PRELIMINARY STUDY OF
SOURCES OF CARBON TETRACHLORIDE
Final Report
GCA
GCA CORPORATION
Technology Division
213 Burlington Road
Bedford, Mass. 01730
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GCA-TR-CH-83-07
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Pollutant Assessment Branch
Strategies and Air Standards Division
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
Contract No. 68-02-3510
Work Assignment No. 24
EPA Project Officer
Karen L. Blanchard
PRELIMINARY STUDY OF
SOURCES OF CARBON TETRACHLORIDE
Final Report
by
Mark G. Smith
June 1983
GCA CORPORATION
GCA/TECHNOLOGY DIVISION
Chapel Hill, North Carolina 27514
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DISCLAIMER
This report was furnished to the U.S. Environmental Protection Agency
by GCA Corporation, GCA/Technology Division, 213 Burlington Road, Bedford,
Massachusetts 01730, in fulfillment of Contract No. 68-02-3510, Work
Assignment No. 24. The options, findings, and conclusions expressed are
those of the authors and not necessarily those of the U.S. Environmental
Protection Agency. Mention of company or product names is not to be
considered as an endorsement by the Environmental Protection Agency.
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EXECUTIVE SUMMARY
This report provides preliminary information on sources of air
emissions of carbon tetrachloride. This information is intended to
assist EPA in the regulatory decision-making process. Potentially
significant sources are identified and described. Source descriptions
include general information on each industry and production process, as
well as emission estimates, applicable regulations and control technology.
Principal sources of carbon tetrachloride air emissions are as follows:
o Carbon tetrachloride production,
o Chlorofluorocarbon (CFC) 11 and 12 production,
o Methanol hydrochlorination/methyl chloride chlorination,
o Ethylene dichloride production,
o Perchloroethylene and trichloroethylene production from ethylene
dichloride,
o Grain fumigant formulation and use, and
o Pharmaceutical manufacturing.
Other sources identified include production processes for phosgene/
isocyanate/polyurethane, pesticides, synthetic rubber, and carbon tetrabromide,
In addition to describing each of these source categories, this
report also presents preliminary information on carbon tetrachloride
emissions and control costs for carbon tetrachloride production plants
and plants which produce CFC 11 and 12 from carbon tetrachloride.
Uncontrolled emissions were estimated for each type of source at these
plants, using available model plant emission factors and production data
for individual sources. Controlled emissions and control costs were
estimated for two control options: Option 1 represents a baseline
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level of control which would be expected without further regulatory
activity, consisting of the most stringent control provided by known
existing controls, applicable State regulations, or Group III control
techniques guidelines (CTG). It was assumed that Group III CTGs will
apply in areas which have received ozone NAAQS attainment date extensions
beyond 1982, and that States required to adopt such CTGs will do so.
Sources were also assumed to be in full compliance with applicable State
regulations. Option 2 consists of estimated best control (EEC) for each
significant emission source, chosen from the highest control levels known
to be in use, as identified under Option 1, and other available high-efficiency
controls, such as best demonstrated technology developed for new source
performance standards.
The carbon tetrachloride emissions, control data, and costs of
control in this report are based on information obtained from existing EPA
reports and other published sources, from EPA data files on the synthetic
organic chemical manufacturing industry, and from telephone contacts with
control equipment vendors, and EPA, State and local agency personnel.
This study did not include plant visits, source testing, or other original
data gathering. The available references contain very little data on
plant-specific emissions of carbon tetrachloride and on related control
costs. In the source assessments for carbon tetrachloride and CFC 11/12
production, available data were used to develop emissions and costs for
representative model plants. Estimated emissions and control costs for
individual plants were then derived from model plant data by assuming that
emissions and costs are directly proportional to carbon tetrachloride
production. This methodology is described in more detail in Chapter 1,
and examples and supporting data are presented in Appendices A and B.
Resulting estimates are summarized in Tables 1 and 2. Due to the number
of simplifications and assumptions involved in this approach, the emissions
and control cost estimates presented in this report must be considered
prelimi nary.
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TABLE 1. SUMMARY: EMISSIONS OF CARBON TETRACHLORIDE FROM CARBON
TETRACHLORIDE AND CHLOROFLUOROCARBON 11/12 PRODUCTION
Source category
Perchloroethylene co-product
process
Process
Fugitive
Storage
Loading
Secondary
Subtotal
Methane chlori nation process
Process
Fugitive
Storage
Loading
Secondary
Subtotal
Carbon disulfide process
Process
Fugitive
Storage
Loading
Subtotal
Chlorofluorocarbon 11/12
process
Process
Fugitive
Storage
Subtotal
TOTAL
Carbon tetrachloride emissions, Mg/yr
Uncontrolled
1.2
203
185
52
1.7
443
5.7
80
27
10.9
0.8
124
7,240
37
50
15
7,342
11.1
40
40
91
8,000
Option 1
1.1
200
57
30
1.2
289
5.6
65
8.0
9.2
0.8
89
362
37
50
15
464
11.1
34
7
52
894
Option 2
0.1
89
9.3
5.2
0.03
104
2.2
35
1.4
1.1
0.8
40
18
16
2
1
37
11.1
18
2
31
212
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TABLE 2. SUMMARY: COSTS OF CONTROL OF CARBON TETRACHLORIDE EMISSIONS
FROM CARBON TETRACHLORIDE AND CHLOROFLUOROCARBON 11/12
PRODUCTION (July 1982 dollars)
Source category
Perchloroethylene
co-product process
Process
Fugitive
Storage
Loading
Subtotal
Methane chlorination
process
Process
Fugitive
Storage
Loading
Subtotal
Carbon disulfide
process
Process
Fugitive
Storage
Loading
Subtotal
Chlorofluorocarbon
11/12 process
Fugitive
Storage
Subtotal
TOTAL
Capital
Option 1
6,700
8,800
2,187,000a
468,600
2,671,100
26,000
63,400
99,800a
38,100
227,300
71,500
--
--
--
71,500
14,700
1,837,300
1,852,000
4,821,900
costs
Option 2
40,200
327,600
3,833,400a
1,085,100
5,286,300
549,600
258,400
156,800a
251,200
1,216,000
242,500
30,700
570,000
83,900
927,100
46,300
2,966,000
3,012,300
10,441,700
Annual i zed
Option 1
2,100
5,000
573,500
129,000
709,600
10,900
44,700
27,800a
10,300
93,700
(2,804,000)
--
--
--
(2,804,000)
8,500
518,700
527,200
(1,473,500)
costs
Option 2
12,700
152,600
l,028,600a
314,800
1,508,700
163,200
150,300
43,700a
73,200
430,400
(2,856,000)
10,000
144,900
19,900
(2,681,200)
26,500
843,000
869,500
127,400
Storage costs for two-process plants are in totals for perch!oroethylene
co-product process.
( ) indicates credit
indicates no control
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There are currently nine carbon tetrachloride production facilities
in the U.S., with a total production capacity of 478,000 Mg/yr. Sixty-five
percent of this capacity is in Texas and Louisiana, where there are two
plants in each State. Other plants are located in West Virginia,
Alabama, Kentucky, Kansas, and California. The three carbon tetrachloride
production processes and their approximate percentages of national
production capacity are as follows: (1) chlorinolysis or chlorination
of hydrocarbons with perch!oroethylene co-product (70 percent); (2) carbon
disulfide chlorination (20 percent); and (3) methane chlorination
(10 percent). Three plants use a perch!oroethylene co-product process
exclusively, while three more use it in conjunction with a methane
chlorination process. Two small plants use methane chlorination exclusively.
Only one plant currently uses carbon disulfide chlorination, although
two other large carbon disulfide-based plants have been closed since
1975.
Six of the nine carbon tetrachloride plants have some control of
storage emissions under Option 1. Option 1 also includes loading controls
at three plants, process controls at three plants, process fugitive
controls at two plants, and secondary emission controls at two plants.
Option 1 results in overall reductions over estimated uncontrolled
emissions of about 35 percent and 30 percent for the perchloroethylene
co-product and methane chlorination processes, respectively. Most of
this reduction is due to the storage controls.
Under Option 2, the following were selected as EBC for emission
sources common to all three carbon tetrachloride production processes
(control efficiencies in parentheses): process fugitive emission control
by monthly inspection and repair, with equipment specifications (56 percent);
storage emission control by refrigerated condenser (95 percent); and
loading control by vapor recovery and refrigerated condenser (90 percent).
EBC process controls include a refrigerated condenser for perchloroethylene
co-product processes (90 percent), a chloroform-based absorber system
controlling two of three methane chlorination process emission points
(62 percent), and an additional refrigerated condenser on the existing
condenser "for the carbon disulfide process (combined control of 99.8 percent)
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EEC for secondary emissions at perch!oroethylene co-product plants
includes steam-stripping of waste caustic, as well as vapor balance,
condensation and recycle for waste products (98 percent). Control of
the small secondary emissions at methane chlorination plants is not
practical, since at least six emission points are involved.
As shown in Table 1, EBC for the three production processes is
estimated to result in a total carbon tetrachloride emission reduction
of 661 Mg/yr over Option 1, for an incremental control efficiency of
about 79 percent. Slightly more than half of this reduction is due to
EBC on the process vent at the single carbon disulfide plant, where the
plant-wide control efficiency over Option 1 is about 92 percent. Corresponding
overall incremental reductions are 185 Mg/yr (64 percent) for the
perchloroethylene co-product processes and 49 Mg/yr (55 percent) for the
methane chlorination processes.
Table 2 presents preliminary estimates of the total costs of Option 1
and 2 controls for each emission category at carbon tetrachloride plants.
For the three plants which use both the perchloroethylene co-product
process and methane chlorination, joint product storage was assumed, and
all control costs are included in totals for the perchloroethylene co-
product process. Costs for Option 2 are totals for implementation of
EBC, and are not adjusted to reflect current or anticipated costs under
Option 1. Thus these costs represent worst case estimates. Total
capital costs for Option 1 and 2 controls for the perchl oroethylene
co-product process and methane chlorination are estimated at $2,898,000
and $6,502,000, and corresponding net annualized costs total $803,000
and $1,939,000 for Options 1 and 2, respectively. For the carbon disulfide
plant, capital costs are estimated at $71,500 for Option 1 and $927,100
for Option 2. Both process controls at this plant result in net credits
due to recovery of carbon tetrachloride. Product recovery by the Option 1
control at this plant results in large annual credits for Options 1 and 2
($2,804,000 and $2,681,200).
VI 1
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About 90 percent of domestic carbon tetrachloride use is as a
feedstock for production of CFC 11 and 12. There are eight CFC 11/12
production locations, which were estimated to produce 74,000 Mg of
CFC 11 and 147,000 Mg of CFC 12 in 1981. Two of these plants are in
California, with one each in New Jersey, Kentucky, Illinois, Michigan,
Louisiana and Kansas. Plant-specific data on CFC 11/12 production and
carbon tetrachloride use are available for only one plant; thus most of
the emission and control cost estimates cited in this report are based
on CFC 11/12 production capacities which were estimated by assuming
uniform distribution of available total CFC capacities at the plant or
company level. A total of six plants have Option 1 controls on carbon
tetrachloride feedstock storage, and one plant has no storage on site.
Option 1 includes process fugitive controls at three plants. There are
no Option 1 controls in place or required for carbon tetrachloride
process emissions at CFC 11/12 plants. Option 1 is estimated to result
in 40 percent control over total uncontrolled emissions of carbon tetrachloride
from CFC 11/12 plants. Under Option 2, EBC consists of 56 percent
control of process fugitive emissions by a monthly inspection and repair
program, with equipment specifications, and 95 percent control of carbon
tetrachloride feedstock storage by a refrigerated condenser. There is
no EBC for process emissions. As shown in Table 1, applying EBC to all
plants is estimated to result in an overall emission reduction over
Option 1 of 21 Mg, or 40 percent. Table 2 shows the corresponding
estimated capital and net annual costs, which total about $1,852,000 and
$527,000 respectively for Option 1, and $3,012,000 and $870,000 for
Option 2.
Three other synthetic organic chemical production processes have
been reported to result in incidental formation and emission of small
amounts of carbon tetrachloride. These processes include: production of
methyl chloride, methylene chloride and chloroform by methanol hydrochlorination
and subsequent chlorination of methyl chloride; production of ethylene
dichloride; and production of trichloroethylene and perch!oroethylene from
ethylene dichloride.
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There are seven plants in the U.S. producing chlorinated methanes
by hydrochlorination of methanol and chlorination of methyl chloride.
There are two plants each in West Virginia and Louisiana, and one each
in Kentucky, Texas, and Kansas. Carbon tetrachloride is formed in the
methyl chloride chlorination step, and can be emitted as process fugitives,
as well as from storage and handling of the distillation bottoms.
Information is not available on existing controls for these sources, and
also is not sufficient to assess applicability of other Option 1 controls
or EEC.
There are 19 plants in the U.S. producing ethylene dichloride, and
1 under construction, including 11 plants in Louisiana, 8 plants in
Texas and 1 in Kentucky. Ethylene dichloride can be produced by direct
chlorination or oxychlorination of ethylene. These processes are typically
used together in a balanced process which recycles HC1 from vinyl chloride
monomer production to the oxychlorination step. Oxychlorination can be
based on air or oxygen. All the ethylene dichloride processes produce
some carbon tetrachloride by-product, which is emitted from reactor
vents, distillation column vents, fugitive process sources, liquid waste
storage and waste incineration. Available information indicates that
process vent controls exist or are planned at most plants. There are no
current controls on process fugitives. Information is not available on
existing or potential controls for the other carbon tetrachloride
sources cited above.
There are four plants in the U.S. which produce perchloroethylene
and/or trichloroethylene by chlorination or oxychlorination of ethylene
dichloride. Two are in Texas, and two in Louisiana. Carbon tetrachloride
formed in the initial reaction may be emitted from at least four process
vents, from process fugitive sources, and from light ends storage.
Available data on the processes and known emission controls at these
plants indicate considerable variability between plants, but are not
sufficient for detailed assessment.
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Carbon tetrachloride is the major component of all major liquid
grain fumigant formulations. From 60 to 80 percent carbon tetrachloride
is present in these products, principally as a carrier and to reduce
risks of fire and explosion. These fumigants are applied to grains
during storage, transfer, milling, distribution and processing, at
locations including on-farm storage, subterminal, terminal and port
elevators, mill holding facilities and in transport vehicles. Emission
of carbon tetrachloride from treated grain occurs during application and
subsequent storage, turning, ventilation, loading, and further processing
resulting in eventual loss of essentially all fumigant to the atmosphere.
Possible measures for reduction of air emissions from fumigant use
include expanded use of alternative fumigants and more efficient use of
existing formulations. Additional emissions may occur in the mixing and
packaging of fumigants, but no specific data are available.
Carbon tetrachloride is used as a solvent in the manufacturing of
pharmaceutical products, which is typically done in small batch operations.
Solvent emissions would be expected from all process components, especially
dryers, reactors and distillation units, and from solvent storage and
transfer. Specific locations are not available for manufacturers using
carbon tetrachloride.
A number of other reported or potential sources of carbon tetrachloride
air emissions were also identified during the data-gathering phase of
the study- Carbon tetrachloride is apparently used as a scrubber absorbent
in a phosgene production process at one or more phosgene/isocyanate/
polyurethane plants. There are 15 phosgene production plants in the U.S.,
of which all but 2 small plants produce phosgene for captive use in isocyanate
production. Potential emission points include storage and the scrubber
vent.
Carbon tetrachloride has been identified as a solvent in production
of several pesticides, including chlorothalonil, Linuron, and sulfuryl
fluoride. Chlorothalonil is sold as Daconil, Forturf, Termil, and Bravo,
and is produced at one plant in Texas. Linuron is a tradename for
XI
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N'-(3,4-dichlorophenyl)-N-methylurea, and is produced at a plant in Texas
and one in Indiana. Sulfuryl fluoride, sold as Vikane, is produced at
one plant in California.
One plant in Texas produces a vulcanizable elastomer called Hypalon®.
This synthetic rubber is produced by reacting polyethylene with chlorine
and sulfur dioxide in a solvent medium. Potential emission points for
carbon tetrachloride solvent include storage, process vents, and the
solvent recovery system.
Three plants in New York, Arkansas and Texas are reported to produce
carbon tetrabromide by reacting carbon tetrachloride with aluminum tribromide
Storage, handling and process vents are the potential emission points at
these locations. Carbon tetrabromide is a small-volume chemical for which
production statistics are not available.
A carbon tetrachloride emission inventory for Texas also reported
the following sources: a chlorine liquefaction operation, a resinous
chlorowax production, a plant with symmetrical tetrachloropyridine and
4-amino-3,5,6-trichloropical inic acid processes, and storage and loading
at tank farms not owned by known carbon tetrachloride producers or
users. An inventory for New Jersey reported carbon tetrachloride emission
points related to several polymer productions and one dye production
process. Other potential carbon tetrachloride sources which could not
be verified include laboratory uses, metal cleaning, production of
paint, adhesives, textiles, and embalming supplies.
XT i
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CONTENTS
EXECUTIVE SUMMARY in
FIGURES xvii
TABLES Xv111
ACKNOWLEDGMENTS '.'.'.'.'.'. xxi i
1 .0 INTRODUCTION 1 _1
1.1 OVERVIEW 1-1
1.2 SOURCE ASSESSMENT METHODOLOGY 1-2
1 .3 REFERENCES 1-7
2.0 CARBON TETRACHLORIDE PROPERTIES AND CURRENT REGULATIONS
AFFECTING EMISSIONS 2-1
2.1 PROPERTIES OF CARBON TETRACHLORIDE 2-2
2.2 REGULATIONS AFFECTING EMISSIONS OF CARBON TETRACHLORIDE... 2-5
2.2.1 Existing State Regulations 2-5
2.2.2 Group III Control Techniques Guidelines 2-21
2.3 REFERENCES 2-24
3.0 CARBON TETRACHLORIDE PRODUCTION WITH PERCHLOROETHYLENE
CO-PRODUCT 3-1
3.1 PERCHLOROETHYLENE CO-PRODUCT PROCESS DESCRIPTION 3-1
3.1.1 General Information 3-1
3.1.2 Process Description 3-1
3.1.3 Carbon Tetrachloride Emission Factors for the
Perchloroethylene Co-Product Process 3-3
3.2 UNCONTROLLED PERCHLOROETHYLENE CO-PRODUCT
PLANT EMISSIONS 3-6
3.2.1 Model Plant 3-6
3.2.2 Capacity Apportionment in Two-Process
PI ants 3-7
3.2.3 Proportionality and Scales of Production 3-8
3.2.4 Capacity Utilization 3-8
3.2.5 Uncontrolled Emissions 3-9
3.3 OPTION 1 CONTROLS AND EMISSIONS FOR PERCHLOROETHYLENE
CO-PRODUCT PLANTS 3-10
3.3.1 Existing Controls 3-10
3.3.2 State Regulations 3-13
3.3.3 Group III Control Techniques Guidelines 3-17
xm
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Contents (continued)
3.3.4 Combined Option 1.Controls 3-18
3.3.5 Estimated Option 1 Emissions 3-19
3.4 OPTION 2 CONTROLS AND EMISSIONS FOR PERCHLOROETHYLENE
CO-PRODUCT PLANTS 3-20
3.4.1 Estimated Best Controls 3-20
3.4.2 Estimated Option 2 Emissions 3-21
3.5 CONTROL COSTS FOR PERCHLOROETHYLENE CO-PRODUCT PLANTS 3-22
3.5.1 Option 1 Control Costs 3-22
3.5.2 Option 2 Control Costs 3-37
3.6 REFERENCES 3-41
4.0 CARBON TETRACHLORIDE PRODUCTION BY METHANE CHLORINATION 4-1
4.1 METHANE CHLORINATION PROCESS DESCRIPTION 4-1
4.1.1 General Information 4-1
4.1.2 Process Description 4-1
4.1.3 Carbon Tetrachloride Emission Factors for the
Methane Chlorination Process 4-3
4.2 UNCONTROLLED METHANE CHLORINATION PLANT EMISSIONS 4-3
4.2.1 Model Plant 4-3
4.2.2 Capacity Apportionment in Two-Process
PI ants 4-3
4.2.3 Proportionality and Scales of Production 4-3
4.2.4 Uncontrolled Emissions 4-5
4.3 OPTION 1 CONTROLS AND EMISSIONS FOR METHANE
CHLORINATION PLANTS 4-6
4.3.1 Existing Controls 4-6
4.3.2 State Regulations 4-7
4.3.3 Group III Control Techniques Guidelines 4-7
4.3.4 Combined Option 1 Controls 4-7
4.3.5 Estimated Option 1 Emissions 4-8
4.4 OPTION 2 CONTROLS AND EMISSIONS FOR METHANE
CHLORINATION PLANTS 4-9
4.4.1 Estimated Best Controls 4-9
4.4.2 Estimated Option 2 Emissions 4-10
4.5 CONTROL COSTS FOR METHANE CHLORINATION PLANTS 4-11
4.5.1 Option 1 Control Costs 4-11
4.5.2 Option 2 Control Costs 4-17
4.6 REFERENCES 4-21
5.0 CARBON TETRACHLORIDE PRODUCTION BY CARBON DISULFIDE
CHLORINATION 5-1
5.1 CARBON DISULFIDE PROCESS DESCRIPTION 5-1
5.1.1 General Information 5-1
5.1.2 Process Description 5-1
5.1.3 Carbon Tetrachloride Emission Factors for
the Carbon Disulfide Process 5-3
5.2 UNCONTROLLED CARBON DISULFIDE PLANT EMISSIONS '. 5-4
xiv
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Contents (continued)
5.3 OPTION 1 CONTROLS AND EMISSIONS FOR THE CARBON
DISULFIDE PLANT 5-4
5.3.1 Existing Controls 5-4
5.3.2 State Regulations 5-4
5.3.3 Combined Option 1 Controls 5-5
5.3.4 Estimated Option 1 Controls 5-5
5.4 OPTION 2 CONTROLS AND EMISSIONS FOR THE CARBON
DISULFIDE PLANT 5-6
5-4.1 Estimated Best Controls 5-6
5.4.2 Estimated Option 2 Emissions 5-6
5.5 CONTROL COSTS FOR THE CARBON DISULFIDE PLANT 5-9
5.5.1 Option 1 Control Costs 5-9
5.5.2 Option 2 Control Costs 5-10
5.6 REFERENCES 5-15
6.0 CHLOROFLUOROCARBON PRODUCTION FROM CARBON TETRACHLORIDE
FEEDSTOCK 6-1
6.1 CHLOROFLUOROCARBON 11/12 PROCESS DESCRIPTION 6-1
6.1.1 General Information 6-1
6.1.2 Process Description 6-3
6.1.3 Carbon Tetrachloride Emission Factors for
Chlorofluorocarbon Production 6-3
6.2 UNCONTROLLED CHLOROFLUOROCARBON PLANT EMISSIONS 6-6
6.2.1 Model Plants 6-6
6.2.2 Capacity Apportionment 6-6
6.2.3 Proportionality and Scales of Production 6-7
6.2.4 Capacity Utilization 6-8
6.2.5 Uncontrolled Emissions 6-8
6.3 OPTION 1 CONTROLS AND EMISSIONS FOR CHLOROFLUOROCARBON
PRODUCTION 6-10
6.3.1 Existing Controls 6-10
6.3.2 State Regulations 6-12
6.3.3 Group III Control Techniques Guidelines 6-16
6.3.4 Combined Option 1 Controls 6-17
6.3.5 Estimated Option 1 Emissions 6-17
6.4 OPTION 2 CONTROLS AND EMISSIONS FOR CHLOROFLUOROCARBON
PRODUCTION 6-19
6.4.1 Estimated Best Controls 6-19
6.4.2 Estimated Option 2 Emissions 6-19
6.5 CONTROL COSTS FOR CHLOROFLUOROCARBON PLANTS 6-21
6.5.1 Option 1 Control Costs 6-21
6.5.2 Option 2 Control Costs 6-25
6.6 REFERENCES 6-29
7.0 PROCESSES WITH CARBON TETRACHLORIDE BY-PRODUCT 7-1
7.1 METHANOL HYDROCHLORINATION/METHYL CHLORIDE CHLORINATION... 7-1
7.1.1 Process Description 7-1
7.1.2 Carbon Tetrachloride Emissions 7-2
xv
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Contents (continued)
7.2 ETHYLENE DICHLORIDE PRODUCTION 7-2
7.2.1 Process Description 7-2
7.2.2 Carbon Tetrachloride Emissions 7-6
7.2.3 Emission Controls 7-11
7.3 PERCHLOROETHYLENE AND TRICHLOROETHYLENE PRODUCTION
FROM ETHYLENE DICHLORIDE 7-11
7.3.1 Process Description 7-11
7.3.2 Carbon Tetrachloride Emissions 7-14
7.3.3 Emission Controls 7-14
7.4 REFERENCES 7-20
8.0 GRAIN FUMIGANT FORMULATION AND USE 8-1
8.1 GENERAL INFORMATION 8-1
8.2 LIQUID FUMIGANT FORMULATION DESCRIPTION 8-2
8.3 LIQUID FUMIGANT APPLICATION DESCRIPTION 8-4
8.4 REGULATIONS AND EMISSION CONTROL 8-6
8.5 REFERENCES 8-12
9.0 PHARMACEUTICAL MANUFACTURING 9-1
9.1 SOURCE DESCRIPTION 9-1
9.2 PHARMACEUTICAL MANUFACTURING SOLVENT EMISSION SOURCES 9-3
9.3 EMISSION CONTROLS 9-4
9.4 REFERENCES 9-5
10.0 OTHER POTENTIAL SOURCES OF CARBON TETRACHLORIDE EMISSIONS 10-1
10.1 PHOSGENE/ISOCYANANTE/POLYURETHANE PROCESSES 10-1
10.2 PESTICIDE PRODUCTON 10-3
10.3 HYPALON SYNTHETIC RUBBER PRODUCTION 10-4
10.4 CARBON TETRABROMIDE PRODUCTION 10-5
10.5 MISCELLANEOUS 10-6
10.6 REFERENCES 10-8
APPENDIX A - BASES FOR CARBON TETRACHLORIDE EMISSIONS ESTIMATES A-l
APPENDIX B - BASES FOR CAPITAL AND ANNUALIZED CONTROL COST
ESTIMATES B_!
xvi
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FIGURES
Number Page
2-1 Carbon tetrachloride vapor pressure 2-4
3-1 Process flow diagram for hydrocarbon chlorinolysis process 3-4
3-2 Estimated annual costs of condensers for carbon
tetrachloride storage 3-28
3-3 Bulk Gasoline Terminal NSPS control costs 3-31
4-1 Process flow diagram for methane chlorination process 4-2
5-1 Process flow diagram for carbon disulfide chlorination
process 5-2
6-1 Process flow diagram for fluorocarbon production 6-4
7-1 Process flow diagram for methanol hydrochlorination/methyl
chloride chlorination process 7-3
7-2 Process flow diagram for ethylene dichloride production by
balanced air-based process 7-8
7-3 Process flow diagram for ethylene dichloride production by
oxygen-based process, oxychorination step 7-9
7-4 Process flow diagram for perch!oroethylene and
trichloroethylene production by chlorination of
ethylene dichloride 7-15
7-5 Process flow diagram for perch!oroethylene and
trichloroethylene production by oxychlorination of
ethylene dichloride 7-16
8-1 Process flow diagram for liquid pesticide formulation 8-3
8-2 Residual carbon tetrachloride fumigant as a function of
days grain aired 8-5
9-1 Process diagram for typical synthetic pharmaceutical
manufacturing process 9-1
xv t
-------
TABLES
Number
1 Summary: Emissions of Carbon Tetrachloride from Carbon
Tetrachloride and Chlorofluorocarbon 11/12 Production v
2 Summary: Costs of Control of Carbon Tetrachloride Emissions
from Carbon Tetrachloride and Chlorofluorocarbon 11/12
Production vi
2-1 Physical Properties of Carbon Tetrachloride 2-2
2-2 Estimated Control Efficiencies for State VOC Regulations 2-20
3-1 Carbon Tetrachloride Producers 3-2
3-2 Uncontrolled Model Plant Carbon Tetrachloride Emission
Factors for Hydrocarbon Chlorinolysis (Perchloroethylene
Co-Product) Process 3-5
3-3 Capacity Apportionment in Two-Process Plants 3-7
3-4 Perchloroethylene Co-Product Plant Capacity Factors 3-8
3-5 Perchloroethylene Co-Product Model Plant Emissions 3-9
3-6 Uncontrolled Emissions for Perchloroethylene Co-Product
Plants 3-9
3-7 Known Existing Controls at Carbon Tetrachloride Production
Plants 3-11
3-8 Current State Regulations Applying to Carbon Tetrachloride
Production Facilities 3-14
3-9 Ozone NAAQS Attainment Status for Carbon Tetrachloride
Production Facilities 3-18
3-10 Option 1 Control Summary for Perchloroethylene Co-Product
Plants 3-19
3-11 Option 1 Controls for Storage Emissions at Perchloroethylene
Co-Product Plants 3-19
3-12 Option 1 Controlled Emissions for Perchloroethylene
Co-Product Plants 3_2Q
3-13 Option 2 Controlled Emissions for Perchloroethylene
Co-Product Plants 3-21
3-14 Model Plant Fugitive Emission Sources 3_25
xvi i i
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Tables (continued)
Number Page
3-15 Perch!oroethylene Co-Product Model Plant Storage 3-26
3-16 Methane Chlorination Model Plant Storage 3-26
3-17 Estimated Model Plant Annual Costs for Refrigerated
Condenser Storage Control 3-27
3-18 Annualized Refrigerated Condenser Control Costs for Existing
Bottom-Loaded Bulk Gasoline Terminals 3-32
3-19 Distribution of Annual Costs for Loading Control by
Refrigerated Condenser 3-33
3-20 Option 1 Perch!oroethylene Co-Product Model Plant Control
Costs 3-35
3-21 Option 1 Perchloroethylene Co-Product Plant Control Costs 3-36
3-22 Net Annualized Costs for Option 2 Control of Process
Emissions at Perchloroethylene Co-Product Plants 3-37
3-23 Option 2 Perchloroethylene Co-Product Model Plant Control
Costs 3-40
3-24 Option 2 Perchloroethylene Co-Product Plant Control Costs 3-40
4-1 Uncontrolled Model Plant Carbon Tetrachloride Emission
Factors for Methane Chlorination Process 4-4
4-2 Methane Chlorination Plant Capacity Factors 4-5
4-3 Methane Chlorination Model Plant Emissions 4-5
4-4 Uncontrolled Emissions for Methane Chlorination Plants 4-6
4-5 Option 1 Control Summary for Methane Chlorination Plants 4-8
4-6 Option 1 Controls for Storage Emissions at Methane
Chlorination Plants 4-8
4-7 Option 1 Controlled Emissions for Methane Chlorination
Plants 4-9
4-8 Option 2 Controlled Emissions for Methane Chlorination
Plants 4-10
4-9 Emissions and Recovery Credits for 50 Percent Methane
Chlorination Process Control at Plant 6 4-11
xix
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Tables (continued)
Number Page
4-10 Control Cost Summary for 50 Percent VOC Removal by
Refrigerated Condenser ....................................... 4-12
4-11 Model Plant Fugitive Emission Sources .......................... 4-14
4-12 Option 1 Methane Chlorination Model Plant Control Costs ........ 4-16
4-13 Option 1 Methane Chlorination Plant Control Costs .............. 4-16
4-14 Option 2 Methane Chlorination Model Plant Control Costs ........ 4-20
4-15 Option 2 Methane Chlorination Plant Control Costs .............. 4-20
5-1 Uncontrolled Carbon Tetrachloride Emission Factors for
Carbon Disulfide Chlorination Process ........................ 5-3
5-2 Uncontrolled Emission Estimates for the Carbon Disulfide
Plant [[[ 5-4
5-3 Option 1 Controlled Emissions for the Carbon Disulfide Plant... 5-5
5-4 Option 2 Process Controls for the Carbon Disulfide Plant ....... 5-7
5-5 Option 2 Controlled Emissions for the Carbon Disulfide Plant... 5-8
5-6 Carbon Disulfide Plant Storage ................................. 5-12
5-7 Option 2 Carbon Disulfide Plant Control Costs .................. 5-14
6-1 Chlorofluorocarbon Producers ................................... 6-2
6-2 Uncontrolled Carbon Tetrachloride Emission Factors for
Chlorofluorocarbon 11 and 12 Production ...................... 6-5
6-3 Capacity Apportionment for CFC 11/12 Plants .................... 6-7
6-4 CFC Plant Capacity Factors ..................................... 6-8
6-5 CFC 11/12 Uncontrolled Model Plant Emissions ................... 6-9
6-6 Uncontrolled Carbon Tetrachloride Emissions for CFC 11/12
Producti on [[[ 5.9
6-7 Existing Carbon Tetrachloride Storage Controls at CFC 11/12
Production Plants ............................................ 6-11
6-8 Current State Regulations Applying to Carbon Tetrachloride
-------
Tables (continued)
Number Page
6-9 Ozone NAAQS Attainment Status for CFC 11/12 Plants 6-16
6-10 Option 1 Control Summary for CFC 11/12 Production Plants 6-17
6-11 Option 1 Controlled Emissions for CFC 11/12 Production Plants.. 6-18
6-12 Option 2 Controlled Emissions for CFC 11/12 Production Plants.. 6-20
6-13 Carbon Tetrachlqride Storage at CFC 11/12 Plants 6-23
6-14 Estimated CFC 11/12 Model Plant Costs for Refrigerated
Condenser Control of Carbon Tetrachloride Storage 6-24
6-15 Option 1 CFC 11/12 Model Plant Control Costs 6-25
6-16 Option 1 CFC 11/12 Plant Control Costs 6-26
6-17 Option 2 CFC 11/12 Model Plant Control Costs 6-27
6-18 Option 2 CFC 11/12 Plant Control Costs 6-28
7-1 Methylene Chloride and Chloroform Producers 7-4
7-2 Uncontrolled Carbon Tetrachloride Emission Factors for
Methanol Hydrochlorination/Methyl Chloride Chlorination
Process 7-5
7-3 Ethylene Dichloride/Vinyl Chloride Monomer Producers 7-7
7-4 Uncontrolled Carbon Tetrachloride Emission Factors for
Ethylene Dichloride Production by the Balanced process 7-10
7-5 Emission Controls Used by the Ethylene Dichloride Industry 7-12
7-6 Perchloroethylene and/or Trichloroethylene Production by
Chlorination of Ethylene Dichloride 7-17
7-7 Uncontrolled Carbon Tetrachloride Emission Factors for a
Plant Producing Perchloroethylene by Ethylene Dichloride
Chlorination 7-18
8-1 Fumigant Application Rates 8-5
8-2 On-Farm Grain Storage 8-8
8-3 Off-Farm Grain Storage 8-10
10-1 Phosgene Producers 10-2
10-2 Carbon Tetrachl ori de Producers 10-5
xx i
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ACKNOWLEDGEMENTS
The following personnel provided invaluable assistance in the data
gathering phase of this project.
Steve Riva, EPA Region II
Michael Koral, Munroe County (NY) Bureau of Air Resources
Tom Marriott, New York Division of Air
Ernest Mancini, New Jersey Division of Environmental Quality
Israel Milner, EPA Region III
Eric Soto, EPA Region IV
Micahel DeBusschere, Jefferson County (KY) Air Pollution Control District
Dick Eberhart, Jefferson County (KY) Air Pollution Control District
Bill Dills, Kentucky Division of Air Pollution Control
Jerry Goebel, Kentucky Division of Air Pollution Control
Lyle Bentley, Alabama Air Pollution Control Commission
Wayne Montney, Illinois Environmental Protection Agency
Greg Gasperecz, Louisiana Air Quality Division
Bharot Contractor, Louisiana Air Quality Division
Nan Killeen, Louisiana Air Quality Division
Joe Panketh, Texas Air Control Board
Barbara Fry, California Air Resources Board
Steve Hill, Bay Area Air Quality Management District
Art Netzley, South Coast Air Quality Management District
Rich Waldrop, Edwards Engineering, Inc.
Larry Botkin, Fruehauf, Inc.
xxi
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1.0 INTRODUCTION
1.1 OVERVIEW
This report provides preliminary information on sources of air emissions
of carbon tetrachloride to assist EPA in regulatory decision-making.
Potentially significant sources are identified and described, including
carbon tetrachloride production, its use in chlorofluorocarbon (CFC)
production, processes resulting in carbon tetrachloride by-product, and
solvent and fumigant uses. Source descriptions include general information
on each industry and production process, as well as emission estimates,
applicable regulations and control technology.
In addition to source descriptions, this report also presents preliminary
estimates of carbon tetrachloride emissions and control costs for carbon
tetrachloride production plants and plants which produce CFC 11 and 12
from carbon tetrachloride. Methodology for this assessment is detailed in
Section 1.2. Controlled emissions and control costs were estimated for
two control options: Option 1 represents the baseline level of control
which would be expected without further regulatory activity, and Option 2
consists of estimated best control (EBC) for each significant emission
source.
The carbon tetrachloride emissions, control data, and costs of control
in this report are based on information obtained from existing EPA reports
and other published sources, from EPA data files on the synthetic organic
chemical manufacturing industry, and from telephone contacts with control
equipment vendors, and EPA, State and local agency personnel. This study
did not include plant visits, source testing, or other original data
gathering.
Chapter 2 describes physical properties of carbon tetrachloride
relevant to its uses and emission control. A detailed listing of
State regulations which may apply to sources of carbon tetrachloride
1-1
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air emissions is also provided and control efficiencies are estimated
where they are not prescribed in the regulations.
Chapters 3 through 6 contain process descriptions and estimates of
emissions and control costs for the three types of carbon tetrachloride
production processes and for production of CFC 11 and 12. Controlled
emissions and control costs are estimated for control Options 1 and 2.
Examples and details of emission and cost estimates are provided in Appendices A
and B.
Chapters 7 through 10 provide information on other carbon tetrachloride
source categories, including chemical production processes with carbon
tetrachloride by-product, grain fumigant formulation and use, and pharmceutical
manufacturing. Each chapter includes a description of the source category,
its carbon tetrachloride emission sources, and existing or feasible
control technology.
1.2 SOURCE ASSESSMENT METHODOLOGY
This section describes the general methodology common to the source
assessments for the three carbon tetrachloride production processes and
CFC 11/12 production, which are presented in Chapters 3 through 6. Each
chapter includes: (1) general information on production facilities and
capacities, a process description and emission factors for a representive
model plant, for the process under consideration; (2) estimates of uncontrolled
emissions; (3) identification of existing controls, current State regulations
and Group III CTGs applicable to each plant, and estimates of Option 1
emissions based on the most stringent of these controls; (4) identification
of estimated best controls and estimation of Option 2 emissions with these
controls; and (5) estimation of control costs for each plant under Options 1
and 2. These areas are addressed individually below, followed by a brief
discussion of the uncertainties involved in emission and cost estimates.
EPA reports and other published sources provide the information on
plants, capacities and processes. Carbon tetrachloride emission factors
were taken from a draft EPA report currently undergoing external review.
These emissions factors were based on all available data, including some
emission sources which were documented for single plants. They include
1-2
-------
factors for each identified source, including process vents, process
fugitive emissions, storage, handling and secondary emissions. These
factors and the emission and cost estimates in this report are based on
representative model plants for each production process, which had been
developed in a previous EPA study. These model plants include the
elements common to documented production processes, assuming typical
feedstocks, reaction types, purification and recycle steps, as well as
typical storage facilities and process fugitive emission sources.
Emission factors were combined with production capacities of the
respective model plants to estimate uncontrolled model plant emissions
for each production process. Full-time operation was assumed to estimate
process fugitive emissions. Uncontrolled emissions from each production
process and related storage and loading were estimated from model plant
emissions by assuming that emissions are directly proportional to carbon
tetrachloride production. Emissions were adjusted to current production
levels by assuming that all plants are operating at an industry-wide
capacity utilization rate based on current national production and total
production capacity. Production capacities are available for each carbon
tetrachloride production location. Uncontrolled emissions for each
process at the three locations with more than one production process were
estimated using a typical distribution of capacities between processes
which had been assumed for model plants in previous EPA studies. Available
CFC production data consist of total CFC production capacities for each
company, and a breakdown of recent national production of individual
CFCs. Plant-specific CFC 11/12 production was estimated by assuming
uniform distribution of capacities and CFC product mixes.
Existing controls at carbon tetrachloride and CFC 11/12 plants were
identified through recent EPA surveys. Relevant State or local regulations
were summarized for each plant. When possible, existing controls,
applicability of regulations to specific plants, and appropriate control
efficiencies were confirmed through contacts with State or local agencies.
Where efficiencies for existing controls or regulations could not be
obtained from these sources, preliminary engineering analyses were used to
arrive at estimates. Existing draft Group III CTGs, related EPA documentation
1-3
-------
and contacts with responsible EPA personnel were used to determine CTG
control requirements which would be applicable to sources at carbon
tetrachloride and CFC 11/12 plants. Option 1 emissions were estimated by
applying the most stringent of these controls to estimated uncontrolled
emissions. Option 2 emissions were estimated by applying EEC to uncontrolled
emissions for each plant.
Capital and annual costs of Option 1 and 2 controls for each plant
were estimated as follows. Detailed costs were developed for each controlled
emission source at each model plant. These costs were based mainly on
existing EPA cost estimates developed for general synthetic organic
chemical manufacturing sources. In some cases, direct cost estimates were
made by performing preliminary engineering assessments of controls for
specific emission sources. Control costs for individual plants were
estimated from model plant costs by assuming that costs are directly
proportional to carbon tetrachloride or CFC 11/12 production. Emission
reductions and product recovery credits in model plant cost analyses were
derived by applying feasible control efficiencies to estimated uncontrolled
emissions for each model plant emission source to which Option 1 or
Option 2 controls apply. Since estimated model plant emissions were based
on full production capacity, the emission reductions in model plant costs
include an industry-wide capacity utilization factor. Where it was
possible to estimate control of pollutants other than carbon tetrachloride
by Option 1 and 2 controls, a separate model plant control cost analysis
considering joint control of carbon tetrachloride and these other components
is also provided. For consistency, however, model plant costs based on
recovery of carbon tetrachloride alone were used in estimation of all
plant-specific costs. The July 1982 price for carbon tetrachloride used
in computing recovery credits is $418/Mg ($0.19/lb).2 All control costs
are also in July 1982 dollars, except where noted. Costs in original
references were inflated to July 1982 using the Chemical Engineering plant
cost index. When estimation of capital and annual costs was necessary,
cost factors cited in the original cost data reference were used on the
assumption that they are more applicable than more general cost factors
from other sources.
1-4
-------
Due to the methods and data used to derive emissions and costs
described above, the estimates made in the report should be considered
preliminary. Critical assumptions are discussed below.
Use of model plant parameters did not allow consideration of variations
between different production facilities. In reality no two plants are the
same and several have been reported to vary from the model plants in ways
that may affect the accuracy of emission and control cost estimates.
Feedstocks, reaction types, purification steps, and in-plant recycle are
some of the variables that have been documented. Emission data used in
emission factor development often were obtained from single plants, and
may not apply to all production processes. The relative volume and type
of storage capacity and storage/loading throughputs and associated emissions
and costs may vary considerably from the model plant assumptions. For
example, proximity of carbon tetrachloride plants to CFC 11/12 plants can
affect the amount of carbon tetrachloride storage, loading and transportation
necessary, since transfers may be made directly by pipeline.
The accuracy of emission and cost estimates is further dependent on
assumptions regarding capacity utilization, and on the correct distribution
of production capacities at two-process carbon tetrachloride plants, at
plants producing a variety of CFCs, and between various plants for which
only company-wide total CFC capacity is known. Some of these assumptions
may not affect the accuracy of emission and control cost estimates at the
plant or national level, but the cumulative effects of individual assumptions
could not be addressed in detail.
In most cases, existing control costs were used as the basis of
estimates in this preliminary analysis. Some uncertainty is involved in
deriving carbon tetrachloride-specific costs from costs developed for
general synthetic organic chemical manufacturing sources and extrapolating
from costs for other source types. This uncertainty is due mainly to lack
of sufficient information on the emission sources, and the assumptions
which had to be made in applying existing cost estimates to the specific
cases of interest. In some cases, direct cost estimates were made by
performing preliminary engineering assessments of controls for specific
emission sources. These estimates also entail considerable uncertainty due
1-5
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to the limited technical data available and the tentative nature of the
engineering and cost analyses. In some cases, control cost estimates may
be somewhat underestimated because they were based on costs for new
equipment rather than retrofit controls. Expenses such as remote utility
connection and ducting and piping for vapor recovery and recovered product
were based on standardized installation cost factors. Site-specific
factors which would add to the estimated base control costs were neglected,
since plant-specific data which would allow explicit consideration of
these potential cost variations were not available. Thus the costs
presented should be considered rough estimates (i.e. +50 percent).
1-6
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1 .3 REFERENCES
1. Anderson, M.E., and W.H. Battye, GCA/Technology Division. Locating and
Estimating Air Emissions from Sources of Carbon Tetrachloride, Final
Draft Report. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Air Management Technology Branch,
Research Triangle Park, NC. Contract No. 68-92-3510, Work Assignment
No. 22. September 1982.
2. Current Prices of Chemicals and Related Materials. Chemical Marketing
Reporter. Schnell Publishing Co., New York, NY. July 12, 1982. p. 40.
3. Economic Indicators. Chemical Engineering, McGraw-Hill, Inc.
November 15, 1982; November 17, 1980; November 3, 1980; March 24, 1980;
November 5, 1979. Annual indexes for 1978, 1975 and 1974 taken from
citations in: R.B. Neveril, GARD, Inc., Niles IL. Capital and Operating
Costs of Selected Air Pollution Control Systems. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standard, Research
Triangle Park, NC. EPA-450/5-80-002. December 1978.
1-7
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2.0 CARBON TETRACHLORIDE PROPERTIES AND REGULATIONS
AFFECTING EMISSIONS
This chapter is divided into two sections: Section 2.1 describes
the physical properties of carbon tetrachloride; Section 2.2 presents
existing and anticipated regulations affecting emissions of carbon
tetrachloride from various sources.
2.1 PROPERTIES OF CARBON TETRACHLORIDE
Carbon tetrachloride, CCl^, is a clear, colorless, nonflammable
liquid at normal temperatures and pressures. Physical properties of
carbon tetrachloride are presented in Table 2-1.
Carbon tetrachloride is miscible with most organic solvents, but is
essentially insoluble in water. It is a powerful solvent for asphalt,
benzyl resin (polymerized benzyl chloride), bitumens, chlorinated rubber,
ethyl cellulose, fats, gums, resin, and waxes. It is relatively volatile,
with a vapor pressure of 11.94 kPa (90 mm Hg, 1.74 psi) at 20°C.
Figure 2-1 shows the vapor pressure of carbon tetrachloride as a function
of temperature in the range of available condenser control systems.
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 before dispersing
2
into the ambient air.
Carbon tetrachloride decomposes to phosgene at high temperatures.
Thermal decomposition occurs very slowly at temperatures up to 400°C
(750°F). At temperatures of 900 to 1300°C (1650 to 2370°F), extensive
dissociation occurs to form perchloroethylene, hexachloroethane and some
chlorine. Reaction of carbon tetrachloride with steam at high temperatures
results in the formation of chloromethanes, hexachloroethane, and
perchloroethylene.
-------
TABLE 2-1. PHYSICAL PROPERTIES OF CARBON TETRACHLORIDE,
Property
Value
Synonyms: Tetrachloromethane, methane tetrachloride, perch!oromethane.
benzinoform
Molecular weight
Melting point, °C
Boiling point, °C
Refractive index, 15°C
Specific gravity
20/4°C
Autoignition temperature, °C
Flash point, °C
Vapor density, air = 1
Surface tension, mN/m(=dyn/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, 20CC
Vapor, bp
Average coefficient of volume expansion,
0-40°C
Dielectric constant
Liquid, 20°C
Liquid, 50°C
Vapor, 87.6°C
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
2-2
-------
TABLE 2-1. (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
Soly of CCU in water, 25°C, g/100 g H20
Soly of water in CCU, 25°C, g/100 g CC1
-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
2-3
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soo
200
100
90
80
70
60
50
40
30
en
I
E
j:
UJ
cc
•=>
CO
CO
LJ
cc
CL
cc
o
Q_
UJ
o
cc
o
x
o
<
cc
z
O
CD
CC
20
I
J I
1 1
J I
I/T(°K) 0.0032 0.0034 0.0036 0.0038 0.0040 0.0042 0.0044 0.0046 0.0048
40
30
20
10
-10
-20
-30
-40
-50
-60
Figure 2-1. Vapor pressure of carbon tetrachloride
2-4
1,2
-------
Carbon tetrachloride is relatively stable in the atmosphere, with
various recent estimates of its atmospheric lifetime ranging from 18 to
100 years. Ultraviolet photolysis in the stratosphere has been proposed
as the dominant atmospheric removal mechanism. The major product of
this reaction is phosgene. Reaction with oxygen radicals may also
account for some removal. Due to uncertainties in overall tropospheric
levels, cumulative world emissions and removal rates, there is some
disagreement as to the existence of significant natural sources of
carbon tetrachloride. However, a number of recent studies suggest that
2
atmospheric levels can be attributed directly to anthropogenic emissions.
2.2 REGULATIONS AFFECTING EMISSIONS OF CARBON TETRACHLORIDE
Current and anticipated regulations which may affect existing
sources of carbon tetrachloride emissions include State regulations for
volatile organic compounds (VOC) and toxic substances. In addition,
there are several EPA Control Techniques Guidelines (CTGs) which will
affect carbon tetrachloride sources when adopted in areas requesting
ozone National Ambient Air Quality Standard attainment date extensions
beyond 1982. Control requirements are described individually below, and
corresponding control efficiencies are summarized in tabular form. It
should be noted that the actual applicability of a given regulation to a
specific source can be influenced by a number of variables (location,
size, type of operation, etc.) The applicability of specific regulations
to individual plants is discussed in the chapters dealing with specific
source categories.
2.2.1 Existing State Regulations
State regulations applicable to carbon tetrachloride production
facilities and processes in which carbon tetrachloride is a feedstock or
by-product are summarized in this subsection on a State-by-State basis.
Regulations applicable to the use of carbon tetrachloride as a solvent
are not included. Requirements which are not relevant to carbon tetrachloride
were also omitted, such as those applying to VOC which do not include
carbon tetrachloride (gasoline, crude oil, etc.). Detailed specifications
for floating roof VOC storage tanks were not summarized because refrigerated
2-5
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condensers are the dominant control for carbon tetrachloride. Control
efficiencies for carbon tetrachloride were either taken from the regulations
or estimated when not specified in the regulation. The applicable
definition of VOC as related to carbon tetrachloride is provided for
each State.
In cases where carbon tetrachloride is not subject to regulation
solely due to the definition of affected compounds, regulations are
cited to allow assessment of the impact of revision of the definition or
regulatory interpretation to include carbon tetrachloride.
ALABAMA
Section 6.3 of the Alabama Air Pollution Rules, Loading and Storage of VOC,
is the only regulation which applies to the Stauffer carbon tetrachloride
plant at LeMoyne, Alabama. This statute requires:
1. VOC storage tanks over 1,000 gallons must be a pressure tank
or be equipped with one of the following:
a. submerged fill pipe,
b. external or internal floating roof,
c. vapor recovery system, or
d. other equipment or means of equal efficiency.
2. Loading of tanks, trucks or trailers from terminal or bulk
storage must use the following:
a. vapor collection and disposal system, or loading system
allowing 95 percent submerged fill, or equivalent,
b. prevention of liquid drainage from the loading device,
and
c. vapor-tight and automatic-closing loading line connectors
unless hatch-loaded.
Submerged fill is the minimum requirement in both these regulations.
Since submerged fill is part of the baseline case in available emission
factors, the Alabama storage and loading regulations have been assumed
to provide no additional emission control.
2-6
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Definition: "'Volatile organic compound1 (also denoted as VOC) means
any organic compound excluding methane, ethane, 1,1,1-trichloroethane
(methyl chloroform) and trichlorotrifluoroethane with a true vapor
pressure of 1.5 psia under a storage condition."
ARKANSAS
The carbon tetrabromide plant at El Dorado is not subject to any
limits which affect carbon tetrachloride emissions.
Definition: '"Volatile Organic Compound' (VOC) means any compound of
carbon that has a vapor pressure greater than 0.1 millimeters of mercury
at standard conditions excluding carbon monoxide, carbon dioxide, carbonic
acid, metallic carbides or carbonates, and ammonium carbonates. The
term includes hydrocarbons controlled by new source standards of performance,
and by the national ambient air quality standards."
Exemptions: Methane, ethane, 1,1,1-trichloroethane, methylene chloride,
CFC-11, CFC-12, CFC-22, CFC-23, CFC-113, CFC-114, and CFC-115.
CALIFORNIA4
Bay Area Air Quality Management District (BAAQMD)
1. Regulation 8, Rule 5 - Storage of Organic Liquids requires
that organic liquid storage tanks between 260 gallons and 40,000 gallons
must be equipped with a submerged fill pipe or equivalent device. Tanks
over 40,000 gallons, other than pressure tanks, must have either an
external floating roof with secondary seal, an equivalent internal
floating roof, a vapor recovery system of 95 percent efficiency or other
control of 95 percent efficiency. See Organic Liquid definition, below.
2. Regulation 8, Rule 22 - Valves and Flanges at Chemical Plant
Complexes applies to organic compounds, and requires annual inspection
and repair or minimization of 10,000 ppm (as methane) leaks within
fifteen days, depending on whether the valve or flange is essential.
Essential valve leaks must be repaired at the next scheduled turnaround
but no longer than six months later than discovered. Any unit exceeding
75,000 ppm (as methane) must be repaired within fifteen days.
2-7
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Rule 22 is assumed to provide negligible control of fugitive emissions.
This assumption is based on coverage of only valves and flanges, with no
control of pumps or compressors, and ineffectiveness of annual as opposed
to quarterly monitoring, as shown for SOCMI valves in EPA assessment of
various monitoring intervals.
3. There are no BAAQMD rules for loading or process controls
which would apply to carbon tetrachloride.
Definitions: Organic Liquids (Regulation 8. Rule 1): "All organic
compounds containing hydrogen and which would exist as liquids at actual
conditions of use or storage." Since carbon tetrachloride does not
contain hydrogen, Rule 5, above, would not apply to carbon tetrachloride
storage tanks.
Organic Compound (Regulation 8, Rule 22): "Any compound of
carbon (excluding carbon monoxide, carbon dioxide, carbonic acid, metallic
carbides or carbonates, ammonium carbonate and methane). If the person
responsible for an emission of organic compounds can demonstrate that
the emission contains ethane and the emission would not be in violation
of the requirements of this Rule if the ethane were not present, then
that emission shall not be considered a violation of this Rule."
South Coast Air Quality Management District
The Allied CFC plant at El Segundo must meet the following requirements:
1. Rule 463 - Storage of Organic Liquids requires tanks over
39,630 gallons to be pressure tanks or be equipped with one of the
following:
a. an external floating roof,
b. a fixed roof with internal-floating-type cover,
c. a vapor recovery system with 95 percent control efficiency,
or
d. other equipment with 95 percent control efficiency.
2. Rule 466 - Pumps and Compressors requires seals or other
devices of equal efficiency, maintained to prevent: (a) leakage of more
2-8
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than three drops per minute, (b) visible liquid mist or vapor and (c) any
visible indication of leakage at or near the shaft/seal interface of gas
compressors. Pumps and compressors leaking over 10,000 ppm VOC must be
repaired or replaced at the next scheduled process turnaround, with
interim requirements depending on availability of operable spare units.
Visual inspections are required daily, once every 8 hours for units
within 3 miles of a continuously manned control center. Hydrocarbon
detection instrument inspections are required annually for pumps, and
quarterly for compressors. Exemptions include units which have drivers
with less than one horsepower, which operate over 260°C, which are
vented to an emission control system, which handle liquids or gases with
VOC content of 20 percent or less, and which have dual seals.
Rule 466.1 - Valves and Flanges requires annual inspection of
valves and flanges at chemical plants, repair of leaks exceeding three
drops per minute of liquid VOC or 10,000 ppm of gaseous VOC, and re-inspection
of valves after repair. Valves at the ends of open-ended lines must be
sealed with a blind flange, plug, or cap when not in use, except for
sampling lines, safety valves and bleeder valves in double block and
bleeder valve systems.
Rule 467 - Safety Relief Valves prohibits use of safety pressure
relief valves at pressures over 776 mm Hg absolute pressure, unless the
valve is vented to a vapor recovery or disposal system, protected by a
rupture disk, or maintained by an approved inspection system.
Rules 466, 466.1, and 467 are essentially equivalent to the SOCMI
fugitive CTG, discussed in 2.2.2, which is estimated to provide about
42 percent control of fugitive emissions.
Definition: "Volatile Organic Compounds are compounds of carbon, excluding
carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or
carbonates, ammonium carbonate, ethane, methane, 1,1,1-trichloroethane,
methylene chloride, and trichlorotrifluoroethane, that have a Reid vapor
pressure (RVP) greater than 80 mm Hg (1.55 pounds per square inch), or
an absolute vapor pressure (AVP) greater than 36 mm Hg (0.7 psi) at
20°C."
2-9
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ILLINOIS
Rule 205 (Organic Material Emission Standards and Limitations)
includes the following regulations which would apply to any relevant
carbon tetrachloride sources.
1. Storage: Tanks for volatile organic material (VOM) over
40,000 gallons must be a pressure tank or be equipped with:
a. a floating roof,
b. a vapor recovery system capable of 85 percent collection
of VOM and a disposal system which prevents further
emission to the atmosphere, or
c. equipment or means of equal efficiency.
2. Loading:
a. Facilities loading greater than 40,000 gallons per day
into trucks or trailers must use submerged loading or
equally effective control. Otherwise, emissions must be
restricted to less than 8 pounds per hour.
b. Loading into stationary tanks over 250 gallons must be
done with a permanent submerged loading pipe or equivalent,
unless it is a pressure tank or a vapor recovery system
is used.
Since submerged loading is part of the baseline case in available emission
factors, these loading requirements are assumed to provide no additional
control.
3. Pumps and Compressors: No unit may discharge over two cubic
inches of liquid VOM in any 15-minute period. This is equivalent to
standard industry practice, and provides no additional emission control.
4. Waste Gas Disposal: Any waste gas stream from any petroleum or
petrochemical manufacturing process must be limited to 100 ppm equivalent
methane. Alternatively, existing sources (as of January 1, 1977) can
elect to comply with the limits cited for use of organic material, which
prohibit discharge of more than 8 pounds of organic material per hour
unless emissions are controlled by a system with 85 percent efficiency.
2-10
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Definitions: "Organic Material: Any chemical compound of carbon including
diluents and thinners which are liquids at standard conditions and which
are used as dissolvers, viscosity reducers or cleaning agents, but
excluding methane, carbon monoxide, carbonic acid, metallic carbonic
acid, metallic carbide, metallic carbonates, and ammonium carbonate."
"Organic Vapor: Gaseous phase of an organic material or a mixture
of organic materials present in the atmosphere."
KANSAS
VOC regulations in Kansas apply only to surface coating, gasoline
and other petroleum liquids and cutback asphalt.
Definition: "Volatile organic compounds (VOC) means any carbon compound
having a vapor pressure greater than 0.1 mm of mercury at standard
conditions excluding carbon monoxide, carbon dioxide, carbonic acid,
metallic carbides or carbonates, and ammonium carbonate. For the purposes
of the regulation, methane; ethane; methylene chloride; 1,1,1-trichloroethane
(methyl chloroform) and trichlorotrifluoroethane (fluorocarbon 113)
shall not be considered to be volatile organic compounds."
KENTUCKY
Kentucky's existing source regulations for VOC storage and loading
apply only to "petroleum liquids" and/or gasoline, and do not cover
carbon tetrachloride. Regulations for existing process gas streams only
cover hydrogen sulfide, sulfur dioxide and carbon monoxide.
Definition: Existing source VOC regulations in Kentucky use the following
definition: '"Volatile organic compounds' means chemical compounds of
carbon (excluding methane, ethane, carbon monoxide, carbon dioxide,
carbonic acid, metallic carbides, and ammonium carbonate) which have a
vapor pressure greater than one-tenth (0.1) mm Hg at conditions of
twenty (20) degrees Celsius and 760 mm Hg."
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LOUISIANA
Although carbon tetrachloride is not covered by the Louisiana
definition of VOC, given below, the State agency considers sources of
carbon tetrachloride in Louisiana to be subject to their VOC regulations,
which include the following requirements:
1. VOC storage tanks over 40,000 gallons which are not pressure
tanks must have a submerged fill pipe and one of the following controls:
a. internal or external floating roof,
b. a vapor loss control system equivalent to floating roof, or
c. other equivalent equipment or means.
This is assumed to be equivalent to the Group III CTG for VOL
storage, which gives 95 percent control (see 2.2.2).
2. VOC storage tanks between 250 and 40,000 gallons must have one
of the following controls:
a. submerged fill pipe,
b. vapor recovery system, or
c. other equivalent equipment or means.
This is equivalent to standard industry practice, providing no
additional control.
3. VOC loading facilities with daily throughput of 40,000 gallons
or more must have vapor collection and disposal, or an equivalent, and
spill prevention for the filling equipment. Barge and ship loading is
exempt. The State agency interprets and enforces this regulation as a
90 percent control .requirement.
4. Pumps, compressors, valves, etc. must be equipped with mechanical
seals or equivalent equipment or means. Best practical housekeeping and
maintenance practices are also required. This is equivalent to standard
industry practice.
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5. Halogenated hydrocarbon waste gases must be burned and their
combustion products controlled to an acceptable level (not specified).
Other methods of control may be substituted, such as carbon adsorption,
refrigeration, catalytic and/or thermal reaction, secondary steam stripping,
recycling or vapor recovery system. This requirement can be waived for
sources less than 100 tons per year, for gases which will not support
combustion or if disposal cannot be accomplished without causing economic
hardship. As discussed in 2.2.2, below, thermal oxidation is generally
capable of 98 percent control, or 20 ppmv, whichever is more stringent.
The other permitted substitutes are generally not capable of control at
this level, however, and specific acceptable level of control would
depend on the characteristics of the emissions in question.
Definition: "Any compound containing carbon and hydrogen or containing
carbon and hydrogen in combination with any other element which has a
vapor pressure of 1.5 pounds per square inch absolute (77.6 millimeters
of mercury) or greater under actual flow or storage conditions."
Exemptions: Methane, ethane, 1,1,1-trichloroethane (methyl chloroform),
methylene chloride, dichlorodifluoromethane, chlorodifluoromethane,
trifluoromethane, dichlorotetrafluoroethane, trichlorotrifluoroethane,
chloropentaf1uoroethane.
MICHIGAN
Part 6 of Michigan's air pollution control rules includes the
following controls which would apply to storage or loading of carbon
tetrachloride.
1. R336.1604 Storage of Organic Compounds requires storage tanks
over 40,000 gallons to be pressure tanks, or have either
a. a floating roof, or
b. a vapor recovery system, or equivalent, with 90 percent
control efficiency.
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2. R336.1609 Loading Existing Delivery Vessels with Organic Compounds
requires that all loading facilities handling over 5,000,000 gallons per
year have:
a. submerged loading for facilities outside of ozone
nonattainment areas,
b. vapor recovery such that emissions are less than 0.7 pounds
of organic vapor per 1000 gallons of organic compounds
loaded, in nonattainment areas.
Delivery vessels (tank trucks, trailers, railroad tank cars or any
similar vessel) loaded at facilities subject to (b), above, must be
equipped with vapor collection system interlocks, drainage prevention,
and vapor-tight fittings.
Submerged loading provides no control over the baseline case in
uncontrolled emission factors. The vapor recovery requirement in (b)
would result in approximately 80 percent control over the estimated
0.24 kg/Mg emission factor for handling at carbon tetrachloride production
facilities, presented in Tables 3-2, 4-1 and 5-1.
Definition: "Volatile organic compound means any compound of carbon or
mixture of such compounds, excluding carbon monoxide, carbon dioxide,
carbonic acid, metallic carbides or carbonates, boron carbide, silicon
carbide, ammonium carbonate, ammonium bicarbonate, methane, and ethane,
that has a vapor pressure of more than 0.1 millimeters of mercury at
standard conditions."
NEW JERSEY
New Jersey volatile substances rules include the following requirements
which would apply to storage and loading of carbon tetrachloride.
1 • 7:27-16.2 Storage of Volatile Organic Substances requires that
carbon tetrachloride storage tanks over 300,000 gallons be controlled
with an external or internal floating roof with at least one tight seal.
The minimum affected tank size is based on the vapor pressure of the VOS
stored. For these tanks, control is estimated to be 95 percent, equivalent
to the VOL storage CTG, discussed in 2.2.2.
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2. 7.27-16.3 Transfer Operations requires submerged filling or
equivalent control in transfer of volatile organic substances into any
vessel over 2,000 gallons (marine vessels exempted). This provides no
additional emission control over the assumed baseline.
3. 7:27-16.6 Source Operations other than Storage Tanks. Transfers,
etc.. (a) establishes a sliding scale for control of VOS emissions not
controlled by other rules. This scale is based on the concentration and
vapor pressure of the VOS, and the effective control required or possible
exclusion for low emission rates must be based on data for the specific
source in question.
Paragraph (d) of this section prohibits leakage of VOS from flanges,
manholes, and other non-moving joints and fittings. Paragraph (e)
prohibits leakage from valves, pumps, and compressors resulting in
concentration over 10,000 ppm by volume measured at 1 centimeter, or if
emissions are in the liquid state. Since these paragraphs do not specify
inspection intervals and repair requirements, it is assumed that their
effective control of fugitive emissions is marginal (0 percent).
Definition: "Volatile organic substances, herein abbreviated as VOS,
means any organic substances, mixture of organic substances, or mixture
of organic and inorganic substances including, but not limited to petroleum
crudes, petroleum fractions, petrochemicals, solvents, diluents, and
thinners which have vapor pressures or sums of partial pressures of
organic substances of 0.02 pounds per square inch (1 millimeter of
mercury) absolute or greater measured at standard conditions; and, in
the case of surface coating formulations, includes any coalescing or
other agent, regardless of vapor pressure, which evaporates from the
coating during the drying phase; but does not include methane, trichloro-
fluoromethane, dichlorodifluoromethane, chlorodifluoromethane, trifluoro-
methane, 1,1,2-trichloro-l ,2,2-trifluoroethane, 1,2-dichloro-l,1,2,2-
tetrafluoroethane, and chloropentafluoroethane."
New Jersey toxic substances rules (NJAC 7:37-17) require registration
of carbon tetrachloride emissions and control "at a rate or concentration
equivalent to advances in the art of control" for the type of emission
2-15
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involved. Discharge of toxic volatile organic substances (including
carbon tetrachloride) must be no less than 40 feet above grade, 20 feet
above areas of human use or occupancy and directed upward at a velocity
of 3,600 feet per minute or greater. Emissions of less than 0.1 pounds
per hour are exempt. Control efficiencies under these rules are determined
on a case-by-case basis, depending on the characteristics of each affected
source.
These rules apply to the following "toxic volatile organic substances."
Benzene (Benzol)
Carbon tetrachloride (Tetrachloromethane)
Chloroform (Trichloromethane)
Dioxane (1 ,4-Diethylene dioxide)
Ethylenimine (Aziridine)
Ethylene dibromide (1 ,2-Dibromethane)
Ethylene dichloride (1,2-Dichloroethane)
1 ,1 ,2,2-Tetrachloroethane (sym Tetrachloroethane)
Tetrachloroethylene (Perch!oroethylene)
1 ,1 ,2-Trichloroethane (Vinyl trichloride)
Trichloroethylene (Trichloroethene)
NEW YORK
Part 212 of the New York State Pollution Control Regulations applies
to processes and exhaust and/or ventilation systems not regulated by
other specific rules. Application of this rule requires an "environmental
rating" of the pollutant involved, which is issued when a permit is
applied for. Depending on this rating and the emission rate potential
of the source, a look-up table provides the degree of control required.
Regulations do not exist for VOC emissions from fugitive SOCMI sources,
storage, or loading.
Definition: "Volatile Organic Compound (VOC). Any compound of carbon
excluding carbon monoxide, carbon.dioxide, carbonic acid, metallic
carbides or carbonates, and ammonium carbonate, that has a vapor pressure
greater than 0.10 mm (0.0039 inches) of Hg at a temperature of 20°C
(68°F and a pressure of 760 mm (30 inches) of Hg."
2-16
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New York's toxic pollutant control scheme is based on a policy
document ("Air Guide 1"), which serves as guidance to the State agency's
regional offices in their regular permit review process. This policy
has not been made part of the New York State Pollution Control Regulations,
It establishes three toxicity categories with varying control requirements,
Carbon tetrachloride is in the "high toxicity" category, which requires
best available control technology for sources emitting over 1 pound per
hour. In addition, 0.0167 ppm is used as an acceptable ambient limit,
based on modeling of the ambient concentration attributable to the source.
This number is derived by dividing the ACGIH Threshold Limit Value (TLV)
7 8
of 5 ppm by a safety factor of 300. ' Since determination of best
available control technology is source-dependent, generalized estimates
of control efficiencies are not possible under Air Guide 1.
TEXAS
Texas has two sets of VOC regulations which apply in attainment/
unclassified counties and nonattainment counties, respectively. For
sources related to carbon tetrachloride, requirements for VOC loading
and unloading and for VOC vent gas streams are the same in all counties,
and only VOC storage requirements differ, as described separately below.
The following definitions apply throughout.
Definitions: "Vapor Recovery System. Any control system that reduces
volatile organic compounds (VOC) emissions such that the aggregate
partial pressure of all VOC vapors will not exceed a level of 1.5 psia
(10.3 kPa) or other emission limits specified in Chapter 115 of this
title (relating to Volatile Organic Compounds)."
"Volatile Organic Compound (VOC). Any compound of carbon or mixture
of carbon compounds, excluding methane, ethane, methyl chloroform,
Freon 113, carbon monoxide, carbon dioxide, carbonic acid, metallic
carbides or carbonates, and ammonium carbonate."
1. VOC Vent Gas Streams: VOC vent gas stream control requirements
do not include carbon tetrachloride in the list of affected compounds
and classes of compounds, but the list does include ethylene and other
2-17
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compounds which may occur in vent gases from some carbon tetrachloride
production processes and processes involving carbon tetrachloride as a
byproduct. In Texas nonattainment counties, ethylene dichloride processes
appear to be the only relevant sources. Vent gases must be "properly
burned at a temperature equal to or greater than 704°C (1300°F) in a
smokeless flare or a direct-flare incinerator," or controlled by approved
alternate means. Sources emitting less than 100 Ibs/day of combined
affected VOC or less than 250 Ibs/hr of a combined VOC with vapor pressure
less than 0.44 psia are exempt. Control efficiencies must be estimated
on a case-by-case basis due to variability in vent stream combustibility.
Compounds regulated under this rule include: ethylene, butadiene,
isobutylene, styrene, isoprene, propylene, alpha-methyl-styrene, aldehydes,
alcohols, aromatics, ethers, olefins, peroxides, amines, acids, esters,
ketones, sulfides, and branched chain hydrocarbons (C8 and above).
2. VOC Loading and Unloading: VOC loading and unloading facilities
with average throughputs of 20,000 gallons or more per day must have a
vapor recovery system, vapor-tight seal, and drainage control (ship and
barge loading facilities are exempt).
3. VOC Storage in Attainment/Unclassified Counties: The following
requirements apply to the DuPont plant at Corpus Christi, which is
actually in Ingleside, San Patricio County. Sources there include
production of carbon tetrachloride and chlorofluorocarbons. All other
carbon tetrachloride sources under consideration are covered by the
storage rules for nonattainment counties, below.
a. VOC storage tanks over 25,000 gallons must be a pressure tank
or be equipped with an internal or external floating roof, or
a vapor recovery system.
b. VOC storage tanks over 1,000 gallons must be a pressure tank
or be equipped with a submerged fill pipe or vapor recovery
system.
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4. VOC Storage in Nonattainment Counties: The following storage
regulations apply to VOCs in the vapor pressure range of carbon tetrachloride
and related halogenated compounds unless stored in pressurized tanks.
a. VOC storage tanks between 1,000 and 25,000 gallons must have a
submerged fill pipe.
b. VOC storage tanks between 25,000 gallons and 42,000 gallons
must have an internal or external floating roof (any type) or
a vapor recovery system.
c. VOC storage tanks over 42,000 gallons must have either an
internal floating roof, external floating roof with vapor-
mounted primary seal and secondary seal, or a vapor recovery
system.
It is estimated that the storage and loading controls cited above will
provide about 50 percent control of carbon tetrachloride emissions.
This estimate is based on the 1.5 psi vapor pressure requirement for
vapor recovery systems, the vapor pressure reduction necessary to meet
this requirement from an ambient temperature of 30°C (86°F) and vapor
pressure of 2.9 psi, and an assumed control proportional to vapor pressure
reduction.
WEST VIRGINIA
There are no regulations that apply to sources of carbon tetrachloride
in West Virginia.
SUMMARY
Table 2-2 provides a summary of existing State regulations for VOC
which apply to carbon tetrachloride sources. Cited control efficiencies
and control requirements which can not be assigned specific control
efficiencies are discussed in the state-by-state listings, above. This
tabulation for VOC does not include the toxics regulations for New Jersey
and New York, described above, which are currently in the process of
implementation. The New Jersey regulation requires control "at a rate or
concentration equivalent to advances in the art of control," and specifies
height and velocity of discharges. New York requires best available
control technology and modeling of acceptable source attributed ambient
levels. For carbon tetrachloride the acceptable level is 0.0167 ppm.
2-19
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TABLE 2-2. ESTIMATED CONTROL EFFICIENCIES FOR STATE
VOC REGULATIONS
State
Alabama
Arkansas
California
Bay Area
South Coast
111 i no is
Kansas
Kentucky
Louisiana
Michigan
New Jersey
New York
Texas
Attainment/
Unclassified
Nonattainment
West Virginia
Process
NR
NR
NR
NR
NE
NR
NR
NS
NR
NE
NE
NE
NE
NR
Control efficienci
Fugitive
NR
NR
0
42
0
NR
NR
0
NR
0
NR
NR
NR
NR
es (percent)
Storage
0
NR
95a
95a
85
NR
NR
95a
90a
95b
NR
50
50
NR
Loading
0
NR
NR
NR
0
NR
NR
90
NE
0
NR
50
50
NR
a_ .n nrtn ,, ,, , , i • -ui i
Tanks over 300,000 gallons only. Smaller tanks have negligible control.
NE = No typical control efficiency can be assumed, source-specific
determination necessary. See text for specific requirements.
NR = No regulation applicable to carbon tetrachloride emissions.
NS = Level of control not specified.
0 = Regulation equivalent to no control. These typically represent
standard operating practice or the baseline case in emission
factor development.
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2.2.2 Group III Control Techniques Guidelines
It is anticipated that ozone nonattainment areas which have received
extensions beyond 1982 will be required to adopt all Group III CTGs.
These CTGs were therefore reviewed for applicability to known sources of
carbon tetrachloride. Two Group III CTGs (covering volatile organic
liquid storage and fugitive emissions from synthetic organic chemical,
polymer and resin manufacturing) would apply to operations in post-1982
attainment-date areas which store carbon tetrachloride, use it as a
feedstock, or produce it as a principal product, co-product, by-product
or intermediate. The requirements and anticipated control efficiencies
of these CTGs are discussed individually below.
The Group III CTG for control of VOC emissions from air oxidation
processes in the synthetic organic chemical manufacturing industry also
applies to one potential by-product source of carbon tetrachloride, the
production of ethylene dichloride by oxychlorination. While it does not
apply to the current source assessments, it is discussed below for
possible future reference.
n
Volatile Organic Liquid (VOL) Storage
The June 1981 draft CTG for VOL storage applies to fixed-roof and
floating roof storage tanks with capacities of 40,000 gallons or more
which store VOL with vapor pressure of 1.5 psia or greater at storage
conditions. The principal controls discussed and analyzed in the CTG
are internal and external floating roofs. Add-on vapor control systems
for fixed-roof tanks are also mentioned as alternate control techniques,
including those using carbon adsorption, refrigerated vent condensers,
absorbers and oxidation units for recovery or destruction of the VOC.
Of these choices, refrigerated condensers appear to be the most likely
choice for control of carbon tetrachloride storage. As indicated in
Chapters 3, 4, and 5, refrigerated condensers are the only storage
control known to be currently in use at carbon tetrachloride production
plants. There is apparently one floating roof in use at a chlorofluorocarbon
2-21
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production plant. Industry sources have indicated that floating roofs
are not recommended for carbon tetrachloride service due to its tendency
to degrade floating roof seal components.
The reasonably available control technique (RACT) requirement in
this CTG is based on equipment specifications rather than a specific
control efficiency, which complicates estimation of a control effectiveness.
The June 1981 draft CTG cites control efficiencies of 93 to 98 percent
for the various floating roofs which would qualify as RACT in that
draft.12 For the purposes of this analysis, it is assumed that 95 percent
control will be acceptable for equivalency to RACT. This level of
control appears achievable with refrigerated condensers of adequate
design and cooling capacity. For example, Dow Chemical permit applications
and 114 letter responses both indicate 95 percent control of carbon
tetrachloride storage emissions at Freeport, Texas, with refrigerated
condensers operating at -20°C outlet temperatures. A feasible control
range of 90 to 95 percent for carbon tetrachloride, with this outlet
temperature, is also supported by the assessment of refrigerated condensers
for SOCMI storage performed by IT Enviroscience.
VOC Fugitive Emissions
The August 1981 draft CTG for VOC fugitive emissions from synthetic
organic chemical, polymer and resin manufacturing equipment applies to
pumps, compressors, in-line process valves, pressure relief devices,
open-ended valves, sampling connections, flanges, agitators and cooling
towers. RACT would consist of a quarterly leak detection and repair
program and capping of open-ended lines. Some alternative control
strategies would be possible for valves only, including an "allowable
percentage of valves leaking" approach and skip-period monitoring. RACT
is estimated to achieve an overall emission reduction of 42 percent for
all model units. Exemptions would be provided for unsafe and difficult-
to-reach components, and for plants producing less than 1,000 Mg per year
of any of the SOCMI chemicals listed in Appendix B of the CTG.16'17 It
is not expected that these exemptions will have a significant effect on
CTG emission reductions at carbon tetrachloride plants or chlorofluorocarbon
production facilities.
2-22
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1 o
VOC Emissions from Air Oxidation
The June 1981 draft CTG for VOC emissions from SOCMI air oxidation
applies to production of a total of 36 chemicals by air oxidation. Of
these, only production of ethylene dichloride (1,2-dichloroethane) is
19
known to result in a small percentage of by-product carbon tetrachloride.
The CTG considers thermal oxidation the only universally-applicable
control technique for air oxidation processes, but cites both thermal
oxidation and catalytic incineration as being used on one or more ethylene
dichloride production processes. Condensation and absorption are also
cited as being in use for product or raw material recovery at ethylene
dichloride plants. RACT is based on thermal oxidation, at a control
efficiency of 98 percent or 20 ppmv exit concentration, whichever is less
stringent, for all streams having a total resource-effectivness (TRE)
index value of less than 2.9. (TRE is a measure of the supplemental
total resource requirement per unit VOC reduction by thermal incineration,
including supplemental fuel, capital, labor, electricity, and water and
caustic for control of offgas containing halogenated compounds.)
2-23
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2.3 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. Environment Reporter. Bureau of National Affairs, Inc., Washington,
DC, June 1982. All State regulations were summarized from the
Environment Reporter, except those for California.
4. California regulations were obtained directly from the California
Air Resources Board and the South Coast Air Quality Management
District in June 1982.
5. Fugitive Emission Sources of Organic Compounds--Additona1 Information
on Emissions, Emission Reductions and Costs. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Research Triangle Park, NC. EPA-450/3-82-010, April 1982, p. 4-43.
6. Killeen, N., Louisiana Air Quality Division, Baton Rouge, LA. Personnel
communication with M.G. Smith, GCA. January 21, 1983.
7. Marriott, T., New York Division of Air, Avon, NY. Personal
communication with M.G. Smith, GCA, January 20, 1983.
8. Study of Selected State and Local Air Toxics Control Strategies.
U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards, Research Triangle Park, N.C. EPA 450/5-82-006.
p. 11-109.
9. Control of Volatile Organic Compound Emissions from Volatile Organic
Liquid Storage in Floating and Fixed Roof Tanks - Draft. U.S.
Environmental Protection Agency, Office of Air Quality Planning
and Standards, Research Triangle Park, NC. June 1981.
10. Smith, D.W., E.I. duPont deNemours and Co., Wilmington, DE. Letter
to D.R. Goodwin, EPA, June 7, 1978.
11. Robinson, T.A., Vulcan Materials Co., Wichita, KS. Letter to
D.R. Patrick, EPA, July 9, 1979.
12. Reference 9, p. 4-2.
2-24
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13. Tippitt, W., EPA. Memo to Robert Rosensteel, EPA, February 5, 1982.
14. Beale, J., Dow Chemical USA, Midland, MI. Letter to L. Evans, EPA,
April 28, 1978.
15. Organic Chemical Manufacturing Volume 3: Storage, Fugitive and
Secondary Sources. U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-25. December 1980. Report 1, p. IV-18.
16. Control of Volatile Organic Compound Fugitive Emissions from Synthetic
Organic Chemical, Polymer and Resin Manufacturing Equipment—Draft.
U.S. Environmental Protection Agency, Office of Air Quality Planning
Standards, Research Triangle Park, NC. August 1981.
17. Hustvedt, K.C., EPA. Personal communication with M.G. Smith,
GCA/Technology Division, January 27, 1983.
18. Control of Volatile Organic Compound Emissions from Air Oxidation
Processes in Synthetic Organic Chemical Manufacturing Industry--
Preliminary Draft. U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards, Research Triangle Park, NC.
June 1981.
19. M.E. Anderson and W.H. Battye, GCA/Technology Division, Locating and
Estimating Air Emissions from Sources of Carbon Tetrachloride—Draft.
U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards, Air Management Technology Branch, Research Triangle
Park, NC. Contract No. 68-02-3510, Work Assignment No. 22,
September 1982. p. 59.
20. Mascone, D.C., EPA. Memos to J.R. Farmer, EPA. June 11, 1980 and
July 22, 1980.
2-25
-------
3.0 CARBON TETRACHLORIDE PRODUCTION WITH PERCHLOROETHYLENE CO-PRODUCT
This chapter discusses plants which co-produce carbon tetrachloride
and perch!oroethylene, by chlorinolysis or chlorination of hydrocarbon
feedstocks. A brief process description is followed by estimates of
uncontrolled emissions, Option 1 and Option 2 controlled emissions, and
associated control costs. A number of plants manufacture carbon
tetrachloride by the perchloroethylere co-product process as well as by
the methane chlorination process (which is discussed in Chapter 4).
This chapter addresses a number of assumptions and related information
which apply to the analysis of both processes. It has been assumed that
there will be joint facilities for storage of carbon tetrachloride at
these two-process plants. Total storage control costs are estimated in
this chapter, but assessment of the related emissions is divided between
this chapter and Chapter 4.
3.1. PERCHLOROETHYLENE CO-PRODUCT PROCESS DESCRIPTION
3.1.1 General Information
Table 3-1 lists names, locations, production capacities, and production
processes for the nine carbon tetrachloride production facilities in the
U.S. Over half of the total national carbon tetrachloride production
capacity is at plants using only the perch!oroethylene co-product process
(252,000 Mg/yr). An uncertain additional production by the perch!oroethylene
co-product process is included in the 124,000 Mg/yr total production
capacity for plants which also use methane chlorination, but production
statistics do not include the division of capacity between the two
processes at these plants.
3.1.2 Process Description
At most plants, carbon tetrachloride and perchloroethylene are
produced as co-products by high-temperature chlorinolysis of a variety
3-1
-------
TABLE 3-1. CARBON TETRACHLORIDE PRODUCERS
Plant
number
Company
Location
Carbon tetrachloride
production
capacity
(Mg/yr)
Production
processes
CO
I
ro
1
2
3
4
Linden Chlorine
Stauffer
Stauffer
Dow
Vulcan
Dow
DuPont
Vulcan
Dow
Moundsville, WV
LeMoyne, AL
Louisville, KY
Plaquemine, LA
Geismar, LA
Freeport, TX
Ingleside, TX
Wichita, KS
Pittsburg, CA
4,000
91,000
7,000
57,000
41,000
61,000
154,000
27,000
36,000
478,000
Methane chlorination
Carbon disulfide
chlorination
Methane chlorination
Mixed hydrocarbon chlor-
inolysis with perchloro-
ethylene co-product
Mixed hydrocarbon chlor-
inolysis with perchloro-
ethylene co-product
Methane chlorination and
mixed hydrocarbon
chlorinolysis with per-
ch! oroethylene co-product
Methane and ethylene
chlorination with per- ^
chloroethylene co-product
Methane chlorination and
mixed hydrocarbon
chlorinolysis with per-
ch! oroethylene co-product
Methane chlorination and
mixed hydrocarbon chlor-
inolysis with perch!oro-
ethylene co-product
-------
of hydrocarbon feedstocks. Removal and absorption of chlorine and
hydrogen chloride and distillation of the two co-products are the other
basic process steps. A typical process flow diagram for the perchloroethylene
co-product process is shown in Figure 3-1. Feedstocks may include crude
carbon tetrachloride, ethylene dichloride, acetylene, ethylene, propylene,
napthalene, and paraffinic hydrocarbons of up to four carbons. Major
feedstocks for each perchloroethylene co-product plant are indicated on
Table 3-1. The relative amounts of carbon tetrachloride and perchloroethylene
produced are dependent on the feedstock and reaction conditions. The
largest plant producing carbon tetrachloride (Plant 7, DuPont at Ingleside,
Texas) produces perchloroethylene as a co-product but does not use
hydrocarbon chlorinolysis. The process used at the plant is based on
2 3
chlorination of methane and ethylene feedstocks. Since this process
is similar to hydrocarbon chlorinolysis, and produces both carbon tetrachloride
and perchloroethylene, it has been grouped with hydrocarbon chlorinolysis
processes in this report.
3.1.3 Carbon Tetrachloride Emission Factors for the Perchloroethylene
Co-Product Process
Table 3-2 gives estimated emission factors for the carbon tetrachloride
7 8
emission points identified in Figure 3-1. Existing emission factors '
were reviewed, resulting in revision of the factor for waste caustic
emissions as follows. The IT Enviroscience emission factor for waste
caustic (0.15 kg VOC/Mg plant capacity) was based on an average of two
o
emissions which were very different in magnitude and description. One
estimate was specific to waste caustic (0.0011 kg VOC/Mg), while the
q
other was for total VOC in plant aqueous waste discharges (0.3 kg VOC/Mg).
The original reference indicates that the second figure was actually
based on an estimate of total organic carbon in wastewater. Total
organic carbon is a parameter used in wastewater engineering which, when
properly measured, involves acidification and aeration prior to measurement
of organic carbon. Correct procedure will result in loss of volatile
organics, including carbon tetrachloride, prior to measurement. This
was considered sufficient reason to drop the latter estimate, and the
3-3
-------
OJ
I
CHLORINOLYSIS
REACTOR
CARBON TETRACHLORIDE
FROM METHANOL
HYDROCHLORINATION
HCI SCI,
REMOVAL
COLUMN
AND METHYLCHLORIDE
CHLORINATION PROCESS
CRUDE CARBON
STORAGE TETRACHLORIDE
DISTILLATIi
o:
CARBON
TETRACHLORIDE
STORAGE
DISPOSAL
PERCHLOROETHYLENE
DISTILLATION
LOADING
PERCHLORO-
ETHYLENE
STORAGE
CHLORINE
ABSORPTION
COLUMN
BY-PRODUCT
HCI
STORAGE
NOTE: Letters in this figure refer to process vents
described 1n the text and tables. Numbers refer
to process descriptions in the first reference
cited below. Heavy lines Indicate final product
streams throughout the process.
Figure 3-1. Process flow diagram for hydrocarbon chlorinolysis process.
4,5
-------
TABLE 3-2. UNCONTROLLED MODEL PLANT CARBON TETRACHLORIDE EMISSION
FACTORS FOR HYDROCARBON CHLORINOLYSIS (PERCHLOROETHYLENE
CO-PRODUCT) PROCESS
Uncontrolled
carbon
tetrachloride
Emission Source emission
source designation factor^3
Distillation columns A 0.0058 kg/Mg
Process fugitive0 3.2 kg/hr
Storage B 0.85 kg/Mg
Handling C 0.24 kg/Mg
Hex waste handling and D 0.0046 kg/Mg
disposal and waste
hydrocarbon storage
Waste caustic E <0.003 kg/Mg
Source designation shown in Figure 3-1. A is a process component; D
and E are secondary emissions.
Emission factors in terms of kg/Mg refer to kg of carbon tetrachloride
emitted per Mg of carbon tetrachloride produced. From Reference 7,
except Source E, as described in text.
cFugitive emission rate is independent of production rate.
3-5
-------
first (0.0011 kg VOC/Mg total plant capacity) was adjusted to reflect
the 37.5 percent of total model plant capacity attributed to carbon
tetrachloride. The resulting emission factor (0.003 kg VOC/Mg carbon
tetrachloride production) was used as an upper bound to potential carbon
tetrachloride emissions from waste caustic, because no information was
available on the VOC composition.
3.2 UNCONTROLLED PERCHLOROETHYLENE CO-PRODUCT PLANT EMISSIONS
A number of preliminary steps were required to allow estimation of
uncontrolled carbon tetrachloride emissions from individual production
facilities, and also to facilitate later estimates of controlled emissions
and control costs for Options 1 and 2. These include use of model
plants, apportionment of production capacity to specific production
processes, and development of an industry-wide capacity utilization
rate. These steps are discussed below, and then uncontrolled emissions
for perchloroethylene co-product plants are estimated.
3.2.1 Model Plant
A representative model plant was used as the basis for emission and
control cost estimates. The model plant for the perchloroethylene
co-product process was chosen to be consistent with those used in previous
investigations. ' It was assumed to produce 50,000 Mg/yr of perchloroethylene
and 30,000 Mg/yr of carbon tetrachloride. This basic model plant configuration
is shown in Figure 3-1. More detail on model plant fugitive emission
sources and storage and loading facilities is provided in conjunction
with cost estimates in Section 3.5.
It should be noted that use of model plant parameters did not allow
consideration of variations between different carbon tetrachloride
production facilities. In reality no two processes are the same and
several have been reported to vary from the model plants in ways that
may affect the accuracy of emission and control cost estimates. Feedstocks,
reaction types, purification steps, and in-plant recycle are some of the
1 ?
variables documented by IT Enviroscience. Emission data used in
emission factor development were often obtained from single plants and
may not apply to all production processes. The relative volume and type
3-6
-------
of storage capacity and storage/loading throughputs and associated
emissions and costs may vary considerably from the model plant assumptions.
For example, proximity to end-use fluorocarbon production facilities
will affect the amount of carbon tetrachloride product storage and
transportation necessary, since some transfers may be made directly by
pipeline.
3.2.2 Capacity Apportionment in Two-Process Plants
Plants 6, 8 and 9 (Dow at Freeport, Texas; Vulcan at Wichita,
Kansas; and Dow at Pittsburg, California) produce carbon tetrachloride
by two processes (methane chlorination and perchloroethylene co-product),
but no information is available on the relative contributions of these
processes to total carbon tetrachloride production capacities. To
derive plant-by-plant emissions and costs from model plant data, it was
necessary to apportion the total capacity of these plants to the individual
processes. Available total carbon tetrachloride capacities (Table 3-1)
were divided between the two processes as follows. Since perchloroethylene
production capacities are available for these plants, carbon tetrachloride
capacity by the perchloroethylene co-product processs was estimated by
assuming the proportions of carbon tetrachloride and perchloroethylene
co-product capacity from the perchloroethylene co-product process at
these plants are the same as that of the model plant (62.5 percent
perchloroethylene, 37.5 percent carbon tetrachloride). Remaining carbon
tetrachloride capacity was attributed to the methane chlorination process,
as shown in Table 3-3.
TABLE 3-3. CAPACITY APPORTIONMENT IN TWO-PROCESS PLANTS (Mg/yr)
Perchloroethylene
Plant Capacity!
Carbon
Tetrachloride from
Perchloroethylene
Co-Product Process
Carbon
Total Carbon Tetrachloride
Tetrachloride from Methane
Capacity! Chlorination
6
8
9
68,000
23,000
23,000
40,800
13,800
13,800
61,000
27,000
36,000
20,200
13,200
22,200
3-7
-------
3.2.3 Proportionality and Scales of Production
Throughout the following analysis, direct proportionality of emissions,
control efficiencies and costs over all scales of production was assumed.
This approach may introduce significant errors, especially for capital
costs, but was considered appropriate due to the lack of detailed technical
data and the level of analysis possible in this study. The plant capacity
factors in Table 3-4, derived by dividing each plant's assumed carbon
tetrachloride production process capacity by that of the perchloroethylene
co-product model plant, were used to apply model plant emission estimates
and control costs to each plant. Production capacities for two-process
plants were estimated in Table 3-3; others were taken directly from
Table 3-1.
TABLE 3-4. PERCHLOROETHYLENE CO-PRODUCT PLANT CAPACITY
FACTORS (RELATIVE TO MODEL PLANT)
Plant
capacity
Plant factor
4 1.9
5 1.36
6 1.36
7 5.13
8 0.46
9 0.46
Total 10.67
3.2.4 Capacity Utilization
Based on the 1981 total carbon tetrachloride production of 325,700 Mg,"13
and corresponding national production capacity of 478,000 Mg (Table 3-1),
a uniform capacity utilization rate of 0.68 was applied to all carbon
tetrachloride plants in estimating uncontrolled and controlled emissions.
This factor was used to calculate model plant emission reductions for the
cost analyses in Chapters 3, 4 and 5.
3-8
-------
3.2.5 Uncontrolled Emissions
To estimate uncontrolled emissions for perch!oroethylene co-product
plants, the uncontrolled full-capacity model plant emissions shown in
Table 3-5 were first calculated by multiplying uncontrolled emission
factors (Table 3-2) by the 30,000 Mg/yr model plant carbon tetrachloride
production capacity. The two secondary emission sources were combined
for the purposes of this analysis. The assumed industry-wide capacity
utilization factor of 0.68 and the appropriate plant capacity factors
from Table 3-4 were then applied to the model plant emission estimates
to produce the plant-specific estimates shown in Table 3-6.
TABLE 3-5. PERCHLOROETHYLENE CO-PRODUCT MODEL PLANT
EMISSIONS
Source
Model plant
carbon tetrachloride
emissions (Mg/yr)
Process
Fugitive
Storage
Loading
Secondary
Total
0.17
28.0
25.5
7.2
0.23
61.1
TABLE 3-6. UNCONTROLLED EMISSIONS FOR PERCHLOROETHYLENE CO-PRODUCT PLANTS
Plant
number
4
5
6
7
8
9
Total
Uncontrolled emission
Process
0.21
0.16
0.16
0.59
0.05
0.05
1.22
Fugitive
36.2
25.9
25.9
97.6
8.8
8.8
203.2
Storage
33.0
23.6
23.6
88.9
8.0
8.0
185.1
estimates
Loading
9.3
6.7
6.7
25.1
2.2
2.2
52.2
(Mg/yr)
Secondary
0.30
0.21
0.21
0.80
0.07
0.07
1.66
Total
79.0
56.5
56.5
213.0
19.0
19.0
443.0
3-9
-------
3.3 OPTION 1 CONTROLS AND EMISSIONS FOR PERCHLOROETHYLENE CO-PRODUCT
PLANTS
Option 1 control efficiencies represent the most stringent of
existing, State-required or applicable Group III CTG controls for areas
requesting an ozone NAAQS attainment date extension beyond 1982. These
controls are discussed individually below as they apply to perch!oroethylene
co-product plants. They are then combined to define Option 1 control
efficiencies for each source category at each plant, and used to estimate
controlled emissions under Option 1. Since State regulations and the
Group III CTGs and their assumed control efficiencies are discussed in
detail in Section 2.2, their discussion here is limited to their applicability
to given plants and other plant-specific considerations. For ease of
reference, the tables presented in this section include existing controls
and State regulations for all carbon tetrachloride production facilities,
including the methane chlorination and carbon disulfide process plants
discussed in Chapters 4 and 5.
3.3.1 Existing Controls
Information on control technology currently in place at carbon
tetrachloride production facilities was obtained mainly in telephone
conversations with State agency personnel. Some data were available
from previous EPA industry surveys. Table 3-7 summarizes the information
on existing controls. Control efficiencies were provided either in the
cited references, or derived from technical data in them. In most
cases, unreported efficiencies were estimated to be proportional to
vapor pressure reductions achieved by given condenser outlet temperatures.
Since all carbon tetrachloride plants are believed to have emissions in
all major emission categories (process, fugitive, storage, handling,
secondary), Table 3-7 shows that most emission points at most carbon
tetrachloride plants are not controlled. In addition, some of the
controls listed in Table 3-7 do not cover all emission points in the
applicable emission category, so the listed control efficiency does not
apply to the entire emission category. For perchloroethylene co-product
plants, these include the secondary emission controls at Plants 6 and 7,
which each apply to only one of the two components of secondary emissions
3-10
-------
TABLE 3-7. KNOWN EXISTING CONTROLS AT CARBON TETRACHLORIDE PRODUCTION PLANTS
CO
I
Plant
number
1
2
Emission
category
Process
Process
Control device
Process vent condensation system.
Two-stage refrigerated condenser on chlorination
Control
efficiency
(%)
50
95
Reference
14
15
Storage
Storage
reactor; 120 Ib/hr controlled emissions
Brine-cooled condenser on a 2,400 gallon fixed- 50
roof carbon tetrachloride storage tank and several
tanks for other products.
Vapor recovery (-20°C refrigerated condenser) on 95
single large fixed-roof carbon tetrachloride tank
(five small tanks with no control).
16
17
5
6
Process
Storage
Storage
Secondary
Refrigerated condenser on carbon tetrachloride/ 90
perchloroethylene process tower.
Vapor recovery (-7°C refrigerated condensers) on 80
160,000 and 6,000,000 gallon fixed-roof storage
tanks (four 8,000 gallon product check tanks and
a 13,000 gallon re-run tank with no controls).
Refrigerated condensers and pressuri zed-nitrogen 95
padding on fixed-roof tanks.
Vapor-balance, refrigerated condensation and recycle 99
used on hex waste handling and feed storage tanks
for perchloroethylene co-product process.
14,
17,
14,
20
17
18
19
CONTINUED
-------
TABLE 3-7. (continued)
Plant Emission
number category
7 Secondary3
8
9
Control device
Waste caustic from organic neutralization system
is steam-stripped of VOC, which is recycled to
the process.
No controls exist.
No controls exist.
Control
efficiency
(%)
96
0
0
Reference
20
21
22
Controls only part of this emission category -- see text for details.
GO
I
-------
from this process (waste caustic; hex waste handling and disposal, and
waste hydrocarbon storage). It was necessary to use the original
emission factors for these components (Table 3-2) and the available
control efficiencies (Table 3-7) to estimate overall secondary emission
control of these plants. Thus, 96 percent control of waste caustic
emissions, which comprise about 40 percent of secondary emissions,
results in about 40 percent control of total secondary emissions at
Plant 7. Similarly, 99 percent control of hex waste handling and disposal
and waste hydrocarbon storage at Plant 6 will provide about 60 percent
of total secondary emissions. The carbon tetrachloride control efficiencies
for the larger storage tanks at Plants 4 and 5 were applied to total
storage emissions. Implicit in this is the assumption that the smaller
tanks have negligible emissions, due to their size, the lower carbon
tetrachloride content of crude product, and relatively constant operating
levels.23
3.3.2 State Regulations
Current State regulations applying to carbon tetrachloride production
facilities and related efficiencies were extracted from Section 2.2 and
are summarized in Table 3-8.
Carbon tetrachloride is not covered by the definition of "VOC"
applicable to VOC storage and fugitive VOC in Louisiana, or by the
definition of "organic liquid" which applies to VOC storage in the San
Francisco Bay Area (California). (See 2.2.1 for the full definitions.)
For purposes of this source assessment, however, it has been assumed
that the Louisiana and Bay Area SIP provisions cited for Plants 4, 5 and
9 in Table 3-8 will be enforceable for carbon tetrachloride despite the
current State definitions. This assumption does not appear unreasonable
for Option 1, since the Bay Area definition will probably be changed to
conform with the VOC definition in the VOL storage CTG when this CTG is
adopted there, and since Louisiana is currently applying its VOC regulations
to carbon tetrachloride sources.
Unless otherwise indicated, it is assumed that the plants are
subject to the regulations and control requirements cited in Table 3-8.
3-13
-------
TABLE 3-8. CURRENT STATE REGULATIONS APPLYING TO CARBON TETRACHLORIDE PRODUCTION FACILITIES
Plant
number State
Appl icable
State regulations9
Control
efficiency
wa
West Virginia
Alabama
(Mobile Co.)
GJ
I
-pi
4,5
Kentucky
Louisiana
None.
VOC Storage: Tanks over 1,000 gallons must be
pressure tanks or have either (a) submerged
fill, (b) external or internal floating roof,
(c) vapor recovery system, or (d) other
equipment or means of equal efficiency.
VOC Loading: Loading of tanks, trucks, or trailers
must employ (a) either vapor collection and
disposal or a system allowing 95 percent submerged
fill or equivalent, (b) prevention of liquid
drainage from the loading device, and (c) vapor-
tight and automatic-closing loading line
connectors, unless hatch-loaded.
None (regulations only cover petroleum liquids and/or
gasoline).
VOC Storage: Tanks over 40,000 gallons which are
not pressure tanks must have submerged fill and
either (a) floating roof, (b) a vapor loss control
system equivalent to floating roof, or (c) other
equivalent equipment or means. Tanks from 250 to
40,000 must have submerged fill or vapor recovery
or other equivalent equipment or means.
VOC Loading: Facilities with daily throughput of
40,000 gallons or more must have vapor recovery
and disposal, or an equivalent, and spill
95
90
CONTINUED
-------
TABLE 3-8. (continued)
Plant
number
State
Applicable State regulations1
Control
efficiency
4,5 (continued)
CO
I—"
en
Texas
(Brazoria Co.)
prevention for filling equipment. (Plant 4 is
exempt, as described in the text.)
VOC Fugitives: Pumps and compressors must be equipped 0
with mechanical seals, or equivalent equipment or
means. Best practical housekeeping and maintenance
practices are also required.
Process: Louisiana's requirement for waste gas NA
combustion or equivalent control does not apply
to non-combustible gases or sources under 100 tons
(91 Mg) per year, exempting Plants 4 and 5.
VOC Storage: Tanks from 1,000 to 25,000 gallons must 50
have submerged fill. Tanks from 25,000 to
42,000 gallons must have any type of floating roof
or a vapor recovery system which reduces vent gas
vapor pressure to 1.5 psia. Tanks over 42,000 gal-
lons must have an internal floating roof, an external
floating roof with vapor-mounted primary seal and
secondary seal, or a vapor recovery system which
reduces vapor pressure to 1.5 psia.
VOC Loading: Facilities with average throughputs over 50
20,000 gallons per day must have a vapor recovery
system which reduces the true vapor pressure of vent
gases to 1.5 psia, vapor-tight seal, and drainage
control (ship and barge loading exempt).
Process: Texas regulations do not apply to carbon NA
tetrachloride.
CONTINUED
-------
TABLE 3-8. (continued)
Plant
number
State
Applicable State regulations'
Control
efficiency
Texas
(San Patricio Co.)
CO
I
Kansas
California
(Bay Area)
VOC Storage: Tanks over 1,000 gallons must have 50
submerged fill or vapor recovery if not a pressure
tank. Tanks over 25,000 gallons must be pressure
tanks or have either a floating roof or a vapor
recovery system reducing vent gas vapor pressures
to 1.5 psia.
VOC Loading: Facilities with average throughputs of 50
20,000 gallons per day must have a vapor recovery
system reducing vent gas vapor pressures to 1.5 psia,
vapor-tight seal, and drainage control (ship and
barge loading exempt).
Process: Texas regulations do not apply to carbon NA
tetrachloride.
None.
Valves and Flanges: Annual inspection and repair or 0
minimization of leaks is required in chemical plant
complexes.
VOC Storage: Organic liquid storage tanks between 95
260 and 40,000 gallons must have submerged fill or
equivalent. Tanks over 40,000 gallons must have
floating roof, vapor recovery with 95 percent
efficiency or other control with 95 percent
efficiency.
aSee Section 2.2 for references and discussion of control efficiency estimates. 0 indicates
requirements which have no effect since they are equivalent to the uncontrolled case; NA indicates
controls not required due to size cutoff or other exemption, as discussed in the text.
-------
Exemptions have been identified in the following cases. Plant 4 (Dow/Plaquemine)
has been exempted from loading controls by the Louisiana Air Quality
Division, having demonstrated daily throughput of less than 40,000 gallons
for the facility handling carbon tetrachloride. Plant 5 (Vulcan/Geismar)
is not exempt, due to loading of other products in excess of 40,000 gallons
per day. Process vent emissions at Plants 4 and 5 are also assumed to be
exempt from Louisiana's regulations, since calculations of their uncontrolled
emissions in this study and information available from the Louisiana Air
Quality Division indicate total process VOC emissions are well under
100 tons per year. According to the original source of the data used in
the 0.0058 kg/Mg uncontrolled emission factor for perchloroethylene
co-product process distillation columns, carbon tetrachloride is the only
3
VOC emitted at this point. Thus the 0.21 and 0.16 Mg/yr uncontrolled
process emissions for Plants 4 and 5 (Table 3-6) represent total VOC, and
are well under 100 tons per year. Contacts at the State agency indicate
that both plants have actually been exempted from process control, due to
low emission levels. Vulcan reports process VOC emissions of 1.2 tons
per year, based on tests of the carbon tetrachloride tower reflux drum,
and total Dow process VOC emissions are also believed to be less than
24
5 tons per year. It is assumed that Texas process control regulations
do not apply to process vent emissions at perchloroethylene co-product
plants, because carbon tetrachloride is not on the list of affected
compounds, and, as described above, is believed to be the only VOC in
this vent stream. Plants 6 and 7 are assumed to be covered by the Texas
regulations for VOC loading, since the annual carbon tetrachloride production
capacity for the smaller Plant 6 (61,000 Mg/yr) would result in an average
daily loading rate of over 27,000 gallons. The Texas regulations'
exemption limit is 20,000 gallons per day. Loading of perchloroethylene
and other products would increase the average throughput for these loading
facilities by at least a factor of two, so it was assumed that these
plants would exceed the exemption limit even with substantial barge and
ship loading.
3-17
-------
3.3.3 Group III Control Techniques Guidelines
Table 3-9 summarizes the current status of counties with carbon
tetrachloride production facilities with respect to the National Ambient
Air Quality Standard for ozone. Since it is anticipated that ozone
nonattainment areas which have received extensions beyond 1982 will be
required to adopt all Group III CTGs, it has been assumed that the CTGs
discussed in 2.2.2 apply to the Dow perch!oroethylene co-product plant at
Pittsburg, California (Plant 9), and will result in 42 percent control of
fugitive emissions and 95 percent control of storage emissions. Plant 3
(Stauffer/Louisville, KY) is also subject to these requirements, but is
addressed in Chapter 4 with the methane chlorination process plants.
TABLE 3-9. OZONE NATIONAL AMBIENT AIR QUALITY STANDARD ATTAINMENT
STATUS FOR CARBON TETRACHLORIDE PRODUCTION FACILITIES25,26
Plant
number
1
2
3
4
5
6
7
8
9
3.3.4 Combined Option
Ozone NAAQS
attainment
status
Attainment
Nonattainment
Nonattainment
Nonattainment
Nonattainment
Nonattainment
Attainment
Attainment
Nonattainment
1 Controls
Post-1982
attainment
date granted?
No
Yes
No
No
No
_ _
Yes
Table 3-10 summarizes control efficiencies applicable to perchloroethylene
co-product plants for the Option 1 controls described in 3.3.1, 3.3.2,
and 3.3.3. Each efficiency represents the most stringent of existing,
State-required or Group III CTG controls. Table 3-11 provides more
detail on the estimated efficiencies of these three control categories
with respect to storage emissions. The most stringent level of control for
each plant was selected as the Option 1 storage control shown in Table 3-10.
3-18
-------
TABLE 3-10. OPTION 1 CONTROL SUMMARY FOR PERCHLOROETHYLENE
CO-PRODUCT PLANTS
Plant
4
5
6
7
8
9
Option 1
Process Fugitive
__
90
__
__
__
42
control efficiency
Storage
95
95
95
50
--
95
(percent)
Loading
—
90
50
50
--
--
Secondary
—
--
60
40
--
—
TABLE 3-11. OPTION 1 CONTROLS FOR STORAGE EMISSIONS AT
PERCHLOROETHYLENE CO-PRODUCT PLANTS
Plant
4
5
6
7
8
9
Existing
control
95
80
95
--
--
--
Current
regulations
95
95
50
50
--
95
Group III
CTG
_ _
--
--
--
--
95
3.3.5 Estimated Option 1 Emissions
Applying the control efficiencies in Table 3-10 to uncontrolled
emission estimates (Table 3-6) produced the Option 1 controlled emission
estimates in Table 3-12.
3-19
-------
TABLE 3-12. OPTION 1 CONTROLLED EMISSIONS FOR PERCHLOROETHYLENE
CO-PRODUCT PLANTS
Plant
4
5
6
7
8
9
Process
0.21
0.02
0.16
0.59
0.05
0.05
Option 1
Fugitive
36.2
25.9
25.9
97.6
8.8
5.1
control led
Storage
1.7
1.2
1.2
44.5
8.0
0.4
emissions (Mg/yr)
Loading
9.3
0.7
3.4
12.6
2.2
2.2
Secondary
0.30
0.21
0.08
0.48
0.07
0.07
Total
47.7
28.0
30.7
155.8
19.1
7.8
Total
1.08
199.5
57.0
30.4
1.21
289.2
Option 1
control
efficiency
(%} 11 2
69 42 27 35
3.4 OPTION 2 CONTROLS AND EMISSIONS FOR PERCHLOROETHYLENE CO-PRODUCT
PLANTS
This section describes the estimated best controls (EEC) used in
Option 2, and estimates the emissions expected after application of
these controls to perchloroethylene co-product plants.
3.4.1 Estimated Best Controls
The following control methods were selected as EBC for carbon
tetrachloride plants using the perchloroethylene co-product process.
All control efficiencies cited are specific to carbon tetrachloride.
Process emissions: Refrigerated condensers have been reported to
provide 90 percent control of carbon tetrachloride/perchloroethylene
distillation columns.
3-20
-------
Fugitive emissions: An inspection and repair program similar to
27
the Group III CTG can provide 42 percent control, but EBC include
addition of equipment specifications estimated to raise this to about
28
56 percent.
Storage emissions: Vapor recovery and -20°C refrigerated condensation
systems can be used to control carbon tetrachloride storage at efficiencies
up to 95 percent.14'19'29
Loading emissions: Vapor recovery, refrigerated condensers and tank
truck leakage reduction measures are estimated to provide 90 percent
control of loading emissions. '
Secondary emissions: Combined use of steam-stripping of waste
caustic and vapor balance, condensation and recycle for hex waste and
waste hydrocarbon storage can provide 98 percent control of secondary
20
emissions from carbon tetrachloride/perchloroethylene processes.
3.4.2 Estimated Option 2 Emissions
Table 3-13 summarizes annual emissions and control efficiencies
which can be achieved by perch!oroethylene co-product plants with the
Option 2 controls described in 3.4.1.
TABLE 3-13.
OPTION 2 CONTROLLED EMISSIONS FOR PERCHLOROETHYLENE
CO-PRODUCT PLANTS
Plant
4
5
6
7
8
9
Total
Option 2
control
efficiency
Process
0.02
0.02
0.02
0.06
0.01
0.01
0.14
Option 2
Fugitive
15.9
11.4
11.4
42.9
3.9
3.9
89.4
controlled emissions (Mg/yr)
Storage
1.7
1.2
1.2
4.4
0.4
0.4
9.3
Loading
0.9
0.7
0.7
2.5
0.2
0.2
5.2
Secondary
0.006
0.004
0.004
0.016
0.001
0.001
0.032
r\rt
Total
18.5
13.3
13.3
49.9
4.5
4.5
104.0
-7-7
90
56
95
90
3-21
-------
3.5 CONTROL COSTS FOR PERCHLOROETHYLENE CO-PRODUCT PLANTS
This section presents control cost estimates for the Option 1 and
Option 2 controls discussed in this chapter. Model plant costs are
developed for each source type (process, storage, etc.) and plant-specific
costs for Options 1 and 2 are presented under Summary headings at the end
of 3.5.1 and 3.5.2. In a few cases, the model plant approach could not
be used, and full control costs for individual plants are developed.
Costing methodology and assumptions are discussed further in Chapter 1.
All costs are for July 1982 except where noted. Examples and details of
control requirement calculations are presented in Appendix B.
3.5.1 Option 1 Control Costs
This section provides cost estimates for the Option 1 perchloroethylene
co-product plant controls discussed in 3.3.4.
Process controls: Plant 5 is the only perchloroethylene co-product
plant with Option 1 process control, a refrigerated condenser reported to
14 17
provide 90 percent control. ' Since the same control is used for all
other perchloroethylene co-product plants under Option 2, applicability
of the following cost estimate to these plants is also described.
As discussed below, the gas flowrates and refrigeration requirements
for documented perchloroethylene co-product process vent streams are more
than two orders of magnitude below the operating levels of standard
condensing units for which costs are available. The emissions in
question actually come from in-process condensers in distillation systems.
The control efficiency cited for Plant 5 may represent upgrading of the
in-process condenser or installation of a two-stage condenser system
rather than use of a separate add-on condenser. The type of control
actually in use could not be verified. Since available process data
would not allow assessment of these possibilities, this control device
was assumed to be a retrofit condenser under Options 1 and 2. Technical
data from two perchloroethylene co-product plants were used to specify
flow rate and refrigeration capacity for a small retrofit refrigerated
condenser, as described in Appendix B-l.
3-22
-------
The refrigeration requirement of 22 BTU/hr and flowrates under
0.1 ft /min derived in Appendix B-l reflect the small flow and emission
rates for these process vents. These specifications are far below the
smallest streams for which standardized cost estimates have been developed
3 35
(100 ft /min) , and are considerably smaller than the capacity of the
smallest applicable standard unit available from a major manufacturer of
34
condensation equipment, which has a cooling capacity of 3,600 BTU/hr.
This 3,600 BTU/hr unit would have a base capital cost of about $3,500
and has an outlet brine temperature of -25°C. The cost of a smaller unit
is very difficult to estimate, due to the need for custom engineering,
and procurement and fabrication of non-standard parts. It was assumed
that $3,500 is a reasonable upper-bound estimate of the base capital cost
of a refrigerated condenser for 90 percent control of process emissions
at perch!oroethylene co-product plants, because the specifications above
were developed for Plant 7, the largest plant of this type. In most
other cost estimates, direct proportionality of control costs to plant
size has been assumed. In this case, however, such an approach would not
be appropriate because smaller condensers do not exist. For this reason,
the $3,500 base capital cost was used directly and a model plant-based
costing approach was not used.
Allowing 18 percent of the base cost for taxes, freight, and
instrumentation and 61 percent for installation, total installed
capital cost would be $6,650. A 29 percent annualized cost factor,
including maintenance labor and material (6 percent), taxes, insurance
and administration (5 percent), and capital recovery (18 percent), developed
37
specifically for condensers, results in an annualized capital cost of
$1,930 for each plant. IT Enviroscience estimates electric utility costs
in the range of 2 to 6 percent of annualized capital cost for 95 percent
38
control of a 20 percent VOL stream. Assuming 5 percent results in an
estimated annual utility cost of about $100 for the model plant. The
manufacturer reports that such small, simple units will have minimal
34
operating labor requirements, possibly 10 minutes per week. On an
37
annual basis, at $19/hour, this results in an annual labor cost of
about $165.
3-23
-------
An Option 1 emission reduction of 0.14 Mg/yr (from Tables 3-6 and
3-12) results in the following net Option 1 process control cost and
cost-effectiveness for Plant 5.
Total installed capital cost $6,650
Annualized capital cost $1,930
Utilities and labor $ 265
Total annualized cost for Option 1 $2,195
(Plant 5)
Recovery credit (59)
Net annualized cost $2,136
Emission reduction 0.14 Mg/yr; 90%
Cost-effectiveness $15,300/Mg
Fugitive control: The following procedure was used to estimate
costs of Option 1 fugitive emission controls at Plant 9. Based on the
model plant fugitive emission source inventory and process descriptions
3Q
from IT Enviroscience, estimates of the number of fugitive sources in
carbon tetrachloride service at perchloroethylene co-product plants were
made (Table 3-14). Comparing the carbon tetrachloride sources which
would be included in a fugitive emission control program to those used in
the small model plant in the SOCMI fugitives CTG, it was assumed that use
of control costs for this small SOCMI model plant would result in a
reasonable estimate of the likely control costs for the Option 1 inspection
and maintenance program for the carbon tetrachloride/perchloroethylene
co-product model plant. The small SOCMI model plant is estimated to have
a capital cost of control of $19,200 and an annualized cost of $14,200
for quarterly monitoring, maintenance, and associated administration, a
program estimated to result in 42 percent control.27 Combined with
applicable model plant emission reductions at 0.68 capacity utilization,
net costs and cost-effectiveness for the model plant are estimated below.
These model plant costs were combined with the Plant 9 capacity factor
(Table 3-4) to arrive at the the estimated Plant 9 costs in Table 3-21.
3-24
-------
TABLE 3-14. MODEL PLANT FUGITIVE EMISSION SOURCES
Perch!oroethylene co-product
model plant
Total fugitive
source$39
In carbon tetra-
chloride service
Small SOCMI
fugitives
model
Pumps
Process valves
Relief valves
Compressor
30
800
12
1
10
280
4
0
15
230
12
1
Total installed capital cost
Annualized cost
Recovery credit for carbon tetrachloride
Net annualized cost
Emission reduction
Cost-effectiveness
$19,200
$14,200
(3,343)
$10,857
8.0 Mg/yr; 42%
$l,357/Mg (cost)
Storage controls: This discussion addresses the general assumptions
and cost estimates which apply to both perchloroethylene co-product and
methane chlorination model plants. These costs will then be used to
estimate Option 1 perchloroethylene co-product model plant storage control
costs, which apply to Plants 4, 5 and 7. These basic costs will also be
used to estimate Option 1 storage control costs at Plants 6 and 9, which
use both production processes, assuming joint product storage at these
plants. Storage control costs for the two major carbon tetrachloride
production processes are based on model plant storage parameters and
available cost data for similar control scenarios previously developed by
IT Enviroscience. Storage facilities for the model plants are shown in
Tables 3-15 and 3-16.
3-25
-------
TABLE 3-15. PERCHLOROETHYLENE CO-PRODUCT MODEL PLANT STORAGE
.41
Crude product
Carbon tetrachloride
Carbon tetrachloride
Number
of tanks
1
2
1
Size
(m3)
378
76
757
Turnovers
per year
6
125
25
Temperature
(°C)
38
35
20
TABLE 3-16. METHANE CHLORINATION MODEL PLANT STORAGE
42
Crude product
Carbon tetrachloride
Carbon tetrachloride
Number
of tanks
1
2
1
Size
(m3)
757
38
757
Turnovers
per year
6
166
17
-Temperature
(°C)
35
35
20
Costs for refrigerated condensers on VOC storage tanks were available
43
in Volume 3 of the IT Enviroscience SOCMI study. It was assumed that
costs for condenser control of storage emissions at either of the above
model plants could be derived from the costs for condenser control of the
IT Enviroscience model storage tank which has a capacity of 660 m and
50 turnovers per year. This assumption is based on a number of simplifying
assumptions: (1) a single condensation system can be used for all tanks;
(2) working losses for the crude product tanks are small due to relatively
constant operating levels; (3) condenser size and cost are most dependent
on the maximum rate of working losses, which would be from the large
carbon tetrachloride storage tank for each model plant; and (4) working
losses for the large model plant storage tanks (757 m3, 17-25 turnovers
per year) plus those for the two smaller model plant product storage
tanks will be roughly equivalent to working losses from the IT Enviroscience
model tank, which is somewhat smaller than the large tank but has a
3-26
-------
higher turnover rate. Annualized costs and control efficiencies for two
control scenarios for the cited IT Enviroscience model tank (Case 2,
Case 3) were used to draw Figure 3-2. Case 1 was not used because the
VOC for that scenario was not sufficiently similar to carbon tetrachloride.
Allowance was made for the higher vapor pressure of the VOC in Case 3.
The annualized control costs for Option 1 and 2 control levels in Table 3-17
were estimated using Figure 3-2, and inflated to July 1982. Since the
Enviroscience cost estimates neglected utility and operating labor
costs, it was possible to derive the estimated capital costs in Table 3-17
from the respective annualized costs with the total Enviroscience annualized
cost factor (0.29). This factor includes maintenance, capital recovery
and miscellaneous capital-related costs.
TABLE 3-17. ESTIMATED MODEL PLANT COSTS FOR REFRIGERATED CONDENSER STORAGE
CONTROL (PERCHLOROETHYLENE CO-PRODUCT AND METHANE CHLORINATION)
Control
efficiency
(percent)
95
50
Capital cost
of complete
condenser system
$285,000
26,300
Annualized cost
of complete
condenser system
$82,600
7,600
Applying the above cost estimates to storage control efficiencies
relevant to Option 1 for perchloroethylene co-product plants and model
plant emissions data produces the following net annualized cost and cost-
effectiveness data for the perchloroethylene co-product model plant.
These costs and plant capacity factors (Table 3-4) are the basis for the
storage control costs for Plants 4 and 5 (95 percent control) and
Plant 7 (50 percent control). These plant-specific costs are shown in
Table 3-21.
3-27
-------
100
90
80
o
-------
Total installed capital cost
Annualized cost
Recovery credit
Net annualized cost
Emission reduction
Cost-effectiveness
95 percent
control
$285,000
82,600
(6,900)
$ 75,700
16.5 Mg/yr
$4,600/Mg
50 percent
control
$26,300
7,600
(3,600)
$ 4,000
8.7 Mg/yr
$460/Mg
Option 1 storage controls at two-process plants consist of 95 percent
control at Plants 6 and 9. The $285,000 capital cost and $82,600 annualized
control cost for the model plants (Table 3-17) were scaled to the size
of Plants 6 and 9 using their combined plant capacity factors from
Tables 3-4 and 4-2. This resulted in overall plant capacity factors of
2.37 for Plant 6 and 1.57 for Plant 9. To estimate net annualized cost
and cost-effectiveness, it was necessary to calculate the two Option 1
emission reductions for each plant from Tables 3-6, 3-12, 4-4 and 4-7.
Total installed capital cost
Annualized cost
Recovery credit
Net annualized cost
Emission reduction
Cost-effectiveness
Plant 6
$675.500
195,900
( 12,700)
183,200
Plant 9
$447,500
129,700
(6.700)
123,000
30.3 Mg/yr
95%
16.1 Mg/yr
95%
$ 6,050/Mg $ 7,640/Mg
Loading Controls: The best available costs for loading controls are
47
from the December 1980 Draft EIS for the Bulk Gasoline Terminals NSPS.
To use this information, a number of assumptions were necessary. Gasoline
3-29
-------
terminals for which costs were available ranged in throughput from 380
to 3800 m3 per day, while average carbon tetrachloride model plant
-5 2
throughputs are 34 m /day for methane chlorination and 52 m /day for the
perchloroethylene co-product process. Extrapolation down to these ranges
introduces considerable uncertainty into the costs assumed for carbon
tetrachloride plants. Due to this uncertainty, additional errors introduced
by applying costs of condenser systems designed for control of gasoline
vapors to carbon tetrachloride loading facilities and the use of nearly-identical
retrofit and new-plant control costs in the NSPS are considered minor.
It was also necessary to assume that control costs thus derived from
bottom-loaded gasoline loading facilities would be appropriate to carbon
tetrachloride loading, despite possible differences in equipment, location,
and other factors. It was assumed that the control systems costed in
48
the NSPS could attain a 90 percent control efficiency.
Table 3-18 presents annualized costs for refrigerated condensers at
gasoline bulk terminals from which normalized costs per cubic meter of
throughput were derived. These normalized costs were used to draw the
curve in Figure 3-3, which extrapolates loading control costs for gasoline
terminals (points A through D) to the throughput range of the carbon
tetrachloride model plants. Points 1, 2 and 3 on Figure 3-3 represent
normalized annualized costs for 90 percent control of loading emissions
at the carbon tetrachloride model plant throughputs. From the calculations
on Figure 3-3, the normalized annualized control cost converts to a
July 1982 cost of $31,300/yr for the perchloroethylene co-product model
plant. A corresponding capital cost of $101,700 was estimated by (1) assuming
capital charges to be about 65 percent of the total annualized cost (the
plants in Table 3-18 range from 64 percent for the smallest to 61 percent
for the largest), and (2) applying the 0.20 annualized cost factor used
to derive capital charges in the original reference.49 These costs
result in the following net cost and cost-effectiveness figures, based
on 90 percent reduction of model plant loading emissions (Table 3-5),
and 0.68 capacity utilization.
3-30
-------
»500
I
CO
00.
ac. x
o o
O IT
82
-Ili.
-------
Total installed capital cost $101.700
Annualized cost 31,300
Recovery credit 0>840)
Net annualized cost 29,460
Emission reduction 4.4 Mg/yr; 90%
Cost-effectiveness $ 6,700/Mg
TABLE 3-18. ANNUALIZED REFRIGERATED CONDENSER CONTROL COSTS FOR
EXISTING BOTTOM-LOADED BULK GASOLINE TERMINALS^?
($1,000, mid-1979)
NSPS costs
Direct operating costs
Truck maintenance
Capital charges
Total annual costs
380 mVday
30.1
0.5
54.4
85.0
Throughput
950 md/day
38.1
0.9
65.9
104.9
1,900 mVday
41.0
1.4
69.1
111.5
3,300 mVday
54.6
3.0
91.0
148.6
Normalized cost per
m3/day (total annual
cost 4- throughput)
($/m3) 223 110 59 39
Use of the costs for 90 percent control in estimating costs for
50 percent control under Option 1 requires considerable additional
assumptions, since the bulk gasoline terminal NSPS and other available
sources do not address controls in the 50 percent range. The NSPS
control equipment costs do not include direct estimates of the relative
costs of condenser and refrigeration equipment, which would vary with
control efficiency, and costs of other control components such as the
vapor collection system, which would be expected to be relatively constant'.
For the smallest model gasoline terminal, the breakdown of annualized
costs in the first column of Table 3-19 was calculated.
3-32
-------
TABLE 3-19.
DISTRIBUTION OF ANNUAL COSTS FOR LOADING CONTROL BY
REFRIGERATED CONDENSER
Annual costs for
model 380 m3/day
gasoline
terminal A7
(90% control)47
Estimated
cost
reduction for
50 percent
control
Estimated costs
for 50 percent
control relative
to 90 percent
control
Capital charges
Electricity
Maintenance
Operating labor
64 percent
17 percent
15 percent
4 percent
100 percent
0.5
0.8
0.5
none
32.0 percent
3.4 percent
7.5 percent
4.0 percent
46.9 percent
To obtain an estimate of the overall cost of a 50 percent control
system relative to a 90 percent control system, likely reductions in
each cost category associated with the reduced control efficiency (Column 2,
Table 3-19) were estimated as follows. IT Enviroscience data indicate
that the electricity requirement for condensation systems at 50 percent
efficiency is about one-fifth of that for 90 percent control, and that
the annual amount for operating labor will be constant regardless of
50
control efficiency. Assuming that condenser emission reduction is
proportional to vapor pressure reduction, 50 percent control would
require reduction of 90 mm Hg vapor pressure at inlet temperature of
20°C to 45 mm Hg at outlet temperature of about 6°C, while 90 percent
control would require about -33° to reduce the vapor pressure to 4.5 mm Hg.
Installed capital costs for condenser systems in one reference
indicate that units operating at -33°C are typically about three times
as expensive as 6°C units. Although this indicates that the capital
cost for condenser and refrigeration system with 50 percent efficiency
may be one third of the estimate for 90 percent control, the overall
cost of the control equipment and associated maintenance will not be
3-33
-------
reduced proportionately since vapor collection systems will not be
similarly reduced in cost. Since supporting data on the relative magnitude
of collection and condensation costs are not available, it was assumed
that the overall capital cost of the control system would be reduced by
50 percent. If costs for the collection and condensation systems were
approximately equal, this overall assumption would be equivalent to
assuming a one-third reduction in collection system costs in addition to
the relatively firm two-thirds reduction in condenser system costs.
Maintenance costs were assumed to decrease proportionate to capital
costs of the control system, since the bulk gasoline terminal NSPS
maintenance cost estimates were consistently about 22 percent of capital
costs.47
As shown in Table 3-19, the net result of estimated control costs
reductions in the four cost categories is to reduce overall annualized
costs for 50 percent control to about 47 percent of those estimated for
90 percent control or about $14,700 for the perchloroethylene co-product
model plant. A 50 percent reduction in the estimated capital cost
results in a model plant capital cost of $50,900 for 50 percent control.
These costs produce the following net cost and cost-effectiveness figures
for 50 percent control of perchloroethylene co-product model plant
loading emissions.
Total installed capital cost $50,900
Annualized cost 14,700
Recovery credit (1,QQQ)
Net annualized cost $13,700
Emission reduction 2.5 Mg/yr; 50%
Cost-effectiveness $ 5,470/Mg
Secondary controls: Combined capital costs for a vapor-balance
system for hex-waste handling used on the perchloroethylene co-product
process at Plant 6 and a second system to recycle and condense emissions
from the vapor-balance system and from waste product storage are estimated
3-34
-------
52
at $410,000. Sufficient data were not available to estimate costs of
the waste caustic steam stripper at Plant 6. Due to the relatively
small proportion of total emissions represented by secondary emissions,
and the highly plant-specific nature of these emissions and related
control costs, no estimate of costs of secondary emission controls was
made.
Summary: Table 3-20 summarizes Option 1 model plant control costs
for perch!oroethylene co-product plants developed in this sub-section.
Table 3-21 presents estimated capital and annualized control costs for
each plant. These costs were calculated by multiplying model plant
costs by the plant capacity factors in Table 3-4, except for process
controls at Plant 5 and storage controls at Plants 6 and 9, which were
derived individually above.
TABLE 3-20.
OPTION 1 PERCHLOROETHYLENE CO-PRODUCT MODEL PLANT
CONTROL COSTS
Control
type
Process
Fugitive
Storage
Loading
Control
efficiency
(*)
90
42
50
95
50
90
Capital
cost
($)
No model
19,200
26,300
285,000
50,900
101,700
Net
annual cost
($/yr)
plant costs developed
10,900
4,000
75,700
13,700
29,500
3-35
-------
TABLE 3-21. OPTION 1 PERCHLOROETHYLENE CO-PRODUCT PLANT
CONTROL COSTS
Plant
4
5
6
7
8
9
Total
Plant
4
5
6
7
0
9
Total
Capital costs
Process Fugitive Storage
541,500
6,700 -- 387,600
675,500a
134,900
__
8,800 447,500a
6,700 8,800 2,187,000a
Net annual costs
Process Fugitive Storage
143,800
2,100 -- 103,000
183,200a
20,500
5,000 123,000a
2,100 5,000 573,500a
($)
Loading
--
138,300
69,200
261,100
--
--
468,600
($/yr)
Loading
-_
40,100
18,600
70,300
--
129,000
Total
541,500
532,600
744,700a
396,000
--
456,300a
2,671,100a
Total
143,800
145,200
201,800a
90,800
128,000a
709,600a
Includes joint storage for methane chlorination and perch!oroethylene
co-product processes at Plants 6 and 9.
indicates no optional controls
3-36
-------
3.5.2 Option 2 Control Costs
This section provides estimates for the Option 2 perch!oroethylene
co-product plant controls discussed in Section 3.4.
Process controls: Emission reductions for the estimated 90 percent
Option 2 process emission control by refrigerated condenser were derived
from Tables 3-6 and 3-13. Capital and annualized costs for all plants
under Option 2, below, are the same as those for the Plant 5 Option 1
process control, as explained in 3.5.1. This results in the net costs
and cost-effectiveness figures shown in Table 3-22.
Installed capital cost $6,650
Annualized cost $1,930
Utilities and labor $ 255
Total annualized costs $2,195
TABLE 3-22. NET ANNUALIZED COSTS FOR OPTION 2 CONTROL OF PROCESS
EMISSIONS AT PERCHLOROETHYLENE CO-PRODUCT PLANTS
Plant
4
5
6
7
8
9
Emission
reduction
(Mg/yr)
0.19
0.14
0.14
0.53
0.04
0.04
Recovery
credit
($/yr)
79
59
59
222
17
17
Net
annual
cost
($/yr)
2,116
2,136
2,136
1,973
2,178
2,178
Cost
effectiveness
($/Mg)
11,100
15,300
15,300
3,700
54,500
54,500
3-37
-------
Fugitive control: The 56 percent control under Option 2 requires
equipment specifications for pumps and relief valves to be added to the
Option 1 inspection and maintenance program. The total capital cost for
such program for the small SOCMI fugitives model plant is about $30,700,
with a corresponding annualized cost of $18,000.27 Assuming applicability
of these costs to the perchloroethylene co-product model plant (see
3.5.1), net annualized cost and cost-effectiveness are as follows.
Total installed capital cost $30,700
Total annualized cost 18,800
Recovery credit for carbon
tetrachloride ( 4,500)
Net annualized cost 14,300
Emission reduction 10.7 Mg/yr; 56%
Cost-effectiveness $ 1,340/Mg
Storage controls: Option 2 storage control costs for the perchloroethylene
co-product model plant are identical to those estimated for 95 percent
control under Option 1 in 3.5.1. These costs are as follows:
Total installed captial cost $285,000
Annualized cost 82,600
Recovery credit (6,900)
Net annualized cost 75,700
Emission reduction 16.5 Mg/yr; 95%
Cost-effectiveness $ 4,600/Mg
For the two^process plants, Option 1 control costs also apply to
Plants 6 and 9 for Option 2. The costs for Plant 8, below, were obtained
in the same manner as the Option 1 costs for two-process plants, described
in 3.5.1. The combined plant capacity factor for Plant 8 is 1.12.
3-38
-------
Plant 6 Plant 8 Plant 9
Installed capital cost $675,500 $319,200 $447,500
Annualized cost 195,900 92,600 129,700
Recovery credit (12,700) (5,300) (6,700)
Net annual cost $183,200 $ 87,300 $123,000
Emission reduction 30.3 Mg/yr 12.7 Mg/yr 16.1 Mg/yr
Cost-effectiveness $6,050/Mg $6,870/Mg $7,640/Mg
Loading controls: Model plant costs for Option 2 loading controls
at perchloroethylene co-product plants are identical to those for the
Option 1 90 percent control level, derived in 3.5.1. These costs are as
follows:
Total installed capital cost $101,700
Annualized cost 31,300
Recovery credit (1,840)
Net annualized cost 29,460
Emission-reduction 4.4 Mg/yr; 90%
Cost-effectiveness $ 6,700/Mg
Secondary controls: As explained in 3.5.1, no estimate was made of
secondary emission control costs.
Summary: Table 3-23 summarizes Option 2 model plant control costs
for perchloroethylene co-product plants developed in this sub-section.
Table 3-24 presents estimated capital and annualized control costs for
each plant. These costs were calculated by multiplying model plant
costs by the plant capacity factors in Table 3-4, except for all process
controls, and storage controls of Plants 6, 8 and 9, which are derived
individually, above.
3-39
-------
TABLE 3-23. OPTION 2 PERCHLOROETHYLENE CO-PRODUCT MODEL PLANT
CONTROL COSTS
Control
type
Process
Fugitive
Storage
Loading
Plant
4
5
6
7
8
9
Total
Plant
4
5
6
7
8
9
Total
Control
efficiency
TABLE 3-24.
Process
6,700
6,700
6,700
6,700
6,700
6,700
40,200
Process
2,100
2,100
2,100
2,000
2,200
2,200
12,700
90
56
95
90
OPTION 2
CONTROL
Fugitive
58,300
41,800
41,800
157,500
14,100
14,100
327,600
Fugitive
27,200
19,400
19,400
73,400
6,600
6,600
152,600
Capital
cost
($)
Net
annual cost
($/yr)
No model plant costs developed
30,700 14,300
285,000 75,700
101,700 29,500
PERCHLOROETHYLENE CO-PRODUCT
COSTS
Capital costs
Storage
541,500
387,600
675,500a
1,462,100
319,200a
447,500a
3,833,400a
Net annual costs
Storage
143,800
103,000
183,200a
388,300
87,300a
123,000a
l,028,600a
($)
Loading
193,200
138,300
138,300
521,700
46,800
46,800
1,085,100
($/yr)
Loading
56,100
40,100
40,100
151,300
13,600
13,600
314,800
PLANT
Total
799,700
574,400
862,300a
2,148,000
386,800a
515,100a
5,286,300a
Total
229,200
164,600
244,800a
615,000
109,700a
145,400a
l,508,700a
co-product processes at Plants 6, 8, and 9.
3-40
and perchloroethylene
-------
3.6 REFERENCES
1. Stanford Research Institute, 1982 Directory of Chemical Producers USA,
Menlo Park, CA, 1982.
2. Cooper, J.R., E.I. DuPont deNemours and Co., Wilmington, DE. Letter
to Jack R. Farmer, EPA, September 27, 1979.
3. Smith, D.W., E.I. DuPont deNemours and Co., Wilmington, DE. Letter
to D.R. Goodwin, EPA, March 23, 1978.
4. Anderson, M.E., and W.H. Battye, GCA/Technology Division, Locating
and Estimating Air Emissions from Sources of Carbon Tetrachloride,
Final Draft Report. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Air Management Technology
Branch, Research Triangle Park, NC. Contract No. 68-02-3510,
Work Assignment No. 22, September, 1982, p. 7 to 9.
5. Organic Chemical Manufacturing Volume 8: Selected Processes.
U.S. Environmental Protection Agency, Office of Air Quality Planning
and Standards, Research Triangle Park, NC. EPA-450/3-80-028c,
December 1980. Report 2, Section III.
6. 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.
7. Reference 4, p. 16 to 24.
8. Reference 5, Report 2, p. IV-2 and IV-7.
9. Beale, J., Dow Chemical USA, Midland, MI. Letter to L. Evans, EPA,
March 1, 1978.
10. Reference 4,- p. 16.
11. Reference 5, p. IV-1.
12. Reference 5, p. III-4.
13. Preliminary Report on U.S. Production of Selected Organic Chemicals
(Including Synthetic Plastics and Resin Materials) -- Preliminary
Totals, 1981. U.S. International Trade Commission, Washington, DC.
March 18, 1982.
3-41
-------
14. Tippitt, William, EPA. Memo to Robert Rosensteel, EPA,
February 5, 1982.
15. Bentley, Lyle, Alabama Air Pollution Control Commission, Montgomery,
AL. Personal communication with M.G. Smith, GCA, June 9 and
September 3, 1982.
16. DeBusschere, Michael, Jefferson County Air Pollution_Control District,
Louisville, KY. Personal communication with M.G. Smith, GCA,
June 9, 1982.
17. Gasperecz, Greg, Louisiana Air Quality Division, Baton Rouge, LA.
Personal communication with M.G. Smith, GCA, July 13, 1982.
18. Hobbs, F.D., Hydroscience, Inc. Trip Report: Visit to Vulcan
Materials Co., Geismar, LA, January 4, 1978.
19. Beale, J., Dow Chemical USA, Midland, MI. Letter to L. Evans, EPA,
April 28, 1978.
20. Reference 5, Report 2, p. V-2, 3.
21. Buergin, Ray, Kansas Bureau of Air Quality, Topeka, KS. Personal
communication with M.G. Smith, GCA, June 10, 1982.
22. Fry, Barbara, California Air Resources Board, Sacramento, CA.
Personal communication with M.G. Smith, GCA, June 11, 1982.
23. Reference 5, Report 2, p. IV-4.
24. Gasperecz, Greg, Louisiana Air Quality Division, Baton Rouge, LA.
Personal communication with M.G. Smith, GCA, February 2, 1983.
25. Maps Depicting Nonattainment Areas Pursuant to Section 108 of the
Clean Air Act. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Research Triangle Park, NC.
EPA 450/2-80-062. April 1980.
26. Status Summary of States' Group I VOC RACT Regulations as of
June 1, 1981: Second Interim Report. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Control
Programs Development Division, Contract No. 68-02-5310, Task No. 8,
July 1981.
27. Hustvedt, K.C., EPA, Personal communication with M.G. Smith, GCA,
January 27, 1983.
28. Fugitive Emission Sources of Organic Compounds—Additional Information
on Emissions, Emission Reductions, and Costs. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Emission Standards and Engineering Division, Research Triangle Park,
NC. EPA 450/3-82-010. April 1982. p. B-3.
3-42
-------
29. Organic Chemical Manufacturing Volume 3: Storage, Fugitive and
Secondary Sources. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-25. December 1980. Report 1, p. V-5.
30. Bulk Gasoline Terminals - Background Information for Proposed Standards-
Draft EIS. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Research Triangle Park, North Carolina.
EPA-450/3-80-038a. December 1980. p. 7-2.
31. Reference 29, Report 1, p. IV-18, V-ll.
32. F.D. Hobbs, Hydroscience, Inc. Trip Report: Visit to Vulcan Materials
Co., Geismar, LA, January 4, 1978.
33. Donald W. Smith, E.I. DuPont deNemours and Co., Wilmington, DE.
Letter to D.R. Goodwin, EPA, March 23, 1978.
34. R. Waldrop, Edwards Engineering, Inc., Pompton Plains, NJ. Personal
communication with M.G. Smith, GCA, July 26, 1982.
35. Organic Chemical Manufacturing Volume 5: Adsorption, Condensation,
and Absorption Devices. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-027. December 1980. Report 2, p. III-5.
36. Factors for Developing CTGD Costs. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Economic
Analysis Branch, September 1980.
37. Reference 35, Report 2, p. V-17.
38. Reference 35, Report 2, p. V-9.
39. Reference 5, Report 2, Chapter III and p. IV-5.
40. Reference 28, p. 1-6.
41. Reference 5, Report 5, p. IV-4.
42. Reference 5, Report 5, p. IV-6.
43. Reference 29, Report 1, p. C-16, C-17.
44. Reference 29, Report 1, p. IV-9.
45. Reference 5, Report 2, p. IV-4, and Report 5, p. IV-6.
46. Reference 29, Report 1, p. V-13.
47. Reference 30, p. 8-54.
3-43
-------
48. Reference 30, p. 7-2.
49. Reference 30, p. 8-41.
50. Reference 35, Report 2, pp. V-7 to V-9.
51. R.B. Neveril, CARD, Inc., Miles IL. Capital and Operating Costs of
Selected Air Pollution Control Systems. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standard, Research Triangle
Park, NC. EPA-450/5-80-002. December 1978.
52. Reference 5, Report 2, p. V-3.
3-44
-------
4.0 CARBON TETRACHLORIDE PRODUCTION BY METHANE CHLORINATION
This chapter discusses plants which produce carbon tetrachloride by
methane chlorination. A brief process description is followed by estimates
of uncontrolled emissions, Option 1 and Option 2 controls and emissions, •
and associated control costs. For plants which use methane chlorination
and the perch!oroethylene co-product process, assumptions as to the
amount of carbon tetrachloride made by each process were addressed in
Section 3.2, and will only be mentioned briefly here. Total costs for
storage emission control at these plants are estimated in Section 3.5,
and will not be addressed in this chapter.
4.1 METHANE CHLORINATION PROCESS DESCRIPTION
4.1.1 General Information
As shown in Table 3-1, the two plants using only methane chlorination
to produce carbon tetrachloride have the smallest production capacities
in the country, totalling 11,000 Mg/yr. An unknown amount of additional
production by methane chlorination is included in the 124,000 Mg/yr
total capacity for plants also using the perch!oroethylene co-product
process.
4.1.2 Process Description
In the methane chlorination process, carbon tetrachloride is produced
as a co-product with methyl chloride, methylene chloride and chloroform.
Methane may be chlorinated thermally, photochemically or catalytically,
but typical processes are thermal, operating at about 400°C and 200 kPa.
Four sequential distillations remove the various products with additional
process steps to handle by-product hydrogen chloride. A typical process
flow diagram for methane chlorination is shown in Figure 4-1. Crude
products and methyl chloride can be recycled to alter product mixes, but
no information is available on the actual product mix at individual
plants.
4-1
-------
-p.
I
IV)
"J
®
no»S
~" 1
T<
^
»
_t
j^
^&
M»— ^f
WWtMfWS
I®
TMf AVIt S
l:i^2^
ttt fMTi i nr MI >M(I i nr t*i niti [ Hr i in rmm OHi* cm own* now CM
NOTE: Letters In this figure refer to process vents
described in the text and tables. Numbers refer
to process descriptions 1n the first reference
cited below. Heavy lines indicate final product
streams throughout the process.
Figure 4-1. Process flow diagram for methane chlorination process.
1,2
-------
4.1.3 Carbon Tetrachloride Emission Factors for the Methane Chiorination
Process
Table 4-1 gives estimated emission factors for the carbon tetrachloride
emission points identified in Figure 4-1.
4.2 UNCONTROLLED METHANE CHLORINATION PLANT EMISSIONS
4.2.1 Model Plant
The model plant for the methane chlorination process was chosen to
1 2
be consistent with those used in previous investigations. With a
total chloromethanes production capacity of 200,000 Mg/yr divided into
20 percent methyl chloride, 45 percent methylene chloride, 25 percent
chloroform and 10 percent carbon tetrachloride, model plant carbon
tetrachloride production capacity is 20,000 Mg/yr. The basic model
plant configuration is shown in Figure 4-1. More detail on model plant
fugitive emission sources and storage facilities is provided in conjunction
with cost estimates in Section 4.5. See 3.2.1 for further discussion of
model plants.
4.2.2 Capacity Apportionment in Two-Process Plants
As discussed in 3.2.2, a number of assumptions and calculations had
to be made regarding the distribution of carbon tetrachloride production
capacity between the methane chlorination and perch!oroethylene co-product
processes at two-process plants. After estimating production by the
perchloroethylene co-product process, the following methylene chlorination
production capacities were obtained by subtraction: Plant 6: 20,200 Mg/yr,
Plant 8: 13,200 Mg/yr, Plant 9: 22,200 Mg/yr (see Table 3-3).
4.2.3 Proportionality and Scales of Production
Throughout the following analysis, direct proportionality of emissions,
control efficiencies and costs over all scales of production was assumed.
The plant capacity factors in Table 4-2, derived by dividing each plant's
assumed methane chlorination process capacity by that of the model
plant, were used to apply model plant emission estimates and control
costs to each plant. Production capacities for two-process plants were
cited above; other were taken directly from Table 3-1.
4-3
-------
TABLE 4-1. UNCONTROLLED MODEL PLANT CARBON TETRACHLORIDE EMISSION
FACTORS FOR METHANE CHLORINATION PROCESS
Uncontrolled
carbon
tetrachloride
Emission Source emission
source designation factor"
Recycled methane inert
gas purge vent A <0.042 kg/Mg
In-process storage B 0.031 kg/Mg
Distillation area
emergency inert gas vent
Process fugitive0
Product storage
Secondary
Hand! ing
C
D
E
F
0.052 kg/Mg
4.0 kg/hr
0.60 kg/Mg
0.017 kg/Mg
0.24 kg/Mg
a
;Source designation shown in Figure 4-1. A, B, and C are process
components.
Emission factors in terms of kg/Mg refer to kg of carbon tetrachloride
emitted per Mg of carbon tetrachloride produced. From Reference 3.
Fugitive emissions are independent of production rate.
4-4
-------
TABLE 4-2. METHANE CHLORINATION PLANT CAPACITY
FACTORS (RELATIVE TO MODEL PLANT)
Plant
capacity
Plant factor
1 0.20
3 0.35
6 1.01
8 0.66
9 1.11
Total 3.33
4.2.4 Uncontrolled Emissions
The methane chlorination model plant emissions in Table 4-3 are
based on the model plant carbon tetrachloride production capacity of
20,000 Mg/yr and the uncontrolled emission factors presented in
Table 4-1. The three process emission sources were combined for the
purpose of this analysis. The assumed industry-wide capacity utilization
factor of 0.68 (see 3.2.4) and the appropriate plant capacity factors
from Table 4-2 were applied to the model plant emission estimates to
produce the plant-specific estimates shown in Table 4-4.
TABLE 4-3. METHANE CHLORINATION MODEL PLANT EMISSIONS
Model plant
carbon tetrachloride
Source emissions (Mg/yr)
Process
Fugitive
Storage
Loading
Secondary
Total 54.6
4-5
-------
TABLE 4-4. UNCONTROLLED EMISSIONS FOR METHANE CHLORINATION PLANTS
Plant
number
1
3
6
8
9
Total
Process
0.34
0.60
1.72
1.12
1.89
5.67
Uncontrol
Fugitive
4.8
8.4
24.2
15.8
26.3
79.5
led emission estimates
Storage
1.6
2.9
8.3
5.4
9.0
27.2
Loading
0.65
1.15
3.31
2.16
3.60
10.87
(Mg/yr)
Secondary
0.05
0.08
0.23
0.15
0.26
0.77
Total
7.4
13.1
37.8
24.6
41.0
124.0
4.3 OPTION 1 CONTROLS AND EMISSIONS FOR METHANE CHLORINATION PLANTS
Option 1 control efficiencies represent the most stringent of
existing, State-required or applicable Group III CTG controls for areas
requesting an ozone NAAQS attainment date extension beyond 1982. These
controls are discussed individually below as they apply to carbon tetrachloride
production by methane chlorination. They are then combined to define
Option 1 control efficiencies for each source category at each plant,
and used to estimate controlled emissions under Option 1. State regulations
and Group III CTGs and associated control efficiencies are discussed in
detail in Section 2.2, and existing controls and State regulations
applying to methane chlorination plants are included in Tables 3-7 and
3-8. The discussion below is limited to the applicability of controls
to given plants and other plant-specific considerations.
4.3.1 Existing Controls
Information on control technology currently in place at carbon
tetrachloride production facilities was obtained mainly in telephone
conversations with State agency personnel. Some data were available
from previous EPA industry surveys. Table 3-7 summarizes the information
on existing controls. Control efficiencies were provided either in the
cited references, or derived from technical data in them. In most
cases, unreported efficiencies were estimated to be proportional to
4-6
-------
vapor pressure reductions achieved by given condenser outlet temperatures.
The reference reporting 50 percent control for the process vent condenser
at Plant 1 did not mention control of in-process storage. Control of
the emergency inert gas vent would not be practical, so this control was
assumed to apply only to the recycled methane inert gas purge vent
(Table 4-1). which would result in about 17 percent control of overall
process emissions. Since the existing storage tank condenser at Plant 3
was reportedly brine-cooled, a condenser outlet temperature of 5°C was
assumed, which would provide 50 percent control of carbon tetrachloride
emissions.
4.3.2 State Regulations
As shown in Table 3-8, the only State regulations which can be
assumed to provide some emission control at methane chlorination plants
are storage control requirements at Plants 6 and 9 (50 and 95 percent),
and loading control requirements at Plant 6 (50 percent). Texas process
control requirements are not applicable to methane chlorination process
vents at Plant 6, since the VOC in this vent stream includes only methane
and chlorinated organics, which are not covered by the list of affected
compounds given in Section 2.2.1. Applicability of the Texas loading
regulation is discussed in 3.3.2.
4.3.3 Group III Control Techniques Guidelines
Table 3-9 summarizes the current ozone NAAQS status of counties in
which carbon tetrachloride production facilities are located. Of the
plants using methane chlorination, the Group III CTGs (2.2.2) are assumed
to require 42 percent control of fugitive emissions and 95 percent of
storage emissions at Plants 3 and 9, due to extensions beyond 1982 for
these areas.
4.3.4 Combined Option 1 Controls
Table 4-5 summarizes control efficiencies applicable to methane
chlorination plants for the Option 1 controls described in 4.3.1, 4.3.2,
and 4.3.3. Table 4-6 provides more detail on the storage emission
controls involved. The most stringent level of storage control for each
plant was selected as the Option 1 storage control shown in Table 4-5.
4-7
-------
TABLE 4-5. OPTION 1 CONTROL SUMMARY FOR METHANE CHLORINATION PLANTS
Plant
1
3
6
8
9
Plant
1
3
6
8
9
1.3.5
Option 1 control effici
Process Fugitive Storage
17
42 95
95
__
42 95
TABLE 4-6. OPTION 1 CONTROLS FOR STORAGE
CHLORINATION PLANTS
ency (percent)
Loading Secondary
__
—
50
_.
__
EMISSIONS AT METHANE
Existing control Current regulations Group III CTG
— —
50
95 50
-_
95
Estimated Option 1 Emissions
__
95
—
--
95
Applying control efficiencies in Table 4-5 to uncontrolled emission
estimates (Table 4-4) produced the Option 1 controlled emission estimates
in Table 4-7.
4-8
-------
TABLE 4-7. OPTION 1 CONTROLLED EMISSIONS FOR METHANE CHLORINATION PLANTS
Plant
1 .
3
6
8
9
Total
Option 1
control
efficiency
lo/\
\/o)
Process
0.28
0.60
1.72
1.12
1.89
5.61
1
Option
Fugitive
4.8
4.9
24.2
15.8
15.3
65.0
18
1 controlled emissions
Storage
1.6
0.1
0.4
5.4
0.5
8.0
70
Loading
0.65
1.15
1.66
2.16
3.60
9.22
15
(Mg/yr)
Secondary
0.05
0.08
0.23
0.15
0.26
0.77
—
Total
7.4
6.8
28.2
24.6
21.6
88.6
29
4.4 OPTION 2 CONTROLS AND EMISSIONS FOR METHANE CHLORINATION PLANTS
This section describes the estimated best control (EBC) used in
Option 2, and estimates the emissions expected after application of
these controls to methane chlorination plants.
4.4.1 Estimated Best Controls
The following control methods were selected as EBC for carbon
tetrachloride plants using the methane chlorination process. All control
efficiencies are specific to carbon tetrachloride.
Process emissions: IT Enviroscience performed preliminary design
for a chloroform-based absorption system operating at -40°C and 200 kPa,
which was estimated to provide 92 percent control of the inert gas purge
vent and in-process storage. The intermittent nature of the emergency
inert gas vent emissions makes known controls impractical. Improved
process control may be a feasible method of reducing these emissions,
but sufficient information was not available to permit assessment of
this type of approach. Applying 92 percent control to model plant inert
gas purge vent and in-process storage emissions, and assuming no control
of the emergency inert gas vent, yields an overall process control
efficiency of 62 percent.
4-9
-------
Fugitive emissions: It was estimated that an inspection and repair
—a —— o
program similar to the Group III CTG can provide 42 percent control, and
that EBC would include addition of equipment specifications for pumps,
g
compressors and relief valves, which can raise this to 56 percent control.
Storage emissions: Vapor recovery and -20°C refrigerated condenser
systems can control carbon tetrachloride storage emissions at efficiencies
up to 95 percent.6'10'11
Loading emissions: Vapor recovery, refrigerated condensers and
tank truck leakage reduction measures are estimated to provide 90 percent
12 13
control of loading emissions. '
Secondary emissions: Secondary emission sources include waste
caustic from three process locations, sulfuric acid and high density
salt solution from two different dryers, and heavies from distillation.
Controls for these emissions could not be developed due to lack of
technical data, and it appears that existing control techniques would be
impractical for these disparate sources.
4.4.2 Estimated Option 2 Emissions
Table 4-18 summarizes annual emissions and control efficiencies
which can be achieved by methane chlorination plants with the Option 2
controls described in 4.4.1.
TABLE 4-8. OPTION 2 CONTROLLED EMISSIONS FOR METHANE CHLORINATION PLANTS
Plant
1
3
6
8
9
Process
0.13
0.23
0.65
0.43
0.72
Option 2
Fugitive
2.1
3.7
10.6
7.0
11.6
controlled emissions (Mg/yr)
Storage
0.08
0.15
0.42
0.27
0.48
Loading
0.06
0.12
0.33
0.22
0.36
Secondary
0.05
0.08
0.23
0.15
0.26
Total
2.4
4.3
12.2
8.1
13.4
Total
Option 2
control
efficiency
2.16
62
35.0
56
1.37
95
1.09
90
0.77
40.4
67
4-10
-------
4.5 CONTROL COSTS FOR METHANE CHLORINATION PLANTS
This section estimates control costs for the Option 1 and Option 2
controls discussed in this chapter. Model plant costs are developed for
each source category and plant-specific costs for Options 1 and 2 are
presented under summary headings at the end of 4.5.1 and 4.5.2. Costing
methodology and assumptions are discussed in Chapter 1. All costs are in
July 1982 dollars except where noted. Examples and details of control
requirement calculations are presented in Appendix B. Storage control
costs for Plants 6, 8 and 9 were estimated in Section 3.5, and are not
addressed in this section.
4.5.1 Option 1 Control Costs
This section provides cost estimates for the Option 1 methane
chlorination plant controls discussed in 4.3.4.
Process controls: The only Option 1 process emission control for
methane chlorination is a 50 percent efficiency refrigerated condenser
on the process vents at Plant 1. The following analysis uses the only
available detailed emissions data, which are for Plant 6, to arrive at
model plant control costs which can then be scaled to the size of Plant 1.
Process data presented in Appendix B-2 result in a calculated flow rate
of 87 ft /min and the following estimates of emissions and recovery
credit for Plant 6.
TABLE 4-9. EMISSIONS AND RECOVERY CREDITS FOR 50 PERCENT METHANE
CHLORINATION PROCESS CONTROL AT PLANT 6
voc
component
Methyl chloride
Methylene chloride
Chloroform
Carbon tetrachloride
Uncontrolled
emission
rate
(Mg/yr)
389
9.8
0.6
0.8
1,297
50%
emission
reduction
(Mg/yr)
194
4.9
0.3
0.4
199.6
14
Price1^
($/Mg)
435
528
682
418
Recovery
credit
($/yr)
84,390
2,590
200
170
87,350
4-11
-------
Since the methane chlorination process capacity at Plant 6 is only
1 percent larger than that of the model plant, the recovery credits and
emission reductions above were used directly in the following model
plant cost analysis. IT Enviroscience estimated control costs for
50 percent control of a VOC stream of similar molecular weight and flow
rate, for VOC concentrations from 2 to 20 percent, as follows:
TABLE 4-10. CONTROL COST SUMMARY FOR 50 PERCENT VOC REMOVAL BY
REFRIGERATED CONDENSER^
(Molecular weight = 60; Flow rate = 100 ft /min)
VOC
concentration
(%)
20
10
5
2
Total
installed
capital
cost ($)
104,600
79,200
64,500
53,100
Annual i zed
capital
cost
($/yr)
30,400
23,100
18,700
15,400
Electricity
($/yr)
100
100
100
100
Labor
($/yr)
16,600
16,600
16,600
16,600
The capital costs include all battery-limit costs for new equipment
and a contingency allowance of 30 percent. Linear projection of these
capital costs to a VOC concentration of 30 percent gives an approximate
capital cost of $130,000 and an annualized cost of $38,000. Electricity
and labor were assumed to be constant. It was further assumed that use
3 3
of a 100 ft /min unit for an 87 ft /min flow rate would be appropriate.
Model plant costs and credits for all VOC recovery at full capacity and
for carbon tetrachloride recovery alone at estimated 0.68 capacity
utilization are as follows:
Installed capital cost
Annualized cost
Utilities and labor
Total annualized costs
$130,000
$ 38,000
$ 16,700
$ 54,700
4-12
-------
For all VOC (at full production):
Recovery credit $(87,350)
Net annualized cost (credit) (32,650)
Emission reduction 200 Mg/yr; 50%
Cost-effectiveness (credit) $(163)/Mg
For carbon tetrachloride (at 0.68 capacity utilization):
Recovery credit $( 120)
Net annualized cost $ 54,580
Emission reduction 0.3 Mg/yr; 50%
Cost-effectiveness $ 182,000/Mg
The net annualized cost of $54,580 for 50 percent control by refrigerated
condenser estimated above is greater than the cost estimated for 92 percent
control by an absorption system in Option 2, below. This may be due to
potential overestimation in the Option 1 cost derivation, or the better
efficiency achieved by the less expensive proposed Option 2 control.
Since the Option 1 cost estimate is for an existing control system, it
was assumed the possibility of more efficient controls is not relevant.
A plant size scaling factor of 0.20 results in a net annualized Option 1
process control cost for Plant 1 of $10,920 and an estimated total
installed capital cost of $26,000, for 50 percent control by refrigerated
condensation.
Fugitive controls: Based on the totals for model plant fugitive
emission sources and process descriptions from IT Enviroscience,
estimates of fugitive sources in carbon tetrachloride service at methane
chlorination plants were made. Comparison of these carbon tetrachloride
sources to the medium-sized model plant in the SOCMI fugitive CTG in
Table 4-11 indicates that a capital cost of $43,300 and an annual cost
o
of $34,800 for the CTG inspection and maintenance program would be
appropriate for Option 1 costs for the methane chlorination model plant.
With an emission reduction based on 0.68 capacity utilization, this
results in the following model plant cost analysis.
4-13
-------
TABLE 4-11. MODEL PLANT FUGITIVE EMISSION SOURCES
Pumps
Process
Relief
valves
valves
Compressor
Capital cost
Annual ized cost
Recovery credit
Net annualized
Methane chl
Total
fugitive
sources!6
80
1,930
70
1
for carbon
cost
orination model plant
In carbon
tetrachloride
service
36
840
6
0
$43,
34,
tetrachloride (4,
$30,
Emission reduction
Cost-effectiveness
$3,
Medium SOCMI
fugitives
model
plant1?
29
926
46
2
300
800
180)
620
10.0 Mg/yr; 42%
060/Mg (cost)
Storage controls: This discussion covers only Option 1 control
costs for storage facilities at Plants 1 and 3, since the two-process
plants (Plants 6, 8 and 9) are covered in Section 3.5. The following
Option 1 storage control cost estimates for the methane chlorination
model plant are based on the costs in Table 3-17, which are explained in
Section 3.5.
Total installed capital cost
Annualized cost
Recovery credit
Net annualized cost
Emission reduction
Cost-effectiveness
$285,000
82,600
(3.300)
79,300
7.8 Mg/yr; 95 percent
$10,166/Mg
4-14
-------
Loading controls: The basis for the derviation of annual and
capital costs for loading control is explained in 3.5.1. From Figure 3-3,
July 1982 total annualized costs for 90 percent control of methane
chlorination model plant loading emissions can be estimated at $23,200.
Assuming 65 percent of the total annual cost as capital charges and an
annualized capital cost factor of 0.20 results in a corresponding capital
cost of $75,400. The following annual and capital cost estimates for
the 50 percent Option 1 level were derived from these 90 percent control
costs using the same methods described in 3.5.1. From Table 3-19, the
50 percent control annual cost was assumed to be 47 percent of that for
90 percent control, or $10,900. Based on 50 percent reduction of capital
costs, the corresponding capital cost is estimated at $37,700.
Total installed capital cost $37,700
Annualized cost $10,900
Recovery credit (670)
Net annualized cost 10,230
Emission reduction 1.6 Mg/yr; 50%
Cost-effectiveness $ 6,400/Mg
Secondary controls: No secondary emission controls were identified
for methane chlorination plants.
Summary: Table 4-12 summarizes Option 1 model plant control costs
for methane chlorination plants developed in this sub-section. Table 4-13
presents estimated capital and annualized control costs for each plant.
These costs were calculated by multiplying model plant costs by the
plant capacity factors in Table 4-2.
4-15
-------
TABLE 4-12. OPTION 1 METHANE CHLORINATION MODEL PLANT
CONTROL COSTS
Control
type
Process
Fugitive
Storage
Loading
Control
efficiency
(%)
17
42
95
50
Capital
cost
($)
130,000
43,300
285,000
37,700
Net
annual cost
($/yr)
54,600
30,600
79,300
10,230
TABLE 4-13. OPTION 1 METHANE CHLORINATION PLANT CONTROL COSTS
Capital costs ($)
Plant Process
1 26,000
3
6
0
9
Total 26,000
Fugitive
--
15,200
--
48,200
63,400
Storage Loading
__
99,800
a 38,100
a
99,800a 38,100
Total
26,000
115,000
38,100a
48,200
227,300a
Net annual costs ($/yr)
Plant Process
1 10,900
3
6
8
9
Total 10,900
Fugitive
--
10,700
--
--
34,000
44,700
Storage Loading
--
27,800
a 10,300
--
a
27,800a 10,300
Total
10,900
38,500
10,300a
_ _
34,000a
93,700a
Storage at Plants 6 and 9 was addressed in Chapter 3 and is not included
here.
indicates no Option 1 control
4-15
-------
4.5.2 Option 2 Control Costs
This section provides estimates of the Option 2 methane chlorination
plant controls discussed in Section 4.4.
Process controls: The Option 2 control for the methane chlorination
process was based on a preliminary chloroform absorber design by IT
Enviroscience, which included the following capital and annualized cost
18
estimates for the model methane chlorination plant:
Total installed capital cost $165.000
Annualized cost $ 47,900
Utilities $ 1.500
Total annualized cost $ 49,400
Recovery credit ($220,400)
Net annualized cost (credit) ($171,000)
Emission reduction 504 Mg/yr; 92%
Cost-effectiveness ($ per Mg ($339/Mg)
emission reduction) (savings)
The recovery credit cited above is based on the value of the net recovery
of methyl chloride (97.1 percent), methylene chloride (2.4 percent),
chloroform (0.2 percent), and carbon tetrachloride (0.2 percent), which
are recycled to the process.19 Since this absorber does not control the
emergency inert gas vent, it applies only to the 1.46 Mg/yr of the
2.50 Mg/yr total model plant process emissions which are due to the
controlled purge vent and in-process storage (see Tables 4-1 and 4-3).
The 92 percent efficiency of the absorber on these two sources produces
62 percent control of total carbon tetrachloride process emissions.
With 0.68 capacity utilization, this results in a net emission control
of about 0.91 Mg/yr of carbon tetrachloride for the model plant. The
following analysis would apply to the model plant:
4-17
-------
Total annualized cost $49,400
Recovery credit for carbon
tetrachloride ($ 380)
Net annualized cost $49,020
Emission reduction 0.91 Mg/yr; 92%
Cost-effectiveness $53,900/Mg (cost)
Fugitive control: Option 2 adds equipment specifications for pumps
and relief valves to the Option 1 inspection and maintenance program,
for a total control efficiency of 56 percent. The total capital cost of
such a program for the medium-size SOCMI fugitives model plant is $77,600,
Q
with a corresponding annualized cost of $50,700. Assuming applicability
of these costs to the methane chlorination model plant (see 4.5.1), the
following net cost and cost-effectiveness were derived.
Total installed capital cost $77,600
Annualized cost 50,700
Recovery credit for carbon
tetrachloride ( 5,560)
Net annualized cost 45,140
Emission reduction 13.3 Mg/yr; 56%
Cost-effectiveness $ 3,394/Mg (cost)
Storage controls: This discussion covers only the Option 2 control
costs for Plants 1 and 3, since the two-process plants (Plants 6, 8 and
9) were covered in Section 3.5. The following Option 2 storage control
cost estimates for the methane chlorination model plant are based on the
costs in Table 3-17, which are explained in Section 3.5. They are
identical to Option 1 control costs presented in 4.5.1.
4-18
-------
Total installed capital cost $285,000
Annualized cost 82,600
Recovery credit (3.300)
Net annual ized cost 79,300
Emission reduction 7.8 Mg/yr; 95 percent
Cost-effectiveness $ 10,166/Mg
Loading controls: The basis for the derivation of annual and
capital costs for loading control is explained in 3.5.1. From Figure 3-3,
July 1982 total annualized costs for 90 percent control of loading
emissions at the methane chlorination model plant can be estimated at
$23,200, with a corresponding capital cost of $75,400. These costs
result in the following net cost and cost-effectiveness figures, based
on 90 percent control of model plant emissions (Table 4-3) and 0.68 capacity
utilization.
Total installed capital cost $75.400
Annualized cost 23,200
Recovery credit (1.200)
Net annualized cost 22,000
Emission reduction 2.9 Mg/yr; 90%
Cost-effectiveness $7,586/Mg
Secondary controls: No feasible controls were identified for
control of secondary emissions at methane chlorination plants.
Summary: Table 4-14 summarizes Option 2 model plant control costs
for methane chlorination plants developed in this sub-section. Table 4-15
presents estimated capital and annualized control costs for each plant,
calculated by multiplying model plant costs by the plant capacity factors
in Table 3-4.
4-19
-------
TABLE 4-14. OPTION 2 METHANE CHLORINATION MODEL PLANT
CONTROL COSTS
Control
type
Process
Fugitive
Storage
Loading
TABLE 4-15.
Plant
1
3
6
8
9
Total
Plant
1
3
6
8
9
Total
Process
33,000
57,800
166,700
108,900
183,200
549,600
Process
9,800
17,200
49,500
32,300
54,400
163,200
Control
efficiency
(*)
62
56
95
90
Capital Net
cost annual cost
($) ($/yr)
165,000
77,600
285,000
75,400
OPTION 2 METHANE CHLORINATION PLANT CONTROL
Fugitive
15,500
27,200
78,400
51,200
86,100
258,400
Fugitive
9,000
15,800
45,600
29,800
50,100
150,300
Capital costs ($)
Storage Loading
57,000 15,100
99,800 26,400
a 76,200
a 49,800
a 83,700
156,800a 251,200
Net annual costs ($/yr)
Storage Loading
15,900 4,400
27,800 7,700
a 22,200
a 14,500
a 24,400
43,700a 73,200
49,000
45,100
79,300
22,000
COSTS
Total
120,600
211,200
321,300a
209,900a
353,000a
l,216,000a
Total
39,100
68,500
117,300a
76,600a
128,900a
430,400a
Storage at Plants 6, 8, and 9 was addressed in Chapter 3 and is not
included here.
4-20
-------
4.6 REFERENCES
1. Anderson, M.E., and W.H. Battye, GCA/Technology Division, Locating
and Estimating Air Emissions from Sources of Carbon Tetrachloride,
Final Draft Report. U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards, Air Management Technology Branch,
Research Triangle Park, NC. Contract No. 68-02-3510, Work Assignment
No. 22, September, 1982. p. 8-12.
2. Organic Chemical Manufacturing Volume 8: Selected Processes. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards, Research Triangle Park, NC. EPA-450/3-80-028c.
December 1980. Report 5, Section III.
3. Reference 1, p. 18.
4. Reference 1, p. 16.
5. Reference 2, p. IV-1.
6. Beale, J., Dow Chemical USA, Midland, MI. Letter to L. Evans, EPA,
April 28, 1978.
7. Reference 2, Report 5, p. V-2.
8. Hustvedt, K.C., EPA. Personal communication with M.6. Smith, GCA,
January 27, 1983.
9. Fugitive Emission Sources of Organic Compounds—Additional Information
on Emissions, Emission Reductions, and Costs. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Emission Standards and Engineering Division, Research Triangle Park,
NC. EPA-450/3-82-010. April 1982. p. B-3.
10. Tippitt, W., EPA. Memo to Robert Rosensteel, EPA, February 5, 1982.
11. Organic Chemical Manufacturing Volume 3: Storage, Fugitive and
Secondary Sources. U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-25. December 1980. Report 1, p. IV-18.
12. Bulk Gasoline Terminals - Background Information for Proposed Standards'
Draft EIS. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Research Triangle Park, North Carolina.
EPA-450/3-80-038a. December 1980. p. 7-2.
4-21
-------
13. Reference 11, Report 1, p. V-ll.
14. Chemical Marketing Reporter, July 12, 1982.
15. Organic Chemical Manufacturing Volume 5: Adsorption, Condensation,
and Adsorption Devices. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-027. December 1980. Report 2, p. V-2 and V-7.
16. Reference 2, Report 5, p. IV-5 and Chapter III.
17. Reference 9, p. 1-6.
18. Reference 2, Report 5, p. VI-4.
19. Reference 2, Report 5, p. IV-4.
4-22
-------
5.0 CARBON TETRACHLORIDE PRODUCTION BY CARBON DISULFIDE CHLORINATION
This chapter discusses the one domestic plant known to produce
carbon tetrachloride by chlorination of carbon disulfide. A brief process
description is followed by estimates of uncontrolled emissions, Option 1
and Option 2 controls and emissions, and control costs.
5.1 CARBON DISULFIDE PROCESS DESCRIPTION
5.1.1 General Information
As shown in Table 3-1, the Stauffer plant at LeMoyne, Alabama (Plant 2),
is the only domestic plant producing carbon tetrachloride by chlorination
of carbon disulfide. The 91,000 Mg/yr production capacity of this plant
is the second largest in the U.S. Two other carbon disulfide-based
plants (FMC Corp. at South Charleston, WV, and Stauffer at Niagara Falls,
NY) have been closed down since 1975, but formerly had production capacities
from 75,000 to 150,000 Mg/yr.1
5.1.2 Process Description
In the carbon disulfide chlorination process, a solution of carbon
disulfide and sulfur chloride in carbon tetrachloride is fed to a chlorina-
tion reactor where chlorine is sparged through the solution to yield a
mixture of carbon tetrachloride and sulfur chloride. Crude product carbon
tetrachloride is distilled off, purified and dried. The sulfur chloride
is then reacted with carbon disulfide. producing carbon tetrachloride and
elemental sulfur. The carbon tetrachloride produced in this reaction and
2 3
excess carbon disulfide are recycled to the chlorination reactor. '
Figure 5-1 is a process flow diagram for Plant 2.
5-1
-------
CAUSTIC
SCRUBBER
CHLORINATOR
(A)
^
CRUDE
PRODUCT
DISTILLATION
COLUMN
DECHLORINATOR
DISTILLATION
COLUMN
WATER
SCRUBBER
IRON
CAUSTIC
CAUSTIC
PURIFICATION
DRYING
COLUMN
n
LOADING
NOTE:
CARBON
TETRACHLORIDE
STORAGE ^
Letters in this figure refer to process vents
described in the text and tables. Numbers refer
to process descriptions in the first reference
cited below. Heavy lines indicate final product
streams throughout the process.
Figure 5-1. Process flow diagram for carbon disulfide chlorination process.
' '
-------
5.1.3 Carbon Tetrachloride Emission Factors for the Carbon Disulfide
Process
Table 5-1 gives estimated emission factors for the Stauffer/LeMoyne
plant emission points shown in Figure 5-1. Existing emission factors
were reviewed, and new information on process emission controls was used
to produce an uncontrolled process emission factor. Information submitted
to the State of Alabama by Stauffer indicates that the existing two-stage
condenser has an efficiency of 95 percent. A source test indicated controlled
carbon tetrachloride emissions of 55 kg/hr. Uncontrolled emissions would
thus be in the range of 1090 kg/hr or 9,560 Mg/yr. Based on production at
the time of the test (81,800 Mg/yr), an uncontrolled emission factor of
117 kg/Mg was calculated. As discussed further in 5.3.1, there may be
some question as to the degree to which this existing condenser should be
considered a process component rather than an emission control. The cost
analysis (5.5.1) shows a very favorable product recovery credit.
TABLE 5-1. UNCONTROLLED CARBON TETRACHLORIDE EMISSION FACTORS
FOR CARBON DISULFIDE CHLORINATION PROCESS
Emission
source
Process
Storage
Handling
Fugitive
Source
designation
A
B
C
Uncontrolled
carbon
tetrachloride
emission
factorb
117 kg/Mg
0.81 kg/Mg
0.24 kg/Mg
0.60 kg/Mg
Source designation shown in Figure 5-1.
Emission factors in terms of kg/Mg refer to kg of carbon tetrachloride
emitted per Mg of carbon tetrachloride produced. From Reference 5,
except Source A, as described in the text.
5-3
-------
5.2 UNCONTROLLED CARBON DISULFIDE PLANT EMISSIONS
The uncontrolled emission estimates in Table 5-2 were developed for
Plant 2. These estimates are based on a production capacity of 91,000 Mg/yr
(Table 3-1), the assumed industry-wide capacity utilization factor of 0.68
(see 3.2.4) and full-production uncontrolled emission factors from Table 5-1.
TABLE 5-2. UNCONTROLLED EMISSION ESTIMATES FOR THE CARBON DISULFIDE PLANT
Uncontrolled emissions
Plant
2
Process
7,240
Fugitive
37
Storage
50
(Mg/yr)
Loading
15
Total
7,342
5.3 OPTION 1 CONTROLS AND EMISSIONS FOR THE CARBON DISULFIDE PLANT
The Group III CTGs do not apply to Plant 2, so this section discusses
existing controls and applicable Alabama regulations and then applies them
to estimate Option 1 controlled emissions.
5.3.1 Existing Controls
The only reported existing emission control at Plant 2 is the
refrigerated condenser on the chlorination reactor cited in 5.1.3, which
is reported to reduce uncontrolled emissions by 95 percent. The resulting
reduction in the controlled process emissions is shown in Table 5-3.
The existing condenser might be considered a basic process unit rather
than an emission control. Without it, about 10 percent of total carbon
tetrachloride production would be lost as emissions, along with other
components of the vent stream. Its high product recovery and cost-
effectiveness are shown in the control cost analysis (5.5.1). For this
assessment, however, the existing condenser has been treated strictly as
a control device.
5.3.2 State Regulations
Alabama regulations do exist for VOC storage and loading, as indicated
in Chapter 2, but submerged fill and the additional loading line controls,
which are minimal requirements in these regulations, were included in
5-4
-------
the uncontrolled emission factors for storage and loading since these
controls were assumed to be standard industry practice. Thus they
provide no additional control over the emissions shown in Table 5-2.
5.3.3 Combined Option 1 Controls
The existing condenser on the chlorination reactor is the only
control relevant to Option 1, providing 95 percent control of process
emissions.
5.3.4 Estimated Option 1 Emissions
Table 5-3 provides estimated Option 1 emissions, which reflect
95 percent control of the uncontrolled process emissions in Table 5-2.
TABLE 5-3. OPTION 1 CONTROLLED EMISSIONS FOR THE CARBON DISULFIDE PLANT
Plant Process
2 362
Option 1
control
efficiency
Option
Fugitive
37
1 emissions
Storage
50
(Mg/yr)
Loading
15
Total
464
95 -- — — 94
5-5
-------
5.4 OPTION 2 CONTROLS AND EMISSIONS FOR THE CARBON DISULFIDE PLANT
This section describes the estimated best controls (EBC) used in
Option 2, and estimates the emissions expected after application of
these controls to Plant 2.
5.4.1 Estimated Best Controls
The following control methods were selected as EBC for the carbon
disulfide plant.
Process emissions: Control assessments were performed for additional
refrigerated condensation of the existing -20°C condenser outlet stream,
to -40°C and -62°C. Use of retrofit units at these temperatures would
provide 74 and 95 percent additional control, increasing the total
process control from 95 percent to 98.7 and 99.8 percent, respectively.
These theoretical control efficiencies were calculated from the reduction
in carbon tetrachloride's vapor pressure corresponding to each condenser's
outlet temperature, as shown in Table 5-4. The theoretical -62°C condensation
requirement appears feasible with a retrofit cascade-type refrigeration
system (costs are estimated in 5.5.2). Thus the additional 95 percent
control over emissions with the existing condenser, or 99.8 percent net
control, was chosen as Option 2.
Fugitive emissions: Combination of an inspection and repair program
and equipment specifications, can achieve a total control efficiency of
56 percent.
Storage emissions: Vapor recovery and a -20°C refrigerated condenser
system can control carbon tetrachloride storage emissions at efficiencies
up to 95 percent.8'9'10
Loading emissi-ons: Vapor recovery, refrigerated condensers and
tank truck leak reduction measures are estimated to provide 90 percent
11 12
control of loading emissions.
5.4.2 Estimated Option 2 Emissions
Based on control efficiencies of estimated best controls cited in
5.4.1, controlled emissions were estimated for Option 2, as shown in
Table 5-5.
5-6
-------
TABLE 5-4. OPTION 2 PROCESS CONTROLS FOR THE CARBON DISULFIDE PLANT
CJ1
i
Uncontrolled
Option 1
Existing condenser
Option 2
-40°C condenser
-62°C condenser
Outlet
temperature
(°C)
40.5 (105°F)
-20 (-4°F)
-40 (-40°F)
-62 (-80°F)
Carbon
tetrachloride
vapor
pressure
(mm Hg)
210
10.4
2.7
0.48
Estimated
carbon
tetrachloride
control
relative to
uncontrolled
case (%)
--
95
98.7
99.8
Estimated
carbon
tetrachloride
control
relative to
existing
emissions (%)
—
_ ..
74
95
-------
TABLE 5-5. OPTION 2 CONTROLLED EMISSIONS FOR THE CARBON DISULFIDE PLANT
Option 2 controlled emissions (Mg/yr)
Plant
Process
Fugitive
Storage
Loading
Total
Option 2
control
efficiency
18
99.8
16
56
95
90
37
99
5-8
-------
5.5 CONTROL COSTS FOR THE CARBON DISULFIDE PLANT
This section estimates control costs for the Option 1 and Option 2
controls discussed in this chapter. Since only one plant is involved,
costs were developed directly without a model plant approach. All costs
are for July 1982. Examples and details of control requirement calculations
are presented in Appendix B.
5.5.1 Option 1 Control Costs
This section provides cost estimates for the only Option 1 carbon
disulfide plant control, the process condenser discussed in 5.3.3.
Process control: The refrigeration requirement for the existing
-20°C condenser is calculated in Appendix B-3 as about 28 tons. The
installed capital cost of such a condenser is estimated at $55,000,
excluding coolant/product piping. A total installation cost factor of
14
0.61 was reduced to 0.30, assuming piping is about half of the total
installation cost factor. This results in an installed capital cost of
$71,500. Annualized costs were based on a 29 percent factor which was
developed specifically for condensers, and include maintenance (6 percent);
taxes, insurance, and administration (5 percent); and capital recovery
(18 percent). Utility costs were based on approximate usage rates per
ton of cooling capacity (3 gpm/ton cooling water; 1.5 KW/ton electricity
usage at -20°C)13, at $0.109 per 1000 gallons and $0.083 per kilowatt-hour
(see Appendix B-3). Operating labor is based on $19/hour and 10 percent
of operating time (i.e., 876 hours/year). Recovery credit is based
only on carbon tetrachloride emission reduction at 0.68 capacity utilization
from Tables 5-2 and 5-3, although consideration of concurrent control of
carbon disulfide and sulfur chloride would increase credits.
5-9
-------
Total installed capital cost $71.500
Annualized cost 20,700
Electricity 29,000
Water 4,800
Operating labor 16,000
Total annualized cost 71,100
Recovery credit
(CC14 only) (2,875,000)
Net annualized cost (credit) (2,804,000)
Emission reduction 6,878 Mg/yr; 95%
Cost-effectiveness ($408/Mg)
(credit)
5.5.2 Option 2 Control Costs
This section provides cost estimates for Option 2 disulfide plant
controls discussed in Section 5.4.
Process control: As described in Appendix B-3, it is estimated
that a secondary condenser at -62°C can provide 95 percent control of
the emissions from the existing process condenser, resulting in a net
control of 99.8 percent over estimated uncontrolled emissions. The
costs below assume that the existing condenser is in place, and do not
include Option 1 costs. Thus the Option 2 costs and cost-effectiveness
shown below are incremental relative to Option 1. The capital cost for
the retrofit condenser of $90,000 was obtained from an equipment manufacturer
because a published cost estimate was not available for this specialized
unit. The installed capital cost is based on an additional 18 percent
for taxes, freight and instrumentation and a 61 percent factor for
14
indirect and direct installation costs. Annualized costs were based
on a 29 percent factor which was developed specifically for condensers,
and includes maintenance (6 percent); taxes, insurance, and administration
(5 percent); and capital recovery (18 percent). Utility costs were
based on approximate usage rates per ton of cooling capacity (3 gpm/ton
5-10
-------
cooling water; 15 KW/ton electricity usage at -62°C),13 at $0.109 per
1000 gallons and $0.082 per kilowatt-hour. Operating labor is based on
$19/hour and 10 percent of operating time (i.e., 876 hours/year).
These cost estimates are based on the same cost factors as the previously-
addressed condensers for the perch!oroethylene co-product and methane
chlorination processes, except for utility costs. Utility costs were
estimated as described in Appendix B-3. Previously-used cost estimates
could not be applied directly. Recovery credits are based only on
carbon tetrachloride emission reductions at 0.68 capacity utilization
(see Tables 5-2 and 5-5), although consideration of concurrent control
of carbon disulfide and sulfur chloride would increase credits.
Total installed capital cost $171,000
Annualized cost 49,600
Electricity 25,200
Water 400
Operating labor 16.600
Total annualized cost 91,800
Recovery credit (CC14 only) (143.800)
Net annualized cost (credit) ( 52,000)
Emission reduction 344 Mg/yr; 99.8%
Cost-effectiveness (credit) ($151/Mg)
Fugitive control: The best available information on components of
the carbon disulfide process is depicted in the process flow diagram
presented in Figure 5-1. Since this does not include data on the number
of process valves, pumps and other fugitive emission sources, it was
assumed that approximate control costs could be derived from the Option 2
costs already presented for the perchloroethylene co-product model plant
in 3.5.2. The sections of these two processes in carbon tetrachloride
service consist of similar process units (reactor, condenser, crude
product distillation/dechlorination, carbon tetrachloride drying/distillation),
each with about ten process flow lines in carbon tetrachloride service.
These similarities indicate that the number of necessary pumps and
5-11
-------
valves in carbon tetrachloride service should be about the same for
these two processes. Thus control costs developed for perchloroethylene
co-product model plant were used with an annual carbon disulfide plant
fugitive emission reduction estimate corresponding to 0.68 capacity
utilization in the following cost calculations for Option 2 control.
Total installed capital cost
Annualized cost
Recovery credit for carbon
tetrachloride
$30.700
18,800
Net annualized cost
Emission reduction
Cost-effectiveness
(8,800)
10,000
21 Mg/yr; 56%
$477/Mg (cost)
Storage control: The storage tank inventory reported for the
Stauffer plant at LeMoyne, Alabama is shown in Table 5-6. The number of
turnovers per year for the larger tanks were calculated by assuming
evenly distributed throughput of the plant's annual production capacity
and average tank use at half of capacity. The turnover rates of the
smaller tanks were not estimated due to lack of information on their
uses, but they are probably intermediate product storage or check tanks
with relatively high turnover rates.
TABLE 5-6. CARBON DISULFIDE PLANT STORAGE
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Number of
tanks6
2
2
2
1
Size
(m3)6
869
1,739
60
68
Turnovers
per year
20
20
--
—
5-12
-------
Condenser size and control costs for the tanks in Table 5-6 would
be in the range of those developed by IT Enviroscience for the large
model storage tank (2840 m , 24 turnovers per year). IT Enviroscience's
Case 2 and Case 3 annual cost estimates for the large tank were slightly
3
more than twice those for the 660 m tank used to derive Figure 3-2 and
1 o
Table 3-17. Thus it was assumed, that Option 2 storage capital and
annualized control costs for the Stauffer plant would be in the range of
$570,000 and $165,000, respectively, or about twice the cost for 95 percent
control of the smaller storage control systems addressed in Table 3-17.
Applying this annual cost and recovery credit for a 43 Mg/yr Option 2
emission reduction results in the following net cost and cost-effectiveness.
Total installed capital cost $570,000
Annualized cost $165,000
Recovery credit (20,100)
Net annualized cost 144,900
Emission reduction 48 Mg; 95%
Cost-effectiveness $ 3,020/Mg
Loading control: Basic derivation of annualized and capital costs
for loading controls is explained in 3.5.1. From Figure 3-3, July 1982
total annualized costs for 90 percent control of loading emissions at
the carbon disulfide plant can be estimated at $25,800. Assuming 65 percent
of the total annualized cost as capital charges and an annualized capital
cost factor of 0.20 results in an estimated capital cost of $83,900.
The following net cost and cost-effectiveness are based on an Option 2
emission reduction derived from Tables 5-2 and 5-5.
5-13
-------
Total installed capital cost $83.900
Annualized cost $25,800
Recovery credit (5,900)
Net annualized cost 19,900
Emission reduction 14 Mg/yr; 90%
Cost-effectiveness $ 1,420/Mg
Secondary controls: There were no secondary emissions identified
for the carbon disulfide process.
Summary: Table 5-7 summarizes Option 2 control costs for the
carbon disulfide plant. Process costs include estimates for the existing
condenser cited under Option 1 as well as the Option 2 retrofit condenser.
TABLE 5-7. OPTION 2 CARBON DISULFIDE PLANT CONTROL COSTS
Process Fugitive Storage Loading Total
Plant 2
Capital cost ($) 242,500 30,700 570,000 83,900 927,100
Annual cost ($/yr) (2,856,000) 10,000 144,900 19,900 (2,681,200)
5-14
-------
5.6 REFERENCES
1. Lowenheim, F.A., and M.K. Moran. Faith, Keyes and Clark's Industrial
Chemicals. Fourth Edition. John Wiley and Sons, Inc., New York, NY,
1975. pp. 230-234.
2. Anderson, M.E., and W.H. Battye, GCA/Technology Division. Locating and
Estimating Air Emissions from Sources of Carbon Tetrachloride, Final
Draft Report. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Air Management Technology Branch,
Research Triangle Park, NC. Contract No. 68-02-3510, Work Assignment
No. 22. September, 1982. pp. 12, 13.
3. "Chloromethanes." In: Encyclopedia of Chemical Processing and Design,
Volume 8. J.J. McKetta, ed. Marcel Dekker, New York, NY, 1979.
4. Zaebst, D.D. Walk-Through Survey Report: Stauffer Chemical Company,
Axis, AL. National Institute for Occupational Safety and Health,
Cincinnati, OH, September 1977.
5. Reference 2, p. 19.
6. Bentley, L., Alabama Air Pollution Control Commission, Montgomery, AL.
Personal communication with M.G. Smith, GCA. June 9 and September 23, 1982
7. Hustvedt, K.C., EPA. Personal communication with M.G. Smith, GCA,
January 27, 1983.
8. Organic Chemical Manufacturing Volume 3: Storage, Fugitive and Secondary
Sources. U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, Research Triangle Park, NC. EPA-450/3-80-25.
December 1980. Report 1, p. IV-18.
9. Tippitt, W., EPA. Memo to Robert Rosensteel, EPA, February 5, 1982.
10. Beale, J., Dow Chemical USA, Midland, MI. Letter to L. Evans, EPA,
April 28, 1978.
11. Bulk Gasoline Terminals - Background Information for Proposed Standards--
Draft EIS. U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, Research Triangle Park, North Carolina.
EPA-450/3-80-038a. December 1980. p. 7-2.
12. Reference 8, Report 1, p. V-ll.
5-15
-------
13. R.B. Neveril, GARD, Inc., Niles IL. Capital and Operating Costs
of Selected Air Pollution Control Systems. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standard,
Research Triangle Park, NC. EPA-450/5-80-002. December 1978.
p. 5-73.
14. Factors for Developing CTGD Costs. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Economic
Analysis Branch, September 1980.
15. Organic Chemical Manufacturing Volume 5: Adsorption, Condensation,
and Absorption Devices. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/3-80-027. December 1980. Report 2, p. V-17.
16. R. Waldrop, Edwards Engineering, Inc., Pompton Plains, NJ. Personal
communication with M.G. Smith, GCA. September 3, 1982.
17. Reference 8, Report 1, p. V-8.
18. Reference 8, Report 1, p. C-16, C-17.
5-16
-------
6.0 CHLOROFLUOROCARBON PRODUCTION FROM CARBON TETRACHLORIDE FEEDSTOCK
This chapter discusses the chlorofluorocarbon (CFC) industry and
its associated carbon tetrachloride emissions. Section 6.1 presents a
brief description of the production process for chlorofluorocarbons 11
and 12 and related emissions. Section 6.2 develops estimates of uncontrolled
carbon tetrachloride emissions for existing CFC plants. Section 6.3
discusses existing controls and regulations for this industry, the
resulting level of Option 1 control, and associated carbon tetrachloride
emissions. Section 6.4 presents a discussion of estimated best controls
(Option 2) and Section 6.5 discusses the costs of applying these options.
6.1 CHLOROFLUOROCARBON 11/12 PROCESS DESCRIPTION
6.1.1 General Information
About 90 percent of domestic carbon tetrachloride use is as a
feedstock for production of dichlorodifluoromethane (CFC 12) and trichloro-
fluoromethane (CFC 11). Chlorofluorocarbons 11 and 12 generally are
produced at facilities which also have the capacity to produce a number
of other chlorofluorocarbons. Information on the product mixes of
individual CFC plants is not available in the literature.
A list of CFC production facilities, their locations, and total
production capacities (for all CFC) is presented in Table 6-1. It has
been reported that the DuPont plants at Louisville, Kentucky and Corpus
Christi, Texas and the Allied plants at Elizabeth, New Jersey and Baton
Rouge, Louisiana do not currently make CFC 11 or 12. The Louisville and
Elizabeth plants produce CFC 22, while the Corpus Christi and Baton
2345
Rouge plants produce CFC 113 and 114. ' ' ' One reference does cite a
breakdown of a total 1981 chlorofluorocarbon production of 435,000 Mg,
as follows: CFC 12 -- 147,000 Mg; CFC 11 -- 74,000 Mg; CFC 22 --
114,000 Mg, and others (113, 114, 115) -- 100,000 Mg.6
6-1
-------
TABLE 6-1. CHLOROFLUOROCARBON PRODUCERS
Plant
number
_
1
2
-
3
4
5
-
-
6
7
8
Company
Allied
DuPont
Pennwal t
DuPont
Al 1 i ed
DuPont
Kaiser Aluminum
and Chemical
Allied
DuPont
Essex Chemical
Corp. /Racon
DuPont
Allied
Location
Elizabeth, NJ
Deepwater, NJ
Calvert City, KY
Louisville, KY
Danville, IL
Montague, MI
Gramercy, LA
Baton Rouge, LA
Ingleside, TX
Wichita, KS
Antioch, CA
El Segundo, CA
CFC
production
capacity
(Mg)9
a,b
c
36,000
b,c
a
c
30,000
a,b
b,c
20,000
c
a
Total Allied capacity is estimated at 181,000 Mg, which includes capacity
idled at Elizabeth, NJ and Baton Rouge, LA.9
Allied plants at Elizabeth, NJ and Baton Rouge, LA and the DuPont plants
at Louisville, KY and Ingleside, TX do not product CFC-11 or CFC-12.2,3,4,5
cTotal DuPont capacity is estimated at 227,000 Mg.9
6-2
-------
6.1.2 Process Description
To produce CFC 11 and 12, carbon tetrachloride, anhydrous hydrogen
fluoride and chlorine are reacted in liquid phase in the presence of
antimony pentachloride catalyst at temperatures from 0 to 200°C and
7 8
pressures of 100 to 3,400 kPa. ' Further process steps remove catalyst
entrained in the product stream, recover HC1 and HF, scrub and dry the
product stream, and recover chlorofluorocarbons by distillation. A
typical process flow diagram is shown in Figure 6-1. A number of process
variations are possible, and some of the above steps are not used at
older plants.
6.1.3 Carbon Tetrachloride Emission Factors for Chlorofluorocarbon
Production
Uncontrolled emission factors for the CFC 11 and 12 production
processes are presented in Table 6-2. One source of carbon tetrachloride
process emissions is venting of the reactor through the HC1 recovery
column (Vent A in Figure 6-1). This vent purges noncondensibles and
small amounts of inert gases which enter the reactor with the chlorine
feed stream. The vent stream is not reported to contain carbon tetrachloride
during typical process operation. However, 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 emission point indicated by "B" in Figure 6-1 is a distillation
column purge vent that was reported for the Allied plant at Danville,
Illinois. Emissions from this vent at other plants do not contain any
carbon tetrachloride, but the Danville plant recovers potential CFC 12
losses at this vent with a refrigerated condenser and a scrubber using
carbon tetrachloride feedstock. Emissions from this scrubber have
been estimated at 0.171 kg/hr of carbon tetrachloride at a production
rate of 7,576 kg/hr, which is equivalent to an emission factor of 0.023 kg
13
carbon tetrachloride per Mg of CFC production.
Fugitive emissions can result from leaks in process valves, pumps,
compressors and pressure relief valves. Uncontrolled storage emissions
result from the storage of carbon tetrachloride feedstock in fixed roof
tanks. No secondary emissions of carbon tetrachloride have been reported.
6-3
-------
ANHYDROUS
HF STORAGE
COMI'HtbbOR
cr>
i
AC1IVATEO
AUIMINA
LIQUID HC.I DhYER
fir PRODUCT TO
PRESSURIZED STORAGE
NoOHi
SCRUBBtRISl
CARBON TETRACHLORIDE
STORAGE
PHASE
SEPARATOR
--^
r
FLLIOf
1
"~^
^
/x DRYER
(OCARBON
2
TM
J
»
I,
ra
FLUOHOCARBON
REBROILER
RECYCLE BOTTOMS FROM
PRODUCT RECOVERY COLUMN
FLUOROCARBON 12 FLUOROCARBON II
RECOVERY
DISTILLATION
COLUMN
RECOVERY
DISTILLATION
COLUMN
NOTE: Letters in this figure refer to process vents
described in the text and tables. Numbers refer
to process descriptions in the first reference
cited below. Heavy lines indicate final product
streams throughout the process.
Figure 6-1. Process flow diagram for chlorofluorocarbon production. '
-------
TABLE 6-2. UNCONTROLLED CARBON TETRACHLORIDE EMISSION FACTORS
FOR CHLOROFLUOROCARBON 11 AND 12 PRODUCTION
Uncontrolled
carbon
tetrachloride
Source , emission
Emission source
Reactor venting
Distillation column0
designation
A
B
factorb
0.042 kg/Mg11
0.023 kg/Mg13
Fugitive 0.18 kg/Mg10
Storage C 0.19 kg/Mg14
aRefers to process vents shown in Figure 6-1.
Emission factors in terms of kg/Mg refer to kg of carbon tetrachloride
emitted per Mg of production of CFC 11 and 12.
cThe Allied plant at Danville, Illinois reports emissions from a scrubber
that uses carbon tetrachloride to recover CFC 12 losses from a
distillation column purge vent.12
6-5
-------
6.2 UNCONTROLLED CHLOROFLUOROCARBON PLANT EMISSIONS
A number of preliminary steps were required to allow estimation of
uncontrolled carbon tetrachloride emissions from individual CFC 11/12
production facilities, and also to facilitate later estimates of controlled
emissions and control costs for Options 1 and 2. These include use of
model plants, apportionment of CFC production capacity to specific
plants, and development of an industry-wide capacity utilization rate.
These steps are discussed below. Uncontrolled emissions are then estimated,
6.2.1 Model Plants
Emissions and control cost estimates for the production of CFC 11
and 12 are based on a representative model plant. This model plant was
chosen to be the same as that used in previous investigations of CFC 11
and 12 production processes. ' A flow diagram for the model plant is
shown in Figure 6-1. The total annual production capacity of the model
plant producing CFC 11 and 12 is 66,400 Mg, based on 8,760 hours per
year of operation. It should be noted that use of model plant parameters
does not allow consideration of variations between different CFC 11 and
12 production facilities. Several processes have been reported to vary
from the model plant in ways that may affect the accuracy of emission
and control cost estimates. These differences are discussed in more
detail in 6.3.1 .
6.2.2 Capacity Apportionment
To derive plant-by-plant emissions and costs from model plant data,
it was necessary to apportion the known total capacity of these plants
to the individual CFC 11 and 12 processes. Plant-specific CFC production
data were only available for three plants, as shown in Table 6-1. For
the Allied plant at El Segundo, California, 2,100 Mg of CFC 11/12 were
c
reportedly produced in 1981. Applying the industry-wide CFC capacity
utilization factor of 88 percent (see 6.2.4) results in an estimated
plant capacity of 2,400 Mg. Since individual plant capacities for other
CFC 11/12 production facilities were not reported, apportionment was
based on the percentage of industry-wide CFC production devoted to CFC
11 and 12, estimated to be 50.8 percent in 1981. This percentage was
6-6
-------
multiplied by the available total CFC capacities of each producer
(Table 6-1) to derive an estimate of CFC 11 and 12 capacity for each
producer.
The capacity of the Allied plant at Danville, Illinois (Plant 3;
89,500 Mg/yr) was estimated by subtracting the estimated Allied/El
Segundo (Plant 8) capacity of 2,400 Mg/yr from the estimated Allied
total capacity of 91,900 Mg/yr. The capacities of the three active
DuPont CFC 11/12 plants were estimated at 38,400 Mg/yr each by assuming
equal distribution of the estimated 115,300 Mg/yr company CFC 11/12
capacity. Estimated capacity apportionment for the individual plants is
presented in Table 6-3. In 1981, the ratio of nationwide CFC 11 production
to that of CFC 12 was 1:2.6
TABLE 6-3. CAPACITY APPORTIONMENT FOR CFC 11/12 PLANTS
Estimated
CFC 11/12
Plant capacity (Mg)
1 38,400
2 18,300
3 89,500
4 38,400
5 15,200
6 10,200
7 38,400
8 2,400
Total 250,800
6.2.3 Proportionality and Scales of Production
Throughout the analysis, direct proportionality of emissions,
control efficiencies and costs over all scales of production was assumed.
The plant capacity factors in Table 6-4, derived by dividing each plant's
assumed CFC 11/12 production capacity (Table 6-3) by that of the model
6-7
-------
plant (66,400 Mg/yr), were used to apply model plant emission estimates
and control costs to each plant.
TABLE 6-4. CFC PLANT CAPACITY FACTORS (RELATIVE
TO MODEL PLANT)
Plant
1
2
3
4
5
6
7
8
Total
CFC 11/12
factor
0.58
0.28
1.35
0.58
0.23
0.15
0.58
0.04
3.79
6.2.4 Capacity Utilization
Based on the 1981 total chlorofluorocarbon production of 435,000 Mg ,
q
and the corresponding domestic production capacity of 494,000 Mg , a
uniform capacity utilization rate of 0.88 was applied to all plants in
estimation of emissions and also to the model plant emission reductions
used in cost estimates.
6.2.5 Uncontrolled Emissions
Uncontrolled carbon tetrachloride emissions for the CFC 11/12 model
plant (Table 6-5) were based on the model plant capacity of 66,400 Mg/yr
and the uncontrolled emission factors from Table 6-2. The industry-wide
capacity utilization of 0.88 and the plant capacity factors shown in
Table 6-4 were applied to the model plant emission estimates to produce
the plant-specific uncontrolled emission estimates presented in Table 6-6.
Process emissions for the Allied plant at Danville, Illinois (Plant 3)
6-8
-------
include emissions from reactor venting as well as the scrubber which
uses carbon tetrachloride to recover CFC 12 losses from the distillation
12
column purge vent. Process emissions from all other plants are from
reactor venting. No uncontrolled storage emissions were listed for the
Essex plant at Wichita, Kansas (Plant 6) because there is no storage of
carbon tetrachloride on site. Carbon tetrachloride is piped directly
from the adjacent Vulcan carbon tetrachloride production facility.16
TABLE 6-5. UNCONTROLLED CFC 11/12 MODEL PLANT CARBON
TETRACHLORIDE EMISSIONS
Source
Reactor venting
Distillation column
Fugitive
Storage
Total
Model plant
emissions
(Mg/yr)
2.79
1.53a
12.0
12. 6b
28.9
aOnly at Allied/Danville, IL (Plant 3).
Does not apply at Essex/Wichita, «S (Plant 6).
TABLE 6-6. UNCONTROLLED CARBON
CFC 11/12 PRODUCTION
TETRACHLORIDE EMISSIONS FROM
FACILITIES
Uncontrolled emission estimates (Mg/yr)
Plant
1
2
3
4
5
6
7
8
Total
Process
1.42
0.69
5.13
1.42
0.56
0.37
1.42
0.09
11.10
Fugitive Storage
6.12
2.96
14.26
6.12
2.43
1.58
6.12
0.38
39.97
6.43
3.10
14.97
6.43
2.55
oa
6.43
0.40
40.31
Total
13.97
6.75
34.36
13.97
5.54
1.95
13.97
0.87
91.38
aNo storage at Plant 6.
6-9
-------
6.3 OPTION 1 CONTROLS AND EMISSIONS FOR CHLOROFLUOROCARBON PRODUCTION
Option 1 emission controls relating to the production of CFC 11 and
12 are discussed in this section. These include existing controls at
individual plants, currently applicable State regulations, and Group III
CTG controls which will be required in ozone NAAQS nonattainment areas
requesting extensions beyond 1982.
6.3.1 Existing Controls
Information on control technology currently in place at CFC 11/12
production facilities was obtained in telephone conversations with State
agency personnel and from previous EPA surveys. No existing controls
were identified for carbon tetrachloride emissions from the venting of
the reactor through the HC1 recovery column during maintenance (emission
point "A" in Figure 6-1), or for the carbon tetrachloride emissions
induced by use of a carbon tetrachloride scrubber to control CFC 12
emissions from the first distillation column of the Allied plant at
Danville, Illinois (Plant 3).
Storage of carbon tetrachloride is in fixed roof tanks with no
controls at all of the CFC 11/12 production facilities except the DuPont
plants at Deepwater, New Jersey (Plant 1) and Montague, Michigan (Plant
4) and the Essex/Racon plant at Wichita, Kansas (Plant 6) as shown in
Table 6-7. The Deepwater plant uses a floating roof tank for storage of
carbon tetrachloride and the Montague plant uses vapor balance during
unloading of carbon tetrachloride into a fixed roof tank. Storage of
carbon tetrachloride at the Wichita plant is not required because it is
obtained directly through a pipeline from storage tanks at the adjacent
Vulcan carbon tetrachloride production facility.
6-10
-------
TABLE 6-7. EXISTING CARBON TETRACHLORIDE STORAGE CONTROLS AT CFC 11/12
PRODUCTION PLANTS
Plant
number
1
2
3
4
5
6
7
8
Control
device
Floating roof
No control
No control
Vapor balance
No control
No on-site storage
No control
No control
Control
efficiency Reference
88 11,
18
12
77a 15,
20
16
21
22
17
19
a 19
Based on a 90 percent control of working losses from a fixed roof tank.
Working losses were estimated as 86 percent of total losses from carbon
tetrachloride storage as discussed in Apendix A-6.
6-11
-------
No controls other than normal inspection and maintenance procedures
were identified as currently being used by any plants to control fugitive
emissions.
6.3.2 State Regulations
State regulations pertaining to CFC 11/12 production plants are
presented in Table 6-8. Control efficiencies presented in the table are
discussed in 2.2.1.
Carbon tetrachloride is not included in the "VOC" definition for
VOC storage and fugitive VOC in Louisiana. Also, it is not included in
the "organic liquid" definition which is applied to VOC storage in the
San Francisco Bay Area (California). However, for purposes of this
source assessment, it has been assumed that the Louisiana and Bay Area
SIP provisions cited for the Kaiser plant at Gramercy, Louisiana (Plant 5)
and the DuPont plant at Antioch, California (Plant 7), will be enforceable
for carbon tetrachloride despite the current State definitions. This is
because the Bay Area definition will probably be changed to conform with
the VOC definition in the VOL storage CTG when this CTG is adopted
there, and because Louisiana is currently applying its VOC regulations
4
to carbon tetrachloride sources. The New Jersey toxics regulation,
which requires control of carbon tetrachloride emissions "of a rate
equivalent to advances in the art of control", was assumed to be equivalent
to the estimated best controls discussed in 6.4.1. These controls
will provide 95 percent control of storage emissions and 56 percent
control of fugitive emissions, but effective controls do not appear to
be available for the maintenance-related process emissions from CFC
11/12 production.
The carbon tetrachloride storage tank at the Allied plant at El
Segundo (Plant 8) is under the 39,630 gallon exemption level of South
Coast Air Quality Management District Rule 463, so no State control
pi
requirement was assumed for storage emissions there.
6-12
-------
TABLE 6-8. CURRENT STATE REGULATIONS APPLYING TO CARBON TETRACHLORIDE
EMISSIONS FROM CFC 11/12 PRODUCTION FACILITIES
Plant
number
1
State
New Jersey
Applicable State regulations3
VOC Storage: Carbon tetrachloride tanks over
Control
efficiency
(%)b
95
cr>
i
2
3
Kentucky
Illinois
Michigan
Louisiana
300,000 gallons must be equipped with an external or
internal floating roof with at least one tight seal.
Toxics: New Jersey toxic substances rules require
registration of carbon tetrachloride emissions and
control "at a rate or concentration equivalent to
advances in the art of control" for the type of emission
involved.
None (regulations only cover petroleum liquids and/or
gasoline).
VOC Storage: Tanks over 40,000 gallons must be a pressure
tank or be equipped with a floating roof, a vapor recovery
system capable of 85 percent collection which includes a
disposal system, or equipment or means of equal efficiency.
VOC Fugitive: No pump or compressor may discharge over
2 cubic inches of liquid VOC in any 15-minute period.
VOC Storage: Tanks over 40,000 gallons must be pressure
tanks or have either a floating roof, vapor recovery
system, or equivalent with 90 percent control.
VOC Storage: Tanks over 40,000 gallons which are not
pressure tanks must have submerged fill and either
(a) floating roof, (b) a vapor loss control system
equivalent to floating roof, or (c) other equivalent
equipment or means. Tanks from 250 to 40,000 gallons must
have submerged fill or vapor recovery or other equivalent
equipment or means.
85
0
90
95
CONTINUED
-------
TABLE 6-8. (continued)
Plant
number
State
Applicable State regulations'
Control
efficiency
5 (con't)
Kansas
Cal i form'a
(Bay Area)
CTi
I
California
(South Coast)
VOC Fugitives: Pumps and compressors must be equipped 0
with mechanical seals, or equivalent equipment or means.
Best practical housekeeping and maintenance practices
are also required.
None.
VOC Storage: Organic liquid storage tanks between 260 95
and 40,000 gallons must have submerged fill or equivalent.
Tanks over 40,000 gallons must have floating roof, vapor
recovery with 95 percent efficiency or other control with
95 percent efficiency.
Valves and Flanges: Annual inspection and repair or 0
minimization of leaks in chemical plant complexes.
VOC Storage: Tanks over 39,630 gallons must be pressure 95C
tanks or be equipped with one of the following: (a) external
floating roof, (b) fixed roof with internal-floating-type
cover, (c) 95 percent vapor recovery system, or (d) other
equipment with 95 percent control efficiency.
Pumps and Compressors: Seals or other devices of equal 42
efficiency are required and must be maintained to prevent:
(a) leakage of more than 3 drops/minute, (b) visible liquid
mist or vapor, and (c) any visible indication of leakage at
or near the shaft/seal interface of gas compressors.
Valves and Flanges: Annual
re-inspection are required,
lines.
inspection, repair and
as well as seals on open-ended
CONTINUED
-------
TABLE 6-8. (continued)
CTl
I
cn
Plant
number State
Applicable State
regulations9
Control
efficiency
(%)b
8 (con't) Safety Relief Valves: Must be vented to a vapor recovery/
disposal system, protected by a rupture disk or maintained
by an approved inspection system.
Refer to 2.2.1 for references to State regulations.
Refer to 2.2.1 for discussion of control efficiency estimates.
GAssumed to be equivalent to estimated best controls which have a control efficiency of 95 percent
for storage emissions and 56 percent for fugitive emissions.
Storage at Plant 8 is below the 39,630 gallon cutoff in Rule 463.
-------
6.3.3 Group III Control Techniques Guidelines
Since it is anticipated that ozone nonattainment areas which have
received extensions beyond 1982 will be required to adopt all Group III
CTGs, these CTGs were reviewed for applicability to known sources of
carbon tetrachloride at CFC 11/12 production facilities. Two Group III
CTGs (covering volatile organic liquid storage and fugitive emissions
from synthetic organic chemical, polymer and resin manufacturing) would
apply to operations in post-1982 attainment-date areas which store
carbon tetrachloride or produce chlorofluorocarbons 11 or 12. Table 6-9
presents ozone NAAQS nonattainment status for CFC 11/12 production
plants. As shown in the table, only Plants 1, 7, and 8 (DuPont at
Deepwater and Antioch and Allied at El Segundo, respectively) are currently
anticipated to be subject to these CTGs. As discussed in 2.2.2, these
CTGs are expected to result in 95 percent of storage emissions and 42
percent control of fugitive emissions at affected plants.
TABLE 6-9. OZONE NATIONAL AMBIENT AIR QUALITY STANDARD ATTAINMENT
STATUS FOR CFC 11/12 PLANTS2^,24
Plant
1
2
3
4
5
6
7
8
Ozone NAAQS
attainment
status
Nonattainment
Nonattainment
Nonattainment
Nonattainment
Nonattainment
Attainment
Nonattainment
Nonattainment
Post-1982
attainment
date granted?
Yes
No
No
No
No
--
Yes
Yes
6-16
-------
6.3.4 Combined Option 1 Controls
Control efficiencies for the Option 1 controls applicable to carbon
tetrachloride emissions from CFC 11/12 production plants are summarized
in Table 6-10. Each efficiency represents the most stringent of existing,
State-required or Group III CTG controls as discussed above.
TABLE 6-10. OPTION 1 CONTROL SUMMARY FOR CFC 11/12
PRODUCTION PLANTS
Plant
number
1
2
3
4
5
6
7
8
Option 1 control efficiency
Process Fugitive
56
__
__
__
__
__
42
42
(percent)
Storage
95
--
85
90
95
--
95
95
6.3.5 Estimated Option 1 Emissions
Table 6-11 summarizes annual emissions from CFC 11/12 production
plants which would result from the use of the Option 1 controls. These
emission estimates were derived by applying the Option 1 control efficiencies
in Table 6-10 to uncontrolled carbon tetrachloride emission rates in
Table 6-6.
6-17
-------
TABLE 6-11. OPTION 1 CONTROLLED EMISSIONS FOR CFC 11/12
PRODUCTION PLANTS
Plant
number
1
2
3
4
5
6
7
8
Total
Option 1
control
efficiency
Process
1.42
0.69
5.13
1.42
0.56
0.37
1.42
0.09
11.10
Option 1 controlled
Fugitive
2.69
2.96
14.26
6.12
2.43
1.58
3.55
0.22
33.81
emissions (Mg/yr)
Storage
0.32
3.10
2.25
0.64
0.13
0
0.32
0.02
6.78
Total
4.43
6.75
21.64
8.18
3.12
1.95
5.29
0.33
51.69
15
83
43
6-18
-------
6.4 OPTION 2 CONTROLS AND EMISSIONS FOR CHLOROFLUOROCARBON PRODUCTION
6.4.1 Estimated Best Controls
The following control methods were selected as potentially applicable
control technology for carbon tetrachloride emissions from CFC 11/12
production. No feasible controls were identified for emissions which
occur as a result of venting of the reactor during mechanical maintenance
operations. This is due to the intermittent and fugitive nature of these
emissions. Also, no feasible controls were identified for emissions from
the existing scrubber at the Allied/Danville plant which uses carbon
tetrachloride to recover CFC 12 from a distillation column.
Fugitive emissions can be controlled with a quarterly inspection
and repair program similar to the Group III CTG at efficiencies up to
42 percent, but it was estimated that monthly inspections and equipment
25
specifications can raise this to about 56 percent. Emissions from
storage of carbon tetrachloride can be controlled with vapor recovery
efrigeral
26,27,28
and -20°C refrigerated condensation systems, at efficiencies up to
95 percent.
6.4.2 Estimated Option 2 Emissions
Table 6-12 summarizes annual carbon tetrachloride emissions and
control efficiencies which can be achieved by CFC 11/12 production
plants with the Option 2 controls described in 6.4.1.
6-19
-------
TABLE 6-12. OPTION 2 CONTROLLED EMISSIONS FOR CFC 11/12
PRODUCTION PLANTS
Plant
number
1
2
3
4
5
6
7
8
Total
Option 2
control
efficiency
Process
1.42
0.69
5.13
1.42
0.56
0.37
1.42
0.09
11.10
OjDtion 2 controlled
Fugitive
2.69
1.30
6.27
2.69
1.07
0.70
2.69
0.17
17.58
emissions (Mg/yr)
Storage
0.32
0.16
0.75
0.32
0.13
0
0.32
0.02
2.02
Total
4.43
2.15
12.15
4.43
1.76
1.07
4.43
0.28
30.70
56
95
66
6-20
-------
6.5 CONTROL COSTS FOR CHLOROFLUOROCARBON PLANTS
This section presents control cost estimates for the Option 1 and
Option 2 controls discussed in this chapter. Model plant control costs
are developed for storage and fugitive controls, and plant-specific control
costs for Options 1 and 2 are presented under Summary headings at the end
of 6.5.1 and 6.5.2. As discussed in Sections 6.3 and 6.4, no process
controls were identified, and loading and secondary emissions of carbon
tetrachloride do not occur at CFC plants. Costing methodology and
assumptions are discussed further in Chapter 1. All costs are for
July 1982.
6.5.1 Option 1 Control Costs
This section provides cost estimates for the Option 1 CFC plant
controls discussed in 6.3.4.
Fugitive control: Option 1 fugitive emission controls include
42 percent control at Plants 8 and 9 and 56 percent control at Plant 1.
The available information on fugitive emission sources in carbon tetra-
chloride service at CFC plants consists of an overall count of 110 for
Plant 8 and a breakdown for Plant 7 as follows: 28 valves, 52 flanges,
21 22
and 5 quick-disconnect couplings, with a total of 90. ' Since the
breakdown for Plant 7 totals 85 units, it is likely that the remaining
5 units were pumps. These counts are much smaller than the totals for the
small SOCMI fugitives model plant shown in Table 3-15. The SOCMI model
plant also includes compressors and relief valves, while flanges are not
included in the SOCMI fugitive CTG. Due to these differences, SOCMI model
plant costs could not be used and the costs in the following paragraph for
the CFC model plant were estimated. It was assumed that the relevant CFC
model plant fugitive source inventory is equivalent to about 40 valves and
5 pumps, based on the breakdown and totals cited above (quick-disconnect
couplings were assumed to be equivalent to two valves for costing purposes)
Costs of the monitoring instrument are the same for both Option 1
control efficiencies, and include a capital cost of $11,900, annualized
29
capital cost of $2,744 and annual operating cost of $4,256. Capital
costs for initial leak detection and repair of pumps and valves under
either control program are about $40 per pump and $2.80 per valve, with
6-21
-------
30
annualized capital costs of $8.75 per pump and $0.50 per valve. Annual
costs for monthly inspection and repair (56 percent control) are $330 per
pump and about $19 per valve. To estimate annual costs for a quarterly
inspection and repair program (42 percent control), the cost of monitoring
labor hours for a monthly program was reduced by 75 percent. Assuming no
change in repair labor hours, costs of $280 per pump and $9.50 per valve
31
were estimated for the quarterly program. These unit costs for 40 valves
and 5 pumps result in the following model plant costs.
42 percent control 56 percent control
Capital costs
Monitoring instrument $11,900 $11,900
Pumps 200 200
Valves 112 112
Total $ 12,212 $ 12,212
Annual operating and capital costs
Monitoring instrument $ 7,000 $ 7,000
Pumps 1,444 1,695
Valves 400 780
Total $ 8,844 $ 9,475
These costs and estimated model plant emission reductions at 0.88 percent
capacity utilization result in the following net cost and cost-effectiveness
analysis.
42 percent control 56 percent control
Total installed capital cost $ 12,200 $ 12,200
Annualized costs 8,800 9,500
Recovery credit (1,850) (2,470)
Net annualized cost $ 6,950 $ 7,030
Emission reduction 4.4 Mg 5.9 Mg
Cost-effectiveness $ 1,580/Mg $ 1,191/Mg
6-22
-------
Storage controls: Previous assessments of CFC plants did not include
model plant data on carbon tetrachloride feedstock storage. Table 6-13
provides available data on storage and estimated production capacities at
CFC 11/12 plants. The tank at Plant 8 (DuPont/Antioch, CA) is below the
39,360 gallon regulatory exemption level, but other data in the original
reference indicate that it is at least 33,000 gallons (125 m). At the
plant where actual CFC 11/12 production capacity and carbon tetrachloride
storage capacity estimates are available (Plant 8), production is about
10 times the storage capacity. Applying this factor to the model plant
production capacity (66,400 Mg/yr), the model plant storage tank is
estimated at 7,000 Mg (4,300 m3).
TABLE 6-13. CARBON TETRACHLORIDE STORAGE AT CFC 11/12 PLANTS
Main storage tank CFC 11/12
capacity production
Plant
1
2
3
4
5
6
7
8
(md)
5280
s380
950
160
<150
(gallons)
1,394,000
slOO,000
250,000
42,636
< 39, 360
(Mg)
8,364
Not available
Not available
£604
1,510
No on-site storage
257
<239
Reference
37
32
33
16
34
34
capacity (Mg)
38,400
18,300
89,500
38,400
15,200
10,200
38,400
2,400
aFrom 6.2.2 and Table 6-3.
Available costs for SOCMI storage control by refrigerated condensers
are for tanks from 150 to 2,840 m . For the case most similar to this
control requirement (Case 3), graphical projection of these costs to the
•3
range of 4,300 m results in annual costs between 2.7 and 2.8 times the
costs for the 660 m tank presented in 3.5.1 and Figure 3-2. The
annual control costs for Option 1 control levels in Table 6-14
6-23
-------
were estimated by inflating costs taken from Figure 3-2 to July 1982 and
then applying a factor of 2.75 to account for the difference in tank
sizes. Capital costs were then estimated using the original 0.29 annualiza-
tion factor, which includes maintenance, capital recovery and miscellaneous
capital-related costs.
TABLE 6-14. ESTIMATED CFC 11/12 MODEL PLANT COSTS FOR REFRIGERATED
CONDENSER CONTROL OF CARBON TETRACHLORIDE FEEDSTOCK
STORAGE
Control
efficiency
(percent)
95
90
85
Capital cost
of complete
condenser
system
$783,300
$481,700
$325,200
Annual ized
cost of
complete
condenser system
$227,200
$139,700
$94,300
Combining the above control cost estimates with corresponding model
plant emission reductions and the 0.88 capacity utilization factor produces
the following net annualized cost and cost-effectiveness data.
Total installed capital cost
Annualized cost
Recovery credit
Net annualized cost
Emission reduction
Cost-effectiveness
95 percent
control
$783,300
$227,200
(4,400)
$222,800
10.5 Mg
$21,200/Mg
90 percent
control
$481,700
$139,700
(4,200)
$135,500
10.0 Mg
$13,600/Mg
85 percent
control
$325,200
$ 94,300
(3,900)
$ 90,400
9.4 Mg
$9,600/Mg
6-24
-------
Summary: Table 6-15 summarizes Option 1 model plant control costs for
CFC 11/12 plants developed in this section. Table 6-16 presents estimated
capital and annualized control costs for each plant. These costs were
calculated by multiplying model plant costs for the Option 1 control
efficiencies indicated in Table 6-10 by the plant capacity factors in
Table 6-4.
TABLE 6-15. OPTION 1 CFC 11/12 MODEL PLANT CONTROL COSTS
Control
type
Fugitive
Storage
6.5.2 Option 2
Control
efficiency
(*)
42
56
85
90
95
Control Costs
Capital
cost
($)
12,200
12,200
325,200
481,700
783,300
Net
annual cost
($/yr)
7,000
7,000
90,400
135,500
222,800
This section provides estimates for the Option 2 CFC production plant
controls discussed in Section 6.4.
Fugitive controls: Model plant control costs for 56 percent control
under Option 2 are identical to those for 56 percent control under Option 1
in 6.5.1. These costs are as follows:
Total installed capital costs
Annualized costs
Recovery credit
Net annual cost
Emission reduction
Cost-effectiveness
$ 12,200
9,500
(2,470)
$ 7,030
5.9 Mg
$ 1,191/Mg
6.-2 5
-------
TABLE 6-16. OPTION 1 CFC 11/12 PLANT CONTROL COSTS
Plant
1
2
3
4
5
6
7
8
Total
Plant
1
2
3
4
5
6
7
8
Total
Fugitive
7,100
—
--
--
--
--
7,100
500
14,700
Fugitive
4,100
--
--
--
--
--
4,100
300
8,500
Capital costs ($)
Storage
454,000
--
439,000
279,000
180,000
--
454,000
31,300
1,837,300
Net annual costs ($)
Storage
129,000
--
122,000
78,600
51,200
--
129,000
8,900
518,700
Total
461,100
--
439,000
279,000
180,000
—
461,100
31,800
1,852,000
Total
133,100
--
122,000
78,600
51,200
--
133,100
9,200
527,200
indicates no Option 1 control
6-26
-------
Storage control: Model plant control costs for 95 percent control
and/or Option 2 are identical to those for 95 percent control under
Option 1, in 6.5.1. These costs are as follows:
Total installed capital cost $ 783.300
Annualized cost 227,200
Recovery credit (4,400)
Net annualized cost $ 222,800
Emission reduction 10.5 Mg
Cost-effectiveness $ 21,200/Mg
Summary: Table 6-17 summarizes Option 2 model plant control costs
for CFC 11/12 plants developed in this section. Table 6-18 presents
estimated capital and annualized control costs for each plant. These
costs were calculated by multiplying model plant costs in Table 6-17
by the plant capacity factors in Table 6-4.
TABLE 6-17. OPTION 2 CFC 11/12 MODEL PLANT CONTROL COSTS
Control
type
Control
efficiency
(X)
Capital
cost
($)
Net
annual cost
($/yr)
Fugitive
Storage
56
95
12,200
783,300
7,000
222,800
6-27
-------
TABLE 6-18. OPTION 2 CFC 11/12 PLANT CONTROL COSTS
Plant
1
2
3
4
5
6
7
8
Total
Plant
1
2
3
4
5
6
7
8
Total
Fugitive
7,100
3,400
16,500
7,100
2,800
1,800
7,100
500
46,300
Fugitive
4,060
1,960
9,450
4,060
1,610
1,050
4,060
280
26,530
Capital costs ($)
Storage
454,000
219,000
1,057,000
454,000
180,000
117,000
454,000
31,000
2,966,000
Net annual costs ($/yr)
Storage
129,000
62,000
301,000
129,000
51,000
33,000
129,000
9,000
843,000
Total
461,100
222,400
1,073,500
461,100
182,800
118,800
461,100
31,500
3,012,300
Total
133,060
63,960
310,450
133,060
52,610
34,050
133,060
9,280
869,530
6-28
-------
REFERENCES
1. "Chemical Briefs 1: Carbon Tetrachloride." Chemical Purchasing,
January 1981. pp. 25-29.
2. Lesher, Theron, Air Pollution Control District of Jefferson County,
Louisville, Kentucky. Personal communication with David Misenheimer,
GCA, December 16, 1982.
3. Palmer, Tom, Texas Air Control Board, Corpus Christi, Texas.
Personal communication with David Misenheimer, GCA,
January 6, 1983.
4. Gasperecz, G., Louisiana Air Quality Division, Baton Rouge, LA.
Personal communication with M.G. Smith, GCA, July 13, 1982.
5. Turetsky, W.S., Allied Chemical Corp., Morristown, NJ. Letter to
David Patrick, EPA, May 28, 1982.
6. "Fluorocarbons", Chemical Products Synopsis, Mannsville Chemical
Products, Mannsville, NY, August 1982.
7. Organic Chemical Manufacturing Volume 8: Selected Processes. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards, Research Triangle Park, NC. EPA-450/3-80-028c. December
1980. Report 3. pp. III-l to III-6.
8. 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.
9. Stanford Research Institute, 1981 Directory of Chemical Producers
USA, Menlo Park, CA, 1981.
10. Anderson, M.E., and W.H. Battye, GCA/Technology Division, Locating and
Estimating Air Emissions from Sources of Carbon Tetrachloride, Final
Draft Report. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Air Management Technology Branch,
Research Triangle Park, NC. Contract No. 68-02-3510, Work Assignment
No. 22. September, 1982. pp. 26-31.
11. Smith, D.W., E.I. duPont deNemours and Co., Wilmington, DE. Letter
to D.R. Goodwin, EPA, June 7, 1978.
12. Pitts, D.M., IT Enviroscience, Inc. Trip Report: Visit to Allied
Chemical Corp., Morristown, NJ, March 16, 1978.
6-29
-------
13. Reference 7, pp. V-l.
14. Reference 7, pp. IV-1 to IV-9.
15. Kruger, Mary, Department of Natural Resources, Grand Rapids, MI.
Personal communication with D.C. Misenheimer, GCA,
December 28, 1982.
16. Morris, Dana, Kansas Bureau of Air Quality, Topeka, KS. Personal
communication with D.C. Misenheimer, GCA, December 17, 1982.
17. Mancini, E.A., New Jersey Division of Environmental Quality, Trenton,
NJ. Letter and attachments to M.G. Smith, GCA/Technology Division,
January 20, 1983.
18. Murphy, Sam, Kentucky Department for Environmental Protection,
Frankfort, KY. Personal communication with D.C. Misenheimer, GCA,
December 20, 1982.
19. Norton, R.L., R.R. Sakaida, and M.M. Yamada. Hydrocarbon Control
Strategies for Gasoline Marketing Operations. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Research Triangle Park, NC. EPA-450/3-78-017, April 1978. p. 5-2.
20. Louisiana Air Quality Division, Baton Rouge, LA. Information
contained in files pertaining to Kaiser Aluminum/Gramercy facility.
21. Ziskind, R.A., Inventory of Carcinogenic Substances Released into
the Ambient Air of California: Phase II. Science Applications,
Inc., Los Angeles, CA. November 1982. pp. 127-131, 177.
22. Reference 21, pp. 120-126, 177.
23. Maps Depicting Nonattainment Areas Pursuant to Section 107 of the
Clean Air Act. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Research Triangle Park, NC.
EPA-450/2-80-062. April 1980.
24. Status Summary of States' Group I VOC RACT Regulations as of
June 1, 1981: Second Interim Report. U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Control
Programs Development Division, Research Triangle Park, NC. Contract
No. 68-02-5310, Task No. 8. July 1981.
25. Hustvedt, K.C., EPA. Personal communication with M.G. Smith, GCA,
January 17, 1983.
26. Tippitt, W., EPA. Memo to Robert Rosensteel, EPA, February 5, 1982.
6-30
-------
27. Beale, J., Dow Chemical USA, Midland, MI. Letter to L. Evans, EPA,
April 28, 1978.
28. Organic Chemical Manufacturing Volume 3: Storage, Fugitive and
Secondary Sources. U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards, Research Triangle Park, NC.
August 1981.
29. Fugitive Emission Sources of Organic Compounds—Additional Information
on Emissions, Emission Reductions, and Costs. U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Emission Standards and Engineering Division, Research Triangle Park,
NC. EPA 450/3-82-010. April 1982. p. B-4, B-5.
30. Reference 29, p. 3-10, B-4, B-5.
31. Reference 29, p. 5-9, 5-21.
32. DeKraker, Dale, Michigan Department of Natural Resources, Grand Rapids,
MI. Personal communication with D.C. Misenheimer, GCA, December 17, 1982.
33. Contractor, B., Louisiana Air Quality Division, Baton Rouge, LA.
Personal communication with M.G. Smith, GCA, February 7, 1983.
34. Reference 21, p. 177.
35. Reference 28, Report 1, Appendix C.
36. Reference 28, Report 1, p. 5-13.
37. Mancini, E.A., New Jersey Division of Environmental Quality, Trenton,
NJ. Personal communication with M.G. Smith, GCA, February 17, 1983.
6-31
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7.0 PROCESSES WITH CARBON TETRACHLORIDE BY-PRODUCT
Several organic chemical manufacturing process have been reported to
result in the formation and emission of carbon tetrachloride. These
processes, which are discussed individually in this chapter, include
methanol hydrochlorination/methyl chloride chlorination, ethylene dichloride
production, and production of trichloroethylene and perch!oroethylene from
ethylene dichloride.
Carbon tetrachloride emission sources at the plants addressed in this
chapter may be subject to a number of regulations, including State regulations
on process and fugitive emissions and the Group III SOCMI fugitive CTG
discussed in Section 2.2. Storage and loading of carbon tetrachloride
will not exceed the cut-off levels in State regulations and the VOL storage
CTG. Detailed examination of the applicability and effects of these
regulations was not possible within the scope of this project. Existing
controls and other regulations which may apply are included in the sections
below.
7.1 METHANOL HYDROCHLORINATION/METHYL CHLORIDE CHLORINATION
7.1.1 Process Description
In this two-stage process, gaseous methanol typically is hydrochlorinated
to produce methyl chloride, and methyl chloride is then chlorinated to
produce methylene chloride and chloroform as principal products. Some
plants produce methyl chloride by methane chlorination, and some methyl
chloride producers do not use it as an intermediate in producing methylene
chloride and chloroform. Carbon tetrachloride by-product is formed in
the second step of the process. Here, methyl chloride is reacted with
chlorine, forming a combination of hydrogen chloride, methylene chloride,
chloroform, and a small amount of carbon tetrachloride. Further steps
remove the hydrogen chloride and distill the principal products, leaving
carbon tetrachloride and other heavier components as the final distillation
7-1
-------
bottoms. In some cases, this crude carbon tetrachloride mixture is used
onsite as a feedstock for a carbon tetrachloride/perchloroethylene
chlorinolysis operation, but in other cases it is sold.
Figure 7-1 is a typical process flow diagram for a combined methanol
hydrochlorination/methyl chloride chlorination process. Table 7-1
lists plants which produce chloroform and methylene chloride by methyl
chloride chlorination.
7.1.2 Carbon Tetrachloride Emissions
Table 7-2 presents available emission factors for carbon tetra-
chloride from methyl chloride chlorination with source designations
referring to Figure 7-1. These factors are based on a model plant
assumed for previous EPA studies in which the carbon tetrachloride
by-product was chosen to be 2 percent of a product mix which included
25 percent methyl chloride, 48 percent methylene chloride and 25 percent
7 8
chloroform. ' The emission factors for storage and handling are based
on the assumption that the final distillation bottoms containing carbon
tetrachloride are stored and then shipped off-site. Table 3-1 shows
that the Dow and Vulcan plants have mixed hydrocarbon chlorinolysis
production of carbon tetrachloride and perch!oroethylene on-site.
No information was found on existing emission controls for the
sources of carbon tetrachloride listed in Table 7-2.
7.2 ETHYLENE DICHLORIDE PRODUCTION
7.2.1 Process Description
Carbon tetrachloride is formed as a by-product during the production
of ethylene dichloride (EDC). EDC can be produced from ethylene and
chlorine by direct chlorination, and from ethylene and hydrogen chloride
(HC1) by oxychlorination. These processes generally are used together,
in what is known as the balanced process, wherever EDC and vinyl chloride
monomer (VCM) are produced at the same facility. In VCM production, EDC
is cracked to yield VCM and by-product HC1. In the balanced process,
by-product HC1 from VCM production is used in the oxychlorination process
7-2
-------
--J
CO
METHANOL
HYDROCHLORINATION QUENCH
REACTOR TOWER
METHYL HYDROGEN
CHLORIDE CHLORIDE
CHLORINATION STRIPPER
REACTOR
CRUDE
STORAGE
METHYLENE SURGE
CHLORIDE TANK
DISTILLATION
METHYLENE
CHLORIDE
STORAGE
CHLOROFORM
DISTILLATION
AND HEAVIES (TO FURTHER
PROCESSING)
NOTE: Letters In this figure refer to process vents
described 1n the text and tables. Numbers refer
to process descriptions 1n the first reference
cited below. Heavy lines Indicate final product
streams throughout the process.
Figure 7-1. Process flow diagram for methanol hydrochlorination/methyl chloride
chlorination process.1>2
-------
TABLE 7-1. METHYLENE CHLORIDE AND CHLOROFORM PRODUCERS
Annual capacity
(xlO3 Mg)3
EPA
region
III
IV
VI
VII
Company
Diamond Shamrock
Linden Chemicals
and Plastics
Stauffer Chemical Co.
Dow Chemical U.S.A.
Vulcan Materials Co.
Dow Chemical U.S.A.
Vulcan Materials Co.
Location
Belle, WV
Moundsville, WV
Louisville, KY
Plaquemine, LA
Geismar, LA
Freeport, TX
Wichita, KS
Chloroform
18
14
34
45
28
45
50
234
Methyl ene
chloride
45
23
27
86
36
93
59
369
Ozone
NAAQS
attainment
status4,5
NA
A
NA
NA
NA
NA
A
Post-1982
attainment
date
granted ?4'b
No
--
Yes
No
No
No
"
A -- Attainment
NA -- Nonattainment
-------
TABLE 7-2. UNCONTROLLED CARBON TETRACHLORIDE EMISSION FACTORS FOR
METHANOL HYDROCHLORINATION/METHYL CHLORIDE CHLORINATION
PROCESS
Uncontrolled
carbon
tetrachloride
Emission
source
Storage
Handling
Process fugitive
Source
designation
A
B
emission
factorb
0.15 kg/Mg
0.52 kg/Mg
0.77 kg/hr
an.c +. 4-u • r • •
negligible carbon tetrachloride emissions.
Emission factors in terms of kg/Mg refer to kg of carbon tetrachloride
emitted per Mg of carbon tetrachloride produced, from Reference 6.
cEmission factor developed for cases in which impure by-product carbon
tetrachloride is not transferred for further processing at hydrocarbon
chlorinolysis co-facility.
Fugitive emission rate is independent of process rate.
7-5
-------
to produce about half of the EDC required for VCM production. The
g
remaining EDC is produced by direct chlorination. Table 7-3 lists EDC
and VCM producers.
Assuming use of the balanced process at all plants producing VCM,
which include about 87 percent of national EDC operating capacity, it
follows that only 13 percent of the national EDC capacity is based on
processes other than the balanced process. At these plants, EDC must be
produced by direct chlorination of ethylene unless a supply of hydrogen
chloride is available for oxychlorination. Adequate process and emissions
data are available only for the balanced process, so the data presented
here may not apply directly to the smaller plants which may use a single
process. Most balanced process plants use air in the oxychlorination
step, but three plants have been reported to use purified oxygen.
Figure 7-2 is a full process flow diagram for EDC production by the
balanced air-based process; Figure 7-3 provides details for the oxychlorination
step of the oxygen-based process.
7.2.2 Carbon Tetrachloride Emissions
Table 7-4 gives estimated carbon tetrachloride emission factors for
both variations of the oxychlorination step and other emission points
common to the balanced process. Carbon tetrachloride process emissions
for both oxychlorination process variations are based on VOC emission
factors and vent gas composition data for the air-based process, which
indicated a carbon tetrachloride composition of 1.4 percent of total
VOC. Adjustments were made for differences in the proportion of chlorinated
hydrocarbons in the VOC from the two process variations.
For the direct chlorination process and column vents, the carbon
tetrachloride emission factor is based on VOC emission factors, but
direct estimates of carbon tetrachloride content are not available.
Since an estimate of chloroform content was available, a factor was
obtained by assuming that carbon tetrachloride and chloroform are
present in the same proportions as in the oxychlorination process.
Similarly, a light ends carbon tetrachloride content of 17 percent was
used directly to obtain carbon tetrachloride factors from VOC emission
7-6
-------
TABLE 7-3. ETHYLENE DICHLORIDE/VINYL CHLORIDE MONOMER PRODUCERS
—I
—I
EPA
region Company
IV B.F. Goodrich
VI Borden, Inc.
Dow Chemical , U.S. A
E.I. duPont
Ethyl Corp.
Formosa Plastics Corp.
Georgia Pacific Corp.
B.F. Goodrich Co.
PPG Industries, Inc.
Shell Chemical Co.
Union Carbide Corp.
Vulcan Materials Co.
Atlantic Richfield Co.
Dow Chemical U.S. A
Dow Chemical U.S. A
Ethyl Corp.
B.F. Goodrich Co.
B.F. Goodrich Co.
Shell Chemical Co.
Union Carbide Corp.
Annual capacity
(xlO3 Mg)3
Location
Calvert City, KY
Geismar, LA
Plaquemine, LA
Lake Charles, LA
Baton Rouge, LA
Baton Rouge, LA
Plaquemine, LA
Convent, LA
Lake Charles, LA
Norco, LA
Taft, LA
Geismar, LA
Port Arthur, TX
Freeport, TX
Oyster Creek, TX
Pasadena, TX
Deer Park, TX
La Porte, TX
Deer Park, TX
Texas City, TX
EDC
450
230
860
525
320
250
750
360
1,225
545
70
160
205
725
475
100
145
720
635
70
8,820
VCM
450
280
565
320
140
140
450
--
410
320
--
--
--
70
340
--
--
450
380
--
4,315
Ozone Post-1982
NAAQS attainment
attainment date
status4'5 granted4'5
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
No
No
No
No
No
No
No
No
No
No
No
No
No
No
No
Yes
Yes
Yes
Yes
No
M _ j_ _ . r*j . . .C-C^ ... PL.-.™..:-*-*.! r*«. n 1 -. «4- -i .-. f -* ,-,- « « PA !_.-.*-. ,-J-?,-~n-.-t«4-~1<-.s-l -i ^ 1 noo -^ '-'
NA -- Nonattainment
-------
t©
AIR
I
co
HEADS
COLUMN "^
WASTE-
WATER
TREATMENT
HCI 1 LIQUID-
REMOVAL | wflsTE
^
STORAGE
^
TO
SALES*
TAR
STORAGE
TO
SALES
LIQUID
CHLORINATED
HYDROCARBONS
INCINERATOR
NOTE:
Letters in this figure refer to process vents
described in the text and tables. Numbers refer
to process descriptions in the first reference
cited below. Heavy lines indicate final product
streams throughout the process.
Figure 7-2. Process flow diagram for ethylene dichloride production by balanced air-based process.12'13
-------
<*_._<£_
(BY PIPELINE I
HC... <£>._
(BY PIPELINE)
ETHYLENEV/
(BY PIPELINE) <
NOTE: Letters 1n this figure refer to process vents
described in the text and tables. Numbers refer
to process descriptions 1n the first reference
cited below. Heavy lines Indicate final product
streams throughout the process.
Figure 7-3. Process flow diagram for ethylene dichloride production by
oxyqen-based process, oxychlorination step.14,15
-------
TABLE 7-4. UNCONTROLLED CARBON TETRACHLORIDE EMISSION FACTORS
FOR ETHYLENE DICHLORIDE PRODUCTION BY THE BALANCED
PROCESS
Uncontrolled
carbon
tetrachloride
Source emission
Emission source designation factorb
Oxychlorination vent
Air process A 0.10 kg/Mg
Oxygen process A 0.034 kg/Mg
Direct-chlorination vent
0.86 kg/Mg
Column vents C
Liquid waste storage D 0.0050 kg/Mg
Incinerator E 0.032 kg/Mg
Fugitive0 0.95 kg/hr
Refers to process vents in Figure 7-2, except for the oxygen-based
process oxychlorination vent which is shown in Figure 7-3. Unlabeled
emission points have negligible carbon tetrachloride emissions.
Emission factors in terms of kg/Mg refer to kg of carbon tetrachloride
emitted per Mg of ethylene dichloride produced by both components of
the balanced process, from Reference 16.
Fugitive emission rate independent of process rate.
7-10
-------
factors for liquid waste storage and incineration. A fugitive VOC emission
rate was calculated assuming that fugitive emissions have the same composition
1R
as total process emissions (3.9 percent carbon tetrachloride).
7.2.3 Emission Controls
Process emission controls used at ethylene dichloride plants include
thermal and catalytic oxidization, solvent absorption, water scrubbing,
refrigerated condensation and process-related control techniques. Existing
controls are summarized in Table 7-5. In addition, five plants in Louisiana
currently using air-based oxychlorination have agreements with the State to
convert to the oxygen-based process and to vent the emissions to a thermal
oxidizer. These conversions are scheduled to be complete by the end of
1984, and include Conoco/Westlake: Ethyl/Baton Rouge, Formosa Plastics/Baton
Rouge, Shell/Norco, and Vulcan/Geismar.
The National Emission Standard (NESHAP) for vinyl chloride (40 CFR 61.62)
includes the following limits for ethylene dichloride plants: Vinyl chloride
must not exceed 10 ppm in exhaust gases from ethylene dichloride purification
equipment, and emissions from oxychlorination reactors must not exceed
0.2 g/kg of ethylene dichloride product. The controls in Table 7-5 indicate
that the principal method used for meeting these limits is thermal oxidation,
which is estimated to have a VOC control efficiency of 98 percent or 20 ppm,
21
whichever is less stringent. Specific information is not available on
carbon tetrachloride control efficiencies for the other controls cited in
Table 7-5, and for process modifications, another potential control under
the vinyl chloride NESHAP. In addition to State regulations and the SOCMI
fugitive CTG, the Group III CTG for air oxidation processes described in
2.2.2 will also apply to a number of these plants, depending on the process
used and NAAQS attainment status (see Table 7-3). Further investigation of
the effectiveness of these controls for carbon tetrachloride was beyond the
scope of this study.
7.3 PERCHLOROETHYLENE AND TRICHLOROETHYLENE PRODUCTION FROM ETHYLENE
DICHLORIDE
7.3.1 Process Description
Carbon tetrachloride is formed as a by-product in the chlorination
or oxychlorination of ethylene dichloride to produce perch!oroethylene
and trichloroethylene. Other chlorinated hydrocarbons may also be used
7-11
-------
TABLE 7-5. EMISSION CONTROLS USED BY THE ETHYLENE DICHLORIDE INDUSTRY
20
Company and
location
Process
used
Emission sources
Control technique
or device used
Allied
Baton Rouge, LA
Borden
Geismar, LA
Conoco
Westlake, LA
Diamond Shamrock
Deer Park, TX
La Porte, TX
Dow
Freeport, TX
Oyster Creek, TX
B.F. Goodrich
Calvert City, KY
Air
Air
Air
Air
Air
Not reported
Oxygen
Air
Oxychlorination vent
Stripper ejector
Purification vent
Oxychlorination vent
Direct-chlorination vent
Purification vents
Oxychlorination vent
Direct-chlorination vent
Purification vents
Oxychlorination vent
Direct-chlorination vent
Purification vents
Process vents
Process vents
Process vents
Oxychlorination vent
Direct-chlorination vent
None
None
Return to process
Thermal oxidizer
Thermal oxidizer
Thermal oxidizer
Post reactor
Refrigerated condenser
Water scrubber
Catalytic oxidizer
Refrigerated condenser
Vent condensers
Thermal oxidizer
Thermal oxidizer
Thermal oxidizer
Solvent absorption
Refrigerated vent condenser
CONTINUED
-------
TABLE 7-5. (continued)
Company and
location
Process
used
Emission sources
Control technique
or device used
PPG
Lake Charles, LA
Guayanilla, PR
Shell
Deer Park, TX
Vulcan
Geismar, LA
Oxygen
Oxygen
Air
Air
Oxychlorination vent
Direct-chlorination vent
Process vents
Oxychlorination vent
Direct-chlorination vent
Purification vents
Storage vents
Oxychlorination vent
Purification vents
Thermal oxidizer
Thermal oxidizer
Thermal oxidizer
Post reactor
Thermal oxidizer
Chilled water scrubber
None
-------
as feedstock. In the chlorination process, the feed materials and
chlorine are combined at about 400°C (750°F), followed by hydrogen
chloride by-product removal, product treatment and distillation, and
recycle or incineration at the column ends. In oxychlorination, reaction
of ethylene dichloride, chlorine or hydrogen chloride, and oxygen results
in an initial product comprised of water, carbon dioxide, and hydrogen
chloride, as well as perch!oroethylene, trichloroethylene and by-product
organics such as carbon tetrachloride. Water removal, hydrogen chloride
absorption and inert gas purging result in a crude product which is
22
refined further and neutralized. Figures 7-4 and 7-5 show these
process flows and related carbon tetrachloride emission points.
Process variations make it possible to direct production partly or
entirely to either principal product. As shown in the list of producers,
Table 7-6, two producers currently produce only one of the two possible
principal products.
7.3.2 Carbon Tetrachloride Emissions
The only available emissions data for these processes are for the
27
Diamond Shamrock plant, which produces only perchloroethylene.
Table 7-7 presents emission factors derived from those data. Carbon
tetrachloride formation may be affected significantly by the process
variations necessary to produce only perchloroethylene. It is not known
how these emission factors might change for the other plants in Table 7-6.
7.3.3 Emission Controls
The Diamond Shamrock plant has a chilled-water condenser on its
drying column with an estimated 80 percent VOC reduction efficiency, and
also uses various condensers on in-process and product storage. The
Ethyl plant has a refrigerated condenser with 80 percent VOC control
efficiency on its distillation column vents, after which vent gases are
recycled into another process. The Dow plant is reported to use water
scrubbers on process vents, but these will have a marginal effect on any
carbon tetrachloride emissions. In-process storage is in pressurized
tanks with regulators which are estimated to provide 70 percent control.
PPG uses a thermal oxidizer on the HC1 absorber and drying column vents
7-14
-------
HYDROGEN CHLORIDE
TO OTHER
PROCESSES
CHLORINE
I
I—»
en
• LOADING
STORAGE
.LOADING
PCE
STORAGE
1
C2 CHLORINATED
ORGANICS FROM
OTHER PROCESSES
TARS TO
INCINERATION
NOTE: Letters In this figure refer to process vents
described in the text and tables. Numbers refer
to process descriptions in the first reference
cited below. Heavy lines indicate final product
streams throughout the process.
Figure 7-4.
Process flow diagram for perchloroethylene and trichloroethylene
production by chlorination of ethylene dichloride.23,24
-------
OH
PROCESS
WATER —
MAKEUP
CATALYST
/^HYDROCHLORIC ACID
<«j cwT "Ef-'/T ^•1">"««*JL ^
HCI
ABSORBER
AQUEOUS WASTE
**STE
OXYGEN
CHLORINE OR
HYDROGEN — /.
CHLORIDE
N5^
BED 1
TOR
a
co
RECYCLE
ORGANIC
STORAGE
Cj CHLORINATED ORGANICS _.
FROM OTHER PROCESSES
KD e
.E
1C
3E
f
<®
1©
ORGANIC
RECYCLE
SYSTEM
1
*
^
LQAOItM
TARS TO
INCINERATION
PCE TRAIN
NOTE: Letters 1n this figure refer to process vents
described 1n the text and tables. Numbers refer
to process descriptions in the first reference
cited below. Heavy lines Indicate final product
streams throughout the process.
Figure 7-5. Process flow diagram for perchloroethylene and trichloroethylene production
by oxychlorination of ethylene dichloride.25,26
-------
TABLE 7-6. PERCHLOROETHYLENE AND/OR TRICHLOROETHYLENE PRODUCTION BY
CHLORINATION OF ETHYLENE DICHLORIDEa
Annual capacity
(xlO3 Mg)b
EPA
region
VI
Company
Ethyl Corp.
PPG Industries, Inc.
Diamond Shamrock Corp.
Dow Chemical , U.S.A.
Location
Baton Rouge, LA
Lake Charles, LA
Deer Park, TX
Freeport, TX
Perchloro-
ethylene
23
91
75
--
Trichloro-
ethylene
20
91
c
55
Ozone Post-1982
NAAQS attainment
attainment date
status4'5 granted?4'5
NA
NA
NA
NA
No
No
Yes
No
Does not include Vulcan plants at Geismar, LA and Wichita, KS which use ethylene dichloride with
chlorination bottoms to produce perchloroethylene and carbon tetrachloride — these plants are
described under carbon tetrachloride producers.
Includes only perchloroethylene and trichloroethylene produced from ethylene dichloride.
GTrichloroethylene capacity of 23 x 103 Mg/yr placed on standby in 1978.
NA -- Nonattainment
-------
TABLE 7-7. UNCONTROLLED CARBON TETRACHLORIDE EMISSION FACTORS
FOR A PLANT PRODUCING PERCHLOROETHYLENE BY ETHYLENE
DICHLORIDE CHLORINATION
Uncontrolled
carbon
tetrachloride
emission
Emission source factorb
Process
Neutralization 0.016 kg/Mg
Drying column 0.063 kg/Mg
Distillation column 0.027 kg/Mg
Light ends/heavy ends mix tank 0.039 kg/Mg
Storage - light ends 0.11 kg/Mg
Process fugitive 2.8 kg/hr
Emission factors in terms of kg/Mg refer to kg of carbon
tetrachloride emitted per Mg of perchloroethylene produced, from
Reference 28.
Fugitive emission rate independent of plant rate.
7-18
-------
as well as many other sources in other processes. Estimated VOC control
of this unit is 99 percent. Water scrubbers used to control distillation
29
and product neutralization vents will have little effect on VOC emissions.
Evaluation of the effect of these controls on carbon tetrachloride
emissions is not possible with available data.
7-19
-------
7.4 REFERENCES
1. Organic Chemical Manufacturing—Volume 8: Selected Processes. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards, Research Triangle Park, NC. EPA-450/3-80-028c.
December 1980. Report 6, p. III-l to III-4.
2. Anderson, M.E. and W.H. Battye, GCA/Technology Division. Locating
and Estimating Air Emissions from Sources of Carbon Tetrachloride--
Final Draft Report. U.S. Environmental Protection Agency, Office of
Air Quality Planning and Standards, Research Triangle Park, NC.
Contract No. 68-02-3510, Work Assignment No. 22. September 1982.
Page 12-15.
3. Stanford Research Institue, 1982 Directory of Chemical Producers
USA, Menlo Park, CA, 1982.
4. Map Depicting Nonattainment Areas Pursuant to Section 107 of the
Clean Air Act. U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Research Triangle Park, NC. EPA-450/
2-80-062, April 1980.
5. Status Summary of States' Group I VOC RACT Regulations As of June 1, 1981
Second Interim Report. U.S. Environmental Protection Agency, Office
of Air Quality Planning and Standards, Control Programs Development
Division, Research Triangle Park, NC. Contract No. 68-02-5310,
Task No. 8, July 1981.
6. Reference 2, p. 20.
7. Reference 2, p. 16.
8. Reference 1, p. IV-1.
9. Reference 1, Report 1, p. III-l to III-7.
10. Parker, T., California Air Resources Board, Sacramento, CA. Personal
communication with M.G. Smith, GCA, June 14, 1982.
11. Reference 1, Report 1, p. F-l, 2.
12. Reference 2, p. 55.
13. Reference 1, Report 1, p. III-3.
7-20
-------
14. Reference 2, p. 57.
15. Reference 1, Report 1, p. III-6.
16. Reference 2, p. 60.
17. Reference 2, p. 61 .
18. Reference 2, p. 62.
19. Reference 1, Report 1, p. V-l to V-6.
20. Reference 1, Report 1, p. F-2, 3.
21. Mascone, D.C., EPA. Memos to J.R. Farmer, EPA. June 11, 1980 and
July 22, 1980.
22. Reference 2, p. 65-69.
23. Reference 2, p. 66.
24. Reference 1, Report 4, p. 111-10.
25. Reference 2, p. 68.
26. Reference 1, Report 4, p. 111-12.
27. Worthington, J.B., Diamond Shamrock, Cleveland, OH, Letter to
D.R. Goodwin, EPA, January 16, 1979.
28. Reference 2, p. 70.
29. Reference 1, Report 4, p. D-l to D-3.
30. G. Gasperecz, Louisiana Air Quality Division, Baton Rouge, LA. Personal
communication with E. Anderson, GCA, December 21, 1982.
7-21
-------
8.0 GRAIN FUMIGANT FORMULATION AND USE
8.1 GENERAL INFOMATION
Air emissions of carbon tetrachloride occur during the formulation,
storage, handling, application and subsequent release of liquid grain
fumigant mixtures. Carbon tetrachloride is used in essentially all of
the liquid grain fumigant mixtures available for application to stored
grain. While it is somewhat active against pests by itself, carbon
tetrachloride is used as a carrier and to reduce risk of fire and
2
explosion in the most common liquid grain fumigant formulations. The
most common 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 77.7 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
2
o Carbon tetrachloride 75 percent, ethylene dichloride 25 percent.
The carbon tetrachloride/carbon disulfide formulation is estimated
to account for 65 percent of all liquid fumigants, with the remaining
35 percent divided among the three mixtures containing ethylene dibromide.
3
Use of the last formulation above is reported to be negligible. One
reference lists about 120 different brand names under which these products
are distributed and sold, as well as about 65 facilities at which they
8-1
-------
are formulated. Since this listing provides no data which would allow
estimation of carbon tetrachloride emissions, it is not included here.
Combining all formulations, the following average distribution of major
fumigant ingredients is reported for 1976-1979 in weight percent:
Carbon tetrachloride 76.7 percent
Carbon disulfide 12.1 percent
Ethylene dichloride 7.1 percent
Ethylene dibromide 1.6 percent
Other ingredients 2.5 percent
The best available estimates for average annual carbon tetrachloride
use in these products are 11,500 to 14,800 Mg (12,680 to 16,300 tons)
between 1976 and 1979,6 and 12,800 Mg (14,000 tons) for 1977 and 1978.7
This estimate is based on actual application, and does not include any
losses in formulation. Formulation and application are discussed
individually below. It should be noted that this section covers only
pesticides which actually include carbon tetrachloride. Carbon tetrachloride
is also used in synthesis or processing of other pesticide and herbicide
products, such as several of the miscellaneous sources discussed in
Section 10.2.
8.2 LIQUID FUMIGANT FORMATION DESCRIPTION
Pesticide formulation systems typically are batch mixing operations,
such as the one shown in Figure 8-1. Ingredients or solvents received
in bulk are transferred to holding tanks for storage. Smaller-volume
o
components are usually kept in the original container until needed.
Batch mixing tanks are typically open-topped vessels fitted with an
agitator. The mixing tank may also be equipped with a heating or cooling
system. Ingredients are fed into the mix tank, with the quantity determined
by meters, scales, or by measuring the level in the mix tank. Other
blending agents (such as emulsifiers) may be added directly to the mix
tank. The formulated material may be filtered by cartridge or polishing
filters and pumped to a holding tank before being put into containers
8-2
-------
EXHAUST VtNT
CO
I
ItSTIClDE
155 GAL. DRUM)
PHOOUCT
455 GAL. DRUM)
I
SCALE
PUMP
Q
Figure 8-1. Process flow diagram for liquid pesticide formulation.
-------
for shipment. Storage and holding tanks, mixing tanks and container-filling
lines are provided with an exhaust connection or hood to remove any
vapors. The exhaust from the system is vented to a scrubber or directly
o
to the atmosphere.
Sources of carbon tetrachloride emissions from pesticide formulation
include storage vessels, mixing vessel vents, and leaks from pumps,
P
valves, and flanges. There is not sufficient information for the
development of carbon tetrachloride emission factors for liquid fumigant
formulation facilities.
8.3 LIQUID FUMIGANT APPLICATION DESCRIPTION
Liquid fumigants based on carbon tetrachloride are used to control
insect infestations during storage, transfer, milling, distribution and
processing of grain. They are applied to grain in on-farm storage, at
subterminal, terminal and port elevators, at mill holding facilities,
and in transport vehicles. In addition to storage, about two percent of
all carbon tetrachloride formulations are used to fumigate grain mill
9
equipment.
Almost all on-farm grain fumigation is done with carbon tetrachloride-based
liquid formulations. The principal alternative fumigant, aluminum
phosphide, is applied in pellets or tablets which release phosphine gas,
the actual active ingredient. Phosphine escapes quickly from typical
loosely-constructed on-farm storage facilities, and must be applied by
trained, certified personnel. Thus, it has been used very little on
farms. Use of aluminum phosphide is more common at off-farm storage
facilities, due to tighter construction, availability of trained personnel,
and the ability to turn stored grain, facilitating uniform distribution
of the fumigant tablets. It has been estimated that aluminium phosphide
is used on 70 percent of the grain fumigated in large elevators.
Thus the proportion of use of carbon tetrachloride formulations is
greatest on the farm and at loosely-constructed smaller elevators, while
terminal and port elevators are more likely to use aluminum phosphide
formulations. The low reactivity of aluminium phosphide formulations
at low ambient temperatures leads to the increased use of carbon tetrachloride
8-4
-------
formulations at off-farm storage facilities in the winter. Carbon
tetrachloride formulations are also the most practical fumigants for
grain in transit, since they can be applied to the surface of the load
and are effective at all temperatures. The best available estimates of
the distribution of fumigant use are for 1977. They indicate that about
3,900 Mg (4,300 tons) of carbon tetrachloride were used in on-farm grain
storage, while about 8,900 Mg (9,800 tons) were used at off-farm facilities.11
Average application rates for various grains were used with these usage
figures to estimate that liquid fumigants were applied to 6.4 to 11.7 percent
of total U.S. grain production from 1976 to 1979.12 These average
application rates are shown in Table 8-1.
TABLE 8-1. FUMIGANT APPLICATION RATES13
Application rate
(gal/103 bu)
Grain
Wheat
Corn
Rice, Oats, Barley, Rye
Grain sorghum
On-farm
3 -
4 -
3 -
5 -
4
5
4
6
Off-farm
2 -
3 -
2 -
4 -
3
4
3
5
Liquid fumigants typically are applied by the "gravity distribution"
method, which consists of pouring or spraying the liquid on the surface
of stored grain. This may be done to the entire stored mass, or to
individual layers, and may occur as grain is first stored, or upon
turning (shifting from one storage facility to another). Grain in
railroad cars may be treated by pouring the fumigant through roof vents
or by spraying it into the car with a power sprayer. In addition to
hand application and pumped or pressurized delivery systems, metering
14
devices are also used to treat streams of moving grain.
3-5
-------
After application of liquid fumigants, grain must be left undisturbed
for a few days to allow diffusion and proper pesticidal action. In most
cases, the grain is not disturbed until turning or transfer is necessary.
At some facilities, release of the fumigant after an adequate treatment
period may be facilitated by turning the grain or by ventilating tightly-sealed
15
facilities with fresh air.
Emissions of carbon tetrachloride from fumigant mixtures occur
during fumigant application, and when fumigated grain is exposed to the
atmosphere, during storage, turning, ventilation, or loading. Because
of the relatively high vapor pressure of carbon tetrachloride, it is
estimated that essentially all carbon tetrachloride used in fumigants
evaporates. 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 8-2 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 aeration.
The grain was fumigated and aerated under conditions comparable to
commercial fumigation and aeration conditions.
Specific information on geographic distribution of fumigant use
does not appear to be available. Tables 8-2 and 8-3 provide statistics
on on-farm and off-farm grain storage facilities and capacities by
State. Fumigant use is not distributed evenly by production or storage
capacity, because the degree to which stored grain is subject to attack
by pests is highly dependent on temperature and humidity. For example,
in on-farm storage, insects can be a serious problem throughout the
storage period in the southern States, while little if any damage would
on
be expected in the first season's storage in drier northern States.
8.4 REGULATIONS AND EMISSION CONTROL
The EPA Office of Pesticide Programs issued a Notice of Rebuttable
Presumption Against Registration (RPAR) on October 15, I9604 for all
pesticide products containing carbon tetrachloride. While further
action under this RPAR may lead to a significant reduction or elimination
8-6
-------
00
I
10
20
30 40 50
DAYS OF AIRING
60
70
Figure 8-2. Residual carbon tetrachloride fumigant as a
function of days grain aired.16
-------
TABLE 8-2. ON-FARM GRAIN STORAGE18
Region
and State
Northeast:
Maine
New Hampshire
Vermont
Massachusetts
Rhode Island
Connecticut
New York
New Jersey
Pennsylvania
Delaware
Maryland
Lake States:
Michigan
Wisconsi n
Minnesota
Corn Belt:
Ohio
Indiana
111 i noi s
Iowa
Mi ssouri
Northern Plains:
North Dakota
South Dakota
Nebraska
Kansas
Appalachian:
Virginia
West Virginia
North Carolina
Kentucky
Tennessee
Southeast:
South Carolina
Georgia
Florida
Al abama
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
1,357,627 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
8-8
-------
TABLE 8-2. (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
315,157
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 8,116,812 100%
8-9
-------
TABLE 8-3. OFF-FARM GRAIN STORAGE
19
State
Alabama
Arizona
Arkansas
Cal iforni a
Colorado
Delaware
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Jersey
New Mexico
New York
North Carol ina
North Dakota
Ohio
Oklahoma
Oregon
Pennsyl vania
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
(103 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
8-10
-------
of the use of carbon tetrachloride in fumigants, the possible outcome of
the RPAR process is not known. Existing measures for reduction of air
emissions of these fumigants might include expanded use of alternatives
such as aluminum phosphide and more efficient use of the currently-used
formulations. Implementation of either of these control measures could
involve a combination of storage facility modifications (such as improving
existing grain storage structures and installing ventilation/recirculation
systems), and improved work practices, which might be possible through
application guidelines and applicator training/certification.
8-11
-------
8.5 REFERENCES
1. 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. p. 1-6.
2. Reference 1, p. II-l.
3. Reference 1, p. V-l.
4. Carbon Tetrachloride; Pesticide Programs; Rebuttable Presumption
Against Registration and Continued Registration of Certain Pesticide
Products. Federal Register 4(202): 68534-68584, October 15, 1980.
5. 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, p. 13.
6. Reference 5, p. 3.
7. Reference 1, p. V-3.
8. Development Document for Effluent Limitations Guidelines for the
Pesticide Chemicals Manufacturing Point Source Category. U.S.
Environmental Protection Agency, Washington, DC, EPA-440/l-78-060e,
April 1978, p. 50-52.
9. Reference 1, p. V-2.
10. Reference 1, p. VI-18.
11. Reference 1, p. V-3.
12. Reference 5, p. 61.
13. Reference 5, p. 60.
14. Ludvik, G.F. Fumigants for Bulk Grain Protection: Biological
Aspects and Relevant Data. U.S. Environmental Protection Agency,
Washington, DC, August 1981. p. 19.
15. Reference 14, Appendix 4.
3-12
-------
16. Jagielski, J., K.A. Scudamore and S.G. Heuser. Residues of Carbon
Tetrachloride and 1,2-Dibromoethane in Cereals and Processed Foods
after Liquid Fumigant Grain Treatment for Pest Control. Pesticide
Science 9(2):117-126, April 1978.
17. Reference 4, p. 68569.
18. Reference 1, p. VIII-4.
19. Reference 1, p. VIII-19.
20. Storey, C.L., R.D. Speirs and L.D. Henderson. Insect Control in
Farm-Stored Grain. USDA/SEA Farmer's Bulletin No. 2269, 1979.
8-13
-------
9.0 PHARMACEUTICAL MANUFACTURING
9.1 SOURCE DESCRIPTION
Carbon tetrachloride is used as a solvent in the manufacturing of
pharmaceutical products. 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 five 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).
Data on geographic distribution of carbon tetrachloride use at these
plants are not available.
Synthetic Pharmaceuticals are normally manufactured in a series of
batch operations. Figure 9-1 presents a typical flow diagram for a
batch synthesis operation. 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 by-products. The solvent used in washing generally is
9-1
-------
SOLIDS
SOLVENT
VENT
J !
VENT
VENT
REACTOR
HOLDING
TANK
t
SOLVENT SOLVENT
RECEIVER I
SOLVENT
DISTILLATION
CRYSTALLIZE
H20
SOLVENT VENT
BATCH
CENTRIFUGE
H20
SOLVENT
VENT
DRYER
PRODUCT
o
Figure 9-1. Process diagram for typical synthetic pharmaceutical manufacturing process.
-------
evaporated from the reaction product. The crude product may then be
dissolved in another solvent and transferred to a crystallizer 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.
o
Tray, rotary, or fluid-bed dryers are employed for final product finishing.
9.2 PHARMACEUTICAL MANUFACTURING SOLVENT EMISSION SOURCES
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
can be expected to vary widely within and among operations, but information
on individual operations involving carbon tetrachloride does not exist.
Therefore, it is impossible to cite typical emission rates for various
operations. 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
5
A survey of 26 ethical drug manufacturers published in 1978 cites
a total annual carbon tetrachloride purchase of 1,850 Mg (2,030 tons) by
these manufacturers. The survey was estimated to cover about 85 percent
of all volatile organic compounds used by the reporting manufacturers,
who accounted for 53 percent of domestic sales of ethical Pharmaceuticals
in 1975. Estimated final disposition of the above total carbon tetrachloride
9-3
-------
usage was reported as 210 Mg (230 tons) air emissions (11 percent),
120 Mg (130 tons) sewer disposal (7 percent) and 1,510 Mg (1,660 tons)
incineration (82 percent). The survey did not provide data on individual
plants, processes, or related carbon tetrachloride use.
9.3 EMISSION CONTROLS
Condensers, scrubbers, and carbon adsorbers can be used to control
emissions from all the emission sources listed in Section 9.2. 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. This source category is the subject
of a Group II Control Techniques Guideline, which cites the above
control techniques. Although control efficiencies may vary with the
specific process, overall control of 90 percent of carbon tetrachloride
emissions or better should be achievable for most processes.
9-4
-------
9.4 REFERENCES
1. Control of Volatile Organic Emissions from Manufacture of Synthesized
Pharmaceutical Products. U.S. Environmental Protection Agency,
Research Triangle Park, NC, EPA-450/2-78-029, December 1978, p. 1-2.
2. Reference 1, p. 2-3.
3. Reference 1, p. 2-2.
4. Reference 1, p. 2-5.
5. Reference 1, Appendix A.
6. Reference 1, Chapters 3 and 4.
9-5
-------
10.0 OTHER POTENTIAL SOURCES OF CARBON TETRACHLORIDE EMISSIONS
This section summarizes information on other reported or potential
sources of carbon tetrachloride air emissions identified during the
data-gathering phase of this study. Many of these sources may be relatively
small and some appear to be one-of-a-kind plants. However, there are
several which may have fairly high individual or collective emissions
relative to other identified carbon tetrachloride sources. Only limited
verification and follow-up of these preliminary source identifications
was possible.
10.1 PHOSGENE/ISOCYANATE/POLYURETHANE PROCESSES
Phosgene is produced by reacting chlorine gas and carbon monoxide
in the presence of activated carbon, at 200°C (390°F). Hot reactor
effluent gases are condensed to remove most of the phosgene, and then
are scrubbed with a hydrocarbon solvent to remove entrained phosgene.
As indicated by the list of phosgene producers in Table 10-1, almost all
of the phosgene produced in this country is used directly in other
operations at the same plant. The principal use is in manufacture of
isocyanates, which are then used in making polyurethane resins.
A 1977 emission inventory by the West Virginia Air Pollution Control
Commission cited by A.D. Little indicates that carbon tetrachloride is
used as the absorbent in a scrubber which is part of the phosgene production
process at the Union Carbide plant at Institute, West Virginia.
Identified as Process 25S, the carbon tetrachloride sources cited included
two storage tanks of unknown size with total estimated emissions of
98.6 Mg/yr (108.5 tons/yr) and a unit appearing to be a scrubber which
had estimated emissions of 10.7 Mg/yr (11.8 tons/yr) and a temperature
of 300°C (570°). Except for inconsistencies in the temperatures involved,
these data are consistent with typical scrubbing of non-condensible gases
with hydrocarbon solvent after the primary post-reactor condenser in
phosgene production.
10-1
-------
TABLE 10-1. PHOSGENE PRODUCERS'
EPA
region Company
II DuPont
Van De Mark
III Essex
Mobay
01 in
Union Carbide
V General Electric
PPG
VI BASF Wyandotte
ICI Americas
01 in
Dow
Mobay
PPG
Upjohn
TOTAL
Location
Deepwater, NJ
Lockport, NY
Baltimore, MD
New Marti nsvi lie, WV
Moundsville, WV
Institute, WV
Mount Vernon, IN
Barberton, OH
Geismar, LA
Geismar, LA
Lake Charles, LA
Freeport, TX
Cedar Bayou, TX
La Porte, TX
La Porte, TX
Phosgene
production
capacity
(x 103 Mg)
81
4a
4
111
45
64
41
2
25
68
55
59
114
30a
136
839
These two plants are believed to be the only ones producing phosgene for
sale; All others produce for captive consumption.
10-2
-------
A Texas emission inventory cites a carbon tetrachloride emission
source of about 0.46 Mg/yr (0.51 tons/yr) as part of a toluene diisocyanate
production process at the Dow Plant "B" at Freeport, Texas. This may be
another example of carbon tetrachloride scrubbing of a phosgene process
stream, which would be considered part of the isocyanate production.
This plant was also reported to have a carbon tetrachloride storage tank
emitting 0.9 Mg/yr (1.0 tons/yr), and a 9.3 Mg/yr (10.2 tons/yr) carbon
tetrachloride source in a latex production. This latex may be a further
step in the same sequence, such as an intermediate stage in polyurethane
processing.
10.2 PESTICIDE PRODUCTION
Emissions of carbon tetrachloride were reported to be associated
with several pesticide production operations, beyond the use of carbon
tetrachloride as a major ingredient of grain fumigants discussed
earlier. Carbon tetrachloride is apparently used as a solvent or reaction
medium in these processes, which are discussed individually below.
Chlorothalonil: Chlorothalom'l is also known by the Diamond Shamrock
tradenames Daconil, Forturf, Termil and Bravo, and as tetrachloro-
isophthalonitrile; 2,4,5,6-tetrachloro-l,3-benzenedicarbonitrile; and
1,3-dicyano-2,4,5,6-tetrachlorobenzene. ' Cited uses include agricultural
5
and horticultural fungicide, bactericide and nematocide. It is made by
dissolving tetrachloroisophthalic acid chloride in an organic solvent
and adding ammonia. A wide range of solvents can be used, although one
reference cites xylene or dioxane as preferred solvents.
Carbon tetrachloride is probably used as the solvent or in
subsequent product refinement steps at the Diamond Shamrock Daconil
plant at Houston, Texas. The 1980 Texas emission inventory cites two
emission points at this plant as emitting 133 and 87 Mg/yr (143 and
96 tons/yr) of carbon tetrachloride, respectively. This plant, also
cited as being in Greens Bayou, is reported to be the only one in the
2
U.S. producing Chlorothalonil.
10-3
-------
Linuron : Linuron is a DuPont tradename for N'-(3,4-dichlorophenyl)-N-
methoxy-N-methylurea, also known as DuPont Herbicide 326 and Lorox.
7 8
Its principal use is as a selective herbicide. ' Production locations
are reported to include DuPont plants at East Chicago, Illinois, and
LaPorte, Texas. The 1980 Texas emission inventory cites the LaPorte
plant as emitting 1.9 and 0.7 Mg/yr (2.1 and 0.8 tons/yr) of carbon
tetrachloride from two emission points associated with the Linuron
process. One process description indicates use of benzene as a solvent
for the two feed materials, 0,N-dimethyl-hydroxylamine and
3,4-dichlorophenylisocyanate. Air emissions of 0.5 kg hydrocarbon
solvent per megagram (1 Ib/ton) of Linuron product were also cited by
o
this source. It may be that carbon tetrachloride has been substituted
for benzene as the hydrocarbon solvent in this process.
Sulfuryl flouride: Sulfuryl flouride is an insecticide! fumigant
marketed by Dow Chemical under the tradename Vikane. It can be produced
by heating barium fluorosulfonate to produce barium sulfate and sulfuryl
g
flouride, or by burning flourine in sulfur dioxide. It is produced at
2
the Dow plant in Pittsburg, California. A contact at the Bay Area Air
Quality Management District indicates that this process is a source of
carbon tet
available.
carbon tetrachloride air emissions, but no additional information was
10.3 HYPALON@ SYNTHETIC RUBBER PROCESS
Hypalon is the tradename for a DuPont synthetic rubber which is
produced by reacting polyethylene with chlorine and sulfur dioxide,
transforming the thermoplastic polyethylene into a vulcanizable elastomer.
The reaction is conducted in a solvent reaction medium. A Texas
emission inventory for 1980 includes eight emission points for carbon
tetrachloride at the DuPont plant at Beaumont, Texas. The cited emissions
range from 1 to 65 Mg/yr (1.1 to 72 tons/yr), totalling 105 Mg/yr (116 tons/yr).
p
This plant is apparently the only one in the U.S. producing Hypalon.
10-4
-------
10.4 CARBON TETRABROMIDE PRODUCTION
Carbon tetrabromide is produced by reaction of carbon tetrachloride
and aluminum tribromide at about 100°C (212°F).12 Carbon tetrachloride
emissions are likely to occur from process waste streams as well as from
raw material storage. The three plants listed in Table 10-2 are
2
reported to produce carbon tetrabromide. A Texas emission inventory
for 1980 does not mention carbon tetrabromide production or carbon
tetrachloride storage at the Diamond Shamrock plant at Deer Park.
There are three emission points, each described only as an "organic
recovery systems," with carbon tetrachloride emissions of 0.87, 0.86,
and 0.008 Mg/yr (0.96, 0.95, and 0.009 tons/yr), respectively. It is
not known whether one or more of these recovery systems is associated
with the carbon tetrabromide production. No information could be
located on the Great Lakes Chemical Corp. plant at El Dorado, Arkansas,
15
through the Arkansas Department of Pollution Control and Ecology. New
York Division of Air records on the 01 in plant at Rochester do not
mention carbon tetrabromide production, although a carbon tetrachloride
storage tank with annual uncontrolled emissions of about 91 kg (200 pounds)
and 99 percent control by carbon adsorption is registered. A number of
other sources emitting very small amounts of carbon tetrachloride, in
the range of 0.07 kg/yr (0.15 Ib/yr), were reported for this plant. '
10-5
-------
TABLE 10-2. CARBON TETRABROMIDE PRODUCERS
CD
I
CTl
EPA
region
II
VI
VI
Company
01 in Corporation
Great Lakes Chemical
Corporation
Diamond Shamrock
Corporation
Location
Rochester, NY
El Dorado, AR
Deer Park, TX
Ozone NAAQS
Attainment
status13'14
NA
A
NA
Post-1982
attainment
date granted?13'14
No
—
Yes
A—Attainment
NA--Nonattainment
-------
10.5 MISCELLANEOUS
The 1980 Texas emission inventory also reported the following
carbon tetrachloride sources.4
Chlorine liquefaction: A chlorine liquefaction operation at the
Diamond Shamrock facility in Deer Park, Texas, was reported to emit
about 61 Mg/yr (67 tons/yr) of carbon tetrachloride from one point source.
One description of the chlorine liquefaction process does not indicate
i p
any specific potential sources of carbon tetrachloride emission.
Carbon tetrachloride may be part of a noncondensible by-product stream
cited in this reference as amounting to 20 kg per Mg (40 Ibs per ton) of
product chlorine.
Resinous chlorowax production: Three emission points associated
with a resinous chlorowax process at Diamond Shamrock facility in Deer
Park, Texas were reported to have total carbon tetrachloride emissions
of about 9 Mg/yr (10 tons/yr).
Tetrachloropyridine/picolinic acid processes: Four emission points
at the Dow Chemical Plant "A" in Freeport, Texas, were cited as having
total carbon tetrachloride emissions of about 0.6 Mg/yr (0.7 tons/yr).
Two of these points were in a symmetrical tetrachloropyridine process,
and two were in a 4-amino-3,5,6-trichloropicalinic acid process. These
chemicals are closely related, and may be part of the production process
for a Dow product called N-Serve (2-chloro-6-(trichloromethyl)pyridine).
N-Serve is a fertilizer additive used to control nitrification and
19
prevent loss of soil nitrogen.
Miscellaneous storage and loading: The Texas emission inventory
included several entries for carbon tetrachloride storage and loading at
tank farms not affiliated with carbon tetrachloride producers. One tank
at GATX Terminals Corp. and one loading operation at PAK Tank Gulf Coast
Inc. were each cited as having 1 Mg/yr (1.1 tons/yr) carbon tetrachloride
emissions, while several other entries for these companies had no emissions
reported.
10-7
-------
A retrieval from the New Jersey Air Pollution Enforcement Data
System indicated several reported carbon tetrachloride emission points
20 21
related to several polymer productions and one dye production process. '
Other potential carbon tetrachloride sources which could not be verified
include laboratory uses, metal cleaning, production of paint, adhesives,
textiles, and embalming supplies.
-------
10.6 REFERENCES
1. Industrial Process Profiles for Environmental Use: Chapter 6--The
Industrial Organic Chemicals Industry. Industrial Environmental
Research Laboratory, U.S. Environmental Protection Agency, Research
Triangle Park, NC, EPA-600/2-77-023f, February 1977. p. 6-475.
2. Stanford Research Institute, 1982 Directory of Chemical Producers
USA, Menlo Park, CA, 1982.
3. A.D. Little, Inc. An Integrated Geographic Study of Potential
Toxic Substance Control Strategies in the Kanawha River Valley,
West Virginia. Office of Pesticides and Residual Management, U.S.
Environmental Protection Agency, Washington, DC, 1977- Appendix A,
pp. 101, 102.
4. 1980 Emissions Inventory Questionnaire Data Retrieval for Carbon
Tetrachloride. Abatement Requirements and Analysis Division, Texas
Air Control Board, Austin, TX, June 10, 1982.
5. The Merck Index, Ninth Edition. M. Windholz, ed. Merck & Co.,
Rahway, NJ, 1976. p. 1184.
6. Pesticide Manufacturing and Toxic Materials Control Encyclopedia.
M. Sitting, ed. Noyes Data Corp., Park Ridge, NJ, 1980. p. 193.
7. Reference 5, p. 720.
8. Reference 6, p. 471-473.
9. Reference 6, p. 437.
10. Hill, S., Bay Area Air Quality Management District, San Francisco,
CA. Personal communication with M.G. Smith, GCA, June 14, 1982.
11. Shreve, R.N., and J.A. Brink. Chemical Process Industries. Fourth
Edition. McGraw-Hill Book Co., New York, NY, 1977, p. 635.
12. Reference 1, p. 6-416.
13. Maps Depicting Nonattainment Areas Pursuant to Section 108 of the
Clean Air Act, U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards, Research Triangle Park, NC.
EPA 450/2-80-062. April 1980.
10-9
-------
14. Status Summary of States' Group I VOC RACT Regulations as of
June 1, 1981: Second Interim Report, U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Control
Programs Development Division, Contract No. 68-02-5310, Task No. 8,
July 1981
15. Tolefree, W., Arkansas Department of Pollution Control and Ecology,
Little Rock, AR. Personal communication with M.E. Anderson,
GCA/Technology Division, July 6, 1982.
16. Koral, Michael A. Munroe Country Bureau of Air Resources, Rochester,
NY. Personal communication with M.G. Smith, GCA/Technology Division,
January 11, 1983.
17. Marriott, T. New York Division of Air, Region 8, Avon, NY. Personal
communication with M.G. Smith, GCA/Technology Division, January 20, 1983.
18. Industrial Process Profiles for Environmental Use: Chapter 15--The
Brine and Evaporite Chemicals Industry. Industrial Environmental
Research Laboratory, U.S. Environmental Protection Agency, Research
Triangle Park, NC, EPA-600/2-77-0230, 1977, p. 199.
19. Reference 5, p. 873.
20. Mancini, E.A., New Jersey Division of Environmental Quality, Trenton,
NJ. Personal communication with M.G. Smith/Technology Division,
January 28, 1983.
21. Mancini, E.A., New Jersey Division of Environmental Quality, Trenton,
NJ. Letter and attachments to M.G. Smith, GCA/Technology Division,
January 20, 1983.
10-10
-------
APPENDIX A
BASES FOR CARBON TETRACHLORIDE EMISSION ESTIMATES
This Appendix provides examples of calculations and other details for
emission estimates in Chapters 3 through 6. Many examples apply to similar
estimates in more than one chapter, and the specific sections or tables are
indicated. For information taken from the text, no references are supplied
here.
A-l
-------
Capacity Apportionment in Two-Process Carbon Tetrachloride Plants
(Table 3-3)
Example: Plant 6 (Dow/Freeport)
Perchloroethylene co-product model plant produces 62.5 percent
perch!oroethylene, 37.5 percent carbon tetrachloride. Plant 6
perch!oroethylene capacity is 68,000 Mg/yr. Assumed perch!oroethylene
co-product process carbon tetrachloride capacity calculated as:
x0'375 = 40,800 Mg/yr
Total carbon tetrachloride capacity is 61,000 Mg; carbon
tetrachloride production by methane chlorination calculated by
subtraction:
61,000 Mg/yr - 40,800 Mg/yr - 20,200 Mg/yr
2. Plant Capacity Factor (Tables 3-4, 4-2, 6-4)
Example: Plant 6 (Dow/Freeport)
Carbon tetrachloride production by perchloroethylene co-product
process estimated at 40,800 Mg/yr; model plant produces 30,000 Mg/yr.
Plant capacity factor calculated as follows:
40,800 Mg/yr = ] 3g
30,000 Mg/yr
3. Uncontrolled Model Plant Emissions (Tables 3-5, 4-4, 6-5)
Example: Perchloroethylene Co-product Model Plant Process Emissions
(Table 3-5)
Emission factor for process emissions is 0.0058 kg/Mg (Table 3-2),
model plant capacity is 30,000 Mg/yr of carbon tetrachloride. Model
plant emissions are:
0.0058 kg/Mg x 30,000 Mg/yr = Q>17 Mg/yf
1000 kg/Mg
A-2
-------
4. Uncontrolled Emissions (Tables 3-5, 4-4, 6-6)
Example: Plant 6 (Dow/Freeport) Perch!oroethylene Co-Product Process
Emissions (Table 3-5)
Model perch!oroethylene co-product process emissions are 0.17 Mg/yr,
plant capacity factor for Plant 6 is 1.36, industry-wide capacity
utilization is 0.68, and estimated process emissions are:
0.17 Mg/yr x 1.36 x 0.68 = 0.16 Mg/yr
5. Controlled Emissions (Tables 3-12, 13; 4-7, 8; 5-3, 5; 6-11, 12)
Example: Plant 6 (Dow/Freeport) Option 2 Perchloroethylene Co-product
Process Emissions (Table 3-13)
Calculation is identical to (4), above, with 90 percent control
added (0.10 controlled emission factor):
0.17 Mg/yr x 1.36 x 0.68 x 0.10 = 0.02 Mg/yr
6. Calculation of Emissions from Storage of Carbon Tetrachloride in a
Fixed Roof Tank (Table 6-7)
In this appendix, working and breathing losses are calculated for a
typical fixed roof storage tank containing carbon tetrachloride. Working
and breathing losses are added to obtain an estimate for total losses from
the tank. Since 90 percent control of working losses has been predicted
as a result of the use of vapor balance, the percentage of total emissions
accounted for by working losses is then multiplied by 90 percent to
obtain an overall storage control efficiency for vapor balance, for Table 6-7.
The equations used to calculate breathing and working losses are as
follows:
2. 4 I K02 xV5 M (w£p) °'68 D1'73 H°'51 AT0'5 Fp C KQ
3. Lw = 1.09 x 10"5 M P KN Kc TT
where, LT = total loss (Mg/yr)
LD= breathing loss (Mg/yr)
D
A-3
-------
LW = working loss (Mg/yr)
M = molecular weight; 154 Ib/lb mole
P = true vapor pressure; 1.4 at 60°F
D = tank diameter; 26 ft.
H = average vapor space height; assumed half of tank height; 16 ft.
AT = average ambient diurnal temperature change; 20°F
Fp = point factor; 1.0 for clean white paint
C = adjustment factor; approximately 1.0
Kr = product factor; 1.0 for volatile organic compounds
K., = turnover factor; 0.73 for 50 turnovers
No 3
T\ = tank throughput (10 gal/yr); based on 127 x 10 Mg/turnover
t 3
and 50 turnovers/yr; 6350 x 10 Mg/yr.
Substituting the numbers into the equations yields:
LB = (1.02 x 10-5(154)( 14-V_V4 )°-68 (26)1'73 (16)0'51 (20)0'5
LB = 1.75 Mg/yr
Lw = (1.09 x 10"5) (154)(1.4)(0.73)(1.0)(6350)
LW = 10.89 Mg/yr
LT - 1.75 + 10.89 = 12.64 Mg/yr
Therefore, working losses represent 86 percent of total losses.
Multiplying by the vapor balance control efficiency for working losses
results in a control efficiency of 77 percent for total losses from carbon
tetrachloride storage.
REFERENCES FOR APPENDIX A
1. Control of Volatile Organic Compound Emissions from Volatile Organic
Liquid Storage in Floating and Fixed Roof Tanks - Draft. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards, Research Triangle Park, NC, June 1981, p. 2-10, 2-16.
A-4
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APPENDIX B
BASES FOR CAPITAL AND ANNUALIZED CONTROL COST ESTIMATES
This Appendix provides technical data, control design calculations and
other details related to control cost estimates in Chapters 3 through 6.
B-l
-------
APPENDIX B-l
PERCHLOROETHYLENE CO-PRODUCT PROCESS CONTROL
The following technical data were used to estimate the flow rate and
refrigeration requirement for condensers which would control process vent
emissions from perchloroethylene co-product plants, for cost estimates in
Section 3.5.
A. DuPONT/INGLESIDE (PLANT 7) PROCESS EMISSIONS
(Ethylene feed, perchloroethylene co-product, CC1. production
capacity = 154,000 Mg/yr)
1. Carbon Tetrachloride Distillation
FLOW: 0.324 Ib/hr
COMPOSITION (weight percent): 20% CC14, 50% N2, 30% COC12.
TEMP: 30°C
CC1. Emission Rates CC1. Emission Factor
0.0648 Ib/hr = 568 Ib/yr
0.029 kg/hr = 258 kg/yr * 154,000 Mg/yr = 0.0168 kg CCl4/Mg CC14
2. Perchloroethylene Distillation
FLOW: 0.324 Ib/hr
COMPOSITION (weight percent): 50% CC14> 50% N2
TEMP: 30°C
CC14 Emission Rates CC14 Emission Factor
0.162 Ib/hr = 1,419 Ib/yr
0.074 kg/hr = 645 kg/yr * 154,000 Mg/yr = 0.0042 kg CCl4/Mg CC14
B-2
-------
3- Combined Distillation Vents
COMBINED RATES ABOVE:
CC14 Emission Rates
0.029
+ 0.074
258
+ 645
0.103 kg/hr 903 kg/yr
FLOW RATE: 0.648 Ib/hr; 0.294 kg/hr
TEMPERATURE: 30°C + 273.2 = 303.2°K
COMPOSITION
(weight percent):
CC1. Emission Factor
0.00168
+ 0.0042
0.0059 kg/Mg CC14
Emission Rate
Molecular Wt.
35% CC14
50% N2
15% COC12
0.103 kg/hr
0.147 kg/hr
0.044 kg/hr
153.8 g/mole
28 g/mole
98.9 g/mole
0.294 kg/hr
Emission Rate
0.67 mole/hr
5.25 moles/hr
0.48 mole/hr
6.37 moles/hr
v (f+*\ _ n RT _ (6.37 g • moles)(2.20 mm Hg • ft3/g-mole-°K) (303°K)
v (Ji ; p - 76Q mm Hg
VOLUMETRIC FLOW RATE: 5.59 ft3/hr; 0.093 ftVmin
4. Basis of Data
DuPont calculated the original flow, composition and temperature data
(1 and 2) based on system instrumentation and operating temperature, with
some analytical data in (2). All original data from DuPont-designated
Streams 2a and 3b, Reference 1.
B. VULCAN/GEISMAR (PLANT 5) PROCESS EMISSIONS
(Ethylene dichloride and other mixed hydrocarbon feed; perch!oroethylene
co-product, CC14 production capacity = 41,000 Mg/yr)
1. Carbon Tetrachloride Distillation
Type of emission:
Flow during emission:
Normal emission:
Intermittent
0.01 ftVmin
None
Estimated intermittent emissions: 0.8 Ib/day, 0.15 tons/yr CC1. (assumed
to be uncontrolled rate)
B-3
-------
This distillation vent is reported to be ducted directly to a crude CC1.
product tank, and then recycled through the process, under normal
operating conditions.
2. Perchloroethylene Pisti1lation
Type of emission: Intermittent
Flow during emission: 0.003 ft3/min
Normal emission: 0.002 Ib/hr, 0.01 tons/yr CC1.
According to Vulcan, this vent had not had an emission for about 2 years
when described in January 1977.
3. Combined Distillation Vents
The two vents above apparently would have a combined uncontrolled emission
rate of about 0.035 Ib/hr (0.016 kg/hr) and a maximum combined flow rate
of 0.013 ft3/min. Annual combined uncontrolled emissions would be about
0.16 tons/yr (0.15 Mg/yr), for an emission factor of 0.004 kg/Mg. Note
that although this emission factor was not used in earlier emission
factor development due to the uncertain nature of these intermittent
emissions, it correlates well with the 0.0059 kg/Mg derived from data
for Plant 7 in A(3), above.
4. Basis of Data
Vulcan characterized all data presented above as their "rough estimates."
All data are for Vulcan-designated emission sources #12 and #13, from
Reference 2.
Tentative condenser design and costs were based on the following estimates
of cooling and condensation required for the inlet composition for perchloro-
ethylene co-product process vents shown in A(3), above. A condenser system
reducing the outlet temperature to -20°C will reduce the carbon tetrachloride
content to about 0.05 mole/hr. This reduction is based on an estimated
emission reduction of 92 percent assumed to be associated with a 92 percent
reduction of carbon tetrachloride's vapor pressure from 127 mm Hg at 30°C to
10 mm Hg at -20°C. (Information in B was only used to provide some
perspective on the data in A, since designing for the intermittent flows at
Plant 5 would require additional data. The relative size of the system designed
below does appear to be capable of handling these flows, however.)
B-4
-------
COOLING:
Component
cci4
coci2
N2
Content
(in)
0.67 mole/hr
0.48 mole/hr
5.25 mole/hr
Heat
capacity
19.9
s 20
7
cal/mole
cal/mole
cal/mole
Cooling
requirement
13.3 cal/hr
9.0 cal/hr
36.7 cal/hr
59.0 cal/hr
CONDENSATION:
Only carbon tetrachloride will condense out at -20°C:
0.67 mole/hr CC1. x 8,270 cal/mole = 5,540 cal/hr condensation
(heat of vapor- requirement
ization)
TOTAL REFRIGERATION REQUIREMENT: 59 + 5,540 s 5,600 cal/hr
s 22 BTU/hr
B-5
-------
APPENDIX B-2
METHANE CHLORINATION PROCESS CONTROL
The following technical data were used to estimate the flow rate and VOC
emissions for the process vent at Plant 6, for Section 4.5.1.
DOW/FREEPORT (PLANT 6) PROCESS EMISSIONS
(methane chlorination, producing methyl chloride, methylene chloride,
chloroform and carbon tetrachloride; CC1. production capacity =
20,200 Mg/yr by this process)
Reaction Area Vents
FLOW: 325 Ibs/hr; 148 kg/hr
COMPOSITION:
Oxygen
Nitrogen
Methane
Methyl
chloride
Methylene
chloride
Chloroform
Carbon
tetrachloride
Weight
percent
0.2
21.3
47.7
Uncontrolled
emission
rate
(kg/hr)
0.30
31.5
70.6
Molecular
weight
(g/mole)
32
28
18
Moles/
hour
9.4
1,125
3,922
30.0
44.4
50.5
879
0.76
0.05
0.06
1.12
0.07
0.09
85
119
153.8
13.2
0.6
0.6
148.08
5,955.2
TEMPERATURE: 30°C (estimated)
VOLUMETRIC FLOW RATE:
V(ftVhr) = n RT = (5,955.2g- moles/hr) (2.20 mm Hg-ft3/g-mole-°K(303°K)
P 760 mm Hg
V = 5,223 ftVhr; 87 ft3/min
B-6
-------
BASIS OF DATA:
Gas chromatograph and flow meter measurements. Original flow and
composition data from Reference 3.
B-7
-------
APPENDIX B-3
CARBON DISULFIDE PROCESS CONTROLS: OPTIONS 1 AND 2
The following information relates to Section 5.5.
A. CONTROL REQUIREMENTS
To estimate Option 1 and Option 2 control costs for existing and retrofit
refrigerated condensers at the Stauffer plant at Le Moyne, the reported
current emissions and control efficiencies for the major process emission
components were used to estimate uncontrolled emission's, emission reductions
and the amount of refrigeration required, as shown below. The -62°C
retrofit condenser was assumed to provide incremental control over the
existing control of 95 percent, the efficiency for carbon tetrachloride
estimated by vapor pressure reduction, for a net emission reduction of
99.8 percent. Preliminary calculations for a -40°C retrofit condenser are
also shown for comparison purposes.
Carbon
tetrachloride
Carbon
di sulfide
Sulfur
chloride
Current
(Option 1)
emissions at
full production
after existing
condenser^
Ib/hr kg/hr
120
85
46
54
39
21
Design removal
efficiency of
existing condenser
(percent)6
95
53
95
Estimated
uncontrolled
emissions at
full production
Ib/hr kg/hr
2,400
180
920
1,090
82
418
-------
The following physical constants were used to estimate cooling requirements
for condensation, below (sensible heat loads were not considered since they are
small relative to latent heat loads):
Molecular Heat of vaporization
weight (g/mole) (gm-cal/mole)
Carbon tetrachloride 154
Carbon disulfide 76
Sulfur chloride 135
Option 1: Existing
8,271
6,787
8,000
(assumed)
condenser (-20°C)
Emission Condensation
reduction required
kg/hr mol/hr 106 cal/hr 103 Btu/hr
Carbon tetrachloride 1,036 6,730
Carbon disulfide 43 570
Sulfur chloride 397 2,940
-40°C Condenser (retrofit
Estimated Incremental
emissions reduction
(kg/hr) kg/hr mol/hr
55.7 222
3.9 16
23.5 94
332
to existing unit)
Condensation
required
106 cal/hr 103 Btu/hr
Carbon
tetrachloride
Carbon
disulfide
Sulfur
chloride
14.1
10.1
5.4
39.9
28.9
15.5
259
380
115
2.1
2.6
0.9
8.5
10.2
3.7
22.4
B-9
-------
Option 2: -62°C condenser (retrofit to existing unit)
Estimated Incremental Condensation
emissions reduction required
(kg/hr) kg/hr mol/hr 106 cal/hr 103 Btu/hr
Carbon
tetrachloride 2.7 51.3 333 2.8 10.9
Carbon
disulfide 2.0 37.0 487 3.3 13.2
Sulfur
chloride 1.1 19-9 148 1.2 4.7
28.8
The refrigeration requirements for the existing and retrofit condensers
are summarized as follows:
Refrigeration
required
103 Btu/hr Tons
Existing condenser (-20°C) 332 28
Retrofit condenser (-40°C) 22 1.87
Retrofit condenser (-62°C) 29 2.40
B. UTILITY COSTS FOR CARBON DISULFIDE PROCESS CONTROL
The electric utility rate used in 5.5.1 and 5.5.2 ($0.080/KWH) is based
on averages of national rates for four industrial size categories in
January 1982 ($0.075/KWH) inflated by 8 percent to July 1982. The 8 percent
inflation for a half year was based on previous annual increases of 19 and
16 percent from 1980 through 1982.5
The cooling water cost was based on a 1980 EPA estimate of $0.0733 per
1,000 gallons, inflated by 49 percent to $0.109 per 1,000 gallons. This
49 percent inflation factor is the result of compounding the rates from
1980 through July 1982, above, and was chosen because electricity for pumping
is the principal cost for cooling water use.
B-10
-------
Examples:
Cooling water cost for Option 1:
3 gpm/ton x 28 tons x (5.26 x 105 min/yr) x $0.109/103 g = $4,820/yr
Electricity for Option 1:
1.5 KW/ton x 28 tons x 8,760 hr/yr x $0.082/KWH = $29,000/year
B-ll
-------
REFERENCES FOR APPENDIX B
1. Donald W. Smith, E.I. DuPont de Nemours & Co., Wilmington, DC. Letter to
D.R. Goodwin, EPA, March 23, 1978.
2. F.D. Hobbs, Hydroscience, Inc. Trip Report: Visit to Vulcan Materials
Co., Geismar, LA, January 4, 1978.
3. J. Beale, Dow Chemical USA, Midland, MI. Letter to L. Evans, EPA,
April 28, 1978.
4. Lyle Bentley, Alabama Air Pollution Control Commission, Montgomery, AL.
Personal communication with M.G. Smith, GCA, June 9 and September 3, 1982.
5. Typical Electric Bills, January 1, 1980-1982. Energy Information
Administration, U.S. Department of Energy. December 1980, November 1981,
November 1982.
6. Factors for Developing CTGD Costs. U.S. Environmental Protection Agency,
Office of Air Quality Planning and Standards, Economic Analysis Branch,
September 1980.
B-12
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