EPA-450/4-84-007b
March 1984
Locating And Estimating Air Emissions
From Sources Of Carbon Tetrachloride
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office Of Air And Radiation
Office Of Air Quality Planning And Standards-
Research Triangle Park, North Carolina 27711
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This report has been reviewed by the Office Of Air Quality Planning And Standards, U.S. Environmental
Protection Agency, and has been approved for publication as received from GCA Technology. Approval does
not signify that the contents necessarily reflect the views and policies of the Agency, neither does mention of
trade names or commercial products constitute endorsement or recommendation for use.
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CONTENTS
Figures . . . 1v
Tables ....;.:.:: ii
1. Purpose of Document 1
2. Overview of Document Contents .............'" 3
3. Background ..'.!* 5
Nature of Pollutant. '....!!!!"! 5
Overview of Production and Use ...."! 8
4. Carbon Tetrachloride Emission Sources 11
Carbon Tetrachloride Production. ........! i ! n
Fluorocarbon Production. .....!* 26
Carbon Tetrabromide Production ! ! ! 32
Liquid Pesticide Formulation *. 35
Pharmaceutical Manufacturing ! " 39
Use of Pesticides Containing Carbon Tetrachloride.' .* ! 42
Ethylene Dichloride Production 56
Perch!oroethylene and Trichloroethylene
Production 65
Other Potential Sources of Carbon Tetrachloride
Emissions 73
5. Source Test Procedures '.'.'.'.'.'. 80
References 32
Appendix - Emission Factors for Carbon Tetrachloride Production! ! ! A-l
References for Appendix A-32
iii
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. FIGURES
Number Page
1 Chemical use tree for carbon tetrachloride 10
2 Basic operations that may be used in carbon
tetrachloride production by the hydrocarbon
chlorinolysis process 13
3 Basic operations that may be used in carbon
tetrachloride production by the methane chlorination
process 15
4 Basic operations that may be used in carbon tetrachloride
production by the carbon disulfide chlorination
process 17
5 Basic operations that may be used in the methanol
hydrochlorination/methyl chloride chlorination
process 19
6 Basic operations that may be used in the production of
f 1 uorocarbons 11 and 12 27
7 Basic operations that may be used in carbon
tetrabromide production . . 33
8 Basic operations that may be used in synthetic
pharmaceutical manufacturing 40
9 Residual carbon tetrachloride fumigant as a function
of the number of days grain is aired 51
10 Basic operations that may be used in ethylene dichloride
production by the balanced process, with air-based
oxychlorination 57
11 Basic operations that may be used in ethylene dichloride
' production by the balanced process, oxygen-based
oxychlori nation step 59
12 Basic operations that may be used in perch!oroethylene
and trichloroethylene production by chlorination of
ethylene dichloride 66
13 Basic operations that may be used in perch!oroethylene
and trichloroethylene production by oxychlorination of
ethylene dichloride 68
iv
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Figures (continued)
Number
14
A-l
A-2
A-3
Method 23 sampling train ..... 81
Process flow diagram for hypothetical plant using
hydrocarbon chlorinolysis (perch!oroethylene
coproduct) process '
A-22
Process flow diagram for hypothetical plant using
methane chlorination process
Process flow diagram for hypothetical plant using
methanol hydrochlorination/methyl chloride
chlorination process
A-26
A-29
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TABLES
Number " page
1 Physical Properties of Carbon Tetrachloride, CC14 6
2 Controlled and Uncontrolled Carbon Tetrachloride Emission
Factors for a Hypothetical Carbon Tetrachloride
Production Facility (Hydrocarbon Chlorinolysis Process). 21
3 Controlled and Uncontrolled Carbon Tetrachloride Emission
Factors for a Hypothetical Carbon Tetrachloride
Production Facility (Methane Chiorination Process) ... .22
4 Controlled and Uncontrolled Carbon Tetrachloride Emission
Factors for a Hypothetical Carbon Tetrachloride
Production Facility (Carbon Disulfide Chlorination
Process) ..... 23
5 Controlled and Uncontrolled Carbon Tetrachloride Emission
Factors for a Hypothetical Facility Using the Methanol
Hydrochlorination/Methyl Chloride Chlorination Process . 24
6 Carbon Tetrachloride Production Facilities 25
7 Controlled and Uncontrolled Carbon Tetrachloride Emission
Factors for a Hypothetical Facility Producing
Fluorocarbons 11 and 12 29
8 Facilities Producing Fluorocarbons 11 and 12 31
9 Carbon Tetrabromide Production Facilities. . ....... 34
10 Registrants and Applicants for Registration of Pesticidal
Products Containing Carbon Tetrachloride 36
11 Carbon Tetrachloride Fumigant Brand Names. ......... 43
12 Fumigant Application Rates .....' 50
13 On-Farm Grain Storage. 53
14 Off-Farm Grain Storage ............ 55
15 Controlled and Uncontrolled Carbon Tetrachloride Emission
Factors for a Hypothetical Facility Producing Ethylene
Dichloride by the Balanced Process ........... 61
16 Ethylene Dichloride Production Facilities 64
vi
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Tables (continued)
Number
Page
17 Controlled and Uncontrolled Carbon Tetrachloride
Emission Factors Reported by a Plant Producing
Perch!oroethylene by Ethylene Dichloride
Chlorination - 70
18 Facilities Producing Perch!oroethylene and/or
Trich!oroethylene 72
19 Chlorine Production Facilities 74
20 Phosgene Production Facilities .78
A-l Summary of Calculations of Carbon Tetrachloride Emission
Factors A-6
A-2 Storage Tank Parameters for Hydrocarbon Chlorinolysis
(Perch!oroethylene Coproduct) Process . . A-7
A-3 Summary of Composition Calculations for Hydrocarbon
Chlorinolysis (Perch!oroethylene Coproduct) .- Crude
Product Storage Tank A-9
A-4 Storage Tank Parameters for Methane Chlorination Process. A-ll
A-5 Summary of Composition Calculations for Methane
Chlorination - Crude Product Tank A-12
A-6 Storage Tank Parameters for Methanol Hydrochlorination/
Methyl Chloride Chlorination Process A-l3
A-7 Summary of Composition Calculations for Methanol
Hydrochlorination/Methyl Chloride Chiorination-Crude
Product Tank A-14
A-8 Summary of Composition Calculations for Methano!
Hydrochlorination/Methyl Chloride Chiorination-Surge
Tank A-15
A-9 Storage Tank Parameters for Carbon Disulfide
Chlorination Process A-l6
vii
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SECTION 1
PURPOSE OF DOCUMENT
EPA, States and local air pollution control agencies are becoming
increasingly aware of the presence of substances in the ambient air that
may be toxic at certain concentrations. This awareness, in turn, has led
to attempts to identify source/receptor relationships for these substances
and to develop control programs to regulate emissions. Unfortunately,
very little information is available on the ambient air concentrations of
these substances or on the sources that may be discharging them to the
atmosphere.
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such
as this that compiles available information on sources and emissions of
these substances. This document specifically deals with carbon tetrachloride.
Its intended audience includes Federal, State and local air pollution
personnel and others who are interested in locating potential emitters
of carbon tetrachloride and making gross estimates of air emissions therefrom.
Because of the limited amounts of data available on carbon tetrachloride
emissions, and since the configuration of many sources will not be the same
as those described herein, this document is best used as a primer to inform
air pollution personnel about 1) the types of sources that may emit carbon
tetrachloride, 2) process variations and release points that may be expected
within these sources, and 3) available emissions information indicating
the potential for carbon tetrachloride to be released into the air from
each operation.
The reader is strongly cautioned against using the emissions
Information contained in this document to try to develop an exact assessment
of emissions from any particular facility. Since insufficient data are
available to develop statistical estimates of the accuracy of these emission
factors, no estimate can be made of the error that could result when these
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factors are used to calculate emissions from any given facility. It is •
possible, in some extreme cases, that orders-of-magnitude differences
could result between actual and calculated emissions, depending on
differences in source configurations, control equipment and operating
practices. Thus, in situations where an accurate assessment of carbon
tetrachloride emissions is necessary, source-specific information should
be obtained to confirm the existence of particular emitting operations,
the types and effectiveness of control measures, and the impact of operating
practices. A source test and/or material balance should be considered
as the best means to determine air emissions directly from an operation.
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SECTION 2
OVERVIEW OF DOCUMENT CONTENTS
As no.ted in Section 1, the purpose of this document 1s to assist
Federal, State and local air pollution agencies and others who are Interested
In locating potential air emitters of carbon tetrachloride and making
gross estimates of air emissions therefrom. Because of the limited background
data available, the information summarized in this document does not and
should not be assumed to represent the source configuration or emissions
associated with any particular facility.
This section provides an overview of the contents of this document.
It briefly outlines the nature, extent and format of the material presented
in the remaining sections of this report.
Section 3 of this document provides a brief summary of the physical
and chemical characteristics of carbon tetrachloride, Its commonly occurring
forms and an overview of its production and uses. A chemical use tree
summarizes the quantities consumed in various end use categories in the
United States. This background section may be useful to someone who needs
to develop a general perspective on the nature of the substance and where
it is manufactured and consumed.
Section 4 of this document focuses on major industrial source categories
that may discharge carbon tetrachloride air emissions. This section
discusses the production of carbon tetrachloride, its use as an industrial
feedstock, and processes which produce carbon tetrachloride as a byproduct.
For each major industrial source category described in Section 4, example
process descriptions and flow diagrams are given, potential emission
points are identified, and available emission factor estimates are presented
that show the potential for carbon tetrachloride emissions before and
after controls employed by industry. Individual companies are named that
are reported to be involved with either the production or use of carbon
tetrachloride, based primarily on trade publications.
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The final section of this document summarizes available procedures
for source sampling and analysis of carbon tetrachloride. Details are
not prescribed nor is any EPA endorsement given or implied to any of
these sampling and analysis procedures. At this time, EPA has generally
not evaluated these methods. Consequently, this document merely provides
an overview of applicable source sampling procedures, citing references
for those interested in conducting source tests.
The appendix located at the end of this document presents derivations of
carbon tetrachloride emission factors for carbon tetrachloride production
processes which are presented in Section 4. The development of these emission
factors is discussed in detail for sources such as process vents, storage tank
vents, liquid and solid waste streams, handling, and leaks from process valves,
pumps, compressors, and pressure relief valves.
This document does not contain any discussion of health or other
environmental effects of carbon tetrachloride, nor does it Include any
discussion of ambient air levels or ambient air monitoring techniques.
• \
Comments on the contents or usefulness of this document are welcomed,
as is any information on process descriptions, operating practices,
control measures and emissions 'information that would enable EPA to
improve its contents. All comments should be sent to:
Chief, Source Analysis Section (MD-14)
Air Management Technology Branch
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
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SECTION 3
BACKGROUND
NATURE OF POLLUTANT
Carbon tetrachloride, CCl^, is a clear, colorless, nonflammable
liquid at normal temperatures and pressures. Physical properties of
carbon tetrachloride are presented in Table 1.
Carbon tetrachloride is miscible with most organic solvents, but is
essentially insoluble in water. It is relatively volatile, with a vapor
pressure of 11.94 kPa at 20°C. Due to its high thermal capacity, carbon
tetrachloride increases the lower explosion limits of gaseous, mixtures
and has an extinctive effect on flames. The density of carbon tetrachloride
vapor is over five times that of air; thus, in cases where concentrated
gaseous emissions occur, the plume will tend to settle to the ground
2
before dispersing into the ambient air.
Carbon tetrachloride decomposes in fires to phosgene. Thermal
decomposition of carbon tetrachloride occurs very slowly at temperatures
up to 400°C. At temperatures of 900 to 1300°C, extensive dissociation
occurs forming perchloroethylene, hexachloroethane, and some chlorine.
Reaction of carbon tetrachloride with steam at high temperatures results
in the formation of.chloromethanes, hexachloroethane, and perchloroethylene.
Carbon tetrachloride is very stable in the atmosphere, with a residence
time of about 30 years. Residence time is defined as the time required
for the concentration to decay to 1/e of its original value (e = 2.7183).
The major mechanisms that remove carbon tetrachloride from the air are
ultraviolet photolysis and reaction with oxygen radicals in the stratosphere.
The major products of carbon tetrachloride photo-oxidation are phosgene and
chloride radical.2'3
1
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TABLE 1. PHYSICAL PROPERTIES OF CARBON TETRACHLORIDE, CCV
Property
Value
Synonyms:
Tetrachloromethane, methane tetrachloride, perch!oromethane.
benzinoform
CAS Registry No.
Molecular weight
Melting point, °C
Boiling point, °C
Refractive index, 15CC
Specific gravity
20/4°C
Autoignition temperature, °C
Flash point, °C
Vapor density, air - 1
Surface tension, mN/m(sdyn/cm)
0°C
20°C
60°C
Specific heat, J/kg
20°C
30°C
Critical temperature, °C
Critical pressure, MPa
Critical density, kg/m
Thermal conductivity, mW/(m-K)
Liquid, 20°C
Vapor, bp
Average coefficient of volume expansion,
0-40°C
Dielectric constant
Liquid, 20°C
Liquid, 50°C
Vapor, 87.6°C
56-23-5
153.82
-22.92
76.72
1.46305
1.59472
>1,000
None
5.32
29; 38
26.77
18.16
866
837
283.2
4.6
558
118
7.29
0.00124
2.205
1.874
1.00302
CONTINUED
6
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TABLE 1. (continued)
Property
Value
Heat of formation, kJ/mol
Liquid
Vapor
Heat of combustion, liquid, at constant
volume, 18.7°C, kJ/mol
Latent heat of fusion, kJ/mol
Latent heat of vaporization, kJ/kg
Viscosity, 20°C, mPa-s
Vapor pressure, kPa
0°C
20°C
40°C
60°C
150°C
200°C
Solubility of CC1* in water, 25°C,
g/100 g H20
Solubility of water in CCK, 25°C,
g/100 g
-142
-108
365
2.535
194.7
0.965
4.410
11.94
28.12
58.53
607.3
1,458
0.08
0.013
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OVERVIEW OF PRODUCTION AND USE
Carbon tetrachloride was first manufactured on a large scale in the
United States in 1907, primarily as a drycleaning agent and for use in
fire extinguishers.
Carbon tetrachloride is currently produced in the United States by
five companies at nine manufacturing sites. Domestic production in 1980
was 710 million pounds. Approximately 95 million pounds of carbon
tetrachloride were exported and 7 million pounds imported.
Carbon tetrachloride is produced domestically by three processes:
chlorlnolysis of hydrocarbons, methane chlorination, and carbon disulfide
chlorination. Hydrocarbon chlorinolysis (perch!oroethylene coproduct),
the predominant manufacturing process, involves the chlorination of
hydrocarbons at high temperatures to yield carbon tetrachloride and
perch!oroethylene, which are then separated by distillation. The relative
amounts of these two coproducts depend on the nature of the hydrocarbon
starting material and conditions of chlorination.
In the methane chlorination process, methane is chlorinated at a
temperature of about 400°C and a pressure of about 200 kPa to produce
carbon tetrachloride, methyl chloride, methylene chloride and chloroform.
The chloromethane coproducts are separated by four sequential distillations.
The methyl chloride in the overheads from the first column can be recycled
(
to the chlorination reactor to enhance the yield of the other chloromethanes.
In the carbon disulfide chlorination process, a solution of carbon
disulfide and sulfur chloride in carbon tetrachloride is fed to a chlori-
nation reactor where chlorine is sparged through the solution to yield a
mixture of product carbon tetrachloride and sulfur chloride. The sulfur
chloride is then reacted with carbon disulfide, producing carbon tetra-
chloride and elemental sulfur. The carbon tetrachloride produced in this
reaction and excess carbon disulfide are recycled to the chlorination
reactor.
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Carbon tetrachloride may also be produced as a byproduct of the
manufacture of methyl chloride, methylene chloride, and chloroform by the
methanol hydrochlorination/methyl chloride chlorination process. • However,
the crude carbon tetrachloride-containing bottoms from this process
commonly are used on-site in the chlorinolysis process for manufacturing
Q
carbon tetrachloride and perch!oroethy!ene.
The current uses of carbon tetrachloride are listed in Figure 1
with the percentage of carbon tetrachloride consumed for each use. The
major end use of carbon tetrachloride is in the production of trichloro-
fluoromethane (fluorocarbon 11) and dichlorodifluoromethane (fluorocarbon 12),
which accounted for 81 percent of 1981 consumption. Prior to the restriction
by the Environmental Protection Agency on the use of fluorocarbons as aerosol
propel!ants, both fluorocarbons 11 and 12 were widely used for this
purpose. Currently, fluorocarbon 12 is used as a refrigerant and fluorocarbon 1!
is used as a blowing agent in the manufacture of plastic foams.
Miscellaneous and solvent applications of carbon tetrachloride
accounted for 7 percent of 1981 consumption. These applications include
2
use as a feedstock in carbon tetrabromide manufacture; in pesticide
formulations; as a solvent in pharmaceutical manufacture; and as a
solvent and thinner in shoe and furniture polishes, paints, lacquers,
printing inks, floor waxes,, and stains. The use of carbon tetrachloride
in fire extinguishers has been discontinued because of its tendency to
7
decompose and form phosgene when sprayed into flames.
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SECTION 4
CARBON TETRACHLORIDE EMISSION SOURCES
This section discusses carbon tetrachloride emissions from direct
sources such as carbon tetrachloride production, fluorocarbon production,
carbon tetrabromide production, liquid pesticide formulation, pharmaceutical
manufacture, and the use of pesticides containing carbon tetrachloride.
Indirect emission sources are also discussed. Indirect sources of
carbon tetrachloride include ethylene dichloride production and the
manufacture of perch!oroethylene and trichloroethylene. Process and
emissions information are presented for each source for which data are
available.
CARBON TETRACHLORIDE PRODUCTION ,
In the most widely used carbon tetrachloride production process, the
chlorinolysis process, hydrocarbons are chlorinated at or near pyrolytic
conditions to produce a mixture of carbon tetrachloride and perch!oroethylene..
A second process involves the direct chlorination of methane to produce
chloromethanes, including carbon tetrachloride. Direct chlorination of
methane is used currently at only one plant. Another facility formerly
employed this process but has changed to a different production process.
The details of this new process are not currently available. Carbon
tetrachloride is also produced by the chlorination of carbon disulfide at
one facility. In addition, carbon tetrachloride is formed as a byproduct
in the manufacture of chloroform and methylene chloride by the hydrochlorination
of methyl chloride in the methanol hydrochlorination/methyl chloride
chlorination process. This process is included in this section because
it is integrated at many facilities with the .chlorinolysis process. At
these facilities, the impure carbon tetrachloride from methyl chloride
chlorination is frequently used as feedstock for the chlorinolysis
process.
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Process Descriptions
Hydrocarbon Chlorinolysis (Perch!oroethylene Coproduct) Process ~.
The major products of the chlorinolysis process are carbon tetrachloride
and perch!oroethylene. A variety of hydrocarbons and chlorinated hydrocarbons
may be used as feed materials including crude carbon tetrachloride,
ethylene dichloride, acetylene, ethylene, propylene, paraffinic hydrocarbons "
of up to four carbons, and napthalene. *
Basic operations that may be used in the chlorinolysis process are
shown in Figure 2. Preheated feed material (Stream 1) and chlorine
(Stream 2) are fed to the chlorinolysis reactor, a fluid bed reactor
maintained at about 500°C which contains copper and barium chloride on
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graphite as a catalyst.
i
The reaction products (Stream 3) pass through a cyclone for removal
of entrained catalyst and then on to a condenser. Uncondensed materials
(Stream 4), consisting of hydrogen chloride, unreacted chlorine, and
some carbon tetracriloride, are removed to the hydrogen chloride purification
system. The condensed reactor products (Stream 5) are fed to a hydrogen
chloride and chlorine removal column, with the overheads (Stream 6) from
this column going to the hydrogen chloride purification operation. The
bottoms (Stream 7) from the column are fed to a crude storage tank.
Material from crude storage is fed to a series of two distillation
columns.' The first column extracts carbon tetrachloride (Stream 8)
which is transferred either to a storage and loading operation or to
the hydrogen chloride purification system (Stream 9) for use as a scrubber
liquid. The bottoms (Stream 10) from the carbon tetrachloride distillation
column are fed to a perch!oroethylene distillation column. In this
column, perchloroethylene is extracted as overheads (Stream 11) and
transferred to storage and loading. Bottoms from the perchloroethylene
distillation column are incinerated.®
The feed streams (Streams 4 and 6) to the hydrogen chloride purification
operation are compressed, cooled, and scrubbed in a chlorine absorption
column with chilled carbon tetrachloride (Stream 9) to remove chlorine.
The bottoms and condensable overheads (Stream 12) from this column are
12
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combined and recycled to the chlorinolysis reactor. Uncondensed overheads
(Stream 13) from the chlorine absorption column are water-scrubbed In
the hydrogen chloride absorber. Hydrochloric add solution 1s removed
from the bottom of this absorber to storage for eventual reprocessing or
for use in a separate facility. Overheads from the absorber and vented
gases from byproduct hydrochloric acid storage are combined (Stream 14)
and passed through a caustic scrubber to remove residual hydrogen chloride.
Inert gases are vented from the scrubber.
Methane Chiorination Process —
In the methane chlorination process, carbon tetrachloride is produced
as a coproduct with methyl chloride, methylene chlorfde and chloroform.
Methane can be chlorinated thermally, photochemically, or catalytically,
with thermal chlorination being the most commonly used method.
Figure 3 presents basic operations that may be used in the methane
chlorination process. Methane (Stream 1) and chlorine (Stream 2) are
mixed and fed to a chlorination reactor, which is operated at a temperature
of about 400°C and a pressure of about 200 kPa. Gases exiting the reactor
(Stream 3) are partly condensed and then scrubbed with chilled crude
product to absorb most of the product chloromethanes from the unreacted
methane and byproduct hydrogen chloride. The unreacted methane and
byproduct hydrogen chloride from the absorber (Stream 4) are fed serially
to a hydrogen chloride absorber, caustic scrubber, and drying column to
remove hydrogen chloride. The purified methane (Stream 5) is recycled to
the chlorination reactor. The condensed crude chloromethane stream
(Stream 6) is fed to a stripper where 1t is separated into overheads
containing hydrogen chloride; methyl chloride and some higher boiling
chloromethanes; and bottoms containing methylene chloride, chloroform,
and carbon tetrachloride.
Overheads from the stripper (Stream 7) are fed to a water scrubber,
where most of the hydrogen chloride is removed as weak hydrochloric acid
(Stream 8). The offgas from the water scrubber 1s fed to a dilute
sodium hydroxide scrubber solution to remove residual hydrogen chloride.
Water is then removed from the crude chloromethanes in a drying column.
14
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The chloromethane mixture from the drying column (Stream 9) is
compressed, condensed, and fed to a methyl chloride distillation column. •
Methyl chloride from the distillation column can be recycled back to the
chlorination reactor (Stream 10) to enhance the yield of the other
chloromethanes, or condensed and then transferred to storage and loading
as a product (Stream 11).
Bottoms from the stripper (Stream 12) are neutralized, dried, and
combined with bottoms from the methyl chloride distillation column
(Stream 13) in a crude storage tank. The crude chloromethanes (Stream 14)
pass to three distillation columns in series which extract methylene
chloride (Stream 15), chloroform (Stream 17), and carbon tetrachloride
(Stream 19). Condensed methylene chloride, chloroform, and carbon
tetrachloride product streams are fed to day storage tanks, where inhibitors
may be added fqr stabilization. The product streams are then transferred
to storage and loading facilities. Bottoms from the carbon tetrachloride
distillation column are incinerated.
Carbon Disulfide Chlorination Process —
Basic operations that may be used in the carbon disulfide chlorination
process are shown in Figure 4. A solution of carbon disulfide (Stream 1)
and sulfur chloride in carbon tetrachloride is fed to a chlorination
reactor where chlorine (Stream 2) is sparged through the solution. The
reaction products, carbon tetrachloride and sulfur chloride (Stream 3),
are pumped to a distillation column. The carbon tetrachloride overhead
stream from the column (Stream 4) is treated with caustic and then fed
(Stream 6) to a distillation column where it is dried via a carbon
tetrachloride-water distillation. Product carbon tetrachloride (Stream 7)
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is then pumped to storage tanks.
Sulfur chloride in the bottoms from the crude product distillation
column (Stream 5) is transferred to a dechlorinator where it is mixed
and reacted with carbon disulfide producing carbon tetrachloride and
elemental sulfur. The carbon tetrachloride and unreacted carbon disulfide
(Stream 8) are distilled off (Stream 9) and recycled to the chlorination
reactor. Residual sulfur and sulfur chloride (Stream 10) are pumped to
16
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a water scrubber where the sulfur chloride is removed from the sulfur.
The sulfur byproduct (Stream 12) is transferred to a holding tank and
from there as needed to a sulfuric acid plant. Sulfur chloride (Stream 11)
1s scrubbed with caustic and the residual is vented to the atmosphere.
Methanol Hydrochlorination/Methy! Chloride Chiorination Process —
Carbon tetrachloride is produced as a byproduct of the methanol
hydrochlorination/methyl chloride chlorination process. The major
products are chloroform, methyl chloride, and. methylene chloride.
Basic operations that may be used in methanol hydrochlorination/methyl
chloride chlorination are shown in Figure 5. Equimolar proportions of
gaseous methanol (Stream 1) and hydrogen chloride (Stream 2) are fed to a
hydrochlorination reactor, maintained at a temperature of about 350 C.
The hydrochlorination reaction is catalyzed by one of a number of catalysts,
including alumina gel, cuprous or zinc chloride on activated carbon or
pumice, or phosphoric acid on activated carbon. Methanol conversion of
95 percent is typical.
The reactor exit gas (Stream 3) is transferred to a quench tower,
where unreacted hydrogen chloride and methanol are removed by water
scrubbing. The water discharged from the quench tower (Stream 4) is
stripped of virtually all dissolved methyl chloride and most of.the
methanol, both of which are recycled to the hydrochlorination reactor
(Stream 5). The outlet liquid from the stripper (Stream 6) consists of
dilute hydrochloric acid, which is used in-house or is sent to a wastewater
12
treatment system.
Methyl chloride gas from the quench tower (Stream 7) is fed to the-
drying tower, where it is contacted with concentrated sulfuric acid to
remove residual water. The dilute sulfuric acid effluent (Stream 8) is
12
sold or reprocessed.
A portion of the dried methyl chloride (Stream 9) is compressed,
cooled, and liquefied as product. The remainder (Stream 10) is fed to
the chlorination reactor along with chlorine gas (Stream 11). The
methyl chloride and chlorine react to form methylene chloride and chloroform,
along with hydrogen chloride and a small amount of carbon tetrachloride.
18
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The product stream from the chlorination reactor is condensed and
then stripped of hydrogen chloride. The hydrogen chloride is recycled
to the methanol hydrochlorination reactor (Stream 12). The crude mixture
of methylene chloride, chloroform, and carbon tetrachloride from the
stripper (Stream 13) is transferred to a storage tank, and then fed to a
distillation column to extract methylene chloride. Bottoms from methy!ene
chloride distillation (Stream 15) are distilled to extract chloroform.
The chloroform and methylene chloride product streams (Streams 14 and
16) are fed to day tanks where inhibitors are added and then sent on to
storage and loading facilities. Bottoms from chloroform distillation
(Stream 17) consist of crude carbon tetrachloride which is stored for
subsequent sale or used onsite in a chlorinolysis process (described .
previously).
Emissions
12
Carbon tetrachloride emission factors for the hydrocarbon chlorinolysis
process, the methane chlorination process, the carbon disulfide chlorination
process, and the methanol hydrochlorination/methyl chloride chlorination
process are presented, respectively, in Tables 2 through 5. Each table
lists uncontrolled emission factors for various sources, potentially
applicable control techniques, and controlled emission factors associated
with the identified emission reduction techniques. The derivations of
these emission factors are presented in Appendix A. As described in the
appendix, the emission factors were based on hypothetical plants. Actual
emissions for a given facility may vary because of such factors as differences
in process design and age of equipment.
Source Locations
. Table 6 presents a published list of major producers of carbon
tetrachloride.
20
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FLUOROCARBON PRODUCTION
The primary use for carbon tetrachloride is as a feedstock for the
production of dichlorodlfluoromethane (fluorocarbon 12) and trichlorofluoro-
methane (fluorocarbon 11). Currently, fluorocarbon 12 1s used as a refrigerant
and fluorocarbon 11 1s used as a blowing agent in the manufacture of plastic
foams.
Process Description
Fluorocarbons 11 and 12 are produced by the liquid-phase reaction of
anhydrous hydrogen fluoride (HF) and carbon tetrachloride. Basic operations
that may be used in the fluorocarbon production process are shown in Figure 6.
Carbon tetrachloride (Stream 1), liquid anhydrous HF (Stream 2), and chlorine
(Stream 3) are pumped from storage to the reactor, along with the recycled
bottoms from the product recovery column (Stream 15) and the HF recycle stream
(Stream 9). The reactor contains antimony pentachloride catalyst and is
operated at temperatures ranging from 0 to 200°C and pressures of 100 to
3,400 kPa.19
Vapor from the reactor (Stream 4) is fed to a catalyst distillation
column, which removes as. overheads hydrogen chloride (HC1), the desired
fluorocarbon products, and some HF (Stream 6). Bottoms.containing vaporized
catalyst, unconverted and underfluorinated species, and some HF (Stream 5) are
returned to the reactor. The overhead stream from the column (Stream 6) is
18
condensed and pumped to the HC1 recovery column.
" Anhydrous HC1 byproduct is removed as overheads (Stream 7) from the HC1
recovery column, condensed, and transferred to pressurized storage as a liquid.
The bottoms stream from the HC1 recovery column (Stream 8) is chilled until it
separates Into two immiscible phases: an HF phase and a denser fluorocarbon
phase. These are separated in a phase separator. The HF phase (Stream 9),
which contains a small amount of dissolved f1uorocarbons, 1s recycled to the
reactor. The denser phase (Stream 10), which contains the fluorocarbons plus
trace amounts of HF and HC1, is evaporated and ducted to a caustic scrubber to
neutralize the HF and HC1. The stream is then contacted with sulfuric acid
and subsequently with activated alumina to remove water
18
26
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The neutralized and dried fluorocarbon mixture (Stream 11) is compressed
and sent to a series of two distillation columns. Fluorocarbon 12 is taken as
overheads from the first column, dried with activated alumina, and sent to
pressurized storage (Stream 12). The bottoms from the first distillation
(Stream 13) are sent to the second distillation column, where fluorocarbon 11
1s removed overhead, dried with activated alumina, and sent to pressurized
storage (Stream 14). The bottoms from the second distillation (Stream 15) are
recycled to the reactor.
There are a number of process variations in fluorocarbon production. HF
may be separated from product f1uorocarbons prior to hydrogen chloride removal.
the HC1 removal system can vary with respect to the method of removal and the
type of byproduct acid obtained. After anhydrous HC1 has been obtained as
shown in Figure 6, it can be further purified and absorbed in water. Alternatively,]
the condensed overhead from catalyst distillation (Stream 6) can be treated
with water to recover an aqueous solution of HC1 contaminated with HF and
possibly some fluorocarbons.. In this case, phase separation of HF and products,
and HF recycle are not carried out. This latter procedure is used at many
18
older plants in the industry.
Emissions
Uncontrolled carbon tetrachloride emission factors for the fluorocarbon 11
and 12 production processes are listed in Table 7 with potential control
techniques and associated controlled emission factors. Potential sources of
carbon tetrachloride emissions include process vents, carbon tetrachloride
storage tanks, and fugitive emission sources such as process valves, pumps,
compressors, and pressure relief valves. However, one facility has reported
fugitive emissions of carbon tetrachloride to be negligible.
Process Emissions —
As indicated in Figure 6, there are three sources of process emissions in
the manufacture of fluorocarbons. Vents on the product recovery columns emit
only fluorocarbons. A vent on the hydrogen chloride recovery column accumulator
(Vent A, Figure 6) purges noncondensibles and small amounts of inert gases
which enter the reactor with the chlorine feed stream. This vent stream is
not reported to contain carbon tetrachloride during typical process operation.
28
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During mechanical maintenance operations, the fluorination reactor is vented
through the HC1 column accumulator, and at these times the vent stream contains
carbon tetrachloride. The uncontrolled carbon tetrachloride emission factor
for reactor venting is from reference 21. This reference did not indicate the
frequency of reactor venting or the duration and emission rate associated with
each such occurrence.
At one facility, a carbon tetrachloride scrubber is used to remove fluorocarbo]
emissions from the fluorocarbon 12 distillation vent (Vent B, Figure 6). The
vent stream from the scrubber contains carbon tetrachloride. The emission
rate for this source was 0.17 kg/hr at a fluorocarbon production rate of
7.6 Mg/hr.18 The extent of the use of this control technique at other facilities
is unknown.
Storage Emissions —
The uncontrolled emission factors for carbon tetrachloride feedstock
storage in fixed roof tanks (Vents C, Figure 6) are from references 18 and 20.
Source Locations
A list of facilities producing fluorocarbons 11 and 12 is presented in
Table 8.
30
-------
TABLE 8. FACILITIES PRODUCING FLUOROCARBONS 11 AND i215,20,22,23
Company
Location3
Allied Chemical Corp.*
E.I. duPont de Nemours
and'Co., Inc.
Essex Chemical Corp.
(Racon Inc., Subsidiary)
Kaiser Aluminum and
Chemical Corp.
Penwalt Corp.
Danville, IL
El Segundo, CA
Antioch, CA
Deepwater, NJ
Montague, MI
Wichita, KS
Gramercy, LA
Calvert City, KY
Note: This list is subject to change as market conditions change,
facility ownership changes, or plants are closed down. The
reader should verify the existence of particular facilities
by consulting current lists or the plants themselves. The
level of emissions from any given facility is a function of
variables such as throughput and control measures, and
should be determined through direct contacts with plant
personnel.
31
-------
CARBON TETRABROMIDE PRODUCTION
A small proportion of carbon tetrachloride is used as feedstock for the
manufacture of carbon tetrabromide. Less than 25 Mg of carbon tetrabromide
was produced in the United States in 1975.
Process Description
Carbon tetrabromide is produced by a chlorine displacement process. In
this process, carbon tetrachloride and anhydrous hydrogen bromide (HBr) are
reacted in a series of batch reactors. Basic operations that may be used in
the production of carbon tetrabromide by chlorine displacement are shown in
.Figure 7. Three reaction vessels are charged with a solution of aluminum
tribromide catalyst in the starting chlorocarbon, which in the case of
carbon tetrabromide production is carbon tetrachloride. Gaseous anhydrous
HBr is fed into Reactor 1 below the li'quid surface. Gas evolved from Reactor 1
is passed into the liquid in Reactor 2, and gas from Reactor 2 is passed
into the liquid of Reactor 3. The gas from Reactor 3 is primarily hydrogen
chloride and is vented to an acid scrubber. When the contents of Reactor 1
are sufficiently converted to carbon tetrabromide, the HBr stream is diverted
to Reactor 2 and the contents of Reactor 1 are discharged for product recovery.
The crude product is washed with water to remove the catalyst and is dried.
Reactor 1 is then recharged with chlorocarbon and catalyst and becomes the
24
third vessel in the reaction series.
Emissions
Potential sources of carbon tetrachloride in the manufacture of carbon
tetrabromide include £he storage of carbon tetrachloride feedstock, the vent
scrubber, and fugitive emissions. Insufficient information is available for
the development of carbon tetrachloride emission factors for carbon tetrabromide
production.
Source Locations
Table 9 lists companies and their locations that produce carbon tetrabromide,
32
-------
Sir
S8
J
.!•»
£
o
i
CO
I
^1
•""1
o
K
^*
s
U
%
£
I
O
•5
—-H
1
1
•8
.o
2
+j
-------
TABLE 9. CARBON TETRABROMIDE PRODUCTION FACILITIES
15
Plant
Location
Diamond Shamrock Corp.
Industrial Chems. and Plastics
Unit, Electro Chemicals Division
Great Lakes Chemical Corp.
01 in Corp.
01 in Chemicals Group
Deer Park, TX
El Dorado, AK
Rochester, NY
NOTE: This list is subject to change as market conditions change,
facility ownership changes, or plants are closed down. The
reader should verify the existence of particular facilities
by consulting current lists or the plants themselves. The
level of emissions from any given facility is a function of
variables such as throughput and control measures, and
should be determined through direct contacts with plant
personnel.
34
-------
LIQUID PESTICIDE FORMULATION
Carbon tetrachloride is used 1n a number of liquid pesticide formulations,
primarily in fumigants. These formulations generally are mixtures of carbon
tetrachloride and other active ingredients such as ethylene dibromide, sulfur
25
dioxide, and carbon disulfide. '
Process Description
Pesticide formulation systems are typically batch mixing operations.
Technical grade pesticide is usually stored in its original shipping container
in the warehouse section of the plant until it is needed. If the material is
received in bulk, it is transferred to holding tanks for storage. Solvents
are normally stored in bulk tanks.
Batch mixing tanks are typically closed vessels. The components of the
formulation are fed into the tank, measured by weight, and mixed by circulation
with a tank pump.27 The. formulated material is then pumped to a holding tank
before being put into containers for shipment.
26
The blend tank is vented to the atmosphere through a vent dryer, which
prevents moisture from entering the tank.27 Storage and holding tanks and
container-filling lines are typically provided with an exhaust connection or
hood to remove any vapors. The exhaust from the system is vented to a control
device or directly to the atmosphere.26
Emissions
Sources of carbon tetrachloride emissions from pesticide formulation
include storage vessels, mixing vessel vents, and leaks from pumps, valves,
and flanges. Insufficient information is available for the development of
carbon tetrachloride emission factors for liquid pesticide formulation
facilities.
Source Locations
Registrants and applicants for registration of pesticidal products
containing carbon tetrachloride are listed in Table 10. Some of the listed
companies may buy a preformulated or prepackaged product from larger producers
and therefore may not be actual sources of emissions. In addition, this list
may change as facility ownership changes or plants are closed down.
35
-------
TABLE 10. REGISTRANTS AND APPLICANTS
PRODUCTS CONTAINING CARBON
FOR REGISTRATION OF PESTICIDAL
TETRACHLQRTDE?5 •
Company
Location
Southland Pearson & Co.
Cardinal Chemical Co.
Coyne Chemical Co.
Hockwaldchem, Division of Oxford Chemicals
Stauffer Chemical Co.
M.F. Canle & Co.
Dettelbach Chemicals Corp.
H111 Manufacturing, Inc. .
Lester Laboratories
Monrnr, Inc.
Oxford Chemicals
The'Selig Chemical Industries
Stephenson Chemical Co., Inc.
Woolfolk Chemical Works, Inc.
ZEP Manufacturing Co.
Riverdale Chemical Co.
Brayton Chemicals, Inc.
MFA Oil Co.
Midland Laboratories, Inc.
Bartels & Shores Chemical Co.
Chemi Sol Chemicals & Sales Co.
Industrial Fumigant Co.
PBI-Gordon Corp.
Mobile, AL
San Francisco, CA
Los Angeles, CA
Brisbane, CA
Richmond, CA
Tampa, FL
Atlanta, GA
Atlanta, GA
Atlanta, GA
Atlanta, GA
Atlanta, GA
Atlanta, GA
College Park, GA
Ft. Valley, GA
Atlanta, GA
Chicago Heights, IL
West Burlington, IA
Shenandoah, IA
Des Moines, IA
Kansas City, KS
Hutchison, KS
Olathe, KS
Kansas City, KS
CONTINUED
36
-------
TABLE 10. (continued)
Company
Location
Research Products Co.
Thompson-Hayward Chemical Co.
Vulcan Materials Co., Chemicals Division
Weevil-cide Co.
Grain Conditioners, Inc.
Quinn Drug & Chemical Co.
Dow Chemical USA
Haertel Walter Co.
E.H> Leitte Co.
Universal Cooperatives, Inc.
Douglas Chemical Co.
Farmland Industries, Inc.
Ferguson Fumigants
The Huge Co., Inc.
Knox Chemical Co.
Patterson Chemical Co., Inc.
Steward Sanitary Supply Co., Ltd.
Techne Corp.
Falls Chemicals,.Inc.
Warren-Douglas Chemical Co.
Agway, Inc., Chemical Division
Prentis Drug & Chemical Co., Inc
Bernard Sirotta Co., Inc.
Salina, KS
Kansas City, KS
Wichita, KS
Salina, KS
New Orleans, LA
Greenwood, MS
Midland, MI
Minneapolis, MN
St. Paul, MN
Minneapolis, MN
Liberty, MO
Kansas City, MO
Hazelwood, MO
St. Louis, MO
St. Louis, MO
Kansas City, MO
St. Louis, MO
Kansas City, MO
Great Falls, MT
Omaha, NB
Syracuse, NY
New York, NY
Brooklyn, NY
CONTINUED
37
-------
TABLE 10. (continued)
Company
Location
West Chemical Products, Inc.
Lystad, Inc.
Diamond Shamrock Agricultural Chemicals
B1g F Insecticides* Inc.
Well Chemicals Co.
J-Chem, A Division of Fumigators, Inc.
Soweco, Inc.
The Staffel Co.
Atomic Chemical Co.
Lynbrook, NY
Grand Forks, ND
Cleveland, OH
Memphis, TN
Memphis, TN
Houston, TX
AmariTlo, TX
San Antonio, TX
Spokane, WA
Note: The companies listed are registrants of pesticidal products
containing carbon tetrachloride. Some of these companies may
buy a performulated or prepackaged product and, therefore may
not be actual sources of emissions. In addition, the list is
subject to change as market conditions change, facility
ownership changes, or plants are closed down. The reader
should verify the existence of particular facilities by con-
sulting current listings or the plants themselves. The level
of emissions from any given facility is a function of variables,
such as throughput and control measures, and should be deter-
mined through direct contacts with plant personnel.
38
-------
PHARMACEUTICAL MANUFACTURING
Carbon tetrachloride is used as a solvent in the manufacturing of
28
pharmaceutical products by chemical synthesis.
Process Description
Synthetic Pharmaceuticals are normally manufactured in a series of batch
operations, many of which involve the use of solvents. Figure 8 presents basic
operations that may be used in a batch synthesis process. To begin a production
cycle, the reactor is water washed and dried with a solvent. Air or nitrogen
is usually used to purge the tank after it is cleaned. Solid reactants and
solvent are then charged to the reactor. After the reaction is complete, any
remaining unreacted volatile compounds and solvents are removed from the
reactor by distillation and condensed. The pharmaceutical product is then
transferred to a holding tank. In the holding tank, the product may be washed
three to four times with water or solvent to remove any remaining reactants
and byproducts. The solvent used in washing generally is evaporated from the
reaction product. The crude product may then be dissolved in another solvent
and transferred to a crystal!izer for purification. After crystallization,
the solid material is separated from the remaining solvent by centrifuging.
While in the centrifuge, the product cake may be washed several times with
water or.solvent. Tray, rotary, or fluid-bed dryers are employed for final
product finishing.
Emissions
Where carbon tetrachloride is used as a solvent in the manufacture of a
pharmaceutical product, each step of the manufacturing process may be a source
of carbon tetrachloride emissions. The magnitude of emissions varies widely
within and among operations; therefore, it is impossible to cite typical
emission rates for various operations. Based on an industry wide mass
balance, at the current level of control, about 11 percent of the carbon
tetrachloride used in the industry is emitted to the air. Thus, the industry-wide
controlled emission factor is about 110 kilograms per megagram of carbon
tetrachloride used.
39
-------
is
i
o
£
S
00
CM
pt
(0
(0
u
•»••
+J
O)
-------
An approximate ranking of emission sources has been established and is
presented below in order of decreasing emission significance. The first four
sources typically account for the majority of emissions from a plant.
1. Dryers
2. Reactors
3. Distillation units
4. Storage and transfer
5. Filters
6. Extractors
7. Centrifuges
8. Crystal!izers .
Condensers, scrubbers, and carbon adsorbers can be used to control
emissions from all of the above emission sources. Storage and transfer
emissions can also be controlled by the use of vapor return lines, conservation
vents, vent scrubbers, pressurized storage tanks, and floating roof storage
tanks.28
Source Locations
The Standard Industrial Classification (SIC) code for pharmaceutical
preparations is 2834. There are approximately 800 pharmaceutical plants
producing drugs in the United States and its territories. Most-of the plants
are small and have less than 25 employees. Nearly 50 percent of the plants
are located in 5 States: 12 percent in New York, 12 percent in California,
10 percent in New Jersey, 5 percent in Illinois, and 6 percent in Pennsylvania.
These States also contain the largest plants in the industry. Puerto Rico has
had the greatest growth in the past 15 years, during which 40 plants have
located there. Puerto Rico now contains 90 plants or about 7.5 percent of the
total. EPA's Region II (New Jersey, New York, Puerto Rico, Virgin Islands)
has 340 plants (28 percent of the total); Region V (Illinois, Minnesota,
Michigan, Ohio, Indiana, Wisconsin), 215 plants (20 percent); and Region IX
(Arizona, California, Hawaii, Guam, American Samoa), 143 plants (13 percent).
41
-------
USE OF PESTICIDES CONTAINING CARBON TETRACHLORIDE
i .
The primary use of carbon tetrachloride in pesticides is as a component
of fumigant mixtures. These fumigants are applied to control insect infestations
1n grains during storage, transfer, milling, distribution, and processing.
It has been estimated that 98 percent of liquid fumigant formulations containing
carbon tetrachloride is used on stored grain while 2 percent is used in the
29
fumigation of grain mill equipment.
Carbon tetrachloride is used in over 98 percent of the grain fumigant
30
mixtures available for application to stored grain. Other ingredients of
these mixtures include ethylene dibromide, ethylene dichloride, sulfur dioxide,
and carbon disulfide. The most common grain fumigant formulations are:
o Carbon tetrachloride 80 percent, carbon disulfide 20 percent;
o ' Carbon tetrachloride 80.9 percent, carbon disulfide 16 percent,
ethylene dibromide 1.2 percent, sulfur dioxide 1.5 percent, and
pentane 0.4 percent;
o Carbon tetrachloride 77 percent, carbon disulfide 15.4 percent,
ethylene dibromide 5 percent, sulfur dioxide 1.5 percent, and
pentane 0.4 percent;
o Carbon tetrachloride 60 percent, ethylene dichloride 35 percent,
and ethylene dibromide 5 percent; and
o Carbon tetrachloride 75 percent, ethylene dichloride 25 percent.
Table 11 lists brand names of fumigant products containing carbon
tetrachloride.
Carbon tetrachloride fumigant formulations are used at farms; at
off-farm grain elevators including subterminal, terminal, and port
elevators; at mill holding facilities; and in transport vehicles. In
1977-78, 3.6 million liters of fumigants containing 3,900 Mg of carbon
tetrachloride were applied to grains stored on farms, while 7.6 million
liters containing 8,900 Mg of carbon tetrachloride were used at off-farm
facilities. Carbon tetrachloride formulations are more widely used at
smaller grain elevators than at large elevators. About 70 percent of
the grain stored at large grain elevators such as terminal elevators are
treated with aluminum phosphide formulations, which do not include
29
carbon tetrachloride.
42
-------
TABLE 11. CARBON TETRACHLORIDE FUMIGANT BRAND NAMES
25
Acritet 34-66
Agway Serafume
Big F "LGF" Liquid Gas Fumigant
Best 4 Servis Brand 75-25"Standard Fumigant
Brayton 75-25 Grain Fumigant
Brayton Flour Equipment Fumigant for Bakeries
\
Brayton EB-5 Grain Fumigant
Bug Devil Fumigant
Cardinal Fume
Chemi-Fume Fumigant Type B
Co-op Activated 80-20 Grain Fumigant Fire Inhibited
Co-op New Activated Weevil Killer Fumigant
Crest 15 Grain Fumigant.
De-Pester Weevil Kill
De Pester Fumigant No. 2
De-Pester Grain Conditioner and Weevil Killer
De Pester Super Fumigas
De-Pester Fumigant No. 1
De-Pester Fumigant 82 FR
Diamond 75-25 Grain Fumigant
Diweevil
Douglas Tetrafume Weevile Killer & Grain Conditioner
Douglas Tetrakil Weevil- Killer and Grain Conditioner
Douglas Suffokato #3 Grain and Mill Spot Fumigant
CONTINUED
43
-------
TABLE 11. (continued)
Douglas Tetrakote Liquid Grain Protectant
Douglas Topkote #77 Insect Killer
Douglas Grainkote
Douglas Proteckote
Dowfume EB-15 Inhibited
Dowfume 75
Dowfume EB-5 Effective Grain Fumigant
Dowfume C
Dowfume F
Dowfume EB-59
Dow Vertifume S
Dynafume
Excelcide Excelfume
Extrafume
FC-14 Formula 82-H Grain Fumigant 80-20 Mixture
FC-7 Grain Fumigant
FC-4 SX Grain Storage Fumigant
FC-13 Mill Machinery Fumigant
F.I.A. B80-20" Grain Fumigant
Fire Retarded Mi11fume No. 1 Grain Fumigant with Sulfur Dioxide
Formula 815 (FC-3) Grain Fumigant
Formula 635 (FC-2) Grain Fumigant
Fume-0-Death Gas No. 3
Fumisol
CONTINUED
44 -
-------
TABLE 11. (continued)
Gar-be-dde Special Mill Spray
Gas-o-cide
Grainex New Grain Fumigant
Grain Fumigant
Grainfume MB
Hill's Hilcofume 75
Hydrochlor Fumigant
Hydrochlor GF Liquid Gas Fumigant
Infuco 80-20 with 502 Grain Fumigant
Infuco 80-20 Grain Fumigant
Infuco Bin-fume Grain Fumigant
Infuco 50-50 Spot Fumigant
Infuco Two-in-One Grain Fumigant
Infuco Fumigant 75
Iso-Fume
J-Fume-20
J-Fume 80-20
J-Fume-75
J-Fume-C
J-Fume 80-20 Liquid Grain Fumigant
Larvaracide 15 Liquid Grain Fumigant •
Leitte Spotfume 60
M.F.A. Inhibited 80-20 Plus
Max Spot Kill Machinery Fumigant
CONTINUED
45
-------
TABLE 11. (continued)
Max Kill 10 Liquid Grain Fumigant
Max Kill High Life Liquid Grain Fumigant
Max Kill 75-25
Max Kill Spot - 59 Spot Fumigant for Mills and Milling Machinery
Momar M111-X Fumigant
Momar Grain-Guard Grain Protectant in Liquid Form
Parson Lethogas Fumigant
Patterson's Weevil Killer
Pearson's Fumigrain P-75
Pioneer Brand Grain Fumigant
Proteckote
Riverdale Fumigant
Selig's Grainfume
Selig's Selcofume
Selig's Grain Fumigant No, 15
Selig's Grain Storage Fumigant"
Serfume
Sirotta's Sircofume Liquid Fumigating Gas
Spray-Trol Brand Insecticide Fumi-Trol
Spot Fumigant
Standard 75-25 Fumigant
Staff el's Grain Fumigant
Stauffer 80-20 Grain Fumigant
Stauffer Chemicals F.I.A. "80-20"
CONTINUED
46
-------
TABLE 11. (continued)
Grain Fumigant with S02
Stephenson Chemicals Stored Grain Fumigant
Stephenson Sure-Guard Brand Liquid Grain Protectant and Fumigant
Sure Death Brand Mill fume "66"
Sure Death Brand Mill fume No. 2
T-H Vault Fumigant
T-H Grain Fumigant No. 7 Weevil Killer and Grain Conditioner
Terminal Grain Fumigant (FC-15)
Toxi-Fog
Trlfume A Grain Fumigant
Unico Premium Grain Fumigant
Vertifume
Vulcan Formula 635 (FC-2) Grain Fumigant
Vulcan Formula 72 Grain Fumigant
Waco-50
Warlasco Grain Fumigant No. 3
Wasco Grain Fumigant
Weevil-Cide
914 Weevil Killer and Grain Conditioner
Zep-0-Fume Grain Mill Fumigant
47
-------
Process Description
Liquid grain fumigants are used on approximately 12 percent of the grain
grown in the United States. Fumigants are used during binning (placement in
storage) and turning (shifting from one storage facility to another) operations
and at other times during storage when infestation occurs. Fumigants have a
period of effectiveness of only a few days. Thus, they kill existing insect
populations but do not prevent later reinfestation. Newly harvested grain
typically is fumigated 6 weeks after binning. . Corn grown in the southern
regions of the U.S. usually is fumigated immediately following binning because
^ 31
of field infestation by weevils.
A variety of structures are used for grain storage. Farm grain storage
facilities are mostly metal with some wooden bins of flat, older, and loose-
fitting construction. Country elevators are of two types: small banked
concrete silos and flat storages. At mills, banked silos are predominant.
Terminal elevators are banked silos. Grain transportation vehicles include
trucks, rail cars (box, freight, hopper), inland barges, ocean barges, and
ships. Subterminal and terminal elevators and shipholds are usually almost
air tight, while farm grain storage facilities generally allow considerable
air flow. ' On-farm facilities typically have a capacity of about 3,000 bushels,
while country elevators using carbon tetrachloride fumigants have a capacity
of about 300,000 bushels. Terminal elevators have an average capacity of
4 million bushels.31
Grain fumigants are applied primarily by the "gravity distribution"
method by either surface application or layering. This method is practiced
both on-farm and off-farm. A second method of fumigant application is "outside
of car" application, where the fumigant is either poured from 1- or 5-gallon
containers through vents located in the roof of the car or sprayed into the
25
car with a power sprayer.
Equipment used to apply fumigants includes common garden sprinkling cans
with spray heads removed; 3- to 5-gallon capacity compressed air sprayers from
which the nozzles have been removed; high capacity motor driven pumps to apply
large volumes of liquid materials directly from large drums; metering devices
to treat streams of moving grain; and distribution tube and pressure reduction
valve systems for discharging of liquids stored under pressure.
48
-------
The rate of application of fumigants is dependent on the type of grain
and the type of storage facility. Table 12 presents general application rates
for various types of grain for both on-farm and off-farm storage. .The application
rates for off-farm storage are lower since these types of facilities are
typically more tight-fitting than on-farm storage.
After application of fumigants, grain generally is left undisturbed for
at least 72 hours. The usual practice is to leave the grain for a much longer
period. Fumigants are often left on the grain until the normal turning procedure
is undertaken. Alternatively, the grain may be aerated by turning after
completion of the required treatment period. In tight-fitting facilities
equipped with recirculation or forced distribution blowers, the fumigant is
ventilated from the grain with fresh air by operating the blowers for 3 to
4 hours.
Emissions
Emissions of carbon tetrachloride from fumigant mixtures will occur
during fumigant application and when fumigated grain is exposed to the atmosphere,
for instance, during turning or loading. Because of the relatively high vapor
pressure of carbon tetrachloride, it is estimated that essentially all carbon
tetrachloride 'used in fumigants evaporates. However, the time rate of emissions
is highly variable and depends on the application rate, the type of storage
(whether loose or tight-fitting), the manner in which the grain is handled,
and the rate of release of fumigant residues on and in the grain. Figure 9
presents the results of a laboratory study of the level of residual carbon
tetrachloride fumigant on wheat as a function of the number of days since
32
aeration. The grain was fumigated and aerated under conditions comparable
25
to commercial fumigation and aeration conditions.
Source Locations
The Standard Industrial Classification (SIC) codes for farms at which
grain may be stored are as follows:
49
-------
TABLE 12. FUMIGANT APPLICATION RATES
30
Grain
Application rate
(gal/103 bu)
On-farm
Off-farm
Wheat
Corn
Rice, Oats, Barley, Rye
Grain sorghum
3-4
4-5
3-4
5-6
2-3
3-4
2-3
4-5
50
-------
CM
0)
<0 S-
O) S
om-
O)
nvnatsaa
51
-------
0111 - Agricultural production of wheat
0112 - Agricultural production of rice
0115 - Agricultural production of corn
0116 - Agricultural production of soybeans
0119 - Agricultural production of other grains
0191 - General farms
Table 13 lists the on-farm grain storage capacity by State and the percentage
of total U.S. capacity by region.
SIC codes-for off-farm storage facilities, are as follows:
4221 - Grain elevators, storage only
5153 - Wholesale grain merchants includes country and
terminal elevators and other merchants marketing
grain
4463 - Marine cargo handling - terminal elevators.
Table 14 lists the number of off-farm grain storage facilities and the total
capacity of these facilities by State.
52
-------
TABLE 13. ON-FARM GRAIN STORAGE
29
Region
and State
Northeast:
Maine
New Hampshire
Vermont
Massachusetts
Rhode Island
Connecticut
New York
New Jersey
Pennsylvania
Del aware
Maryland
Lake States:
Michigan
Wisconsin .
Minnesota
Corn Belt:
Ohio
Indiana
Illinois
Iowa
Missouri
Northern Plains:
North Dakota
South Dakota
Nebraska
Kansas
Appalachian:
Virginia
West Virginia
North Carolina
Kentucky
Tennessee
Southeast:
South Carolina
Georgia
Florida
Alabama
Capacity Regional
(103 bu) percentage
142,698 2%
2,866
0
0
9,654
0
222
39,204
5,190
62,498
2,057
21,007
1,357,597 17% — i
116,462
244,827
996,338
2,982,755 37% —80%
225,279
429,981
947,208
1,071,203
309,084
2,132,264 26% — '
681,397
394,381
715,594
340,892
236,607 3%
37,554
5,685
100,938
49,237
43,193
159,132 2%
31,437
87,720
12,145
27,830
CONTINUED
53
-------
TABLE 13. (continued)
Region
and State
Delta States;
Mississippi
Arkansas
Louisiana
Southern Plains;
Oklahoma
Texas
Mountain;
Montana
Idaho
Wyoming
Colorado
New Mexico
Arizona
Utah
Nevada
Pacific;
Washington
Oregon
California
Capacity
(103 bu)
131,593
41,588
50,095
39,910
315,160
76,685
238,472
507,357
278,783
77,960
19,519
97,216
9,136
6,404
15,220
3,119
151,622
60,011
33,552
58,059
Regional
percentage
1%
4%
6%
2%
Total
8,116,815
100%'
54
-------
TABLE 14. OFF-FARM GRAIN STORAGE29
State
Alabama
Arizona
Arkansas
California
Colorado
Delaware
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Mi ssouri
Montana
Nebraska
Nevada
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
South Carolina
South Dakota
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Other States
Number of
facilities
37,290
33,890
179,180
115,710
91,500
17,200
6,070
56,700
64,070
775,260
245,550
635,000
830,000
49,580
87,010
36,940
90,240
366,440
76,350
204,140
54,000
484,600
300
2,200
17,550
70,270
63,420
140,070
228,800
203,520
65,530
26,900
33,470
83,820
43,180
720,350
17,170
29,920
186,370
530
118,920
5,580
5,170
Capacity
(10 3 bu)
178
76
283
226
209
27
27
344
231
1,177
804
1,141
1,086
202
131
64
351
894
183
611
298
740
4
24
27
243
465
580
713
400
238
337
177
386
106
896
55
241
324
9
428
49
80
Total
6,600,030
15,065
55
-------
ETHYLENE DICHLORIDE PRODUCTION
Carbon tetrachloride is formed as a byproduct during the production of
ethylene dichloride (EDC). Ethylene dichloride is produced from" ethylene and
chlorine by direct chlorination, and ethylene and hydrogen chloride (HC1) by
oxychlorination. At most production facilities, these processes are used
together in what is known as the balanced process. This section discusses
carbon tetrachloride emissions from this process.
The balanced process generally is used wherever EDC and vinyl chloride
monomer (VCM) are produced at the same facility. About 81 percent of the EDC
33
produced domestically is used in the manufacture of VCM. In VCM production,
EDC is dehydrochlorinated to yield VCM and byproduct HC1. In the balanced
process, byproduct HC1 from VCM production via the direct chlorination/
dehydrochlorination process is used in the oxychlorination/dehydrochlorination
process.
Process Description
The balanced process consists of an oxychlorination operation, a
direct chlorination operation, and product finishing and waste treatment
operations. The raw materials for the direct chlorination process are
chlorine and ethylene. Oxychlorination involves the treatment of ethylene
with oxygen and HC1. Oxygen for oxychlorination generally is added by
feeding air to the reactor, although some plants use purified oxygen as feed
34
material.
Basic operations that may be used in a balanced process using air for
the oxychlorination step are shown in Figure 10. Actual flow diagrams for
production facilities will vary. The process begins with ethylene (Stream 1)
being fed by pipeline to both the oxychlorination reactor and the direct
chlorination reactor. In the oxychlorination reactor the ethylene, anhydrous
hydrogen chloride (Stream 2), and air (Stream 3) are mixed at molar proportions
of about 2:4:1, respectively, producing 2 moles of EDC and 2 moles of water.
The reaction is carried out in the vapor phase at 200 to 315°C in either a
fixed-bed or fluid-bed reactor. A mixture of copper chloride and other
chlorides is used as a catalyst.
56
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The products of reaction from the oxychlorination reactor are quenched
with water, cooled (Stream 4), and sent to a knockout drum, where EDC and
water (Stream 5) are'condensed. .The condensed stream enters a decanter, where
crude EDC is separated from the aqueous phase. The crude EDC (Stream 6) is
transferred to in-process storage, and the aqueous phase (Stream 7) is recycled
to the quench step. Nitrogen and other inert gases are released to the atmosphere
(Vent A). The concentrations of organics in the vent stream is reduced by
absorber and stripper columns or by a refrigerated condenser (not shown in
Figure 10).27'34
In the direct-chlon*nation step of the balanced process, equimolar
amounts of ethylene (Stream 1) and chlorine (Stream 8) are reacted at a
temperature of 38 to 49°C and at pressures of 69 to 138 kPa. Most commercial
plants carry out the reaction in the liquid phase in the presence of a ferric
34
chloride catalyst.
Products (Stream 9} from the direct chlorination reactor are cooled and
washed with water (Stream 10) to remove dissolved hydrogen chloride before
being transferred (Stream 11) to the crude EDC storage facility. Any inert
gas fed with the ethylene or chlorine is released to the atmosphere from the
cooler (Vent B). The waste wash water (Stream 12) is neutralized and sent to
the wastewater steam stripper along with neutralized wastewater (Stream 13)
from the oxychlorination quench area and the wastewater (Stream 14) from the
drying column. The overheads (Stream 15) from the wastewater steam stripper,
which consist of recovered EDC, other chlorinated hydrocarbons, and water,
are returned to the process by adding them to the crude EDC (Stream 10) going
34
to the water wash.
Crude EDC (Stream 16) from in-process storage goes to the drying column,
where water (Stream 14) is distilled overhead and sent to the wastewater steam
stripper. The dry crude EDC (Stream 17) goes to the heads column, which
removes light ends (Stream 18) for storage and disposal or sale. Bottoms
(Stream 19) from the heads column enter the EDC finishing column, where EDC
(Stream 20) goes overhead to product storage. The tars from the EDC finishing
column (Stream 21) are taken to tar storage for disposal or sale.
Several domestic EDC producers use oxygen as the oxidant in the
oxychlorination reactor. Figure 11 shows basic operations that may be used in
an oxygen-based oxychlorination process as presented in the literature. For
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a balanced process plant, the direct chlorination and purification steps are
the same as those shown 1n Figure 10, and, therefore, are not shown again in
Figure 11. Ethylene (Stream 1) is fed in large excess of the amount used in
the air oxychlorination process, that is, 2 to 3 times the amount "needed to
fully consume the HC1 feed (Stream 2). Oxygen (Stream 3) is also fed to the
reactor, which may be either a fixed bed or a fluid bed. After passing
through the condensation step in the quench area, the reaction products
(Stream 4) go to a knockout drum, where the condensed crude EDC and water
(Stream 5) produced by the oxychlorination reaction are separated from the
unreacted ethylene and the inert gases (Stream 6). From the knockout drums
the crude EDC and water (Stream 5) go to a decanter, where wastewater (Stream 7)
is separated from the crude EDC (Stream 8), which goes to in-process storage
as in the air-based process. The wastewater (Stream 7) is sent to the steam
stripper for recovery of dissolved organics.34
The vent gases (Stream 6) from the knockout drum go to a caustic scrubber
for removal of HC1 and carbon dioxide. The purified vent gases (Stream 9) are
then compressed and recycled (Stream 10) to the oxychlorination reactor as
part of the ethylene feed. A small amount of the vent gas (Vent A) from the
knockout drum is purged to prevent buildup of the inert gases entering with
the feed streams or formed during the reaction.34
Emissions
Uncontrolled carbon tetrachloride emission factors for the balanced
process of EDC production are listed in Table 15. Also listed in this table
are potentially applicable control techniques and associated emission factors
for controlled emissions. Because of variations in process design and age of
equipment, actual emissions vary for each plant.
Carbon tetrachloride emission factors were developed for process vents
and the storage of liquid wastes. Insufficient information was available for
the calculation of carbon tetrachloride emission factors for secondary emissions
of carbon tetrachloride from wastewater treatment or for fugitive emissions
from leaks in process valves, pumps, compressors, and pressure relief valves.
60
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Process Emissions —
t
Carbon tetrachloride process emissions originate from the purging of
inert gases from the oxychlorination vent (Vent A, Figures 10 and 11) and from
the release of gases from the column vents (Vent B, Figure 10), primarily the
heads column. Carbon tetrachloride was not detected in an emissions test of a
direct chlorination vent.
35
The range of emission factors for the oxychlorination vent in the air
based process was determined from carbon tetrachloride emission rates and
associated EDC production rates reported by three facilities. The lowest
emission factor, 0.29 kg/Mg, was calculated from a carbon tetrachloride emission
rate of 14,000 kg/yr36 and an associated EDC production rate of 50,000 Mg/yr.
The highest emission factor, 1.2 kg/Mg, was calculated from a carbon tetrachloride
emission rate of 116,000 kg/yr and an associated EDC production rate of
99,800 Mg/yr.38 An intermediate value, 0.42 kg/Mg, was calculated from a
39
and an EDC production
carbon tetrachloride emission rate of 35,000 kg/yr
An
rate of 83,000 Mg/yr. u
Data on the carbon tetrachloride concentration in the oxychlorination
vent emissions from the oxygen-based process, were not available; therefore,
the emission factor for this process was calculated using emission composition
data from the air-based process. It was assumed that the percentage of carbon
tetrachloride in total chlorinated hydrocarbon emissions is the same for the
air-based and oxygen-based processes. However, according to composition data
for oxychlorination vent emissions for hypothetical plants of the two processes,
chlorinated hydrocarbons are a smaller component of total VOC in the oxygen-
based process (9.6 percent) than in the air-based process.(64 percent).
Thus, the ratio of these two percentages (0.15) was used to account for the
smaller proportion of chlorinated hydrocarbons in the emissions from the
•
oxygen-based process.
The emission factor for the column vents (Vent B, Figure 6) was based on
a published carbon tetrachloride emission factor for the heads column of
0.30 kg of carbon tetrachloride emitted per Mg EDC produced by oxychlorination.
The carbon tetrachloride emission factor for the balanced process was calculated
by multiplying by the hypothetical plant EDC production by oxychlorination of
34
46.3 percent of total EDC production.
41
62
-------
Many plants incinerate vent gases from the oxychlorination reactor and
column vents-to reduce atmospheric emissions of volatile organics. This •
includes plants using the air-based as vtell as the oxygen-based oxychlorination
processes.42 Thermal oxidation is estimated to reduce chloroform emissions by
98 percent or greater. Incineration destruction efficiency varies with
emission stream properties and incinerator operating parameters. The 98 percent
efficiency level is based on incinerator operation at 870°C and 0.75 second
residence time for a compound which is- difficult to incinerate. The emission
reduction may be greater for longer residence times or higher operating
temperatures. •
Storage Emissions --
The uncontrolled carbon tetrachloride emission factor for the storage of
waste-liquid light ends (Vent D, Figure 10) was calculated from a VOC emission
factor of 0.030 kg/Mg.34 It was assumed that the gaseous emissions from this
source have the same concentration of carbon tetrachloride as the light ends
(17 percent).44
Source Locations
Major EDC producers and production locations are listed in Table 16.
63
-------
TABLE 16. ETHYLENE DICHLORIDE PRODUCTION FACILITIES15'27
Manufacturer
Location
Atlantic Richfield Co.
ARCO Chem. Co., div.
Diamond Shamrock
Dow Chem. U.S.A.
E.I. duPont de Nemours & Co., Inc.
Conoco Inc.,. sufasid.
Conoco.Chems. Co. Div.
Ethyl Corp.
Chems. Group
Formosa Plastics Corp., U.S.A.
Georgia-Pacific Corp.
Chem. Div.
The BF Goodrich Co.
BF Goodrich Chem. Group
PPG Indust., Inc.
Indust. Chem. Div.
Shell Chem. Co.
Union Carbide Corp.
Ethylene Oxide Derivatives Div.
Vulcan Materials Co.
Vulcan Chems., div.
Port Arthur, TX
Deer Park, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Lake Charles, LA
Baton Rouge, LA
Pasadena, TX
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
La Porte, TX
Calvert City, KY
Convent, LA
Lake Charles, LA
Deer Park, TX
Taft, LA
Texas City, TX
Geismar, LA
Note: This list is subject to change as market conditions change, facility
ownership changes, or plants are closed down. The reader should
verify the existence of particular facilities by consulting current
lists or the plants themselves. The level of emissions from any
given facility is a function of variables, such as throughput and
control measures, and should be determined through direct contacts
with plant personnel.
64
-------
PERCHLOROETHYLENE AND TRICHLOROETHYLENE PRODUCTION
Carbon tetrachloride is formed as a byproduct during the production of
perch!oroethylene (PCE) and trichloroethylene (TCE). PCE and TCE are produced
separately or as coproducts by either chlorination or oxychlorination of
ethylene dichloride (EDC) or other C2 chlorinated hydrocarbons. The relative
proportions of the two products are determined by raw material ratios and
40
reactor conditions.
Process Descriptions
Ethylene Dichloride Chlorination Process —
The major products of the EDC chlorination process are TCE, PCE, and
hydrogen chloride. Basic operations that may be used in EDC chlorination are
shown in Figure 12.
Ethylene dichloride (Stream 1) and chlorine (Stream 2) are vaporized and
fed to the reactor. Other chlorinated C2 hydrocarbons or recycled chlorinated
hydrocarbon byproducts may also be fed to the reactor. The chlorination is
carried out at 400 to 450°C, slightly above atmospheric pressure. Hydrogen
chloride byproduct (Stream 3) is separated from the chlorinated hydrocarbon
mixture (Stream 4) produced in the reactor. The chlorinated hydrocarbon
mixture (Stream 4) is neutralized with sodium hydroxide solution (Stream 5)
and dried.45
The dried crude product (Stream 7).is separated by a distillation column
into crude TCE (Stream 8) and crude PCE (Stream 9). The crude TCE (Stream 8)
is fed to two columns in series which remove light ends (Stream 10) and heavy
ends (Stream 13). TCE (Stream 12) is taken overhead from the heavy ends
column and sent to TCE storage; the heavy ends (Stream 13) and the light ends
(Stream 10) are combined, stored, and recycled.
The crude PCE (Stream 9) from the PCE/TCE separation column is sent to
the PCE column, where PCE (Stream 14) is removed as an overhead stream to PCE
storage. Bottoms from this column (Stream 15) are sent to a heavy ends column
and separated into heavy ends and tars. Heavy ends (Stream 16) are stored and
recycled, and tars are incinerated.
65
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66
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Ethylene Dichloride Oxychlorination Process —
The major products of the EDC oxychlorination process are TCE, PCE, and
water. The crude product contains 85 to 90 weight percent PCE plus TCE and 10
to 15 weight percent byproduct organics. Essentially all byproduct organics
are recovered during purification and are recycled to the reactor. The process
is very flexible, so that the reaction can be directed toward the production
of PCE and TCE in varying proportions. Side reactions produce carbon dioxide,
hydrogen chloride, and several chlorinated hydrocarbons. Figure 13 presents basic
operations that may be used in EDC oxychlorination.
EDC (Stream 1), chlorine or hydrogen chloride (Stream 2), and oxygen
(Stream 3) are fed in the gas phase to a fluid-bed reactor. The reactor
contains a vertical bundle of tubes with boiling liquid outside the tubes
which maintains the reaction temperature at about 425°C. The reactor is
operated at pressures slightly above atmospheric, and the catalyst, which
contains copper, chloride, is continuously added to the tube bundle with the
crude product.
*
The reactor product stream (Stream 4) is fed serially to a water cooled
condenser, a refrigerated condenser, and a decanter. The noncondensed inert
gases (Stream 5), consisting of carbon dioxide, hydrogen chloride, nitrogen,
and a small amount of uncondensed chlorinated hydrocarbons, are fed to an
absorber, where hydrogen chloride is recovered by absorption in process water
to make byproduct hydrochloric acid. The remaining inert gases are purged
(Vent A).45
In the decanter, the crude product (Stream 7) is separated from the
aqueous phase and catalyst fines (Stream 8) and sent to the drying column for
removal of dissolved water by azeotropic distillation. The dried crude product
(Stream 10) is separated into crude TCE (Stream 11) and crude PCE (Stream 12)
in a PCE/TCE column. The aqueous phase from the decanter (Stream 8) and the
water from the drying column (Stream 9) are sent to waste treatment.45
The crude TCE (Stream 11) is sent to the TCE column, where light ends
(Stream 13) are removed to be stored and recycled. The bottoms (Stream 14),
containing mainly TCE, are neutralized with ammonia and then dried to produce
finished TCE (Stream 15) which is sent to the TCE storage.45
67
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The crude PCE (Stream 12) from the PCE/TCE separation column is fed to a
heavy ends removal column where PCE and lights (Stream 16) go overhead to a
PCE finishing column and the heavies (Stream 17) remaining as the bottoms are
sent to the organic recycle system. Here the organics that can be recycled
(Stream 18) are separated from tars and sent to the recycle organic storage.
The tars are incinerated. The PCE and light ends (Stream 16) from the heavy
ends column are fed to a light ends removal column. Light ends (Stream 20)
are removed overhead and are stored and recycled. The PCE bottoms (Stream 21)
are neutralized with ammonia and then dried to obtain finished PCE (Stream 22)
which is sent to the PCE storage.
Emissions
Potential process sources of carbon tetrachloride emissions for the EDC
chlorination process (Figure 12) are the neutralization and drying area vent
(Vent A) and the distillation column vents (Vents B). Other carbon tetrachloride
emission sources include the recycle organic storage tank (Vent C) and process
45
fugitive emission sources.
In the EDC oxychlorination process (Figure 13), potential process sources
of carbon tetrachloride emissions are the hydrogen chloride absorber vent
(Vent A), the drying column vent (Vent B), the distillation column vents
(Vents C), the TCE and the PCE neutralizer vents (Vents D), and the organic
recycle system vent (Vent E). Other carbon tetrachloride emission sources
include the recycle organic storage tank (Vent F) and process fugitive emission
sources.
table 17 presents uncontrolled carbon tetrachloride emission factors for
a plant which produces perchloroethylene by the chlorination of ethylene
dichloride. Also listed in this table are control techniques used at this
facility and associated emission factors for controlled emissions. Emission
factors for process and storage emissions were calculated from hourly carbon
tetrachloride emission rates and a daily perchloroethylene production rate of
91 Mg reported by plant personnel,46 assuming 24 hours per day operation. The
carbon tetrachloride emission rate for fugitive sources was calculated from a
VOC emission rate of 11 Mg per day46 reported by the plant, assuming the
fugitive emissions to be the same composition as total process emissions
(0.61 percent).
69
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It should be noted that carbon tetrachloride emissions may vary from
plant to plant depending on the product mix produced. Thus, carbon tetrachloride
emissions from other plants producing perch!oroethylene and/or trichloroethylene
may differ from those presented in Table 17.
Source Locations
Major producers of perch!oroethylene and/or trichloroethylene for are
presented in Table 18.
71
-------
TABLE 18. FACILITIES PRODUCING PERCHLOROETHYLENE
AND/OR TRICHLOROETHYLENEl5
Chemical
produced
Company
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Location
Deer Park, TX
Freeport, TX
Pittsburg, CA
Plaquemine, LA
PCEa
X
X
X
X
TCEb
X
I.E. duPont de Nemours
and Co., Inc.
PPG Industries, Inc.
Stauffer Chemical Co.
Vulcan Materials Co.
Corpus Christi, TX
Lake Charles, LA
Louisville, KYC
Geismar, LA
Wichita, KS
X
X
X
X
X
aPCE s perch!oroethylene
bTCE s trichloroethylene
cPlant has been on standby since 1981.
Note: This is a list of major facilities producing perch!oroethylene
and/or trichloroethylene by any production process. Current
information on which of these facilities produce these chemicals
by ethylene dichloride chlorination or oxychlorination is not
available. This list is subject to change.as market conditions
change, facility ownership changes, or plants are closed down.
The reader should verify the existence of particular facilities
by consulting current listings, or the plants themselves. The
level of emissions from any given facility is a function of
variables, such as throughput and control measures, and should
be determined through direct contacts with plant personnel.
72
-------
OTHER POTENTIAL SOURCES OF CARBON TETRACHLORIDE EMISSIONS
This section summarizes information on other potential sources of carbon
tetrachloride air emissions. These source categories were identified using an
emission inventory that reported carbon tetrachloride emissions for individual
plants. It is not known whether these plants are representative of other
facilities within the source category.
Chlorine Production
Chlorine is produced primarily by the electrolysis of aqueous brine
solution. The electrolysis produces a stream of chlorine gas saturated with
water vapor. This gas is cooled to condense out the water and is further
dried by scrubbing with sulfuric acid. The resultant dry chlorine gas may be
purified further by scrubbing with liquid chlorine. The purified chlorine is
compressed and all or part of It may be further cooled by refrigeration to
47 s
produce liquid chlorine.
One company has developed a system using carbon tetrachloride as a
recirculating solvent to recover chlorine from residual gases from the liquefaction
48
process, handling, and storage. The use of carbon tetrachloride as a scrubbing
49
solution results in atmospheric emissions of carbon tetrachloride.
Major producers of chlorine for which location and production data are
available are presented in Table 19. It is not known whether these facilities
use carbon tetrachloride.
Phosgene/Isocynate/Polyurethane Production
Phosgene is produced by reacting chlorine gas and.carbon monoxide in the
presence of activated carbon at 200°C. Hot reactor offgases are condensed to
remove most of the phosgene and are then scrubbed with a hydrocarbon solvent
to remove entrained phosgene.50 Almost all of the phosgene produced domestically
is used directly in other operations in the same plant. The principal use is
in the manufacture of isocyanates which are used in making polyurethane
resins.
One toluene diisocyanate plant reported carbon tetrachloride emissions
in I960.49 This may be due to carbon tetrachloride scrubbing of a phosgene
process stream, which would be considered part of the isocyanate process.
73
-------
TABLE 19. CHLORINE PRODUCTION FACILITIES
15
Company
Location
Aluminum Co. of America
AMAX Inc. „ „
AMAX Specialty Metals Corp.,
subsid.
BASF Wyandotte Corp.
Indust. Chems. Group
Basic Chems. Div.
Brunswick Pulp & Paper Co.
Brunswick Chem. Co., div.
Champion Internat'l Corp.
Champion Papers Div. - Chems.
& Associated Products
Diamond Shamrock Corp.
Indust. Chems. and Plastics Unit
Electro Chems. Div.
Dow Chem. U.S.A.
E.I. duPont de Nemours & Co., Inc.
Chems. and Pigments Dept.
Petrochems. Dept.
Freon® Products Div.
Ethyl Corp.
Chems. Group
FMC Corp.
Indust. Chem. Group
Formosa Plastics Corp. U.S.A.
Fort Howard Paper Co.
Gen. Electric Co.
Engineered Materials Group
Plastics Business Operations
Georgia-Pacific Corp.
Chem. Div.
The BF Goodrich Co.
Convent Chem. Corp., sudsid.
Hercules Inc.
Point Comfort, TX
Rowley, UT
Geismar, LA
Brunswick, GA
Canton, NC
Deer Park, TX
Delaware City, DE
La Porte, TX
Mobile, AL
Muscle Shoals, AL
Freeport, TX
Midland, MI
Oyster Creek, TX
Pittsburg, CA
Plaquemine, LA
Niagara Falls, NY
Corpus Christi, TX
Baton Rouge, LA
South Charleston, WV
Baton Rouge, LA
Green Bay, WI
Muskogee, OK
Mount Vernon, IN
Bellingham, VIA
Plaquemine, LA
Calvert City, KY
Convent, LA
Hopewel1, VA
CONTINUED
74
-------
TABLE 19. (continued)
Company
Location
Kaiser Aluminum & Chem. Corp.
Kaiser Indust. Chems. Div.
Linden Chems. & Plastics, Inc.
LCP Chems. Divisions
Mobay Chem. Corp.
Inorganic Chems. Div.
Monsanto Co.
" Monsanto Chem. Intermediates Co.
Occidental Petroleum Corp.
Hooker Chem. Corp., subsid.
Indust. Chems. Group
01 in Corp.
01 in Chems. Group
Oregon Metallurgical Corp.
Pennwalt Corp.
Chems. Corp.
Inorganic Chem. Div.
PPG Indust., Inc.
Indust. Chem. Div.
RMI Co.
Shell Chem. Co.
Stauffer Chem. Co.
Indust. Chem. Div.
Titanium Metals Corp. of America
TIMET Div.
Vertac Chem. Corp.
Gramercy, LA
Acme, NC
Ashtabula, OH
Brunswick, 6A
Linden, NJ
Moundsville, WV
*Niagara Falls, NY
Orrington, ME
Syracuse, NY
Cedar Bayou, TX
Sauget, IL
Hahnville, LA
Montague, MI
Niagrara Falls, NY
Tacoma, WA
Augusta, GA
Charleston, TN
Mclntosh, AL
Niagara Falls, NY
Albany, OR
Portland, OR
Tacoma, WA
Wyandotte, MI
Barberton, OH
Lake Charles, LA
Natrium, WV
Ashtabula, OH
Deer Park, TX
Henderson, NV
LeMoyne, AL
St. Gabriel, LA
Henderson, NV
Vicksburg, MS
CONTINUED
75
-------
TABLE 19. (continued)
Vulcan Materials Co.
Vulcan Chems., Div.
Weyerhaeuser Co.
Denver City, TX
Geismar, LA
Port Edwards, WI
Wichita, KS
Longview, WA
Joint venture with Occidental Petroleum Corporation, Occidental
Chemical Corporation, subsidiary.
NOTE: Information is not available to determine which of these
facilities use carbon tetrachloride. This list is subject
to change as market conditions change, facility ownership
changes, or plants are closed down. The reader should
verify the existence of particular facilities by consulting
current listings or the plants themselves.
76
-------
Major producers of phosgene for which location and production data are
available are listed in Table 20. It is not known whether these facilities
use carbon tetrachloride.
Pesticide Production
Emissions of carbon tetrachloride were reported to be associated with
49
several pesticide production operations. Carbon.tetrachloride is used as a
solvent or reaction medium in these processes. Carbon tetrachloride may be
used as a solvent in other pesticide production processes; however, data are
not available to estimate total carbon tetrachloride usage in pesticide manufacture.
The Standard Industrial Classification code for agricultural chemical manufacturing
is 287. '
Miscellaneous Industrial Solvent Usage .
As noted in previous subsections, carbon tetrachloride is used as a
solvent in the manufacture of Pharmaceuticals and pesticides. Carbon tetrachloride
is also used as a solvent.in the manufacture of other specialty and small-volume
chemicals. Carbon tetrachloride emissions have been reported for the production
of Hypalon®, a synthetic rubber, for resinous chlorowax production, and for
the production of tetrachloropyridene and 4-amino-3,5,7-trichloropicolinic
49
acid. Data are not available to estimate total carbon tetrachloride solvent
use in chemical manufacture or to identify all industries where carbon
tetrachloride is used. .
Treatment, Storage and Disposal Facilities
Considerable potential exists for volatile substances, including carbon
tetrachloride, to be emitted from hazardous waste treatment, storage and
CO
handling facilities. A California study shows that significant levels of
carbon tetrachloride may be contained in hazardous wastes shipped to various
kinds of disposal facilities. Volatilization of carbon tetrachloride and
other substances was confirmed in this study by significant ambient air
concentrations over one site. Reference 5.3- provides general theoretical
models for estimating volatile substance emissions from a number of generic
kinds of waste handling operations, including surface impoundments, landfills,
landfarming (land treatment) operations, wastewater treatment systems, and
77
-------
TABLE 20. PHOSGENE PRODUCTION FACILITIES
15
Company
Location
BASF Wyandotte Corp.
Polymers Group
Urethanes Chems. Business
Dow Chem. U.S.A.
E.I. duPont de Nemours & Co., Inc.
Polymer Products Dept.
Essex Chem. Corp.
Minerec Corp., subsid.
Gen. Electric Co.
Engineered Materials Group
Plastics Business Operations
ICI Americas Inc.
Rubicon Chems. Inc., subsid.
Mobay Chem. Corp.
Polyurethane Div.
01in Corp.
01 in Chems. Group
PPG Indust., Inc.
Agricultural and Performance
Chems. Div.
Specialty Products Unit
Union Carbide Corp.
Agricultural Products Group
The Upjohn Co.
Polymer Chems. Div.
Van De Mark Chem. Co., Inc.
Geismar, LA
Freeport, TX
Deepwater, NJ
Baltimore, MD
Mount Vernon, IN
Geismar, LA
Cedar Bayou, TX
New Martinsville, WV
Lake Charles, LA
Moundsville, WV
Barberton, OH
La Porte, TXa
Institute, WV
La Porte, TX
Lockport, NYa
aThese two plants are believed to be the only ones producing phosgene
for sale; all others produce phosgene for captive consumption.
Note: Information is not available to determine which of these
facilities use carbon tetrachloride. This list is subject to
change as market conditions change, facility ownership changes,
or plants are closed down. The reader should verify the
existence of particular facilities by consulting current
lists or the plants themselves.
78
-------
drum storage/handling processes. If such a facility is known to handle
carbon tetrachloride, the potential should fae considered for some air
emissions to occur.
Several studies show that carbon tetrachloride may be emitted from
municipal wastewater treatment plants, albeit at quite low levels. In a
bench scale test, the potential was demonstrated-for carbon tetrachloride
54
volatilization from clarifiers and aeration basins, r However, actual
tests at one municipal treatment plant (handling about 50% industrial
sewage) showed carbon tetrachloride emissions to be consistently below
184 grams (0.4 pounds) per day, assuming all carbon tetrachloride in the
•> cc
influent is air stripped during treatment. Furthermore, tests at a
smaller treatment facility (handling about 40% industrial and 60% municipal
sewage) showed carbon tetrachloride emission levels to be virtually
56-
undetectable. -
,79
-------
-------
SECTION 5
SOURCE TEST PROCEDURES
Carbon tetrachloride emissions can be measured using EPA Reference
Method 23, which was proposed in the Federal Register on June 11, 1980.5'7'
EPA has validated Method 23 in the laboratory for carbon tetrachloride5?
but has not validated the method for carbon tetrachloride in the field.59
In Method 23, a sample of the exhaust gas to be analyzed is drawn
into a Tedlar® or aluminized Mylar® bag as shown in Figure 15. The bag
is placed inside a rigid leak proof container and evacuated. The bag is
then connected by a Teflon® sampling line to a sampling probe (stainless
steel, Pyrex® glass, or Teflon®) at the center of the stack. Sample is
drawn into the bag by pumping air out of the rigid container.
The sample is then analyzed by gas chromatography (GC) coupled with
flame ionization detection (FID). Analysis should be conducted within
1 day of sample collection. The recommended GC column is 3.05 m by
3.2 mm stainless steel, filled with 20 percent SP-2100/6.1 percent
Carbowax 1500 on 100/120 Supelcoport. This column normally provides an
adequate resolution of halogenated organics. (Where resolution interferences
are encountered, the GC operator should select the column best suited to
the analysis.) The column temperature should be set at 100°C. Zero
helium or nitrogen should be used as the carrier gas at a flow rate of
approximately 20 ml/min.
The peak area corresponding to the retention time of carbon tetrachloride
is measured and compared to peak areas for a set of standard gas mixtures
to determine the carbon tetrachloride concentration. The range of the
method is 0.1 to 200 ppm; however, the upper limit can be extended by
extending the calibration range or diluting the sample. The method does
not apply when carbon tetrachloride is contained in particulate matter.
80
-------
FILTER
(GLASS WOOL)
PROBE
SAMPLE
LINE
STACK
WALL
SAMPLING
BAG
RIGID
LEAKPROOF
CONTAINER
FLOW
METER
CHARCOAL
TUBE
Figure 15. Method 23 sampling train.
"57
81
-------
REFERENCES
1. Archer, W.L. Chlorocarbons and Chlorohydrocarbons. In: Kirk-Othmer
Encyclopedia of Chemical Technology. Third Edition. Volume 11.
M. Grayson, ed. John Wiley and Sons, New York, NY, 1980.
2. National Research Council. Chloroform, Carbon Tetrachloride, and Other
Halomethanes: An Environmental Assessment. National Academy of Sciences,
Washington, DC, 1978.
3. Cupitt, L. Fate of Hazardous Materials in the Environment. EPA-600/3-80-084,
U.S. Environmental Protection Agency, Research Triangle Park, NC, August 1980.
4. GEOMET, Inc. Carbon Tetrachloride. In: Assessment of the Contribution
of Environmental Carcinogens to Cancer Incidence in the General Population.
Volume II. U.S. Environmental Protection Agency, Research Triangle Park,
NC, December 5, 1977.
5. Chemical Briefs 1: Carbon Tetrachloride. Chemical Purchasing,
January 1981. pp. 25-29. ^
6. Hobbs, F.D. and C.W. Stuewe. Report 5: Chloromethanes by Methane
Chlorination Process. In: Organic Chemical Manufacturing Volume 8:
Selected Processes. EPA 450-3-80-028c, U.S. Environmental Protection
Agency, Research Triangle Park, NC, December 1980.
7. Chloromethanes. Encyclopedia of Chemical Processing and Design.
Volume 8. J.J. McKetta, ed. Marcel Dekker, New York, NY, 1979.
8. Hobbs, F.D. and C.W. Stuewe. Report 2: Carbon Tetrachloride and
Perch!oroethylene by the Hydrocarbon Chlorinolysis Process (Abbreviated
Report). In: Organic Chemical Manufacturing Volume 8: Selected
Processes. EPA-450/3-80-028c, U.S. Environmental Protection Agency,
Research Triangle Park, NC, December 1980.
9. Zaebst, D.D. Walk-Through Survey Report: Stauffer Chemical Company,
Axis, AL. National Institute for Occupational Safety and Health,
Cincinnati, OH, September 1977.
10. Mason, G., Vulcan Materials Co., Witchita, KS. Personal communications
with E. Anderson, GCA Corporation, October 4, 1983.
11. Arnold, S., Dow Chemical U.S.A., Midland, MI. Personal communications
with E. Anderson, GCA Corporation, October 13, 1983.
12. Hobbs, F.D. and C.W. Stuewe. Report 6: Chloromethanes Manufactured by
Methanol Hydrochlorination and Methyl Chloride Chlorination Process. In:
Organic Chemical Manufacturing Volume 8: Selected Processes. EPA-450/
3-80-028c, U.S. Environmental Protection Agency, Research Triangle Park,
NC, December, 1980.
82
-------
13. U.S. Environmental Protection Agency. Fugitive Emission Sources of
Organic Compounds—Additional Information on Emissions,, Emission Reductions,
and Costs. EPA-450/3-82-010, Research Triangle Park, NC, April 1982.
14. Systems Applications, Inc. Human Exposure to Atmospheric Concentrations
of Selected Chemicals. Volume II. U.S. Environmental Protection Agency,
Research Triangle Park, NC, February 1982.
15. SRI International. 1983 Directory of Chemical Producers, United States
of America. Menlo Park, CA, 1983.
16. Smith, D.W. E.I. DuPont deNemours and Company, Wilmington, DE. Letter
to D.R. Goodwin, EPA, March 23, 1978.
17. Cooper, J.R., E.I. duPont deNemours and Co., Wilmington, DE. Letter to
J.R. Farmer, EPA, September 27, 1979.
18. Pitts, D.M. Report 3: Fluorocarbons (Abbreviated Report). In: Organic
Chemical Manufacturing Volume 8: Selected Processes. EPA-450/3-80-028c,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
December 1980.
19. Dow Chemical U.S.A. Industrial Process Profiles for Environmental Use,
Chapter 16: The Fluorocarbon-Hydrogen Fluoride Industry. EPA-600/2-77-023p,
U.S. Environmental Protection Agency, Cincinnati, OH, February 1977.
20. Turetsky, W.S., Allied Chemical, Morristown, NJ. Letter to D. Patrick,
EPA, May 28, 1982. -
21. Smith, D.W., E.I. duPont de Nemours and Co., Wilmington, DE. Letter to
Goodwin, D.R., EPA, June 7, 1978.
22. Montney, W.A., Illinois Environmental Protection Agency, Springfield, IL.
Letter to M. Smith, GCA Corporation, January 20, 1983.
23. Olson, D.S. E.I. duPont deNemours and Company, Wilmington, DE. Letter to
T. Lahre, EPA, August 2, 1983.
24. Bromination and Bromine Compounds. Encyclopedia of Chemical Processing
and Design. Volume 6. J.J. McKetta, ed. Marcel Dekksr, New York, NY,
1977.
25. U.S. Environmental Protection Agency. Carbon Tetrachloride; Pesticide
Programs; Rebuttable Presumption Against Registration and Continued
Registration of Certain Pesticide Products. Federal Register 45(202):
68534-68584, October 15, 1980.
83
-------
26. U.S. Environmental Protection Agency. Development Document for Effluent
Limitations Guidelines for the Pesticide Chemicals Manufacturing Point
Source Category. EPA-440/1-78/060-6, Washington, DC, April 1978.
27. Cox, G.V., Chemical Manufacturers Association, Washington, DC. Letter to
T. Lahre, Office of Air Quality Planning and Standards, U.S. Environmental
Protection Agency, August 18, 1983.
28. U.S. Environmental Protection Agency. Control of Volatile Organic
Emissions from Manufacture of Synthesized Pharmaceutical Products.
EPA-450/2-78-029, Research Triangle Park, NC, December 1978.
29. Development Planning and Research Associates, Inc. Preliminary Benefit
Analysis: Cancellation of Carbon Tetrachloride in Fumigants for Stored
Grain. U.S. Environmental Protection Agency, Washington, DC, April 1980.
30. Holtorf, R.C. and G.F. Ludvik. Grain Fumigants: An Overview of Their
Significance to U.S. Agriculture and Commerce and Their Pesticide Regulatory
Implications. U.S. Environmental Protection Agency, Washington, DC,
September 1981.
31. Ludvik, G.F. Fumigants for Bulk Grain Protection: Biological Aspects
and Relevant Data. U.S. Environmental Protection Agency, Washington, DC,
August 1981.
32. Jagielski, J., K.A. Scudamore and S.G. Heuser. Residues of Carbon Tetrachloride
and 1,2-Dibromoethane in Cereals and Prpcessed Foods after Liquid Fumigant
Grain Treatment for Pest Control. Pesticide Science 9(2):117-126, April 1978.
33. Chemical Producers Data Base System - 1,2-Dichloroethane. U.S. Environmental
Protection Agency, Cincinnati, Ohio, July 1981.
34. Hobbs, F.D. and J.A. Key. Report 1: Ethylene Dichloride. In: Organic
Chemical Manufacturing Volume 8: Selected Processes. EPA-450/3-80-028c,
U.S. Environmental Protection Agency, Research Triangle Park, North
Carolina, December 1980.
35. Gasperecz, G., Louisiana Air Quality Division, Baton Rouge, LA. Personal
communication with M.E. Anderson, GCA Corporation, August 5, 1983.
36. Ethyl Corporation. Revised Compliance Schedule-Control of Volatile
Organic Compound Emissions-Baton Rouge Plant, August 1982. p. 6.
37. Gasperecz, G., Louisiana Air Quality Division, Baton Rouge, LA. Personal
communication with M.E. Anderson, GCA Corporation, December 21, 1982.
38. Louisiana Air Control Commission. Emission Inventory Questionnaire for
Allied Chemical Corp., North Works, Baton Rogue, LA, 1976.
39. Gordon, C.V., Vulcan Chemicals. Memo to E.A. Stokes Vulcan Chemicals
concerning 1980 emission inventory for Geismar, LA facility, May 26, 1982.
84
-------
40. Gasperecz, 6., Louisiana Air Quality Division, Baton Rouge, LA. Personal
communication with M.E. Anderson, GCA Corporation, November 18, 1982.
41. Schwartz, W.A., F.G. Higgins, J.A. Lee, R. Newirth and J.W. Pervier.
Engineering and Cost Study of Air Pollution Control for the Petrochemical
Industry Volume 3: Ethylene Dichloride Manufacture by Oxychlorination.
EPA-450/3-73-006c, U.S. Environmental Protection Agency, Research Triangle
Park, NC, November 1974.
42. Gasperecz, G., Louisiana Air Quality Division, Baton Rouge, LA. Personal
communication with D.C. Misenheimer, GCA Corporation, September 30, 1983.
43. Control of Volatile Organic Compound Emissions from Air Oxidation Processes
in Synthetic Organic Chemical Manufacturing Industry, Control Techniques
Guidelines Series, Preliminary Draft. U.S. Environmental Protection
Agency, Research Triangle Park, NC, June 1981. p. 3-22.
44. Shiver, J.K. Converting Chiorohydrocarbon Wastes by Chlorolysis.
EPA-600/2-76-270, U.S. Environmental Protection Agency, Washington, DC,
• .October 1976.
45. Standifer, R.L. and J.A. Key. Report 4: 1,1,1-Trichloroethane and
Perch!oroethylene, Trichloroethylene,. and Vinylidene Chloride (Abbreviated
Report). In: Organic Chemical Manufacturing Volume 8: Selected Processes.
EPA-450/3-80-28c, U.S. Environmental Protection Agency, Research Triangle
Park, NC, December 1980.
46. Worthington, J.B., Diamond Shamrock, Cleveland, OH. Letter to Goodwin, D.R.,
EPA, January 16, 1979. .
47. U.S. Environmental Protection Agency. Atmospheric Emissions from Chlor-Alkali
• Manufacture. AP-80, Research Triangle Park, NC, January 1971.
48. Chloralkali. Encyclopedia of Chemical Processing and Design. Volume 7.
• McKetta, J.J.,, ed. Marcel Dekker, Inc., New York, NY, 1978.
49. '1980 Emissions Inventory Questionnaire Data Retrieval for Carbon Tetrachloridej
Abatement Requirements and Analysis Division, Texas Air Control Board,
Austin, TX, June- 1982.
50. Liepins, R., F,. Mixon, C. Hudak, and T;B. Parsons. Industrial Process
Profiles, for Environmental JJse Chapter 6: The Industrial Organic
Chemicals Industry. EPA-600/2-77-023f, U.S. Environmental Protection
Agency, Cincinnati, OH, February 1977.
51. Considine, D.M., ed. Chemical and Process Technology Encyclopedia.
McGraw-Hill Book Co., New York, NY, 1974. •
85
-------
52. Scheible, M., G.. Shiroma, G. O'Brien, J. Lara, T. Krakower, and W. Gin.
As Assessment of Volatile and Toxic Organic Emissions from Hazardous
Waste Disposal in California. Air Resources Board, State of California,
February 1982.
53. GCA Corporation. Evaluation of Models for Estimating Air Emissions from
Hazardous. Waste Treatment, Storage and Disposal Facilities. Revised
Draft Final Report. Prepared for the U.S. Environmental Protection
.Agency Under Contract Number 68-02-3168, Assignment No. 77. Bedford,
MA, May 1983.
54. Petrasek, A.C., B.A. Austern and T.W. Neilheisel. Removal and Partitioning
of Volatile Organic Priority Pollutants in Wastewater Treatment. Presented
at the Ninth U.S.-Japan Conference on Sewage Treatment Technology. Tokyo,
Japan. September 13-19, 1983.
55. U.S. Environmental Protection Agency. Fate of Priority Pollutants in
Publicly Owned Treatment Works.: EPA-440/1-82-302, Washington, DC,
July 1982.
56. Pellizzari, E.D. Project Summary - Volatile Organics in Aeration
Gases at Municipal Treatment Plants. EPA-600/52-82-056, U.S. Environmental
Protection Agency, Cincinnati, OH, August 1982.
57. Method 23: Determination of Halpgenated Organics from Stationary Sources.
Federal Register. 45(114)t -39776-39777, 1980.
58. Knoll, J.E.,. M.A. Smith, and M.R. Midgett. Evaluation of Emission Test
Methods for Halogenated Hydrocarbons: Volume 1, CCU, CZ^C12^ CaCl^,
and C2H3C1. EPA-600/4-79-025, U.S. Environmental Protection Agency,
Research Triangle Park, NC, 1979.
59. Knoll, J., U.S. Environmental Protection Agency. Personal communication
with W. Battye, GCA Corporation, September 8, 1982. "
86
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-------
APPENDIX
EMISSION FACTORS FOR CARBON TETRACHLORIDE PRODUCTION
This appendix presents the derivations of carbon tetrachloride
emission factors for carbon tetrachloride production processes that are
presented in Tables 2 through 6. Emission factors for the hydrocarbon
chlorinolysis (perchloroethylene coproduct) process (Table 2) were
developed based on a hypothetical plant with a total production capacity
of 80,000 Mg and a product mix of 37.5 percent carbon tetrachloride and
62.5 percent perchloroethylene. Emission factors for the methane
chlorination process (Table 3) are based on a hypothetical plant with a
total chloromethane production capacity of 200,000 Mg, and a product mix
of 20 percent methyl chloride, 45 percent methylene chloride, 25 percent
o
chloroform, and 10 percent carbon tetrachloride. Emission factors for
the carbon disulfide chlorination process (Table 4) were developed based
34
on operating data on the Stauffer plant in Lemoyne, Alabama, ' the only
plant currently using this production process. Emission factors for the
methanol hydrochlorination/methyl chloride chlorination process were
developed based on a hypothetical plant with a total chloromethane
production capacity of 90,000 Mg/yr and a product mix of 25 percent
methyl chloride, 48 percent methylene chloride, 25 percent chloroform,
and 2 percent byproduct carbon tetrachloride.
The following sections describe the derivations of carbon tetrachloride
emission factors for process vent emissions; in-process and product storage
tank emissions; secondary emissions from liquid, solid, and aqueous waste
streams; handling emissions from loading product carbon tetrachloride; and
fugitive emissions from leaks in process valves, pumps, compressors, and
pressure relief valves.
PROCESS EMISSION FACTORS
Hydrocarbon Chlorinolysis (Perchloroethylene Coproduct)
Carbon tetrachloride process emissions from chlorinolysis process result
from the purging of inert gases from the carbon tetrachloride distillation
condenser (Vent A, Figure 2). The uncontrolled emission factor for emissions
A-l
-------
from the distillation column was derived from the annual carbon tetrachloride
emission rate of 180 kg and associated carbon tetrachloride thruput of
15 x 10 liters reported by one facility6 and the density of carbon
tetrachloride (1.59 g/ml):
Emission factor =
15 x 106 A x 1.59 g/10'3£
180 kg
2.4 x 104 Mg
=0.008 kg/Mg
Another potential source of process emissions is the caustic scrubber
vent (Vent E, Figure 2); however, no emissions have been reported for this
source.
Methane Chlori nation
Carbon tetrachloride process emissions from the methane chlori nation
process result from venting of the inert gases from the recycle methane
stream (Vent A, Figure 3) and from emergency venting of the distillation
area inert gases (Vent C, Figure 3).
Recycled Methane Inert Gas Purge vent—
The uncontrolled emission factor for the recycled methane inert gas
purge vent was •calculated from a carbon tetrachloride emission factor of
4.2 x 10"3 kg per Mg .total chloromethane production capacity and the
representative plant's carbon tetrachloride production of 10 percent of
total chloromethane production. This emission factor represents an
2
upper bound estimate.
Emission factor = 4.2 x 10 kg CCli
x total prod.
Mg total prod.
0.10 CCli» prod.
0.042 kg/Mg
A-2
-------
Distillation Area Emergency Inert Gas Vent—
The uncontrolled emission factor for the distillation area emergency
Inert gas vent was derived from an emission factor for volatile organic
3 2
compounds (VOC) of 0.20 kg/Mg total chloromethane production capacity
and composition data showing carbon tetrachloride to be 2.6 percent of
VOC.^ No information was available on the assumptions upon which the
derivation of this VOC emission factor were based. The calculation of
carbon tetrachloride emissions per unit carbon tetrachloride produced was
made using a carbon tetrachloride production rate of 10 percent of total
chloromethanes production.
Emission factor
0.20 kg VOC
x 0.026 CClu x total prod.
Mg total prod VOC 0.10 CC14 prod
= 0.052 kg/Mg
Carbon Disulfide Chiorination
The main source of carbon tetrachloride process emissions from the
carbon disulfide chlorination process is the chlorination reactor which,
at the Stauffer facility, is controlled with a two-stage refrigerated
condenser (Vent A, Figure 4). The controlled emission factor for this
source was calculated from a carbon tetrachloride hourly emission rate of
54 kg/hr determined from a source test and the plant's annual carbon
tetrachloride production of 82,000 Mg/yr,4 assuming 8,760 hours per year
operation.
Emission factor
(controlled)
= 54 kg/hr x 8,760 hr/yr
82,000 Mg/yr
= 5.8 kg/Mg
The uncontrolled emission factor was calculated from the controlled emission
o
factor and the reproted control efficiency of 95 percent for the condenser.
Emission factor
(uncontrolled)
5.8 kg/Mg
1 - 0.95
116 kg/Mg
A-3
-------
Hethanol Hydrochlorination/Methyl Chloride Chiorination
Process vents are not a significant source of carbon tetrachloride
emissions in this process.
STORAGE EMISSION FACTORS
In calculating storage emission factors, all storage tanks were assumed
to be fixed roof tanks.'2' Uncontrolled carbon tetrachloride emission
factors for in-process and product storage for the hydrocarbon chlorinolysis
process (Vents B, C, and D, Figure 2), methane chlorination process (Vents B,
D, and E, Figure 3), the carbon disulfide chlorination process (Vent B,
Figure 4), and methanol hydrochlorination process (Vents A, B, and C, Figure 5)
were calculated using emission equations for breathing and working losses for
fixed roof tanks from reference 9:
W
1.02 x
where,
4
LB
LW
Mv
P
D
H
14.7-p)
0.68D1.73H0.51T0.5
"8
F CK
p c
1.09 x 10" M
total loss (Mg/yr)
breathing loss (Mg/yr)
working loss (Mg/yr)
molecular weight of product vapor (Ib/lb mole)
true vapor pressure of product (psia)
tank diameter (ft")
average vapor space height (ft): use tank specific values or an
assumed value of one-half the tank height
average diurnal temperature change in °F
paint factor (dimensionless); assume a value of 1 for a white tank
in good condition
tank diameter factor (dimensionless):
for diameter ->, 30 feet, C = 1
for diameter < 30 feet,
' C = 0.0771 D - 0.0013(D2) - 0.1334
product factor (dimensionless) =1.0 for VOL:
A-4
-------
V = tank capacity (gal)
N = number of turnovers per year (dimensionless)
K = turnover factor (dimensionless): '
for turnovers > 36, Kn = 18{?N* N
for turnovers <_ 36, Kn = 1
For the hydrocarbon chlorinolysis, methane chlorination and methanol
hydrochlorination/methyl chloride chlorination processes, hypothetical
plant storage tank conditions from references 1, 2, and 5, respectively, were
used for the calculations. The tank conditions given by these references
include tank volume, number of turnovers per year, bulk liquid temperature,
and an assumed diurnal temperature variation of 20°C. The diameters (D), in
feet, of the tanks were calculated from given tank volumes (V), in gallons,
with heights (h), in feet, assumed at 8 foot intervals,10 from:
.481
D = 2 J * x h
.For tanks containing mixtures, the vapor pressure of the mixture in the tank,
molecular weight of vapor, and weight percent of carbon tetrachloride in the
vapor were calculated. The calculations of emission factors for all . •'
production processes are summarized in Table A-l. Sample calculations
are presented in their entirety for the hydrocarbon chlorinolysis process.
For the other three processes, storage tank parameters and vapor composition
data used in the calculations of the emission factors listed in Table A-l
are presented in tables.
Hydrocarbon Chlorinolysis (Perch!oroethvlene Coproduct)
Emission factors for the crude product tank, two carbon tetrachloride
day storage tanks, and the carbon tetrachloride product tank were calculated
using the tank parameters listed in Table A-2.
Crude Product Tank--
Composition — The composition of the mixture in the crude product tank
is based on the hypothetical plant mixture. The mole fractions of the liquid
components were derived from these weight fractions and molecular weights.
The mole fractions of the components in liquid were then multiplied by
A-5
-------
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-------
TABLE A-2. STORAGE TANK PARAMETERS FOR HYDROCARBON CHLORINOLYSIS
(PERCHLOROETHYLENE COPRODUCT) PROCESS.
Tanks
Number of tanks
Volume (V), gal
Height (h), ft
Vapor space height (H), ft
Diameter (D), ft
Turnovers/yr (N)
Temperature, 8F
Vapor pressure (P), psia
Diurnal temperature change (T), °F
Molecular weight of vapor (Mu),
Ib/lb mole v
Turnover factor (KR)
Tank diameter factor (C)
Crude
1
100,000
32
16
23
6
100
1.95
22
157
1
0.95
Day .
2
' 20,000
'16
8
15
125
95
3.44
22
154
0.41
0.73
Product
1
200,000
40
20
29
25
68
1.73
22
154
1
1.0
A-7
-------
the vapor pressures of each component to determine component partial
pressures, the sum of which is the total vapor pressure, P. Mole fractions
of the components in the vapor phase were calculated as the ratio of component
partial pressures to total vapor pressure. The molecular weight of the
vapor mixture (M ) was calculated as the sum of the products of the component
partial pressures and their molecular weights, ignoring the molecular
weight of the air. The weight percent of components in vapor were
calculated from the ratios of the product of'the mole fraction in vapor
and molecular weight to the molecular weight of the vapor mixture.
These calculations are summarized in Table A-3.
Tank emissions— With the parameters listed in Table A-2, total
tank losses were calculated as follows:
LR - (1.02 x 10-5)(157), I^_)0-68(23)1'73(16)0'51(22)°-5(l)(0.95)(l)
B M4.7-l.95
= (1.02 x 10"5)(157)(0.28)(227)(4.11)(4.69)(0.95)
* 1.86 Mg/yr
(1.09 x 10~8)(157)(1.95)(100,000)(6)(1)(1)
2.00 Mg/yr
•w
B
"w
3.86 Mg/yr
Emission factoi— The carbon tetrachloride emission factor was calculated
from total annual tank loss, fraction of vapor mixture that; is carbon
tetrachloride, and the representative plant production rate of 30,000 Mg/yr:
Emission factor =
(3.86 Mg/yr)(0.76)
30,000 Mg/yr
0.098 kg/Mg
Day Tanks—
Tank emissions—
B
w
(1.02 x 10"
(1.02 x 10"5)(154)(0.45)(108)(2.89)(4.69)(0.73)
0.75 Mg/yr
(1.09 x 10"8)(154)(3.44)(20,000)(125)(0.41)(1)
5.92 Mg/yr
)0-68(15)1-73(8)°-51(22)°-5(l)(0.73)(l)
LT S.LB + Lw = 6'67 M9/yr A-8
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A-9
-------
Emission factor —
Emission factor
Product tank-
Tank emissions—
LB
Mg/yr
« 6.67 tank x 2 tanks
_ 30,000 Mg/yr
= 0.45 kg/Mg
* (1.02 x 10"
« (1.02 x 10'5)(154)(0.254)(339)(4.6)(4.69)
• 2.92 Mg/yr
• (1.09 x 10"8)(154)(1.73)(200,000)(25)
* 14.5 Mg/yr
U * LB + L « 17.4 Mg/yr
Emission factor
Emission factor = 17.4 Mg/yr
w
30,000 Mg/yr
=0.58 kg/Mg
Methane Chiorination •
Emission factors for the crude product tank, two carbon tetrachloride
day tanks, and the carbon tetrachloride product tank were calculated
using the tank parameters listed in Table A-4. The calculations of the
composition of the vapor for the crude product tank are summarized in
Table A-5.
Methanol Hydrochlorination/Methyl Chloride Chiorination
Emission factors for the crude product tank, the surge tank, and the
carbon tetrachloride tank were calculated using the tank parameters listed
in Table A-6. The calculations of the compositions of the vapor for the
crude product tank and the surge tank are presented in Tables A-7 and A-8,
respectively.
Carbon Disulfide Chiorination
Emission factors for two small carbon tetrachloride tanks and two large
t
tanks were calculated from reported tank parameters for the Stauffer facility.'
These parameters and assumed values are summarized in Table A-9.
A-10
-------
TABLE A-4. STORAGE TANK PARAMETERS FOR
METHANE CHLORINATION PROCESS
Tank
Number of tanks
Volume (V), gal
Height (h), ft
Vapor space height (H), ft
Diameter (D), ft
Turnovers/yr (N)
Temperature, °F
Vapor pressure (P), psia
Diurnal temperature change (T), °F
Molecular weight of vapor (Mw),
Ib/lb mole v
Turnover factor (K )
Tank diameter factor (C)
Crude
1
200,000
40
20
29
6
95
9.50
22
93
1
1
Day
2
10,000
• 16
8
10
166
95
3.44
22
154
0.347
0.508
Product
1
200,000
40
20
29
17
68
1.73
22
154
1
1
A-n
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A-12
-------
TABLE A-6. STORAGE TANK PARAMETERS FOR
METHANOL HYDROCHLORINATION/METHYL
CHLORIDE CHLORINATION PROCESS
Tanks
Number of tanks
Volume (V)» gal
Height (h), ft
Vapor space height (H), ft
Diameter (D), ft
Turnovers/yr (N)
Temperature, °F
Vapor pressure (P), psia
Diurnal temperature change (T), eF
Molecular weight of vapor (M ),
Ib/lb mole v
Turnover factor (Kn)
Tank diameter factor (C)
Crude
1
50,000
24
12
19
6
95
10
22
91
1
0.862
Surge
1
20,000
16
8
15
6
104
6.9
22
120
1
0.731
Carbon
Tetrachloride
1
10,000
16
8
10
32
104
4.1
22
154
1
0.508
A-13
-------
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A-15
-------
TABLE A-9. STORAGE TANK PARAMETERS FOR CARBON
DISULFIDE CHLORINATION PROCESS
Tanks
Number of tanks
Volume (V),.gal
Height (h), ft
Vapor space height (H), ft
Diameter (D), ft
Turnovers/yr (N)a
Temperature, °Fb
Vapor pressure (P), psia
Diurnal temperature . change (T), eF&
Molecular weight of vapor (fO,
Ib/lb mole v
Turnover factor (Kn)
Tank diameter factor (C)
Small
2
230,000
29
15
37
10
68
1.73
22
154
1
1
Large
2
460,000
29
15
52
10
68
1.73
22
154
1
1
aTank throughput was estimated by assuming reported production
(1.36 x 10' gal/yr) to be apportioned among the tanks according
to size. Turnover rate was then calculated:
turnover rate s thruput
tank volume
Assumed value.
A-16
-------
SECONDARY EMISSIONS
Hydrocarbon Chlorinolysis (Perch!oroethvlene Coproduct)
Secondary emissions of carbon tetrachloride can result from the handling
and disposal of process waste liquids. Two sources of secondary emissions
from the hydrocarbon chlorinolysis process are the bottoms from the
perch!oroethylene distillation column (Source F, Figure 2), commonly
called hex wastes, and the waste caustic from the caustic rubber (Source G,
Figure 2). It should be noted that, lacking other data, emission factors
for both sources were developed based on data from a plant which uses
operating conditions that are much less severe than the chlorinolysis
process.
Hex Wastes—
The uncontrolled emission factor for the combined sources of hex
waste handling and waste hydrocarbon storage emissions was derived from a
published VOC emission factor of 0.056 kg/Mg pf total production capacity,
composition data showing carbon tetrachloride to be 3.1 percent of VOC,
and the hypothetical plant carbon tetrachloride production of 37.5 percent
total production:
Emission factor
0.031 CClu total prod.
x VOC 0.375 CClu prod.
0.056 kg VOC
Mg total prod.
= 0.0046 kg/Mg
Waste Caustic Handling—
The uncontrolled emission factor for secondary emissions from waste caustic
handling is based on a plant's estimate of total VOC emissions per production
capacity for waste caustic handling and disposal of 0.0011 kg VOC/Mg total
production,1 assuming that carbon tetrachloride is the main component of
the VOC, and using the hppothetical plant's carbon tetrachlbride production
rate of 37.5 percent of total production:
Emission factor
0.0011 kg
Mg total prod.
= 0.0029 kg/Mg
total prod.
0.375 CClij prod.
A-17
-------
Methane Chior1nation
Secondary emissions of carbon tetrachloride from the methane
chlorination process can result from the handling and disposal of-
process waste liquids. These liquid streams are indicated on the process
flow diagram (Source F, Figure 3) and include waste caustic from the
methyl chloride and methane recycle stream scrubbers, waste caustic from
the crude chloromethane neutralizer, and salt solution from the crude
chloromethanes dryer. The uncontrolled emission factor for these
secondary carbon tetrachloride emissions was calculated using a carbon
tetrachloride content of 10 parts per million reported for total
wastewater discharges averaging 68 liters per minute, the assumption
that 100 percent of the carbon tetrachloride will be vaporized during
on-site wastewater treatment, and the hypothetical plant carbon tetrachloride
production of 20,000 Mg/yr:
Emissions
68 & water __'
min
—
£, water
10 kg CC1
10b kg water
5.26 x 10° min
yr
Emission factor
357 kg/yr
20,000 Mg/yr
0.018 kg/Mg
Carbon Disulfide Chlorination
Insufficient data are available to calculate an emission factor for
secondary .emissions of carbon tetrachloride from this process.
Methanol Hydrochlorination/methyl Chloride Chlorination
Potential sources of secondary emissions include the aqueous discharge
from the methanol hydrochlorination stripper and the sulfuric and waste
from the methyl chloride drying tower; however, carbon tetrachloride has
not been reported as a component of these waste streams.
A-18
-------
HANDLING EMISSIONS
The following equation from reference 11 was used to develop an uncontrolled
emission factor for loading of product carbon tetrachloride. Submerged
loading into clean tank cars, trucks, and barges was assumed.
12.46
3
M
P
L .
Loading loss, lb/10 gal of liquid loaded
Molecular weight of vapors, Ib/lb-mole =154
True vapor pressure of liquid loading, psia
T = Bulk temperature of liquid loaded (°R)
S = A saturation factor = 0.5 for submerged file of clean tank trucks,
tank cars, and barges. .
For the hydrocarbon chlorinolysis, methane chlorination, and carbon
1 2
disulfide processes, a bulk liquid temperature of 20°C was assumed. Therefore:
T
P
528°R
1.73 psia
L = 02.46)(0.5)0.73)054)
L 528
= 3.14 lb/103 gal
3
Loading loss in lb/10 gal was converted to an emission factor in terms of
kg/Mg (equivalent to lb/10 lb) by dividing by the density of carbon
tetrachloride (1.59 g/ml =13.3 Ib/gal)
Emission factor =
3.14 lb/10 gal
13.3 Ib/gal
0.24 kg/Mg
For the methanol hydrochlori nation/methyl chloride chlorination
process, the bulk liquid temperature was assumed to be 40°C. Therefore:
T = 564°R
P = 4.08 psia
L, = (12. 46)(0.05)(4. 08)054)
, 564
= 6.94 lb/103 gal
Emission factor = 6.94 lb/103 gal
13.3 Ib/gal
0.52 kg/Mg
A-19
-------
PROCESS FUGITIVE EMISSIONS
Fugitive emissions of carbon tetrachloride and other volatile orgariics
result from leaks in process valves, pumps, compressors, and pressure
relief valves. For the chlorinolysis, hydrochlorination, and methane
chlorination processes, carbon tetrachloride emission rates from process
fugitive sources were based on process flow diagrams, process operation
data, and fugitive source inventories for hypothetical plants, ' ' and
EPA emission factors for individual sources.
The first step in estimating fugitive emissions of carbon tetrachloride
was to list the process streams in the hypothetical plant. Their phases
were then identified from the process flow diagram and their compositions
are estimated. For a reactor product stream, the composition was estimated
based on reaction completion data for the reactor and on the plant product
slate. For a stream from a distillation column or other separator, the
composition was estimated based on the composition of the input stream to
the unit, the unit description, and the general description of stream of
interest (ie, overheads, bottoms, or sidedraw).
After the process streams were characterized, the number of valves
per stream were estimated by dividing the total number of valves at the
plant equally among the process streams. Similarly, pumps were apportioned
equally among liquid process streams, and relief valves were apportioned
equally among all reactors, columns, and other separators. The locations
of any compressors were determined from the process flow diagram.
Emissions were then calculated for pumps, compressors, valves in
liquid and gas line service, and relief valves. Emissions from flanges
and drains are minor in comparison with these sources and "were, therefore
neglected. Fugitive emissions from a particular source were assumed to
have the same composition as the process fluid to which the source is
exposed. For valves in liquid service, for instance, carbon tetrachloride
emissions were determined by taking the product of: (1) the total number
of liquid valves in carbon tetrachloride service; (2) the average carbon
tetrachloride content of the streams passing through these valves; and
(3) the average fugitive emission rate per valve per unit time as measured
A-20
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by EPA. Emissions from valves in gas service, pumps, arid compressors were
calculated in the same manner. For relief valves, fugitive emissions
were assumed to have the composition of the overhead stream from the
reactor or column served by the relief valve. Emissions from the various
fugitive source types were summed to obtain total process fugitive emissions
of carbon tetrachloride.
Because emissions from process fugitive sources do not depend on their
size, but only on their number, total process fugitive emissions are not
dependent on plant capacity. Thus, the overall emissions are expressed in
terms of kilograms per hour of operation.
Hydrocarbon Chlorinolysis (Perch!oroethylene CoProduct)
Hypothetical plant fugitive source inventory—
800 valves
15 pumps (not including spares)
1 compressor
12 relief valves
Process Line Composition—
Of the 28 total process lines, about 9 are in carbon tetrachloride
service (Figure A-l). Composiitons of these streams are estimated as follows;
Stream
number
1
3
5
7
9
10
12
13
13a
Phase
gas
gas
liquid
liquid
liquid
gas
liquid
liquid
liquid
Composition (percent)
HC1
44
ecu
20
21
38
38
38
100
100
100
100 '
c?cu
35
62
62
62
A-21
-------
ls
1 il
m
_l
5
II
ii
J-
(O
u
2
CTJ QJ
c u
f- p
in s-
3 Q.
C 4J
10 U
-------
Valves—
5
i
lines
29 valves per process' line
Assuming 29 valves 1n each of the above lines, and averaging the
carbon tetrachloHde contents for gas and liquid lines, total plant valve
emissions were estimated as follows:
Liquid valves
Gas valves
Component
emission factor
(kg/hr-valve)11
ss 0.0071
0.0056
Valves
CClu service
174
87
Avg composition
(% CClu)
69
47
Emissions
(kg/hr)
0.85
0.23
O8
Pumps—
15 pumps
15 liquid lines
1 pump per liquid process line
.
For one pump in each of the six liquid lines in carbon tetrachloride
service, an emission factor of 0.05 kg/hr/pump,12 and average carbon tetrachloride
concentration of 69 percent, pump emissions from the model plant were estimated
at:
1 pumps/line x 6 lines x 0.05 kg/hr x 0.69 = 0.21 kg/hr
Compressors— .' .
There are no compressors in carbon tetrachloride service.
Relief valves—
12 relief valves „. 2 re^ef valves per reactor or column
7 columns
The chlorinolysis reactor and carbon tetrachloride column heads will
contain carbon tetrachloride at the concentrations estimated for streams 3
and 10, respectively. With an emission factor of 0.104 kg/hr/valve,
hypothetical plant emissions were estimated as follows:
A-23
-------
Reactor
CCly, column
Number of
relief valves
2
2
Emissions factor
(kg/hr)
0.104
0.104
Composition
(% CHC1.O
21
100
Emissions
(kg/hr)
;0.044
0.208
Total process fugitive emissions--
Total process fugitive emissions for chlorinolysis hypothetical plant:
Valves-liquid
gas
Pumps
Compressors
Relief valves
Total
0.85
0.23
0.21
0.25
1.54 kg/hr
Controls which can be used to reduce fugitive emissions include rupture
disks on releif valves, pumps with double mechanical seals, and inspection
and maintenance of pumps and valves. Double mechanical seals and rupture
disks are approximately 100 percent efficient in reducing emissions from
pumps and relief valves. Monthly inspection and maintenance (I/M) is about
73 percent efficient for valves in gas service, 59 percent efficient for
valves in liquid service, and 61 percent efficient for pumps; while quarterly
in I/M is about 64 percent efficient for gas valves, 44 percent efficient for
liquid valves, and 33 percent efficient for pumps.
Overall efficiencies were calculated for three control options. The
first, quarterly I/M for pumps and valves has an overall efficiency for
carbon tetrachloride emissions from chlorinolysis of about 48 percent.
Monthly I/M for pumps and valves has an overall efficiency of about 64 percent;
and the use of double merchanical pumps, application, of rupture disks to
relief vavles, and monthly I/M for other valves has an overall efficiency of
about 73 percent.
A-24
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Methane Chiorination
Hypothetical plant fugitive source inventory--
1,930 process valves
' 40 pumps (not including spares)
1 compressor
70 safety relief valves
Process line composition—
Of the total 50 process lines, about 18 are in carbon tetrachloride service
O
from the chlorination reactor to carbon tetrachloride storage (see Figure A-2).
Compositions were estimated as follows:
Composition
Stream number
4
5,8
11
10,14,16
37,28,39,40,41
44
51
49,52,53,53a
Valves— •
1930
55 1
Phase
Gas
Liquid
Liquid
Liquid
Liquid
Liquid
Gas
Liquid
valves
ines
CH,C1,
28
56
45
56
56
CHCU
16
31
25
31
31
70
CCK CHu HC1
6 3 33
13
10
13
13
30
100
100
CH,C1
12
20
•
35 valves per process line
Assuming 35 valves in each of the above lines and averaging the carbon
tetrachloride contents for gas and liquid lines, total plant valves emissions
were estimated as follows:
Liquid valves
Gas valves
Component
emission factor
(kg/hr-valve)11
0.0071
0.0056
Valves in
ecu
service
560
70
Avg. composition
(% CClu)
36
53
Emissions
(kg/hr)
1.43
1.21
TT64"
A-25
-------
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u
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I
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cn
cn
tu
u
O
O.
C«J
i
I
A-26
-------
Pumps—
40 pumps
1 pump per liquid process line
35 liquid lines
Assuming and average of one pump for each of the 15 liquid process
lines In carbon tetrachloride service, an emission factor of 0.05 kg/yr-pump
and average chloroform composition of 36 percent, pump emissions from the
model plant were estimated as follows:
1 pumps/line x 16 lines x 0.05 kg/yr x 0.36 = 0.29 kg/hr
Compressors—
There are no compressors in chloroform service.
Relief valves—
12
U
5 re11ef Va1ves Per co1umn or reactor
Number of
relief valves
5
5
5
Emission factor
(kg/hr)
0.104
0.104
0.104
Composition
(% CH CU)
6
13
100
Emissions
(kg/hr)
0.03
0.07
0.52
0.62
A number of column and reactor overhead streams contain carbon tetrachloride
12
as shown below. With a relief valve emission factor of 0.104 kg/hr, hypothetical
plant emissions were estimated as follows:
Stream
4
39
51
Total process fugitive emission rate-
Total process fugitive emissions for methane chlorination hypothetical
plant:
Valves - liquid 1.43
- gas 0.21
Pumps 0.29
Relief valves 0.62
Total 2.55 kg/hr
A-27
-------
Controls which can be used to reduce fugitive emissions Include rupture
disks on relief valves, pumps with double mechanical seals, and Inspection and
maintenance of pumps and valves. The efficiencies of these control for
Individual components are described in the previous section of fugitive
emissions from chlorinolysis.
Quarterly I/M for pumps and valves has an overall efficiency for carbon
•tetrachloride emissions from methanol hydrochlor!nation/methyl chloride
chlorination of about 49 percent. Monthly I/M for pumps and valves has an
overall efficiency of about 64 percent; and the use of double merchanical
pumps, application of rupture disks to relief valves, and monthly I/M for
other valves has an overall efficiency of about 75 percent.
Methanol Hydrochlorination/Methy! Chloride Chlorination
Hypothetical plant fugitive source inventory —
725 process valves
15 pumps (not including spares)
2 compressors
25 safety relief valves
Process Line Composition—
Of the total 31 process lines, seven are in carbon tetrachloride service
from the methyl chloride chlorination reactor to carbon tetrachlorde storage
(see Figure A-3).'
follows:
Stream number
17
18
20
24
25
26
29
30
Composiitons of these streams are estimated as
Phase
Gas
Liquid
Liquid
Liquid
Liquid
Gas
Liquid
Liquid
Composition
CH^Cl 7
29
29
64
CHCU
14
14
33
91
91
100
CClu
1.4
1.4
3
9
9
_
100
100
Other
" 55
55
A-28
-------
X
h
« ft;
\
\
UlU
00
OK
o
u
o
o
c
(O
O>
•t—
•v>
•u
c
(O
"o.
18 CO
u to
•r- 0)
•M U
CL
O
o. c
>* o
S- (O
O E
«*- f-
E O
«O t—
S- .JE
O U
>
U J=
O -M
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-------
Valves—
23 valves Per Process I1ne
Assuming 23 valves in each of the above lines, and averaging the carbon
tetrachloride contents for gas and liquid lines, total plant valves emissions
were estimated as follows:
Component
emission factor
(kg/hr-valve)12
Liquid valves
Gas valves
0.0071
, 0.0056
Valves
CClu service
138
23
Avg composition
(% CClu)
37.0
1.4
Emissions
(kg/hr)
0.36
0.002
0736~
Pumps--
'IS
lines
Per I1«uid Process 11ne
For one pump in each of the six liquid lines in carbon tetrachloride
service, an emission factor of 0.05 kg/hr/pump,12 and average carbon tetrachloride
concentration of 69 percent, pump emissions from the model plant were estimated
at:
1 pumps/line x 6 lines x 0.05 kg/hr x 0.37 s 0.11 kg/hr
Compressor—
There are no compressors in carbon tetrachloride service.
Relief valves—
25 8ecofumns1VeS * 3 re1ief valves Per reactor or column
The methyl chloride reactor will contain carbon tetrachloride at the
concentrations estimated for stream 17. With an emission factor of 0.104 kg/hr/
valve,12 hypothetical plant emissions were estimated as follows:
A-30
-------
Number of
relief valves
Emissions factor Composition
(kg/hr) (% CHCU)
reactor
0.104
1.4
Emissions
(kg/hr)
0.0044
Total process fugitive emissions-
Total process fugitive emissions for methanol hydrochlorination/methy!
chloride chlorination hypotetical plant:
Valves-liquid 0.36
gas 0.002
Pumps 0.11
Compressors
Relief valves 0.004
Total 0.48 kg/hr
Controls which can be used used to reduce fugitive emissions include disks
on relief valves, pumps with double mechanical seals, and inspection and
maintenance of pumps and valves. The efficiencies of these controls for individual
components are described in the previous section of fugitive emissions from
chlorinblysis. . •
Overall efficiencies were calculated for three control options.
The first, quarterly I/M for pumps and valves has an overall efficiency
for carbon tetrachloride emissions from methanol hydrochlorination/methyl
chloride chlorination of about 42 percent. Monthly I/M for pumps and
valves has an overall efficiency of about 60 percent; and the use of
double merchanical pumps, application of rupture disks to relief vavles,
and monthly I/M for other valves has an overall efficiency of about
81 percent.
A-31
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REFERENCES FOR APPENDIX
1. Hobbs, F.D. and C.W. Stuewe. Report 2: Carbon Tetrachloride and
Perch!oroethylene by the Hydrocarbon Chlorinolysis Process (Abbreviated
Report). In: Organic Chemical Manufacturing Volume 8: Selected
Processes. EPA-450/3-80-028c, U.S. Environmental Protection Agency,
Research Triangle Park, NC, December 1980.
2. Hobbs, F.D. and C.W. Stuewe. Report 5: Chloromethanes by Methane
Chlorination Process. In: Organic Chemical Manufacturing Volume 8:
Selected Processes. EPA 450-3-80-028c, U.S. Environmental Protection
Agency, Research Triangle Park, NC, December 1980.
3. Bentley, L., Alabama Air Pollution Control Commission, Montgomery, AL.
Memo with attachments to M. Smith, GCA Corporation, June 14, 1982.
4. Bentley, L., Alabama Air Pollution Control Commission, Montgomery, AL.
Personal Communications with M. Smith, GCA Corporation, June 9, 1982.
5. Hobbs, F.D. and C.W, Stuewe. Report 6: Chloromethanes Manufactured
by Methanol Hydrochlorination and Methyl Chloride Chlorination Process.
In: Organic Chemical Manufacturing Volume 8: Selected Processes.
EPA-450/3-^80-028c, U.S. Environmental Protection Agency, Research
Triangle Park, NC, December 1980.
6. Bosky, J.W. Emission Inventory Questionnaire for 1982 for Vulcan
Chemicals, Geismar, LA submitted to Louisiana Department of Natural
Resources, Air Quality Division, June 1983.
7. Beale, J., Dow Chemical, U.S.A., Midland, MI. Letter to L. Evans,
EPA, April 28, 1978.
8. Bentley, L., Alabama Air Pollution Control Commission, Montgomery, AL.
Personal Communications with M. Smith, GCA Corporation, September 1982.
9. U.S. Environmental Protection Agency. Storage of Organic Liquids. In:
Compilation of Air Pollution Emission Factors, Third Edition - Supplement 12.
AP-42, Research Triangle Park, NC, April 1981.
10. uraT-wenser. E.. Motvot- rn.,-?*.•;«„ uT-rm- r«»« M~I
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TECHNICAL REPORT DATA
t- (Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/4-84-007b
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF
CARBON TETRACHLORIDE
3. REPORT DATE
March 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
GCA Corporation
213 Burlington Rd.
8. PERFORMING ORGANIZATION REPORT NO
Bedford, MA 01730
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Office Of Air Quality Planning And Standards
U. Si Environmental Protection Agency
MD 14
Research Triangle, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer: Thomas F. Lahre
16. ABSTRACT
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such
as this to compile available information on sources and emissions of these
substances. This document deals specifically with carbon tetrachloride.
Its intended audience includes Federal, State and local air pollution
personnel and others interested in locating potential emitters of carbon
tetrachloride and in making gross estimates of air emissions therefrom.
This document presents information on 1) the types.of sources that may
emit carbon tetrachloride, 2) process variations and release points that may
be expected within these sources, and 3) available emissions information
indicating the potential for carbon tetrachloride release into the air from
each operation.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Carbon Tetrachloride
Emission Sources
Locating Air Emission Sources
Toxic Substances
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
126
20. SECURITY CLASS (Thispage)
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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