities into secondary
products
5. Releases during production and/or use of secondary
products
6. Use as a component of dielectric fluid and releases
during use
7. Exports
a. Quantity
b. Destinations
c. Who exports and to where
d. Forts of exit
e. Modes of transportation and associated releases
8. Storage
Contact with chlorobenzene Industry; Chemical Economics Handbook
Contact with chlorobenzene Industry; extensive literature search;
Chemical Economics Handbook; American Chemical Society
Contact with manufacturers; Klrk-Othmer; Faith, Keyes and Clark's
Industrial Chemicals; Chemical Economics Handbook; chemical
engineering literature
Quality control offices; laboratory analysis; extensive literature
search
Contacts with Industry; extensive literature search
Contacts with chlorobenzene Industry and electrical Industry;
extensive literature search
Bureau of the Census; Chemical Economics Handbook; contact with
chlorobenzene industry
Chemical Economics Handbook; Bureau of the Census; exports agents;
chlorobenzene industry
Contact with chlorobenzene industry
Bureau of the Census; export agents; chlorobenzene industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Association of R;illroads
port authorities; chlorobenzene industry
Contact with chlorobenzene Industry
A. Production
1. Producers of 1,2,3,5-TECB In 1977
Chemical Economics Handbook; TSCA nonconfIdentlal data on
producers; contacts with Industry
-------
TABLE 6.1 (continued)
00
2. Amounts produced from:
a. chlorinatlon of 1,3,5-TCB
b. Sandmeyer reaction on 2,3,5-trichloroaniline
3. Production processes and releases during production
4. Imports
a. Quantity
b. Origin of Imports
c. Companies that import and from where
d. Ports of entry
e. Modes of transport and associated releases
5. Indirect production by:
a. Metabolism of llndane
b. Marsh grass
B. Us>--a
1. Specific uses of 1,2,3.5-TECB and breakdown of
amounts used
2. Exports
a. Quantity
b. Destinations
c. Who exports and to where •
d. Ports of exit
e. Modes of transportation and associated releases
Chemical Economics Handbook; contacts with industry
Chemical Economics Handbook; contacts with industry;
extensive literature search
Chemical Economics Handbook; USITC; contacts with chlorobenzene
industry
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that import; USITC
USITC; import agents; Coast Guard
Contact with industry importing; Dept. of Transport ion;
Coast Cuard; port authorities; American Association of Railroads
Research required to assess which organisms metabolize llndane
and the rate of metabolism
Research required to assess amounts of TECB produced and quantities
of marsh grass present
Chemical Economics Handbook; contacts with chlorobcnzent Industry;
extensive literature search
Bureau of the Census; Chemical Economics Handbook; contact with
chlorobenzene industry
Chemical Economics Handbook; bureau of the Census; export agents;
chlorobenzene industry
Contact with chlorobenzene Industry
Bureau of the Census; export agents; chlorobenzene industry;
Coast Cuard
Coast Cuard; Dept. of Transportation; American Association of Railroads;
port authoritltes; chlorobenzene industry
3. Storage
Contact with chlorobenzene industry
-------
TABLE 6.1 (continued)
Pcntachlorobenzene
A. Production
1. 1977 producers of PCB
2. Amounts of PCB produced from:
a. Chlorinatlon of benzene
b. Chlorinatlon of lower chlorinated benzenes
c. Heating of tricliloroethyU-ne
3. Production processes for PCB and releases from
production
4. Imports
^
a. Quantity
b. Origin of Imports
c. Companies that Import and from where
- d. Ports of entry
e. Modes of transport and associated releases
5. Indirect production of PCB by:
a. Metabolism of llndane
b. Metabolism of PCNB
Chemical Economics Handbook; TSCA nonconfidentlal data on
producers; contacts with chlorobenzene Industry
Contacts with Industry; Chemical Economics Handbook
Contacts with industry; extensive literature search;
Chemical Economics Handbook
Chemical Economics Handbook; USITC; contacts with chlorobenzene
industry
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that import; USITC
USITC; Import agents; Coast Guard
Contact with Industry importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
Research required to assess which organisms metabolize these
compounds and the rate of metabolism
B. Uses
1. Production processes for PCNB and releases of
PCB during this process
2. More accurate account of impurities of PCB in PCHB
which may be released during use as a soil fungicide
3. Exports
a. Quantity
b. Destinations
Kirk-Othmer; Faith, Keyes and Clark's Industrial Chemicals;
Chemical Economics Handbook; agricultural trade associations;
pesticide manufacturers
Quality control office of PCNB manufacturers; extensive
literature search
Bureau of the Census; Chemical Economics Handbook; contact with
chlorobenzene Industry
Chemical Economics Handbook; Bureau of the Census; exports agents;
chlorobenzene industry
-------
TABLE 6.1 (continued)
c. Who exports and to where
d. Ports of exit
e. Modes of transportation and associated releases
4. Storage
Contact with chlorobenzene Industry
Bureau of the Census; export agents; chlorobenzene Industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Association of Railroads;
port authorities; chlorobenzene industry
Contact with chlorobenzene Industry
H»-xachlorobenzcne
CT>
I
to
O
A. Production
1. 1977 producers of HCB
2. Amount of hexachlorobenzene produced from:
a. Chlorlnatlon of benzene
b. Reaction of hexachlorocyclohexane with
chlorosulfonlc acid
c. Recovery of HCB produced as a by-product
of organic chemical production processes
3. Processes Involved In production of HCB and
releases from these processes
4. Imports
a. Quantity
b. Origin of Imports
c. Companies that Import and from where
d. Ports of entry
e. Modes of transport and associated releases
5. Quantities of HCB produced as:
a. A metabolite of llndane
b. A metabolite of pentachloronltrobenzene
c. A by-product of organic chemical production
processes
I
TSCA nonconfidentlal data on producers; Chemical Economics
Handbook; contacts with chlorobenzene Industries
Contacts with Industry; Chemical Economics Handbook
Contacts with industry; Manufacturing Chemists Association;
literature search
Contact with industries that produce HCB as a byproduct;
contacts with industries that recover HCB; literature search
Contact with industries that produce HCB as a byproduct or
recover HCB; contacts with chlorobenzene industry; extensive
literature search; Chemical Economics Handbook
Chemical Economics Handbook; USITC; contacts with chlorobenzene
industry
Import agents; USITC; Chemical Economics Handbook
Import agents; contact with companies that Import; USITC
USITC; Import agents; Coast Guard
Contact with industry importing; Dept. of Transportation;
Coast Guard; port authorities; American Association of Railroads
Research needed to assess which organisms metabolize these
compounds and the rate of metabolism
Contact with industries that produce HCB as a byproduct or
recover HCB; extensive literature search
.B. Uses
1. Breakdown of amounts used
Chemical Economics Handbook; contacts with chlorobenzenu industry;
extensive literature search
-------
TABLE 6.1 (continued)
2. Specific wood preservatives, aromatic fluorocarbons,
organic compounds and dyes made from HCB
3. Production processes for above compounds and releases
from these processes
4. Use of HCB as a:
a. Grain fungicide
b. Pyrotechnic compound
c. Pcptlzlng agent In rubber
d. Porosity controller
5. Relenseu during above uses
6. Impurities carried over into:
a. Wood preservatives
b. Aromatic* fluorocarbons
c. Organic chemicals
d. Dyes
c. Rubber
7. Releases during uses of products above
8. Exports
a. Quantity
b. Destinations
c. Who exports and to where
d. Ports of exit
e. Modes of transportation and associated releases
9. Storage
Contacts with chlorobenzene Imluutry; extenulve 1llL>rnlure search;
Manufacturing Chemists Association; textile trade associations
Contacts with chlorobenzene Industry; extensive literature search;
textile trade associations; Manufacturing Chemists Association
Contact with pesticide and chlorobenzene industries;
extensive literature search
Contact with Manufacturing Chemists Association; contact with
chlorobenzene industry; extensive literature search
Rubber Manufacturers Association, Inc.; contact with chlorobenzene
Industry; extensive literature search
Contact with Manufacturing Chemists Association; contact with
chlorobenzene industry; extensive literature search
Contact with Industry; extensive literature search
Quality control offices; laboratory analysis; contacts with
industry; extensive literature search; textile trade
associations; Rubber Manufacturers Association, Inc.
Contact with industry; extensive literature search
Bureau of the Census; Chemical Economics Handbook; contacts with
chlorobenzene Industry
Chemical Economics Handbook; Bureau of the Census; export agents;
chlorobenzene Industry
Contact with chlorobenzene industry
Bureau of the Census; export agents; chlorobenzene industry;
Coast Guard
Coast Guard; Dept. of Transportation; American Association of Railroads;
port authorities; chlorobenzene industry
Contact with chlorobenzene Industry
-------
Ni
NJ
TABLE 6.1 (continued)
Mixed Isomers
1. Current use of Polystreau
2. Uses of mixed Isomers
Contact Clyde McKcnzle and co-authors of reports on I'olystream
Contact Dou Chemical Co.; Standard Chlorine; ICC Industries
(producers of mixed Isomers)
-------
LITERATURE CITED
Blackwood, T. R. and Sipes, T. G., "Status Assessment of Toxic Chemicals:
Hexachlorobenzene," prepared for Industrial Environmental Research
Laboratory, U. S. Environmental Protection Agency, Cincinnati, Ohio,
November 1977.
Comer, R., Chen, A., and Lee, A., "Trichlorobenzene and Tetrachlorobenzene,"
JRB Associates, Inc., 1979.
Directory of Chemical Producers, Stanford Research Institute, 1977.
Hahn, A. V., The Petrochemical Industry Market and Economics, McGraw-Hill
Book Co., New York, 1970.
Hancock, E. G. (ed.), Benzene and Its Industrial Derivatives, John Wiley and
Sons, New York, 1975.
Hawley, G. G. (ed), Condensed Chemical Dictionary, 9th ed., Van Nostrand
Reinhold Co., New York, 1977.
Hydroscience, "Emissions Control Options for the Synthetic Organic Chemicals
Manufacturing Industry, Chlorobenzenes Product Report," prepared for
Office of Air Quality and Standards, U. S. Environmental Protection
Agency, Research Triangle Park, North Carolina, August 1978.
"Identification of Organic Compounds in Effluents from Industrial Sources,"
EPA/OTS, EPA 560/3-75-002, April 1975.
"Investigation of Selected Potential Environmental Contaminants: Halogenated
Benzenes," EPA/OTS, July 1977.
Jondorf, W. R., Parke, D. V., and Williams, R. T., "The Metabolism of Halogenated
Benzenes. 1:2:3:4-, 1:2:3:5- and 1;2:4;5-Tetrachlorobenzenes," Biochemical
Journal. Vol. 69, pp. 181-189, 1958.
Journal of Commerce, p. 5, May 24, 1976.
Karapally, J. C., Saha, J. C., and Lee, Y. W., "Metabolism of Lindane - C in
the Rabbit: Ether-Soluble Urinary Metabolites," J. Agr. Food Chem.,
Vol. 21, No. 5, pp. 811-818, 1973.
Kirk-Othmer Encyclopedia of Chemical Technology, 2nd revised ed., Vol. 5, 1964.
Kuchar, E. J. , Geenty, F. 0., Griffith, W. P., and Thomas, R. J., "Analytical
Studies of Metabolism of Terraclor in Beagle Dogs, Rats, and Plants,"
J. Agr. Food Chem., Vol. 17, No. 6, pp. 1237-1240, 1969.
Loosanoff, I., MacKenzie, C. L., Jr., and Shearer, L. W., "Use of Chemicals to
Control Shellfish Predators," Science, pp. 1522-1523, May 20, 1960.
MacKenzie, C. L., "Control of Oyster Drills, Eupleura Caudata and Urosalpinx
Cinerea, with the Chemical Polystream," U. S. Fish and Wildlife Service
Fishery Bulletin, Vol. 68, No. 2, pp. 285-297, May 1970.
-------
Midwest Research Institute, "The Pollution Potential in Pesticide
Manufacturing," prepared for U. S. Environmental Protection Agency,
Office of Water Programs, PB 213-782, June 1972.
Morrison, R. T. and Boyd, R. N., Organic Chemistry, 2nd ed., 1970.
Parke, D. V., and Williams, R. T., "The Metabolism of Halogenobenzenes:
(a) Penta- and Hexa-Chlorobenzenes. (b) Further Observations on
l:3:5-Trichlorobenzene," Biochemical Journal, Vol. 74, pp. 5-9, 1960.
Processes Research, Inc., "Alternatives for Hazardous Waste Management in the
Organic Chemical Pesticides and Explosives Industry-$" Cincinnati, Ohio,
September 1977.
Reed, W. T. and Forgash, A. J., "Metabolism of Lindane to Organic-Soluble
Products by Houseflies," J. Agr. Food Chem., Vol. 18, No. 3, pp. 475-481,
1970.
Saxton, J. C. and Narkus-Kramer, M., "EPA Findings on Solid Wastes from
Industrial Chemicals," Chemical Engineering, pp. 107-112, April 28, 1975.
Schmidlin, H. U., Preparation and Dyeing of Synthetic Fibres, Reinhold
Publishing Co., New York, 1963.
Snell, F. D. and Ettre, L. S., Encyclopedia of Industrial Chemical Analysis,
Wiley Interscience, New York, 1970.
SRI International, " A Study of Industrial Data on Candidate Chemicals
for Testing," PB 274-264, EPA/OTS, August 1977.
Stetcher, P. G. (ed.), The Merck Index, 8th ed., Merck & Co., Inc., 1968.
"Third Report of the TSCA Interagency Testing Committee to the Administrator,
Environmental Protection Agency," EPA/OTS, January 1979.
TRW, "Assessment of Industrial Hazardous Waste Practices, Organic Chemicals,
Pesticides and Explosives Industry," EPA/OSW, 1977.
"U. S. Exports," U. S. Department of Commerce, Bureau of the Census,
FT 410/July 1979, issued September 1979.
U. S. International Trade Commission, "Synthetic Organic Chemicals, United
States Production and Sales, 1977," Publication 920, U. S. Government
Printing Office, Washington, D. C., 1978a.
U. S. International Trade Commission, "Synthetic Organic Chemicals,
United States Production and Sales, 1976," Publication 838, U. S.
Government Printing Office, Washington, D. C., 1977a.
U. S. International Trade Commission, "Synthetic Organic Chemicals,
United States Production and Sales, 1975," Publication 804, U. S.
Government Printing Office, Washington, D. C., 1977b.
-------
U. S. International Trade Commission, "Synthetic Organic Chemicals,
United States Production and Sales, 1974," Publication 776, U. S.
Government Printing Office, Washington, D. C., 1976a.
U. S. International Trade Commission, "Imports of Benzenoid Chemicals
and Products, 1978," Publication 990, U. S. Government Printing
Office, Washington, D. C., 1979.
U. S. International Trade Commission, "Imports of Benzenoid Chemicals
and Products, 1977," Publication 900, U. S. Government Printing
Office, Washington, D. C., 1978b.
U. S. International Trade Commission, "Imports of Benzenoid Chemicals
and Products, 1976," Publication 828, U. S. Government Printing
Office, Washington, D. C., 1977c.
U. S. International Trade Commission, "Imports of Benzenoid Chemicals
and Products, 1974," Publication 762, U. S. Government Printing
Office, Washington, D. C., March 1976b.
Weast, R. C. (ed.), CRC Handbook of Chemistry and Physics, 58th ed.,
CRC Press Inc., 1977.
World Health Organization, "International Agency for Research on
Cancer Monograph: Evaluation of the Carcinogenic Risk of Chemicals
to Man," Vol. 7, 1974.
Unpublished Data, EPA Monitoring and Data Support Division, "Criterion
Document, Chlorinated Benzenes (Other than Dichlorobenzenes),"
Draft, March 1978.
-------
APPENDIX A
STRUCTURES AND NOMENCLATURE
OF CHLOKOBENZENES
Monochlorobenzene
Chlorobenzene, chlorobenzol, benzene chloride, phenyl
chloride
o
Orthodichlorobenzene, ortho-diChlorobenzene, ortho-
dichlorobenzol, 1,2-dichlorobenzene
m-Dichlorobenzene
Metadichlorobenzene, meca-dlchlorobenzol, raeta-dichloro-
benzene, 1,3-dichlorobenzene
jp_-Dichlorobenzene
Paradichlorobenzene, para-dichlorobenzene, para-diehloro-
benzol, 1,4-dichlorobenzene
1,2,3-Trichlorobenzene
1,2,3-Trichlorobenzol
1,2,4-TriChlorobenzene
1,2,4-Trichlorobenzol, uns-criChlorobenzene
1,3,5-TriChlorobenzene
1,3,5-Trichlorobenzol, syo-trichlorobenzene
1,2,3,4-Tetrachlorobenzene
1,2,3,4-Tecrachlorobenzol
1,2,3,5-Tetrachlorobenzene .
1,2,3,5-Tetrachlorobenzol
Cl-
Cl
1,2,4,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzol
Pentachlorobenzene
Quintochlorobenzene
Hexachlorobenzene
Cl Cl
Source; (Investigation of Selected Potential Environmental Contaminants, 197?)
-------
APPENDIX B
PHYSICAL CHARACTERISTICS OF CHLOROBENZENES
COMPOUND
monochlorobenzene
1 t 2-dlchlorobenzenc
1 , 3-d Ichlorobenzene
1,4-dichl orobenzenc
1,2,3-trichloro-
bcnzene
1 ,2 ,4-tricbloro-
bcnzcne
1,3,5-trichloro-
bcnzene
1 ,2,3,4-tetra-
chlorobenzene
1,2,3,5-cetra-
chlorobenzene
1 ,2,4,5-totra-
chlorobcnzene
pentachlorobenzene
bexachlorobcnzene
MOL. WT.
112.56
147.01
147.01
147.01
181.45
181.45
181.45
215.90
215.90
215.90
250.34
284.79
MP(°C)
-45.2
-17.2
-26.3
53.0
52.4
16.6
63.0
47.5
51.0
138.0
87.0
229.0
BP(°C)
132.0
179.2
172.0
174.5
218.0
213.0
208.0
254.0
246.0
244.0
276.0
326.0
DENSITY
(g/cm3)
d1! 1.H7
A2l 1.2973
d2^ 1.2799
d5£ 1.2495
—
d2? 1.4634
4
—
—
—
d22, 1.858
d16/5 1.8342
d23,'6 1.5691
VAPOR PRESSURE
(25°C)
9 (20°C)
1.28
1.89
0.4
0.07
0.29
0.15
—
—
0.05
—
1.09 x 10-5(20°C)
FLASH POINT
(°C)
27 .8 (open,
cup)
71.1 (closed
cupj
—
66.7 (closed.
cup)
112.8 (closed.
CUpj
98.9 (closed.
cup)
107.2 (closed
Aip)
—
—
155.0 (closed.
cup)
—
242.2
DIELECTRIC
CONSTANT(25°C)
5.621
9.93
—
2.41
—
2.24 (20°C)
—
—
—
—
—
—
SURFACE TENSION
(25°C) dynes/era3
32.65
36.61
—
31.4 (60°C)
27.2 (100°C)
—
38.54
—
—
—
—
—
VISCOSITY
(25°C)
0.756
1.0318
—
—
—
1.8848
—
—
—
—
—
REFRACTIVE
INDEX
n5D 1.5275
n2°-< 1.5485
n2°'9 1.5457
I19,'" 1.5267
—
n2p 1.5524
—
—
—
—
—
SOLUBILITY
. WATER
Insol uhle
Insoluble
Insoluble
Insoluble
j nsol uble
insol uble
J nsoluble
Insoluble
soluble(liot)
insoluble
Insoluble
insol uble
Source: (Weast, 1977)
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
EPA-560/13-80-001
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Materials Balance
- Task #4 - Chlorobenzenes
5. REPORT DATE
December 31, 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHORIS)
Pauline Johnston, Virginia Hodge, Karen Slimak
8. PERFORMING ORGANIZATION REPORT NO.
2-800-03-379-11
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
JRB Associates, Inc.
8400 Westpark Drive
McLean, Virginia 22102
11. CONTRACT/GRANT NO.
68-01-5793, Task #4
12. SPONSORING AGENCY NAME AND ADDRESS
Survey and Analysis Division
Office of Pesticides and Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Michael Callahan, Project Officer
16. ABSTRACT
The purpose of the Level 1 materials .balance for chlorobenzenes is to evaluate
the sources of release of the various chlorinated benzenes to the environment.
The major route of commercial production of chlorinated benzenes is the direct
chlbrination of benzene with chlorine. Chlorinated benzenes are indirectly
produced through the metabolism of pesticides, their production by marsh grass
and their production as a byproduct of organic chemical production processes.
Chlorinated benzenes are used consumptively in the production of many organic
chemicals. These include chloronitrobenzene, diphenyl oxide, DDT, 3,4-dichloro-
aniline, 2,5-dichlorophenol, pentachloronitrobenzene, rubber intermediates, dyes,
pesticides, and aromatic fluorocarbons. In addition, chlorinated benzenes
have many noneonsumptive uses, including use as a solvent, pesticide, deodorizer,
dielectric fluid, coolant, lubricant, heat transfer.medium, and synthetic trans-
former oil. The major sources of release of chlorinated benzenes to the environ-
ment appear to be from their various non-consumptive uses. Releases from pro-
duction and consumptive uses appear to be comparatively minor.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
13. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
94
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
-------
2.4.1 Monochlorobenzene (MCB)
Chlorobenzene is produced by the catalytic chlorination of benzene at an
elevated temperature in a batch or continuous process. Sublimed ferric chloride
is the most frequently used catalyst but anhydrous aluminum chloride, stannic
chloride, iron, and aluminum are also used (Investigation of Selected Potential
Environmental Contaminants, 1977; Kirk-Othmer, 1964). The reaction sequence is
as follows:
+ Cl catalyst ^ | ( \ | + HC1
Following chlorination, the crude chlorobenzene (a mixture of chlorobenzene
and dichlorobenzenes) is neutralized with dilute sodium hydroxide and separated
into sludge and supernatant. The sludge contains dichlorobenzenes which are
separated by distillation. The supernatant is fractionally distilled to separate
benzene, chlorobenzene, o-dichlorobenzene, and p-dichlorobenzene (TRW, 1977;
Hydroscience, 1978).
The batch process, described above, is a three-product process which produces
o- and p-dichlorobenzene in addition to chlorobenzene, and is illustrated in
Figure 2.2. The quantities of dichlorobenzenes produced can be controlled by
various additives; fuller's earth reduces dichlorobenzene formation while aluminum
chloride enhances their formation (Investigation of Selected Potential Environmental
Contaminants, 1977).
The continuous process for production of chlorobenzene is similar to the
batch process but it minimizes the formation of dichlorobenzenes. In the continuous
process, the reaction occurs in a series of small vessels, there is a large
benzene to chlorine ratio, and once chlorinated, the chlorobenzene is rapidly
removed to prevent further chlorination. The yield for this process is 95%
(Kirk-Othmer, 1964; Investigation of Selected Potential Environmental Contaminants,
1977).
2-12
-------
FIGURE 2.2 PRODUCTION OF MONOCHLOROBENZENE (TRW, 1977)
CHLOROUEHZENES MANUFACTURE
BASIS: 1 KG CHLOROBENZEIIE
BENZENE OR CHLOROBENZEHE
BENZENE 0.95
CHLORINE 0.875
CATALYST_O.M95
(IRON TURNINGS)
WATER
VENT
DICHLOROBENZENE
SLUDGE TO RECOVERY
BENZENE AND WATER 0.038
BENZENE AND CHLOROBENZENE 0.15
CHLOROBENZENE 1.0
CHLOROBENZENE AND
01CHLOROBENZENE 0.18
POLYCHLORINATED AROMATIC
RESINOUS MATERIALS
AND LOSS 0.044
CHLORINATOR
NEUTRALIZER
SEHLER
BATCH FACTIONATIHG TOWERS
HC1 SCRUBBER VENT
HCL 0.0014
AIR
WASH STREAM DICHLOROBENZENE COLUMN
CHLOROBENZENE 0.00088
DICHLOROBENZENE 0.0037
WATER
ORTHO-DICHLOROBENZENE COLUMN WASTE
CHLOROBENZENE 0.004
DICHLOROBENZENE 0.0001
. I
LAND
Releases are kg/kg product.
-------
2.4.2 Dichlorobenzene (DCB)
When chlorobenzene is chlorinated, essentially two isomers result, in the
following percentages:
Cl Cl Cl
Cl.
catalyst
-h
Cl
ortho (30%) para (70%) meta (trace)
A very small amount of the meta isomer is formed (Morrison and Boyd, 1970).
0- and p-dichlorobenzene are produced primarily from the distillation
residues from the manufacture of chlorobenzene. Another method of obtaining the
dichlorobenzenes is by chlorination of benzene or chlorobenzene, as illustrated
above. The products can be separated by fractional distillation or by crystal-
lization of the para isomer. If the crystals are washed with methanol and
heated to 100°C under vacuum suction to remove the alcohol, the ortho isomer can be
separated from the crystalline para isomer (Snell and Ettre, 1970).
To produce p-dichlorobenzene, the products from the chlorination of chloro-
benzene are further chlorinated. The ortho isomer chlorinates more rapidly than
the para isomer to form 1,2,4-trichlorobenzene which is easily separated from
the para isomer by fractional distillation. Alternatively, the dichlorobenzene
mixture is reacted with chlorosulfonic acid; the ortho isomer forms o-dichloro-
benzene sulfonic acid, and the para isomer is easily extracted by distillation
(Snell and Ettre, 1970; Kirk-Othmer, 1964).
Only trace amounts of the meta isomer are formed from the chlorination of
benzene or chlorobenzene. Isomerization of the ortho or para isomers is one
method for producing the meta isomer; this reaction occurs at 120°C and
4.48 x 10 pascals with aluminum chloride or hydrochloric acid as the catalyst.
M-dichlorobenzene is also formed from hexachlorobenzene or any of the other
higher chlorinated derivatives by reaction at 350°-500°C with hydrogen and
cuprous halide or alumina (Kirk-Othmer, 1964; Investigation of Selected Potential
Environmental Contaminants, 1977).
2-14
-------
2.4.3 Trichlorobenzenes (TCB)
1,2,4-and 1,2,3-trichlorobenzene isoraers are synthesized by the catalytic
chlorination of o-dichlorobenzene at 25-30°C with ferric chloride as the catalyst
(Snell and Ettre, 1970; Kirk-Othmer, 1964; Investigation of Selected Potential
Environmental Contaminants, 1977). If hexachlorobenzene is reacted with alcoholic
caustic potash, all three isomers (1,2,3-, 1,2,4-, and 1,3,5-) can be obtained
(Investigation of Selected Potential Environmental Contaminants, 1977). As
previously mentioned, 1,2,4-trichlorobenzene is a byproduct of p-dichlorobenzene
production.
2.4.4 Tetrachlorobenzene (TECB)
The various tetrachlorobenzenes are synthesized from trichlorobenzene in
the following manner (Investigation of Selected Environmental Contaminants,
1977; Kirk-Othmer, 1964):
Cl
Cl,
catalyst
1,2,3-trichlorobenzene
1,2,3,4-tetrachlorobenzene
Cl
Cl,
aluminum amalgam
Cl' \^ 'Cl Cl' ^^ Cl
1,3,5-trichlorobenzene
1,2,3,5-tetrachlorobenzene
2-15
-------
1,2,4-trichlorobenzene
aluminum amalgam
1,2,4,5-tetrachlorobenzene
Cl
Cl
Sandmeyer reaction
^^^B_««^_^W««V^^B^B_^B«.^_^«^««B«»B_^
(nitration, reduction,
diazotization)
1,2,4-trichlorobenzene
1,2,4,5-tetrachlorobenzene
Cl
Sandmeyer
reaction
2,3,5-trichloroaniline
1,2,3,5-tetrachlorobenzene
The crystallization of these tetrachlorobenzenes is aided by residual
hydrogen chloride formed as a byproduct of the chlorination of benzene or
chlorobenzenes. The 1,2,3,4,5-TECB crystals are filtered, centrifuged or
decanted, and washed with methanol, ethanol, liquid chlorobenzenes or acetone.
Up to half of the 1,2,4,5-TECB produced is still retained in the supernatant,
and will precipitate upon cooling. 1,2,4,5-TECB can be separated from a mixture
of tri-, penta-, and other tetra- isomers by fractional crystallization in an
acid solution, according to the Kiss ling method (Investigation of Selected
Potential Environmental Contaminants, 1977).
2-16
-------
2.4.5 Pentachlorobenzene (PCB)
The chlorination of benzene in the presence of ferric chloride at 150 to
200 C, or chlorination of the lower chlorobenzenes produces pentachlorobenzene.
This process is illustrated in Figure 2.3. Of the tetrachlorobenzenes used to
produce pentachlorobenzene, 1,3,4,5-TECB chlorinates most rapidly while the
1,2,4,5-TECB reaction rate is slowest (Investigation of Selected Potential
Environmental Contaminants, 1977). When trichloroethylene is heated to 700°C, a
mixture of pentachlorobenzene and small amounts of other compounds result (Kirk-
Othmer, 1964) .
2.4.6 Hexachlorobenzene (HCB)
Hexachlorobenzene is produced from benzene or hexachlorocyclohexane. The
chlorination of benzene in the presence of ferric chloride and excess chlorine
at 150-200 C yields hexachlorobenzene, hydrochloric acid, and lesser chlorinated
chlorobenzenes. Hexachlorocyclohexane catalytically reacts with chlorosulfonic
acid or sulfuryl chloride to form hexachlorobenzene. The catalyst is ferric
chloride and the reaction proceeds at a temperature of 130-200 C (Blackwood and
Sipes, 1977). These processes are illustrated in Figure 2.3. Blackwood and
Sipes (1977), however, note that most of the hexachlorobenzene in this country
is recovered as a byproduct from other organic chemical production processes
rather than being produced directly (see section 4.0).
2.4.7 Impurities
As previously mentioned, the production of one chlorobenzene compound will
result in the simultaneous production of lesser and more highly chlorinated
derivatives. These additional compounds will be present as impurities in the
final product. Table 2.6 summarizes the impurities found in the major commercial
grades of chlorinated benzenes. Many of the impurities are present in small
quantities but others (depending on the commercial grade involved) are present
in significant amounts. These impurities are of interest because they will be
released to the environment during the use of a specific chlorobenzene.
2-17
-------
FIGURE 2.3 PRODUCTION OF HIGHER CHLORINATED BENZENES
C!2
BYPRODUCT
HCI
PRIMARY REACTOR
WITH FeCI3
AS CATALYST
CRYSTALLIZER
PARTIALLY CHLORINATED BENZENES
SEPARATION
DRYING
PACKAGING
SHIPMENT OF
LESS CHLORINATED
BENZENES
PENTACHLOROBENZENE. ETC.
SHIPMENT OF
HEXACHLOR03ENZENE
1 SOWERS
CHLOROSULFCMC ACID
OR SULFURYL CHLORIDE
REFIUX-
CON-DEMSER-
REACTOR WITH FeC!3
AS CATALYST
COOLER
FILTER
SHIPMENT
-lEXACHLCROSE^ZENE
2-18
-------
TABLE 2.6 IMPURITIES OF COMMERCIALLY IMPORTANT CHLORINATED BENZENES
(Investigation of Selected Potential Environmental Contaminants, 1977)
Chemical
ch lorobenzene
1,2-dlchlorobenzene
1 , 4-dlchlorobenzene
'•^-ssisSii™-
1,2,4,5-tgtrachloro-
pent ach lorobenzene
hexachlorobenzene
%
99.9
90
99
75-85
82.7
80
60-75
99.95
99.5
. 96
65
100
99
97
-
90-99
chloro-
benzene
X
0.07
X
X
X
X
X
1,2-di-
chlor-
benzene
X
X
X
X
X
35
1,3-dl-
chloro-
benzene
X
0-5
0.5
2
X
X
X
X
1,4-dl-
chloro-
benzene
X
X
15-25
15.4
17
25-40
trl-
ch loco-
benzene
X
X
1.6
X
X
X
X
X
tetra-
chloro-
benzene
X
X
X
penta-
chloro-
benzene
X
9Z
hexa-
chloro-
benzene
X
Key: x - present but amount Is unknown
-------
2.5 RELEASES FROM PRODUCTION
There are two methods for the manufacture of chlorobenzene: the batch
process and the continuous process. Both methods are used commercially, but no
.data were available regarding the quantities produced by each method, table 2.7
summarizes the releases of chlorinated benzenes to land and water from the
manufacturing process. These calculations are based on the production schematic
for the batch process (Figure 2.2), and the assumption that all the chloro-
benzene is produced via the batch process.
The polychlorinated aromatic resinous waste constitutes the majority of the
waste (84%) from the batch process. No specific description of this waste is
available, but it probably contains chlorinated benzenes. .This waste will be
discharged to the land.
Chlorobenzene and dichlorobenzene constitute the remaining 16% of the waste.
This waste will be discharged to land (47%) and water (53%). Of this 16%, 56%
(720 kkg) is monochlorobenzene and 44% (560 kkg) is dichlorobenzene. The dichloro-
benzene present is presumably o- and p-dichlorobenzene.
The paucity of information on the production processes (and the quantities
produced) for di-, tri-, tetra-, penta-, and hexachlorobenzene precluded estimation
of losses during their production. However, the amounts of o- and p-dichloro-
benzene believed to be produced during the production of monochlorobenzene are
noted in Table 2.7.
2.6 RELEASES FROM IMPORTS
A certain amount of chlorinated benzene would be expected to be released
during shipment of these chemicals into the United States. We estimate that 1%
of the chlorinated benzenes imported would be lost due to spillage. Ninety
percent of this amount might be expected to be cleaned up and would be released
to water. Approximately 2% of the amount of monochlorobenzene or dichloro-
benzene would be expected to volatilize due to the high vapor pressure of these
2-20
-------
compounds. Another 8% would be lost to land. Using this estimate, we would
expect that 5 kkg monochlorobenzene, 5 kkg o-dichlorobenzene, 0.2 kkg 1,2,4,5-
tetrachlorobenzene, 0.1 kkg m-dichlorobenzene and 0.1 kkg 1,3,5-trichlorobenzene
would be lost to water during import. In addition, monochlorobenzene or
o-dichlorobenzene losses to air would be 0.4 kkg, while losses to water would
be 0.1 kkg. Losses of the other chlorinated benzenes to air and land appear
to be negligible.
2-21
-------
TABLE 2.7 RELEASES DURING PRODUCTION OF CIILOROBENZENES
l-o
I
PROCESS
Chlorobenzene
Batch Process
AMOUNT OF
PRODUCED
(kkg)
147, 7001
Chlorobenzene
3
8, 900
o-dichloro-
benzene
28, 1003
p-dlchloro-
benzene
POINT SOURCES
OF RELEASES
Wash stream from
dichlorobenzene
column
• Chlorobenzene
• dichlorobenzene
Dichlorobenzene
column waste
• Chlorobenzene
• dichlorobenzene
Polychlorlnated
aromatic resinous
material waste
(probably contains
some chlorinated
benzenes)
QUANTITIES
STORED
"
RELEASES TO THE ENVIRONMENT
Air
Amt
(kkg) Form
Land
Amt
(kkg) Form
5912
152
2
6500 _
Water
Amt
(kkg) Form
1302
5462
-------
Table 2.7 Footnotes:
1. In 1977, 117,700 kkg of monochlorobenzene were produced In the United States (USITC, 1978a).
2. The losses of chlorobenzene, dlchlorobenzenc, and polychlorinated materials during the production of chlorobenzene were calculated
using the Information from the production schematic (Figure 2.2).
a) Dlchlorobenzene Column Wash Stream - to water
(0.00088 kg MCB/kg MCB produced)(147.700 kkg) - 130 kkg
(0.0037 kg UCB/kg MCB produced)(147,700 kg) - 546 kg
b) 0-Dichlorobenzene Column Waste - to land
(0.004 kg MCB/kg MCB produced)(147,700 kg) - 591 kkg
(0.0001 kg DCB/kg MCB produced) (147,700 kkg) = 15 kkg
c) Polychlorinated Aromatic Resinous Materials - to land
K> (0.044 kg/kg MCB produced)(147,700 kkg) - 6,500 kkg
NJ
w 3. The batch process for MCB production simultaneously produces o- and p-dichlorobenzene. The yield is approximately 801 MCB,
51 ODCB, and 15X PDCB (Investigation of Selected Potential Environmental Contaminants, 1977). To calculate the amount of
OOCB and PDCB produced per kilogram of MCB produced, the following assumptions are made: (a) all the chlorobenzene produced
is made via the batch process; and (b) the reaction conditions are such that the yield will be 801 MCB, 5% ODCB, and 15Z PDCB.
If 1 kg MCB is the 80X yield, then the total chlorinated benzene yield is 1.25 kg. The remaining 0.25 kg consists of 0.19 kg
PDCB (15X of the total) and 0.06 kg ODCB (5% of the total).
The amounts of PDCB and ODCB produced via the batch process for chlorobenzene are calculated as follows:
(0.19 kg PDCB/kg MCB)(147,700 kkg MCB) - 28,100 kkg PDCB
(00.06 kg ODCB/kg MCB)(147,700 kkg MCB) - 8,900 kkg ODCB
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