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

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                                    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

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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

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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 20C.
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 400C
(750F).   At temperatures of 900 to 1300C  (1650 to 2370F),  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.

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      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, 15C
Specific gravity
  20/4C
Autoignition temperature,  C
Flash point, C
Vapor density,  air = 1
Surface tension, mN/m(=dyn/cm)
  0C
  20C
  60C
Specific heat,  J/kg
  20C
  30C
Critical temperature, C
Critical pressure, MPa
Critical density, kg/m
Thermal conductivity, mW/(m-K)
  Liquid, 20CC
  Vapor, bp
Average coefficient of  volume expansion,
  0-40C
Dielectric constant
  Liquid, 20C
  Liquid, 50C
  Vapor, 87.6C
   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

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                         TABLE 2-1.   (continued)
              Property
  Value
Heat of formation, kJ/mol
  Liquid
  Vapor
Heat of combustion, liquid, at constant
  volume, 18.7C, kJ/mol
Latent heat of fusion, kJ/mol
Latent heat of vaporization, kJ/kg
Viscosity, 20C, mPa-s
Vapor pressure, kPa
  0C
  20C
  40C
  60C
  150C
  200C
Soly of CCU in water, 25C, g/100 g H20
Soly of water in CCU, 25C, 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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                                            I
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                          10
                                      -10
                                             -20
                                                     -30
                                                              -40
                                                                       -50
                                                                                 -60
           Figure  2-1.   Vapor pressure of carbon  tetrachloride


                                          2-4
                                                                           1,2

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     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 260C, 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
20C."

                                    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."
                                     2-11

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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.
                                    2-14

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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 20C
 (68F 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 704C (1300F) 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.
                                    2-18

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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 30C (86F) 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.
                                   2-20

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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

-------
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 -20C 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

-------
                                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

-------
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 EquipmentDraft.
     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 TetrachlorideDraft.
     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

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     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

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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

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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 (-20C 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 (-7C 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 -20C 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

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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 -25C.  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

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         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
 20C to 45 mm Hg at outlet temperature of about 6C, 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 -33C are typically about three times
 as expensive as 6C 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

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            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

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         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

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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

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       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

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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

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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  CompoundsAdditional 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

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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

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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

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          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 400C 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


noS
~" 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

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               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

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      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 5C 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

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      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 -40C 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 -20C 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

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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

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           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

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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

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     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

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          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

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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 CompoundsAdditional  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

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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

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     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.
                                                                                               '  '

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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

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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

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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 -20C condenser outlet stream,
to -40C and -62C.  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 -62C 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 -20C 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

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                      TABLE 5-4.  OPTION  2  PROCESS  CONTROLS FOR THE CARBON DISULFIDE PLANT
CJ1
i

Uncontrolled
Option 1
Existing condenser
Option 2
-40C condenser
-62C condenser
Outlet
temperature
(C)
40.5 (105F)
-20 (-4F)
-40 (-40F)
-62 (-80F)
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

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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

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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
-20C 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 -20C)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  -62C  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 -62C),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

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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

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     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 200C 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

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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

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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 -20C 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

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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

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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 CompoundsAdditional  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-.-t4-~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 400C (750F),  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
                      "*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  ManufacturingVolume  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

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                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

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                                                                                        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.

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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

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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

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     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

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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

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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

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                               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

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                  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

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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

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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

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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

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                        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

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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

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         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 200C (390F).  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 300C (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

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                      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

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     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

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10.4  CARBON TETRABROMIDE PRODUCTION
     Carbon tetrabromide is produced by reaction of carbon tetrachloride
and aluminum tribromide at about 100C (212F).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

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                                  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
       AAttainment

      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.

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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

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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

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                                 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

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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 (wp) '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 60F
          D   = tank diameter; 26 ft.
          H   = average  vapor space height; assumed half of  tank  height;  16  ft.
          AT  = average  ambient diurnal temperature change;  20F
          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

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                                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:   30C
       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:   30C
       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

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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:  30C + 273.2 = 303.2K
     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) (303K)
              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 -20C 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 30C to
 10 mm Hg at -20C.   (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

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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 -20C:

    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

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                                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:   30C  (estimated)

     VOLUMETRIC  FLOW  RATE:

     V(ftVhr) = n  RT =  (5,955.2g- moles/hr) (2.20  mm Hg-ft3/g-mole-K(303K)
                 P                            760 mm Hg

     V  =  5,223 ftVhr; 87  ft3/min
                                     B-6

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BASIS OF DATA:

Gas chromatograph and flow meter measurements.  Original flow and
composition data from Reference 3.
                                B-7

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                                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 -62C

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 -40C 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

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     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 (-20C)
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
-40C 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

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                        Option  2:   -62C 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  (-20C)            332         28
            Retrofit  condenser  (-40C)             22          1.87
            Retrofit  condenser  (-62C)             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

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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

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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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