Survey of Carbon Tetrachloride Emission Sources


                               EPA-450/3-85-018
Survey of Carbon Tetrachloride
         Emission  Sources
         Emission Standards and Engineering Division
         U.S. ENVIRONMENTAL PROTECTION AGENCY
              Office of Air and Radiation
         Office of Air Quality Planning and Standards
            Research Triangle Park, NC 27711

                   July 1985

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This report has been reviewed by the Emission Standards and Engineering Division of the Office of Air
Quality Planning and Standards, EPA, and approved for publication. Mention of trade names or commercial
products is not intended to constitute endorsement or recommendation for use. Copies of this report are
available through the Library Services Office (MD-35), U.S. Environmental Protection Agency, Research
Triangle Park, N.C.  27711, or from National Technical  Information Services, 5285  Port Royal Road,
Springfield, Virginia  22161.

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                              TABLE OF CONTENTS


                                                                      Page

LIST OF TABLES. .	      vii

LIST, OF FIGURES	       xi

Chapter

  1.0     SUMMARY  .		      1-1

         -1.1  INDUSTRY DESCRIPTION 	      1-1

          1.2  EMISSION ESTIMATES	      1-2

          1.3  REGULATORY REQUIREMENTS.	      1-4

          1.4  ADDITIONAL CONTROL OF CCl^ EMISSIONS ...... .      1-5

  2.0     INTRODUCTION. ...... 	 .......      2-1

          2.1  APPROACH,	      2-1

          2.2  EMISSION SOURCES . 	  ...........      2-2
               2.2.1  Process Vent Emissions.	      2-3
               2.2.2  Equipment Leak Emissions	      2-3
               2.2.3  Storage Emissions	      2-6
               2.2.4  Loading Handling	 .      2-8
               2.2.5  Secondary Emission	      2-8
               2.2.6  Equipment Opening Emissions .........      2-9
               2.2.7  Relief Deluce Discharge  Emissions .....      2-9

          2.3  AVAILABLE CONTROLS FOR EMISSION SOURCES	      2-9
               2.3.1  Process Vent Emission  Controls.  ......      2-9
               2.3.2  Equipment Leak Emission  Controls. .  .  .  . .      2-10
               2.3.3  Storage Emission Controls	      2-13
               2.3.4  Loading/Handling Emission Controls.  .  .  . .      2-13
               2.3.5  Secondary Emission Controls 	      2-15
               2.3.6  Equipment Opening Emission Controls  ....      2-15
               2.3.7  Relief Discharge Controls 	  ...      2-15

          2.4  REFERENCES	      2-16

  3.0     CARBON TETRACHLORIDE PRODUCTION 	 .......      3-1

          3.1  USES  OF CARBON TETRACHLORIDE	      3-1
                                    m

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                        TABLE OF CONTENTS (Continued)
Chapter
Pac
          3.2  HYDROCARBON CHLORINOLYSIS PROCESS	       3-4
               3.2.1  Process Description 	       3-4
               3.2.2  Current Controls and Emissions	       3-7

          3.3  HYDROCHLORINATION/DIRECT CHLORINATION PROCESS.  .  .       3-16
               3.3.1  Process Description 	       3-16
               .3.3.2  Current Controls and Emissions	       3-17

          3.4  CARBON DISULFIDE PROCESS	       3-23
               3.4.1  Process Description 	       3-24
               3.4.2  Current Controls and Emissions	       3-24

          3.5  COST OF ADDITIONAL CONTROLS	       3-28
               3.5.1  Control of Process Vent Emissions	       3-28
               3.5.2  Control of Equipment Leak  Emissions  ....       3-37
               3.5.3  Control of Storage Emissions	       3-37
               3.5.4  Control of Loading Emissions	       3-38

          3.6  REFERENCES	       3-39

  4.0      CHLOROFLUOROCARBON  11 & 12  PRODUCTION	       4-1

          4.1  PROCESS DESCRIPTION	       4-1

          4.2  CURRENT CONTROLS AND EMISSIONS 	       4-4

          4.3  COST OF ADDITIONAL CONTROLS	       4-13
               4.3.1  Control  of Process Vent Emissions	       4-13
               4.3.2  Control  of Equipment Leak  Emissions  ....       4-16
               4.3.3  Control  of Storage Emissions	       4-16

          4.4  REFERENCES	       4-17

  5.0      ETHYLENE  DICHLORIDE PRODUCTION.  .  .	       5-1

          5.1  PROCESS DESCRIPTION	       5-1

          5.2  CURRENT CONTROLS AND ESTIMATED EMISSIONS  	       5-3

          5.3  COST OF ADDITIONAL CONTROLS	       5-13
               5.3.1  Control  of Process  Vent. Emissions	       5-13
               5.3.2  Control  of Equipment Leak  Emissions  ....       5-13
               5.3.3  Control  of Storage Emissions.  .......       5-13

          5.4  REFERENCES	       5-18
                                   IV

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                        TABLE OF CONTENTS (Continued)
Chapter                                                               page

  6.0     CHLORINE PRODUCTION .	  .  .  .  .  .  .••'.  .           6-1

          6.1  TAIL GAS SCRUBBING .  .  .  .  .  .  .	  .  .       6-1
               6.1.1  Process Description  .  ...........       6-1
               6.1.2  Current Controls and Emissions.  	       6-3
               6.1.3  Cost of Additional Controls  ........       6-7
                      6.1.3.1  Control of  Process  Vent Emissions.       6-10
                      6.1.3.2  Controls  for  Equipment  Leak
                                 Emissions	       6-10

          6.2  DILUENT FOR NITROGEN  TRICHLORIDE  ........  .;       6-11
               6.2.1  Process Description  .  .	       6-11
               6.2.2  Current Controls and Estimated Emissions.  .       6-11

          6.3  REFERENCES  .  9 ...............  \  ..       6-15

  7.0     HYPALONR SYNTHETIC RUBBER  PRODUCTION.  .........       7-1

          7,1  CURRENT CONTROLS  AND  EMISSIONS  ........  .  .       7-1

          7.2  COST OF ADDITIONAL CONTROLS.	  .       7-7
               7.2.1  Control of Process Vent  Emissions  .....       7-7
               7.2.2  Control of Equipment Leak  Emission. ....       7-9
               7.2.3  Control of Storage Emission	  .       7-9

          7.3  REFERENCES  ......	       7-10

  8.0     PESTICIDE PRODUCTION	       8-1

          8.1  CHLOROTHALONIL 	  ............       8-1
               8.1.1  Current Controls and Emissions.  ......       8-1

          8.2  DACTHALR PRODUCTION.  .	  .       8-4
               8.2.1  Current Controls and Emissions.  ......       8-4

          8.3  TORDON  ACID.	       8-5
               8.3.1  Current Controls and Emissions.  •.	       8-5

          8.4  COST OF ADDITONAL  CONTROLS  .  .	       8-6
               8.4.1  Control  of  Process Emissions	       8-6
               8.4.2  Control  of  Equipment Leak  Emissions ....       8-6
               8.4.3  Control  of  Storage Emissions	       8-6

          8.5  REFERENCES	       8-10

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                        TABLE OF CONTENTS (Continued)


Chapter                                                               Page

  9.0     CHLORINATED PARAFFINS PRODUCTION	       9-1

          9.1  CURRENT CONTROLS AND EMISSIONS 	       9-1

          9.2  COST OF ADDITIONAL CONTROLS	       9-6
               9.2.1  Control of Process Vent Emissions	-    9-6

          9.3  REFERENCES	       9-9

 10.0     PHARMACEUTICAL MANUFACTURING	      10-1

          10.1 ESTIMATED EMISSIONS.	      10-1

          10.2 REFERENCES	_     10-2

 11.0     MISCELLANEOUS PRODUCTION USES OF CARBON TETRACHLORIDE .      11-1

          11.1  SYMMETRICAL TETRACHLOROPYRIDINE ...  	      11-1
                11.1.1  Current Controls and Emissions	      11-1

          11.2  DOW CONFIDENTIAL PROCESS.  	  .....      11-3
                11.2.1  Current Controls  and Emissions  	      11-3

          11.3  DOW CONFIDENTIAL PROCESS 2	      11-4
                11.3.1  Current Controls and Emissions	      11-4

          11.4  COST OF ADDITIONAL CONTROLS  	  .....      11-4
                11.4.1  Control of Process Vent Emissions  ....      11-4
                11.4.2  Control of Equipment Leak Emissions  .  .  .      11-7
                11.4.3  Control of Storage Emissions	      11-7

          11.5 SUMMARY OF COST-EFFECTIVENESS	      11-7

          11.6 REFERENCES	      11-10

 12.0     OTHER SOURCES OF EMISSION 	  .....      12-1

          12.1  PUBLICLY OWNED TREATMENT WORKS.  . .	      12-1

          12.2  BULK TERMINALS	      12-1

          12.3  DISTRIBUTION FACILITIES 	      12-2

          12.4 REFERENCES	      12-3

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                       TABLE OF CONTENTS (Continued)
Chapter                                                             Page

APPENDIX A:   PHYSICAL PROPERTIES OF CARBON TETRACHLORIDE.  . ...      A-l

APPENDIX B:   METHODS USED FOR ESTIMATING STORAGE  TANK
               AND EQUIPMENT LEAK EMISSIONS ...........      B-l

             B.I  EMISSION FACTORS FOR FIXED-ROOF STORAGE
                   TANKS .......  .......... ...      B-2
                 B.I.I  Emission Equations ...........      B-2
                 B.I. 2  Parameter Values and Assumptions  ....      B-2
                 B.I. 3  Sample Calculations. ..........      B-3

             B.2  EMISSION FACTORS FOR INTERNAL FLOATING. ROOF
                   TANKS . . ........ ..........      B-5
                 B.2.1  Emission Equations ............      B-5
                 B.2.2  Parameter Values and Assumptions  ....      B-5
                 B.2. 3  Sample Calculations. ..... ......      B-8

             B.3  EQUIPMENT LEAK EMISSIONS - SAMPLE  CALCUATIONS  .      B-ll

             B.4  REFERENCES .  .................      B-13

APPENDIX C:   METHODS FOR ESTIMATING EMISSION CONTROL COSTS. ...      C-l

             C.I  PROCESS VENT EMISSIONS CONTROL  COST
                   ESTIMATION ........ ,  . .  .  ......      C-2

             C.2  SAMPLE COST CALCULATIONS FOR CONTROL  OF  PROCESS
                   EMISSIONS USING CARBON ADSORBERS.  ......      C-15
                 C.2.1  Capital Cost .......  .  ......      C-15
                 C.2. 2  Annual Cost ........  .......      C-16

             C.3  COST CALCULATIONS FOR INSTALLING INTERNAL
                   FLOATING' ROOFS IN FIXED ROOF  TANKS ......      C-17
                 C.3.1  Capital Cost .... ....... ...      C-18
                 C.3. 2  Annual Cost. .....  ...... ...      C-19
                 C.3. 3  CC1-/VOC Reduction  . .  .........      C-19
                 C.3. 4  Recovery Credits  ......  ......      C-19
                 C.3. 5  Net Annual Cost .........  ....      C-20
                 C.3. 6  Cost Effectiveness  ..... • ......      C-20

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                        TABLE OF CONTENTS  (Continued)
Chapter

             C.4  COST CALCULATIONS FOR  INSTALLATION OF
                    REFRIGERATED CONDENSERS TO CONTROL STORAGE
                    EMISSIONS  	
                  C.4.1  Capital Cost 	
                  C.4.2  Annual Cost	
                  C.4.3  CC1./VOC Reduction ... 	 ,
                  C.4.4  Recovery Credits 	 ,
                  C.4.5  Net Annual Cost	
                  C.4.6  Cost Effectiveness	,

             C.5  SAMPLE CALCULATIONS FOR EQUIPMENT LEAK CONTROL
                    COST	 . . . ,

             C.6  REFERENCES  	

APPENDIX D:  SUMMARY OF EXISTING STATE AND FEDERAL REGULATIONS
             AFFECTING CARBON TETRACHLORIDE EMISSION SOURCES. . .

             D.I  EXISTING STATE REGULATIONS	
                  D.I.I  Introduction 	
                  D.I.2  General State VOC Regulations for
                           Solvent Use	
                  D.I.3  Prevention of Significant Deterioration
                           Regulations	 . . .
                  D.I.4  State Regulations Affecting Chemical
                           Production	 . . .

             D.2  EXISTING FEDERAL REGULATIONS	
Page
 C-20
 C-21
 C-21
 C-21
 C-21
 C-21
 C-21
 C-22

 C-25


 D-l

 D-2
 D-2

 D-2

 D-2

 D-3

 D-3

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                               LIST OF TABLES


Table                                                                 Page

 1-1      EMISSIONS FROM THE PRODUCTION AND USE OF CC14  ......     1-3

 1-2      ACHIEVABLE CC1. EMISSION REDUCTION AS A FUNCTION OF
            COST EFFECTIVENESS   .	     1-7

 2-1      VOC EMISSION FACTORS FOR EQUIPMENT LEAKS	     2-5

 2-2      CONTROL TECHNIQUES FOR CONTROLLING EQUIPMENT LEAKS. ....  2-11

 3-1      CARBON TETRACHLORIDE PRODUCTION CAPACITIES (1984)  . .'-.  .     3-2

 3-2      SUMMARY OF 1983 ESTIMATED CC1, EMISSIONS FROM CARBON
            TETRACHLORIDE PRODUCTION FACILITIES (MG). .......     3-8

 3-3      CURRENT CONTROLS AND ESTIMATED 1983 EMISSIONS AT
            FACILITIES PRODUCING CARBON TETRACHLORIDE BY THE
            HYDROCARBON CHLORINOLYSIS PROCESS	     3-9

 3-4      CURRENT CONTROLS AND ESTIMATED 1983 EMISSIONS AT
            FACILITIES PRODUCING CARBON TETRACHLORIDE BY THE
            HYDROCHLORINATION/DIRECT CHLORINATION PROCESS 	     3-19

 3-5      CURRENT CONTROLS AND ESTIMATED 1983 EMISSIONS AT
            FACILITIES PRODUCING CARBON TETRACHLORIDE BY THE
            CARBON DISULF1DE PROCESS	     3-26

 3-6      COSTS OF ADDITIONAL CONTROLS FOR CARBON TETRACHLORIDE
            PRODUCTION FACILITIES  ... 	     3-29

 3-7      ACHIEVABLE CCK EMISSION REDUCTION AT CARBON TETRACHLORIDE
            PRODUCTION FACILITIES  (MG/YR)	     3-35

 4-1      CHLQROFLUOROCARBON PRODUCERS^	     4-2

 4-2      SUMMARY OF ESTIMATED  1983 CC1. EMISSION FROM CFC PRODUCTION
            FACILITIES  (MG)	*	     4-5

 4-3      CURRENT CONTROLS AND  ESTIMATED 1983 EMISSIONS AT CFC
            PRODUCTION  FACILITIES	     4-6

 4-4      COSTS  OF ADDITIONAL  CONTROLS AT CFC PRODUCTION
            FACILITIES.  ........  .; • . . . .	     4-14

 4-5      ESTIMATED  CCL,  EMISSION  REDUCTION AS A FUNCTION OF COST
            EFFECTIVENESS	     4-15

 5-1      PRODUCERS  OF  ETHYLENE DICHLORIDE. . -	     5-2

                                     ix

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LIST OF TABLES (Continued)

5-2

5-3

5-4

5-5

6-1

6-2

6-3

6-4

6-5

7-1
7-2

7-3

8-1

8-2

8-3


SUMMARY OF ESTIMATED 1983 CCK EMISSIONS FROM EDC
PRODUCTION FACILITIES (MG). 	
CURRENT CONTROLS AND ESTIMATED 1983 EMISSIONS AT EDC
FACILITIES 	 	
COSTS OF ADDITIONAL CONTROLS FOR EDC PRODUCTION
FACILITIES 	
ACHIEVABLE CC1. EMISSION REDUCTION FOR EDC PRODUCTION
FACILITIES. 1 	
SUMMARY OF ESTIMATED 1983 EMISSIONS FROM CHLORINF
PRODUCTION FACILITIES (MG) 	
CURRENT CONTROLS AND ESTIMATED 1983 EMISSIONS AT
FACILITIES PRODUCING CHLORINE 	
COST OF ADDITIONAL CONTROLS FOR CHLORINE PRODUCTION
FACILITIES 	
ACHIEVABLE CCK EMISSION REDUCTION FOR CHLORINE PRODUCTION
FACILITIES. . . 	
ESTIMATED 1983 EMISSIONS OF CC1, FROM USE AS A DILUENT FOR
NCL3 IN CHLORINE LIQUEFACTION4(MG) 	
SUMMARY OF 1983 CC1,, EMISSIONS FROM HYPALON PRODUCTION
FACILITIES (MG/YRJ 	
CURRENT CONTROLS AND ESTIMATED 1983 EMISSIONS AT
HYPALON 	
COSTS FOR ADDITIONAL CONTROLS AT DUPONT'S HYPALON
FACILITY 	
SUMMARY OF 1983 CC1A EMISSIONS FROM PESTICIDE PRODUCTION
FACILITIES (MG) . 	
COSTS FOR ADDITIONAL CONTROLS AT PESTICIDE PRODUCTION
FACILITIES 	
ESTIMATED CCL EMISSION REDUCTIONS AS A FUNCTION OF COST
EFFECTIVENESS 	


5-4

5-5

5-14

5-17

6-4

6-5

6-8

6-9

6-12
7-2

7-3

7-8

8-3

8-7

8-8

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                         LIST OF TABLES (Continued)


Table                                                                 Page

 9-1      SUMMARY OF ESTIMATED 1983 CC1.,EMISSIONS FROM THE
            DIAMOND SHAMROCK CHLORINATED PARAFFINS PRODUCTION
            FACILITY (MG) ...........  	  .....    9-2

 9-2      CURRENT CONTROLS AND ESTIMATED 1983 EMISSIONS AT THE
            DIAMOND SHAMROCK CHLORINATED PARAFFINS FACILITY ....    9-3

 .9-3      COSTS FOR ADDITIONAL CONTROLS AT THE DIAMOND SHAMROCK
            CHLORINATED PARAFFINS FACILITY.	  .....    9-7

11-1      SUMMARY OF 1983 CC1, EMISSIONS FROM MISCELLANEOUS
            PRODUCTION FACILITIES (MG)	   11-2

11-2      COSTS FOR ADDITIONAL CONTROLS AT MISCELLANEOUS
            PRODUCTION FACILITIES 	  	   11-5

11-3      ESTIMATED CC1,, EMISSION REDUCTIONS AS  A FUNCTION OF
            COST EFFECTIVENESS	   11-8

 A-l ;    PHYSICAL PROPERTIES OF CARBON TETRACHLORIDE, CCT4 .  ...    A-2

 B-l      PAINT FACTORS FOR FIXED ROOF  TANKS. ,	    B-4

 B-2      TYPICAL NUMBER OF COLUMNS AS  A FUNCTION OF TANKS
            DIAMETERS	  .  .	    B-7

 B-3      SUMMARY OF DECK FITTING LOSS  FACTORS (K-)  AND TYPICAL
            NUMBER OF FITTINGS (Nf)	  ........    B-9

 C-l      TOTAL INSTALLED CAPITAL COST  AS  A  FUNCTION OF VENT
            STREAM FLOW RATE.  ... 	  ........    C-3

 C-2      ADDITIONAL DUCT COST.	  .  '  C-4

 C-3      PIPE  RACK COST.	    C-5

 C-4      OPERATING FACTORS FOR  EACH DESIGN  CATEGORY.  . .  .  .  .  .  .    C-6

 C-5      ANNUALIZED COST FACTORS . . .	    C-7

 C-6      SAMPLE CALCULATION FOR INCINERATOR COSTING.  .......  'C-8

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                         LIST OF TABLES (Continued)
Table

 C-7

 C-8


 D-l


 D-2


 D-3
COST CONVERSATION FACTORS
CONTROL TECHNIQUES AND COST FOR CONTROLLING EQUIPMENT
  LEAK EMISSION SOURCES (4TH QUARTER 1984 DOLLARS).  .

GENERAL STATE VOC REGULATIONS FOR PHOTOCHEMICAL
  SOLVENTS	

STATE REGULATIONS AFFECTING CHEMICAL PRODUCTION
  FACILITIES. . .	

SUMMARY OF FEDERAL REGULATIONS AFFECTING CARBON
  TETRACHLORIDE EMITTING SOURCES	
Page

 C-14


 C-24


 D-4


 D-5


 D-ll
                                     xn

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                               LIST OF FIGURES
Figure
 3-1
 3-2

 3-3

 3-4
 4-1
 6-1
 6-2
1983 Production, Sales, and Use Estimates for CC1..  . ,
Carbon Tetrachloride by the Hydrocarbon Chloroanalysis
  Process		'.....
Carbon Tetrachloride by the Hydrochtorination/Direct
  Chlorination Process	.....'	 ,
Carbon Tetrachloride by the Carbon Disulfide Process.
Chlorofluorocarbon 11 and 12 Production .......
Tail Gas Scrubbing With Carbon Tetrachloride. '. .. .  .
Material Balance for Use of CC14 as a Dilute for NCI
Page
 3-5

 3-6

 3-18
 3-25
 4-3
 6-2
 6-14
                                    xm

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                                1.0 SUMMARY  .

     The objective of this study is to identify all major sources of carbon
tetrachloride (CCl^) emissions in the United States and to provide
quantitative estimates of those emissions.  Information on the identified
CC1. sources includes: source location, CC1. emission rates, and present
control technologies.  The information collected in this study was used to
develop a CC1. material balance and to estimate costs to control sources
that are not presently well controlled.  The emissions information will also
be used by the Environmental  Protection Agency (EPA) to estimate human
exposure to CCl^.
     In this study information requests were sent to all producers of CCl.
and all identified major uses of CCl^ under authority of Section 114 of the
Clean Air Act.  Plant specific emissions information was obtained for all
CC14 production and about 95 percent of the 1983 CCl^ use.  An additional
2.7 percent of the use was in grain fumigants.   This use is expected to
cease by the end of 1985.  No specific emission information was obtained on
the remaining 2.3 percent of CCl.'use, however, the companies using all but
660 Mg were identified.  Therefore, there are no remaining unidentified
large uses of CC1..

1.1 INDUSTRY DESCRIPTION

     Carbon tetrachloride (CC1») is produced as a product by six companies
at nine facilities.  The total estimated 1983 production of CC1. at these
facilities is 275,350 megagrams (Mg).  Carbon tetrachloride is also formed
as a byproduct in the production of ethylene dichloride (EDC).  Byproduct
CC1. formed in EDC production is not sold as product CC1-.  It is either
disposed of, sold as crude byproduct, or carried along in the product EDC  as
an impurity.
     In 1983, U.S. CC14 sales totalled 258,096  Mg.   An additional 10,934 Mg
was used captively by CC1* producers.  Therefore, total U.S. CC1, consumption
                                    1-1

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in 1983 is estimated to be 269,030 Mg (this value may not include 3,200 Mg
in exports).  About 93.4 percent of the CC1» was consumed in chlorofluro-
carbon (CFC) 11 and 12 production, 2.7 percent was consumed as grain fumigant,
0.5 percent was used in chlorine production, 1.5 percent was used in pesticide
production, 0.09 percent was used in pharmaceutical production, and  the
remaining 1.8 percent was consumed mainly in miscellaneous chemical processes.
Registration for the use of CC1, as a grain fumigant has recently been
cancelled by the EPA.

1.2 EMISSION ESTIMATES

     The total estimated emissions from production and use of CC1. in 1983
are 3,285 Mg excluding emissions from grain fumigants.  The largest sources
of emissions were from CC1. production (898 Mg), use of CCl^ in chlorine
production (355 Mg), and use of CC1, in pesticide production (1,200 Mg).
The estimated emissions from all sources are presented in Table 1-1.
Estimates presented for CC1. production, CFC production, EDC production,
chlorine production, pesticide production and miscellaneous production
processes are based on companies' responses to EPA information requests.
These specific company responses accounted for all production of CC1» and
about 95 percent of CC1, use.  The responses included emission estimates for
process vents (estimated at full plant capacity), loading/handling
operations, equipment opening losses, pressure relief valve discharges, and
secondary streams.  The plants also provided equipment count data for
equipment in CC1* service.  Total volatile organic compound (VOC) emissions
from equipment leak sources were calculated by applying SOCMI VOC equipment
leak emission factors to the supplied equipment counts.  CC1. emissions were
estimated by applying the fraction of CC1- in the stream for each piece of
equipment to the calculated VOC emissions.  (Actual test data were provided
by one plant for CC1. equipment leak emissions.)  Emissions from storage
tanks were estimated by using AP-42 equations and company supplied storage
tank data.  Methods for estimating these emissions are described in
Appendix B.
                                    1-2

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          TABLE 1-1.   EMISSIONS FROM THE PRODUCTION AND USE OF CC1

1983 CCl4a
Process Production/Consumption Emission
(Mg/yr) (Mg/yr)
CC1. Production
CFC Production
Grain Fumigants
EDC Production
Chlorine Production
Pesticide Production
Pharmaceutical Manufacturing
Miscellaneous Production Processes
Other Uses
Distribution
POTW
TOTAL ;
275,350
251,216
7,160
N/A
1,406
4,105
231
2,042
2,870 .
N/A
N/A

898
132
_b
71
355
1,200
26
374
Not estimated
9
220
3,285
N/A - Not Applicable
aEmission estimates obtained from plant specific Section 114 responses
 total 2,200 Mg.  This value should be used for comparison with potential
 reductions presented in Table 1-2.

 Registration of CC1, in grain fumigants has been cancelled by the EPA.
 This use is expected to cease by the end of 1985.
                                    1-3

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1.3 REGULATORY REQUIREMENTS

     Carbon tetrachloride emissions are not specifically controlled by any
Federal regulations under the Clean Air Act.  However, facilities producing
ethylene dichloride are generally well controlled as a result of the
national emission standards for hazardous air pollutants (NESHAP) for vinyl
chloride (VC).  The VC NESHAP generally requires control of process vent
emission at EDC plants by incineration.  The VC standard also requires a
formal program for control of fugitive VC emissions.
     State and District regulations for VOC are the source of regulatory
requirements at most facilities.  Louisiana and Texas both have VOC regula-
tions requiring control of process vent emission by incineration.  However,
in Texas vent streams emitting less than 110 kg/hr are exempt.  There is no
such exemption in Louisiana.  However, the control requirements can be
waived if the VOC emissions are less than 91 Mg/yr, will not support combus-
tion or cause economic hardship.  Also, the Bay Area Air Quality Management
District (BAAQMD) in California requires recovery, incineration, or
containment of process vessel depressurization emissions.
     Equipment leak emissions are presently regulated by the BAAQMD and the
South Coast Air Quality Management District (SCAQMD) in California.  BAAQMD
regulations require repair of leaks greater than 10,000 ppm VOC within 15
days for accessible nonessential valves and flanges.  For essential valves
and flanges, leaks must be minimized within 15 days and repaired within six
months.  The first inspection was required prior to January 1, 1984, and
subsequent inspections are required at least annually.  Valves and flanges
that are identified as leaking must be inspected quarterly.  The SCAQMD
requires annual inspection for leaks (10,000 ppm VOC) from pumps, valves,
and flanges, and quarterly inspection for compressors.  Repair is required
at the next scheduled turnaround for pumps and compressors and immediately
for valves and flanges.  Open lines are required to be capped and safety
relief valves must be protected by a rupture disc or vented to a control
device.
                                    1-4

-------
     Both Texas and Louisiana have recently enacted equipment leak
regulations with a final compliance date of December 3i} 1987.  The Texas
regulations apply only in Harris, County.  Requirements include annual leak
detection (greater than 10,000 ppm VOC) for pump seals and valves in liquid
service, monthly leak detection for compressor seals and valves in gas
service, and weekly visual inspection of pump seals.  Repair or reasonable
measures to minimize identified leaks is required within 15 days.  Also,
open-ended lines are required to be capped.            .
     Texas, Louisiana, Illinois, Michigan, the BAAQMD, and SCAQMD all have
regulation for VOC emissions from storage tanks.  CC1. storage tanks greater
than 40,000 gallons are required to be controlled by an internal floating
roof with a primary seal, an external roof with both primary and secondary
seals, a refrigerated condenser or a combustion technique.  In New Jersey,
these controls are required for tanks greater than 300,000 gallons.
   •  VOC emissions from loading are regulated by Texas, Louisiana, Michigan,
and Illinois.  Texas and Louisiana require vapor collection and recovery or
disposal for facilities loading greater than 20,000 gal/day (40,000 gal/day
for existing facilities in Louisiana).  Michigan and Illinois only require
submerged fill.  Ship and barge loading are exempt in Texas and Louisiana.

1.4 ADDITIONAL CONTROL OF CC14 EMISSIONS

     Emissions of CC1* from chemical plants producing or using CCl^ can be
reduced by various technically feasible controls.  Process vent emissions
can be controlled by incineration or carbon adsorption.  Fugitive emissions
can be reduced through a combination of leak detection and repair programs
and application of equipment ccmtrol devices.  Storage tank emissions can be
reduced by installation of floating roofs in fixed roof tanks.  Where
floating roofs are not technically feasible (i.e. horizontal tanks or
extremely small diameter tanks), a refrigerated condenser can be used for
control of storage emissions.  Loading emissions can be controlled by
venting displaced vapors to an incinerator.
                                    1-5

-------
     Costs were estimated for the above control techniques for all emission
sources which are not presently well controlled.  These costs estimates are
based on the information provided in the company responses on the emission
stream and process equipment parameters.  It is estimated that about
1,500 Mg/yr CC1. emissions can be controlled by the application of control
techniques on process vent, fugitive, storage tanks, and handling emissions.
This represents c.n overall emission reduction of about 59 percent over
current estimated emissions.
     Table 1-2 shows the emission reduction possible from chemical plants as
a function of cost effectiveness.  Emission reductions are broken down by
type of emission.
                                     1-6

-------
            TABLE 1-2,  ACHIEVABLE CC1, EMISSION REDUCTION AS A
                        FUNCTION OF COST EFFECTIVENESS3

Nationwide CC1,, Emission Reduction, Mg/Yr
Cost Effectiveness
Range, $/Mg of VOC
Credit
0 - 500
500 - 1,000
1,000 - 2,000
2,000 - 5,000
>5,000
TOTAL
Process
Vents
	
229.4
30.8
136.1
243.4
155.3
795.0
Fugitive
	
210.3
240.9
20.1
18.3
36.0
526.6
Storage
Tanks
5.8
41.5
50.3
14.8
12.8
5.1
130.3
Loading Total
	 5.8
	 481.2
	 322.0
— - 171.0
	 274.5
58.2 254.6
58.2 1,510.1
Based on emission estimates and other data for all  plants responding to EPA
information request.  This represents all  CC1. production facilities and
other plants accounting for 95 percent of domestic  CC1. consumption.
                                   1-7

-------

-------
                              2.0 INTRODUCTION

     This document identifies the sources and locations of carbon
tetrachloride (CCl^) emissions, estimates total production volumes and
emission levels, identifies the applicable control technologies for each
emission source, and estimates the costs of controlling emission sources
which are presently not well controlled.  The information collected in this
source assessment study will also be used by the U.S. Environmental
Protection Agency (EPA) to refine estimates of human exposure to CC1*.

2.1  APPROACH
     Information for this document was acquired from various sources.  The
approach to information gathering for each of these sources is discussed in
the following paragraphs.
     Background information such as previous EPA documents and other
published literature was reviewed in an attempt to identify the producers of
CCl^ and the major uses and applications.  Six companies producing CC1* at
ten facilities were identified.  Ethylene dichloride (EDC) production was
identified as a source of byproduct CC14 formation in the literature.  A
total of twelve companies producing EDC were identified, two of which also
produce CC1,.  Nine of these EDC producers and all six companies producing
CCl^ were sent information request under the authority of Section 114 of the
Clean Air Act (CAA).  These letters requested detailed information on CC1.
emissions and control  techniques for all possible emission sources associated
with production and use of CC1 ..  Information on the total quantity of CC1,
produced and sold in 1983 were also requested.
     The available literature was also reviewed to identify major uses of
carbon tetrachloride.   Chlorofluorocarbon 11 and 12 production was
identified as the major use accounting for 90 to 95 percent of total  use.
Five companies producing CFC 11 and 12 at 8 facilities were identified.
                                     2-1

-------
Other potentially large users of CC1, cited in the literature were chlorine
production, phosgene/isocyanate production, production of chlorinated
                  p
paraffins, Hypalon  production, and production of pesticides.  All identified
                                            D
producers of chlorine, phosgene, and Hypalon  were contacted to verify the
use of CC1,..  Six companies producing chlorine and the single producer of
       R
Hypalon  were verified as users of CC1*.  One producer of chlorinated
paraffins was also verified as a user of CCl^.  Of these eight identified
users, five had already received the EPA information request since they were
also CC1, and EDC producers.  Information requests were sent to the remaining
three identified users and all five producers of CFC 11 and 12 under authority
of Section 114 of the CAA.  These letters requested detailed information on
CC1. emissions and control techniques for all sources of emissions associated
with the use of CCK.  A detailed discussion on the types of emission data
provided in company responses is presented in Section 2.2.  All companies
were asked only to estimate emissions.  No testing was required to be done
specifically for this information request.
     Plant trips were taken to Vulcan Chemicals in Geismar, LA, Dow Chemical
U.S.A. in Plaquemine, LA, and Stauffer Chemical in LeMoynea AL to gain
familiarity with each of the CC1. production processes, emission sources,
and emission controls at these facilities.  A visit was also made to Kaiser
Aluminum and Chemical in Gramercy, LA to gain familiarity with the CFC 11
and 12 production process.  Meetings were held with plant representatives to
discuss operating procedures, the process equipment used, potential emission
sources, and methods of emissions control.

2.2  EMISSION SOURCES

     This section presents a brief description of the types of emission
information obtained from Section 114 responses and how this information was
used to estimate emissions.  Emission sources at facilities producing or
using CC1. can be categorized into process vent, equipment leak, storage,
loading/handling, secondary, equipment opening, and relief device discharge
emissions.
                                     2-2

-------
2.2.1  Process Vent Emissions
     Carbon tetrachloride emissions can originate from the purging of inert
gases from reactor vessels, drying beds, finishing columns and other process
vessels.  These emissions may be continuous or intermittent.  The process
vent data provided by companies in Section 114 responses included the vent
steam characteristics before and after the control device (if present), the
estimated uncontrolled CC'I* and VOC emissions (at full capacity), information
on the vent stream control device, and the estimated pollutant efficiency of
the control device.  The estimated process vent emissions presented in this
report are based on the company supplied estimates of uncontrolled emissions
and control device efficiency unless otherwise noted.  All process emission
estimates are at full capacity.  Process vent emissions may vary directly
with capacity utilization of the process.  .

2.2.2  Equipment Leak Emissions
     Equipment leak emissions are considered to be those volatile organic
compound (VOC) emissions that result when process fluid (either liquid or
gaseous) leaks from plant equipment.  Equipment leak emissions were
estimated from the following sources:  pumps, compressors, process valves,
open-ended lines, sampling connections, flanges, and relief valves in gas
service.  Equipment leak emissions are generally random occurrences which
cannot be predicted.
     Chemicals transferred by pumps can leak at the point of contact between
the moving shaft and stationary casing.  Consequently, all seal type pumps
require a seal at the point where the shaft penetrates the housing in order
to isolate the pump's interior from the atmosphere.
     Compressors are similar to pumps in their need for shaft seals to
isolate the process gas from the atmosphere.   As with pumps, these seals are
likely to be the source of emissions.
     The most common piece of equipment in a chemical plant is one of the
following types  of valves:  control, globe,  plug, ball, diaphram, and
check.  All except the check valve are activated by a valve stem.  The stem
requires a seal to isolate the process fluid inside the valve from the
                                     2-3

-------
atmosphere.  The possibility of a leak through this seal makes it a potential
source of emissions.  Check valves and diaphram valves have no stem or seal
and are, therefore, not considered a potential source of equipment leak
emissions.
     Some valves are installed in a system so that they function with the
downstream line open to the atmosphere.  Examples are purge valves, drain
valves, and vent valves.  A faulty valve seat, or an incompletely closed
valve would result in leakage of VOC emissions through the valve.
     The operation of a process unit is checked periodically by routine
analyses of feedstocks and products.  To obtain representative samples for
these analyses, sampling lines must first be purged prior to sampling.  The
purged liquid or vapor is sometimes drained onto the ground or into a sewer
drain, where it can evaporate and release VOC emissions to the atmosphere.
     Flanges are bolted, gasket-sealed junctions used whenever pipe or other
equipment may require isolation or removal.  The primary cause of flange
leakage is due to thermal stress that piping or flanges in some services
undergo; this results in the deformation of the seal between the flange
faces.  Flanges may also become emission sources when leakage occurs due to
improperly chosen gaskets or a poorly assembled flange.
     Relief valves are typically spring-loaded and designed to open when the
process pressure exceeds a set pressure, allowing the release of vapors
until the system pressure is reduced.  The seal is a disk on a seat, and the
possibility of a leak through this seal makes it a potential source of
emissions.
     The quantity of VOC equipment leak emissions from each of these sources
were estimated using VOC emission factors presented in Fugitive Emission
Sources of Organic Compounds - Additional Information Document.   These
factors are presented in Table 2-1.  The number of each type of equipment in
CC1. service was supplied in company responses to the Section 114 letters.
Equipment count data provided by the companies was for six ranges of CC1,
service:  less than 5 percent, 5 to 10 percent, 10 to 25 percent, 25 to
75 percent, 75 to 99 percent, and greater than 99percent.  The methods used
for estimating CC1. emissions based on these data are presented in
                                     2-4

-------
           TABLE 2-1.   VOC.EMISSION FACTORS FOR EQUIPMENT LEAKS0


1.

2.
3.
4.

5.

6.

7.

Equipment Type
Pump Seals
Packed
Mechanical
Double Mechanical
Compressors
Flanges
Valves
Gas
Liquid
Pressure Relief Device
- Gas
Liquid
Sample Connections
Gas
Liquid
Open-Ended Lines
Gas
Liquid
VOC Emission
kg/d

1.19
1.19
0.0
5.47
0.02

0.13
0.17

2.50
0.0

0.36
0.36

0.04
0.04
Factor
Mg/yr

0.43
0.43
0.0
2.0
0.01

0.05
0.06

0.91
0.0

0.13
0.13

0.015
0.015
Reference 1.
                                    2-5

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Appendix B.  Unless a company supplied actual test data, uncontrolled
emission factors were used for estimating fugitive emissions.  It should be
noted that some plants indicated existence of formal leak detection and
repair programs for pumps, valves, and flanges.  However, the plants either
did not report the frequency of repair or the indicated repair frequency was
so infrequent (e.g. annual) that EPA's Leak Detection and Repair Model
(LDAR) estimates minimal emission reductions.   Also, several companies
indicated visual inspection programs, but no emission reduction was estimated
for these programs.  Some companies indicated safety relief valves that are
protected by rupture disc or a control device.  Emissions were not estimated
to be zero for the controlled relief valves.
2.2.3  Storage Emissions
     The three types of CC1, storage tanks used are:

     (1)  fixed roof tanks;
     (2)  internal floating roof tanks; and
     (3)  pressure vessels.

     A typical fixed roof tank consists of a cylindrical  steel  shell  with a
dome- or cone-shaped permanently affixed roof.  The majority of tanks for
storing CC1* are fixed roof.
     The major types of emissions from fixed-roof tanks are breathing and
working losses.  Breathing losses are expulsions of vapor from  the tank
vapor space which expands or contracts because of daily changes in ambient
temperatures and barometric pressures.  These emissions occur in the  absence
of any liquid level changes in the tank.
     Working losses occur when a tank is filled or emptied.  During filling,
the tank liquid level rises, increasing internal pressure in the vapor
space.  To release excess pressure, vapors are vented to  the atmosphere.
Emptying losses occur when the air drawn into the tank during liquid  removal
expands as a result of reaching temperature and saturation equilibrium.
When this occurs, the fixed capacity of the vapor space is exceeded and the
vapors are released through a pressure relief device.
                                     2-6

-------
     Internal floating roof tanks have both permanently affixed roofs and
roofs which float inside the tanks on the liquid surface (contact) or
supported by pontoons several inches above the liquid surface (non-contact).
The internal floating roof rises and falls with the level of liquid change
in the tank.  Internal floating roof tanks may be equipped with primary or
primary and secondary seals.  Primary seals are typically perimeter flexible
seals filled with liquid or gas that slide against the tank well.  Secondary
seals are typically a flexible wiper around the perimeter of the floating
roof.
     Losses of VOC vapors from under floating roofs occur in one of four
ways:  through the annual rim space around the perimeter of the floating
roof (rim or seal losses), through the openings in the deck required for
various types of fittings (fitting losses), through the nonwelded seams
formed when joining sections of the deck material (deck seam losses), and
through evaporation of liquid left on the tank wall following withdrawal of
liquid from the tank  (withdrawal loss).  'There are a number of potential
mechanisms for seal losses which are not discussed here.  The reader is
referred to VOC Emissions from Volatile Organic Liquid Stroage Tanks -
Background Information for Proposed Standards for additional discussion of
seal, fitting, and seam losses.  The seal, fitting, and deck seam losses
occur not only during the working operations of the tank, but also during
free standing periods.  Overall the emissions from internal floating roof
tanks are generally less than 4 Mg/yr.
     Pressure vessels are designed to store materials at their vapor'-
pressure or at high internal pressures.  They are generally used for storing
highly volatile and/or toxic materials and -are constructed in various sizes
and shapes, depending on the operating pressure range.  High pressure
vessels (up to 1827 kPa) can be operated so that virtually no breathing or
working losses occur.  Working losses can occur in low pressure (117 to
207 kPa) tanks due to atmospheric venting during filling operations.
     Methods presented in the background information document (BID) for
Volatile Organic Compound Emissions from VOL storage were used to estimate
uncontrolled CC1. emissions from fixed roof and internal floating roof
                                     2-7

-------
storage tanks.   These methods are presented in Appendix B.  Data on the
tank type, size, height, diameter, and throughput for the 1983 calendar year
were obtained from Section 114 responses.  Emissions from low pressure tanks
were estimated using only the working loss portion of methods for estimating
fixed roof tank emissions.
2.2.4  Loading/Handling Emissions
     Loading emissions occur when loading CC1. into tank trucks, rail tank
cars, barges, etc.. Carbon tetrachloride emissions occur when vapor in empty
cargo spaces is displaced by the CC1. liquid being loaded.  The displaced
vapor contains small to saturation quantities of CC1».  Handling emissions
result during connecting and disconnecting of transfer lines when loading or
unloading CC1,.  Residual quantities of liquid or vapor CC1» may escape from
the line to the atmosphere especially if the lines are not capped after use.
     Estimated loading and handling emissions were supplied by companies in
Section 114 responses.  Most companies provided estimates based on 1983
throughputs.  The emission estimates presented in this report were obtained
from Section 114 responses unless otherwise noted.

2.2.5  Secondary Emissions
     Secondary emissions occur during the treatment and/or disposal of
wastewater, liquid wastes or solid wastes on site.  Companies provided the
estimated CC1, rate (kg/day) in waste streams, the disposal or treatment
method, and estimated the fraction of CC14 emitted to the atmosphere on site
in Section 114 responses.  Secondary emission estimates presented in this
report are based on the reported effluent rate of CCl^, the estimated
fraction going to the atmosphere, and 365 days of operation per year.
Publicly owned treatment works (POTWs) are also a source of CC1. secondary
emissions if CC1. process wastes are not treated on-site.  Emissions from
POTWs are discussed separately in Section 12.1.
                                     2-8

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2.2.6  Equipment Opening Emissions
     Equipment opening emissions occur when process equipment which are
closed during operation are opened for maintenance.  Liquid, and/or vapors
remaining in the lines are then released to the atmosphere.  In Section- 114
responses, companies provided an estimate of the number of equipment
openings in 1983 and the resulting emissions.

2.2,7  Relief Device Discharge Emissions
     Relief devices are used to exhaust excess pressure built-up during
process upset conditions.  The most common type device used, relief valvesi,
are spring-loaded and designed to open when the process pressure exceeds a
set pressure, allowing the release of vapors or liquids until the system
pressure is reduced to its normal operating level.  Circumstances leading to
overpressure conditions and subsequent relief device discharge are random.
Companies supplied the number of relief device discharges which occurred in
1983 and estimated the resulting emissions for each release.

2.3  AVAILABLE CONTROLS FOR EMISSION SOURCES

     Emissions from chemical production facilities can currently be
controlled in a variety of ways.  This section will briefly describe some of
the most efficient control methods for each emission category and identify
those for which costs were evaluated in this study.  All costs presented in
this report are in 4th quarter 1984 dollars.

2.3.1  Process Vent Emission Controls
     Emissions from process vents can be ducted to a control device such as
an  incinerator, condenser, or carbon adsorber.  Destruction efficiencies of
98  percent or greater are achievable for incinerators.  The control efficiency
for condensers typically ranges from 50 percent to 95 percent depending on
stream concentration and condenser operating temperature.  A control
efficiency of 95 percent can normally be obtained with carbon adsorbers.
The control technique for which costs were evaluated in this study was
                                      2-9

-------
incineration.  It was assumed that all process vent emissions for a single
process unit can be ducted to a common incinerator.  The costs for incinera-
tion were estimated using methods presented in Air Oxidation Processes in
                                                        •3 n
Synthetic Organic Chemical Manufacturing Industry - BID. '   Costs estimates
presented in this report for incineration were developed using the new case
factors (i.e. not retrofit).  It should be noted that these incinerator cost
estimates are preliminary.  Attempts are being made to obtain updated cost
information for small incinerators.  The costs of 100 feet of additional
duct and pipe rack were included for each additional vent when incineration
was evaluated for multiple vents.  The cost methods used and a sample
calculation are presented in Appendix C.
     Also, carbon adsorption control was evaluated for control of process
vent emissions at chlorine plants.  Costs for this control  technique were
estimated using techniques presented in Capital and Operating Costs of
Selected Air Pollution Control Systems.   It should be noted that costs
estimates presented in the report are based on costs for steam regeneration
units.  The carbon adsorber presently used by chloride producers are
regenerated by hot nitrogen.  No cost information is available for these
units, but it is expected that they are more expensive.

2.3.2  Equipment Leak Emission Controls
     Equipment leak emissions may be reduced by using process equipment
which are designed specifically to prevent leakage or by implementing a leak
detection and repair program.  The control  that can be achieved by equipment
leak control techniques is presented in Table 2-2 and discussed in the
following paragraphs.
     Pumps and compressors leak at the interface of a moving shaft and a
stationary casing.  Equipment specifications that may be implemented for
pumps include elimination of this junction, improvement  of  the seal  at the
junction, or collection and control  of the  emissions from the junction.
     Emissions from open-ended lines can be controlled by installing a cap,
plug, flange, or second valve to the open end of the valve.   The control
efficiency will  be dependent on the frequency of removal  of the cap  or plug.
                                    2-10

-------
       TABLE  2-2.   CONTROL TECHNIQUES FOR CONTROLLING EQUIPMENT LEAKS'

Equipment Type
(Emission Source)
1.

2.
3.
4.

5.

6.

7.

Pump Seals
Packed
Mechanical
Double Mechanical
Compressors
Flanges
Valves
- Gas
Liquid
Pressure Relief Devices
Gas
Liquid
Sample Connections
Gas
Liquid
Open-Ended Lines
- Gas
Liquid
Percent
Control Techniques Reduction

Monthly LDAR
Monthly LDAR
N/A
Vent to Combustion Device
None Available

Monthly LDAR
Monthly LDAR

0-Ring
N/A

Closed-Purge Sampling Systems
Closed-Purge Sampling Systems

Caps on Open Ends
Caps on Open Ends

61
61
N/A
100
N/A

73
59

100
N/A

100
100

100
100
LDAR - Leak detection and repair.
N/A  - Not applicable.

Reference 6.
                                    2-11

-------
Caps, plugs, etc. for open-ended valves do not affect emissions which may
occur during use of the valve.  These emissions may be caused by line
purging for sampling, draining, or venting through the open-ended valve.
     Equipment leak emissions from sampling connections can be reduced by
using a closed loop sampling system.  The closed loop system is designed  so
that the purged fluid is returned to the process at a point of lower
pressure.  Closed loop sampling is assumed to be 100 percent effective for
controlling emissions from sample connections.
     Emissions from valves occur at the stem or gland area of the valve
body.  Diaphragm and bellows seal valves do not have a stem or gland and,
therefore, are not prone to equipment leak emissions.  Their control effec-
tiveness is approximately 100 percent, although a failure of the diaphragm
or bellows may cause large temporary emissions.  The applicability of these
valves is only limited because of process conditions or cost considerations.
     The use of portable instrument monitors for the detection of leaks
allows plant .personnel to inspect individual components.  There are several
factors which determine the control efficiencies of individual component
surveys; these include:

     -  Action level or leak definition,
     -  Inspection interval or monitoring frequency,
     -  Achievable emission reduction of maintenance, and
     -  Interval between detection and repair of the leak.

Estimates of control efficiencies for such programs vary because of the
factors mentioned above.  Controls specified by the benzene equipment leak
emissions NESHAP were evaluated for control of CCl^ equipment leaks.   Those
control techniques are listed in Table 2-2.  The costs of these techniques
are discussed in the following sections and cost estimating methods are
presented in Appendix C.
                                    2-12

-------
2.3.3  Storage Emission Controls
     Emissions from uncontrolled fixed roof tanks can be reduced through the
use of add-on controls or by equipping the tank with an internal floating
roof.  The add-on controls are actually separate from the tank.  Emissions
from the tank are ducted to the control device.  These devices include
thermal oxidation units (incinerators) and various types of refrigeration
systems.  The efficiency of incinerators is reported to be greater than
98 percent, while greater than 85 percent efficiency can generally be
obtained by a refrigeration system.
     Depending on the type of roof, seal system selected, and the tank
operating parameters, an internal floating roof will reduce fixed roof tank
emissions by as much as 97 percent.  Floating roofs are technically limited
to tanks greater than 2 meters in diameter and are not applicable to
horizontal tanks.
     Refrigerated vent condensers are add-on devices which may be used^on
low pressure tanks for control of working loss emissions.  Condensers are,
however, generally less cost effective than floating roofs.  Three options
were evaluated in this study for control of storage emissions from fixed
roof tanks.  They are a contact internal floating roof with primary seal
only, a contact internal floating roof with primary and secondary seals, and
a refrigerated vent condenser.  The control efficiency of a vent condenser
was assumed to be 85 percent.  Control efficiency of floating roofs were
estimated using storage tank data supplied by companies and emission
estimating techniques presented in Appendix B.  The costs estimates for
installation of floating roofs were developed using methods in the Source
Assessment Document of Ethylene Dichloride Emissions  and tank sizes
supplied in Section 114 responses..  Costs of a refrigerated condenser were
                                                                          5
estimated using methods in Cost of Selected Air Pollution Control Systems.
These methods are presented in Appendix C.

2.3.4  Loading/Handling Emission Controls
     Loading emissions can be reduced by using submerged loading techniques,
vapor recovery systems, incineration, vapor balance systems, and carbon
adsorption.  A brief description of each follows:
                                    2-13

-------
     Submerged loading is the introduction of a liquid into a vessel with
the transfer line outlet below the liquid surface.  Submerged loading
minimizes droplet entrainment, evaporation, and turbulence.  Emission
reductions range from 0 to 65 percent.
     The vapor balance system consists of a pipeline between the vapor
spaces of the receiving vehicle and the unloading storage tank, which
essentially creates a closed system.  This allows the vapor spaces of the
storage tank and the vehicle to balance with each other.  The vapor balance
system cannot be utilized with floating roof storage tanks.
     Vapor recovery systems recover VOC vapors displaced during loading
operations by use of refrigeration (e.g., vent condensers).  Control
efficiencies can range from 90 to 98 percent, depending on the nature of the
emissions and the type of recovery equipment used.  The vapor adsorption
process consists of passing solvent-laden air through a carbon bed.  As the
air passes through the carbon, the solvent is adsorbed and clean air is
exhausted via a valve.  With a carbon adsorption system, it is possible to
recover the adsorbed solvent for reuse.  Efficiencies are generally greater
than 95 percent.
     Venting emissions to an incinerator can provide 97 to 99 percent
emission control.  This is the control technique evaluated for control of
loading emissions in this report.  Handling emissions reported by companies
were generally small and control of handling emissions was not evaluated.
The costs of incineration for control of packing emissions were estimated
using the same methods used for control of process vents.  Only vent stream
characteristics were not supplied in Section 114 responses.  The vent flow
was estimated to be equivalent to the approximate liquid loading rate for
the vessel being loaded.  It was assumed that a common incinerator can be
used for all land based loading operations and a common incinerator can be
used for all marine loading operations.  Vessel loading rates were estimated
to be 1,800 gallons per minute (gpm) for ships, 800 gpm for barges, 200 gpm
for tank truck and rail cars, and 50 gpm for drums.
                                    2-14

-------
2.3.5  Secondary Emission Controls
     the best way to control CCl^ secondary emissions is by reducing the
amount of CC1.4 in the waste stream to be treated.  Reducing CC1. content in
the waste stream may be accomplished by steam stripping, carbon adsorption,
or better housekeeping at the production facility.  Control costs estimates
for secondary emissions were not developed in this study.

2.3.6  Equipment Opening Emission Controls
     Equipment opening emissions occur only during maintenance operations.
These emissions can be easily controlled by purging and collecting the gases
or liquids for further treatment before opening the equipment.  The emissions
may then be treated by incineration, adsorption, condensation, etc.  Reported
emissions from this source were generally small and no control cost estimates
were developed.

2.3.7  Relief Device Discharge Controls                         •
     No costs estimates were developed for control of relief device
discharge emissions in this study.  Control of these emissions will be
evaluated in future work.                      •  .       • -
                                    2-15

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2.4  REFERENCES

1.   U.S. Environmental Protection Agency.  Fugitive Emission Sources of
     Organic Compounds - Additional Information Document.  Research Triangle
     Park, North Carolina.  Publication No. EPA-450/3-82-010.  April 1982.
     pp. 1-4, 4-39, and 4-55.

2.   U.S. Environmental Protection Agency.  VOC Emissions from Volatile
     Organic Liquid Storage Tanks - Background Information for Proposed
     Standards (Draft).  Research Triangle Park, North Carolina.
     Publication No. EPA-450/3-81-003a.  July 1984.  pp. 4-1 through 4-20.

3.   U.S. Environmental Protection Agency.  Process in Synthetic Organic
     Chemical Manufacturing Industry - Background Information Document.
     Research Triangle Park, North Carolina.  Publication No.
     EPA-450/3-82-001a.  January 1982.  Appendix E.

4.   Memo from Pandullo, R. F. and I. M. McKenzie, Radian Corporation, to
     Air Oxidation Processes and Distillation Operations Project Files.
     May 1, 1985.  20p.  Revision to the Incinerator Costing Procedures Used
     for the Proposed Air Oxidation and Distillation NSPS.

5.   Neveril, R. B.  (GARD, Inc.)  Capital and Operating Costs of Selected
     Air Pollution Control Systems.  (Prepared for the U.S. Environmental
     Protection Agency.)  Research Triangle Park, North Carolina.
     Publication No. EPA-450/5-80-002.  December 1978.  pp. 5-39 through
     5-49 and 5-65 through 5-71.

6.   U.S. Environmental Protection Agency.  Benzene Fugitive Emissions -
     Background Information Document.  Research Triangle Park, North
     Carolina.  Publication No. EPA-450/3-80-032b.  June 1982.  Appendix A.

7.   Atkinson, R. D. (MRI) et al.  Source Assessment of Ethylene Dichloride
     Emissions.  (Prepared for the U.S. Environmental Protection Agency.)
     Research Triangle Park, North Carolina.  EPA Contract No. 68-02-3817.
     September 1984.
                                    2-16

-------
                     3.0 CARBON TETRACHLORIDE PRODUCTION

     Three production processes are currently used for the production of
carbon tetrachloride (CC1-).  They are the hydrocarbon chlorinolysis, hydro-
chlorination/direct chlorination, and carbon disulfide processes.  At present,
there are 9 facilities producing CCl^.  The production capacity and process
types for these facilities are presented in Table 3-1.  The total estimated
production capacity of these facilities is about 455,000 Mg/yr.  In 1983,
total production for these facilities was 278,700 Mg for an overall industry
capacity utilization of 61 percent.
     The overall capacity utilization for CCl. is expected to,approach
                    i                        **
100 percent in 1985.   Following a 19 percent increase in CC1,  production
from 1984 to 1985, DuPont has plans to convert its CC1A production facility
                                                      ^      i
in Corpus Christi, Texas, to produce chloroform in late 1985.    This
conversion will shift DuPont from being a 136,000 Mg/yr supplier to a net
68,000 Mg/yr consumer.   Also Dow ceased production of CC1, by  the hydrocarbon
                                   2
chlorinalysis process in June 1985.   Producers are projecting  a further
5 percent expansion in CC1, use in 1985.   The increased demands and
reduction in capacity will be partially offset by Stauffer's planned
expansion in.mid-1985.  Stauffer plans to expand production at  its LeMoyne, .
Alabama facility by 31,700 Mg/yr.'   The elimination of grain fumigant use
(2.6 percent of 1983 use) should reduce CC1. demand slightly.

3.1  CARBON TETRACHLORIDE USES
     One of the objectives of this study was to determine if any large
unidentified uses of CC1, exist.  In order to achieve this objective,
information was obtained from CC1* producers on the amounts of CC1.  sold  to
various users in 1983 and the nature of the end use, if known.   The  CC1,
producers also provided information on the amounts  and nature of any CC1.
used captively in 1983.  Captive use information,  along with the inventory
                                     3-1

-------
       TABLE 3-1.  CARBON TETRACHLORIDE PRODUCTION CAPACITIES (1984)

Company
Location
Process
Capacity
(Mg/Yr)
Diamond Shamrock    Belle, WV
Dow Chemical
E.I. duPont
Freeport, TX
Pittsburg, CA
Plaquemine, LA
Hydrochlorination/            2,000
Direct Chlorination

Hydrocarbon Chlorinolysis    61,200
Hydrocarbon Chlorinolysis    36,000
Hydrocarbon Chlorinolysis    56,700
Corpus Christi, TX  Hydrocarbon Chlorinolysis   136,000
LCP Chemical &
•Plastics
Stauffer Chemical0
Vulcan Materials
TOTAL
Moundsville, WV
LeMoyne, AL
Geismar, LA
Wichita, KS
Hydrochlori nation/
Direct Chlorination
Carbon Disulfide
Hydrocarbon Chlorinolysis^
Hydrocarbon Chlorinolysis
4,000
91,000
41,000
27,000
455,000
aCrude CC1, formed in hydrochlorination/direct Chlorination process fed to
 hydrocarbon Chlorinolysis process.
 DuPont plans to convert this facility to primarily chloroform and methylene
 chloride product in late 1985.
cStauffer plans to increase CCl. production capacity by 31,700 Mg in
 mid-1985.

N/A - Not available.
                                    3-2

-------
change data (supplied by companies), and the 1983 sales information, was
used to estimate 1983 production volume for each company.  In addition,
information on the amounts of CCK purchased from each producer in 1983 was
requested from .identified users of CCK.  This information was used to
verify the amounts reported by the producers.  In some cases, there were
slight discrepancies between the amounts reported by the producers and the
users.  In general, users reported purchasing somewhat higher amounts of
CC1, than the producers reported selling to them.  The reason for these
small discrepancies is not known. Possible explanations are rounding off
errors or incomplete records.  Also, end of the year shipments in 1982 may
have been received in 1983 by the users.
     Using the responses provided by the producers and users of CC1., material
balance calculations were performed.  The producers reported total U.S. sales
of 258,096 Mg in 1983.  An additional 10,505 Mg were exported while 10,934 Mg
were used captively by the producers.  The users of CC1. responding to EPA's
information requests reported total purchases of  258,383 Mg from the U.S.
CC1» producers.  This compares with 253,858 Mg that the producers reported
selling to these users (EPA did not send information requests to all users).
Since the sales volume information provided by the CC1. producers was only
for domestically produced CC1*, it is possible that some of the difference
between the two amounts is due to CC1. imported into the United States from
abroad by the domestic producers for resale in the U.S.  The International
                                                             4
Trade Commission's estimate for 1983 CC1, imports is 3,200 Mg .  No informa-
tion was obtained in this study about the distribution channels for imported
CC14.
     The sales, captive use, and inventory change information provided by
CC1, producers was used to estimate 1983 production of CC1, in the United
States.  It is estimated that 275,350 Mg of CC14 were produced in 1983.  It
should be noted that one producer did not provide data on inventory change.
It was assumed that for this producer CC1. inventory did not change in 1983.
This may explain at least some of the difference between the production
estimates presented in this study and the 259,430 Mg reported by the U.S.
                      4
Department of Commerce .
                                      3-3

-------
     Figure 3-1 presents estimates for CC14 production, sales, and the
amounts used in various applications.  This information is based on the data
provided by the producers (discrepancies with the amounts reported by the
users were ignored).  As can be seen from the figure, there are no large
unidentified uses of CC14.
     In this study, plant specific emission information was obtained for
about 95 percent of the 1983 CC14 use (captive and sales). An additional
2.7 percent of the use was in grain fumigants.  All CC1, used in grain
fumigants is expected to be emitted to the atmosphere.  No specific emission
information was obtained in this study on the remaining 2.3 percent (6,060 Mg)
of CC14 use.  These uses include miscellaneous chemical processes, pesticide
production, and other miscellaneous uses.  The companies and locations were
identified for 5,400 Mg of the remaining use in this study.  Emissions
information for these uses will be obtained in future work.  Only the end
uses of CC14 sold through distributors (660 Mg) are left unidentified.

3.2  HYDROCARBON CHLORINOLYSIS PROCESS

     There are currently six facilities producing CC1, by the hydrocarbon
chlorinolysis process.  As presented in Table 3-1, this process accounts for
approximately 80 percent of CC1- production capacity.   This is often called
the perc/tet process since perch!oroethylene (PCE) is  formed as a co-product.

3.2.1  Process Description
     A variety of feedstocks are used in the production of CC14 by the
hydrocarbon chlorinolysis process  including propane, propylene, acetylene,
napthalene, ethylene dichloride, and crude CC1. from the hydrochlorination/
direct chlorination process.   A process  flow diagram is presented in
Figure 3-2.  Fresh chlorine along  with recycled chlorine,  and hydrocarbon
feed are introduced into a vaporizer where they are mixed  with recycled
chlorides.  The mixed gases at atmospheric pressure, are fed to a refractory
lined reactor.  The reactor operates at  high temperatures, typically between
550°C and 700°C.  A reaction similar to  the following  takes  place depending
on the feed:
                                      3-4

-------
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                 550 to 700°C
  C3H8
8C1.
CC1
c2ci4-
8HC1
(propane) (chlorine) (carbon tetrachloride) (perch!oroethylene) (hydrogen
                                                                 chloride)
After startup, the reaction is self-sustaining.  The diluent action of
recycled chlorides is used to control the CC1./PCE ratio.
     Effluent from the reactor consists mainly of CC1,, PCE, hydrogen
chloride, and excess chlorine along with unreacted hydrocarbons.  The hot
effluent gas is quenched, followed by removal of HC1 and dp.  The liquid
stream from the quench is separated into product CCl^ and PCE by distillation.
Heavy ends are recycled back to the feed tank.

3-2.2  Current Controls and Emissions
     The primary types of emissions from this process are process vent,
fugitive (equipment leaks), storage, and loading emissions.  In addition,
relatively small emissions occur from equipment openings (usually for
maintenance), emergency relief device discharges, and secondary emissions
from waste stream handling and treatment.  A summary of estimated emissions
by facility and type is presented in Table 3-2.  Total emissions from all
facilities using the hydrocarbon chlorinolysis process is estimated to be
513 Mg/yr.
     The estimated emissions for each facility along with present controls
are presented in Table 3-3 by individual emission source.  All  emission
estimates presented in Table 3-3 were obtained directly from company response
to a Section 114 request except equipment leak and storage emissions which
were estimated using EPA estimating methods and company supplied data.
Methods used for estimating equipment leak and storage emissions are
presented in Appendix B.
     As shown in Tables 3-2 and 3-3, total estimated emissions  at individual
facilities range from 29.8 Mg/yr at the Dow/Pittsburg facility  to 113 Mg/yr
at the Vulcan/Wichita facility.  The significantly lower estimated emissions
for the Dow/Pittsburg facility are mainly attributed to the low reported
equipment leak emissions at this facility.  Dow supplied test results from a
                                     3-7

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study by Science Applications Inc. for the California Air Resources Board
(CARB) indicating equipment leak emissions 99 percent lower than those
estimated using methods presented in Appendix B.  The Dow facility in
Pittsburg, California, was the only facility that supplied equipment leak
emissions test data.  Also., Vulcan/Wichita, the plant with the highest
estimated equipment leak emissions supplied equipment count data for the
hydrocarbon chloinolysis and hydrochlorination/direct chlorination processes
combined.  Estimated equipment leak emissions in Tables 3-2 and 3-3 represent
the combined equipment leak emissions.
     All but one facility, Dow/Pittsburg, reported process vent emissions.
Dow did indicate that an unspecified quantity of CC1, is emitted at this
facility from one process vent upon startup or change in reflux temperature.
The total process vent emissions for all facilities are estimated to be
61.7 Mg/yr at full capacity accounting for 12 percent of total emissions from
the hydrocarbon chlorinolysis process.  Only one facility, Dow/Freeport,
presently controls process vent emissions.
     Four of the six facilities producing CC1, by the hydrocarbon chlori-
nolysis process are located in either Louisiana or Texas.  Both States have
regulations requiring control of process vent emissions by combustion or an
                               12 13
approved equivalent technology. .'    All facilities located in Texas, except
Dow/Freeport, are exempt because vent emissions are below the cutoff of
100 lbs/24 hrs.  There is no such exemption in Louisiana; however, the
control requirements can be waived if the stream is less than 100 tons/yr,
will not support combustion without auxiliary fuel, or cause economic
hardship.  Since all of the process vent emissions are less than 100 tons/yr
and will not support combustion, it is most likely that CC1. producers in
Louisiana have obtained waivers.
     Equipment leak emissions account for the majority of the estimated
emissions.  About 66 percent or 341.6 Mg/yr of the estimated CC1. emissions
from facilities using the hydrocarbon chlorinolysis process are from
equipment leak sources.  Although most facilities responded that operators
are instructed to perform regular visual inspections for leaks, only one
facility, Dow/Pittsburg, California, indicated a formal  leak detection and
                                     3-13
-------
repair program.  At this facility annual leak detection and repair is
performed and fixed point monitors are used to aid in leak detection.  This
plant is affected by a Bay Area District regulation requiring repair of leaks
greater than 10,000 ppm VOC (at 1 cm) within 15 days for accessible
                                14
nonessential valves and flanges.    For essential valves and flanges, leaks
must be minimized within 15 days and repaired within 6 months.  The first
inspection was required prior to January 1, 1984, and subsequent inspections
are required at least annually.  Valves and flanges that are identified as
leaking must be inspected quarterly.
     Louisiana has recently enacted similar regulations; however, the final
compliance date is not until December 31, 1987.  Two facilities are located
in Louisiana which will be affected by this regulation.  Requirements include
annual leak detection (greater than 10,000 ppm VOC) for pump seals and valves
in liquid service, monthly leak detection for compressor seals and valves in
gas service, and weekly visual inspection of pump seals.  Repair or reasonable
measures to minimize identified leaks is required within 15 days.  Also, open
ended lines are required to be capped.
     Storage tanks are the second largest emission source for facilities
producing CC1. by the hydrocarbon chlorinolysis process.  Storage emissions
account for about 61.6 Mg or 12 percent of total annual emissions.  As
presented in Table 3-3, five of six facilities presently control storage
emissions from at least one tank.  These five facilities are located in
Texas, California (Bay Area District) or Louisiana and are subject to control
requirements.  All three require control of storage tanks greater than
40,0000 gallons by using pressure tanks, an internal floating roof with
primary seal, an external floating roof with primary and secondary seals,
                                               12 13 14
refrigerated condenser or combustion technique.  '  '    Each of the above-
mentioned control techniques, except an external floating roof is presently
used by at least one of the five facilities.  Refrigerated condensers are
used at Dow/Freeport and Dow/Plaquemine with reported efficiencies of 95 and
90 percent, respectively.  Thermal oxidation with a reported control efficiency
of greater than 98 percent is used for control of one storage tank at Dow/
Plaquemine.  Contact internal floating roofs are presently used by DuPont in
                                     3-14
-------
Corpus Christi, Texas.  Pressure tanks with vapor return are presently used
at Dow in Pittsburg, California, for control of two 25,000 gallon tanks.  It
should be noted that both of these pressure tanks are below the 40,000 gallon
cutoff exempting them from regulatory requirements.  However, one storage
tank at the Dow/Pittsburg facility is above the 40,000 gallon cutoff and
remains uncontrolled.  All other facilities are presently meeting State and
local requirements for control  of storage tank emissions.
     Loading emissions at facilities producing CCK by the hydrocarbon
chlorinolysis process account for about 33 Mg or 6 percent of annual emissions
from this process.  One facility, DuPont/Corpus Christi, controls tank car
loading emissions by 86 percent with a refrigerated condenser system.  Also,
Vulcan in Geismar, Louisiana, controls loading emissions.  However, all
details on the control system are considered'confidential and cannot be
discussed.  Dow/Plaquemine reported control of loading emissions by submerged
fill.  The other facilities did not indicate any loading emission controls in
their responses.                            -
     Four facilities, located in Texas and Louisiana, could be affected by
State regulations requiring control of loading emissions.  Louisiana requires
vapor collection and control for existing VOC loading facilities with greater
than 40,000 gallons per day throughput or new facilities with greater than
20,000 gallons per day throughput.    Based on estimated CC1. production
capacity, neither of the facilities located in Louisiana average more than
40,000 gallons per day throughput.  But they may still be affected if loading
facilities are also used for other VOC products.  At facilities in Texas,
vapor recovery is required for facilities loading VOC with greater than
                                  12
20,000 gallons per day throughput.    Both facilities located in Texas are
estimated to have sufficient production capacity to exceed this cutoff.
     Other sources of emissions are pressure relief device discharges (i.e.,
safety relief valves and rupture discs), opening of equipment for maintenance,
and  secondary emissions from handling and treatment of waste streams.  These
emission sources account for about 3 percent (16 Mg) of total annual emissions.
There are no applicable State regulations governing these emission sources.
                                     3-15
-------
3.3  HYDROCHLORINATION/DIRECT CHLORINATION PROCESS

     There are currently six facilities producing CC1. by the hydrochlori-
nation/direct chlorination process.  Methylene chloride and chloroform are
the desired products of this process.  Carbon tetrachloride is basically a
by-product of the process and is finished for sale as a product at only
two facilities, the LCP Chemicals facility in Moundsville, West Virginia and
the Diamond Shamrock facility in Belle, West Virginia.  At other facilities,
the crude by-product CC14 is typically used as a feed to the hydrocarbon
chlorinolysis process.  Since all of the products of this process are chlori-
nated methanes, it is generally referred to as the chloromethanes process.
This label will be used in the following sections for ease of discussion.

3.3.1  Process Description
     The most common feedstock for this process is methanol.  The methanol is
hydrochlorinated with hydrogen chloride to form methyl chloride as shown
below:
                                   catalyst
     CHgOH
HC1
   (methanol)  (hydrochloric acid)
                                   (340°C)
- »>  CH3C1
 (methyl chloride)
                                             water
Zinc chloride on pumice, cuprous chloride, or activated charcoal is used as
catalyst.   The methyl chloride vapor phase is quenched, washed with caustic
soda solution to remove traces of hydrogen chloride, and dried with sulfuric
acid prior to storage.  The methyl chloride from storage is then directly
chlorinated to produce methylene chloride, chloroform and carbon
tetrachloride.  Reactions occurring in the thermal  chlorinator are;

                                                         +         HC1
                                                     de)  (hydrochloric acid)
                                                         +         HC1
                                                          (hydrochloric acid)
                                                         +         HC1
           O            C-                      *t
   (chloroform)   (chlorine)     (carbon tetrachloride)    (hydrochloric acid)
{methyl chloride) (chlorine)
TH n + n
(methylene chloride) (chlorine)
nwri. + ri .
(methylene chli
*. run
(chlorofon
»- rn
                                     3-16
-------
Methane may also be used as a feed material.  In this case, the first reactor
is not used.  The hydrogen chloride produced in these reactions is either
used in the hydrochlorination reactor or sold as anhydrous HC1.  Products
from the thermal chlorinator are quenched and then separated by distillation.
A schematic of the processes presented in Figure 3-3.

3.3.2  Current Controls and Emissions
     The primary types of emissions from this process are process vent,
equipment leak, and storage emissions.  In addition, relatively small emissions
occur from equipment openings, emergency relief device discharges, secondary
sources, and from loading at two facilities.  A summary of estimated emissions
by facility and type is presented in Table 3-2.  Total emissions from all
facilities using the chloromethanes process is estimated to be 78.7 Mg/yr.
     The estimated emissions for each facility along with present controls
are presented in Table 3-4 by individual emission source.  All information,
presented in Table 3-4 is based on company responses to Section 114^ requests.
Methods used to estimate emissions from company supplied data are presented
in Appendix B.
     As presented in Tables 3-2 and 3-4, total estimated emissions at
individual facilities range from 0.7 Mg/yr to 29.5 Mg/yr.  The relatively
broad range in emissions results from the difference in reported process
emissions and equipment count information used for estimating equipment leak
emissions.  LCP Chemicals in Moundsville, West Virginia, with the highest
total emissions (29.5 Mg/yr) reported process vent emissions of 11.8 Mg/yr
compared to 0.7 Mg/yr or less for other facilities.  Also, the reported
number of potential equipment leak sources (i.e., pumps, valves, compressors,
flanges) in CC1. service vary widely causing estimated CC1, equipment leak
emissions to range from 3.95 Mg/yr to 26.2 Mg/yr.  In addition, the equipment
counts for the Vulcan facility in Wichita, Kansas, were not supplied
separately.  Instead, the combined equipment counts for both the hydrocarbon
chlorinolysis and chloromethanes process were supplied.  Rather than
attempting to apportion equipment leak emission estimates to each of the two
processes, the combined emission estimate was presented in the previous
Section (3.2.2) for the hydrocarbon chlorinolysis process.
                                     3-17
-------
3-18
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                                             3-21
-------
     All facilities producing CC1, by the chloromethanes process reported
process vent emissions.  The total estimated CC1, emissions for all
facilities is 13.6 Mg/yr.  The majority of these emissions were reported by
one facility, LCP Chemicals in Moundsville, West Virginia.  Process vent
emissions at this facility are estimated to be 11.8 Mg/yr from five vents.
Two of these vents are presently controlled.  One process vent is controlled
greater than 98 percent by compression and condensation.  Another process
vent is controlled 84 percent by a condenser, but is still the highest
emitting process vent.  One process vent is also controlled by a condenser
(88.7 percent) at the Diamond Shamrock facility in Belle, West Virginia.  Two
facilities do not control any process vents.  Two facilities, Dow/Freeport
and Vulcan/Wichita, consider all information on process vents confidential.
     Three facilities are subject to State regulations for process vents.
Two facilities, Dow/Plaquemine and Vulcan/Geismar, are located in Louisiana.
Louisiana requires control of process vent emissions by incineration, carbon
adsorption, or refrigeration.  However, the control requirements may be
waived if the stream is less than 100 toris/yr, will not support combustion
without auxiliary fuel, or cause economic hardship.  Process vents from these
two facilities meet the first two criteria for obtaining a waiver.  Texas
requires incineration or an approved substitute control for facilities
located in Brazoria County.  But, there is an exemption for process vents
emitting less than 45.4 Kg/24 hrs (100 lbs/24 hrs).  Therefore, the
Dow/Freeport facility is exempt from process vent control requirements.
     Equipment leak emissions account for the majority of the estimated total
emissions from facilities using the chloromethanes process.  About 58.4 Mg or
74 percent of estimated annual CC1» emissions are from equipment leaks.
Presently, none of the facilities have a formal program for control of
equipment leak emissions.  Two facilities reported the use of fixed point
monitors to help identify leaks, but the effectiveness of these practices is
unknown and expected to be minimal.
     Two of the facilities are affected by recent regulations enacted in
Louisiana requiring control of equipment leak emissions.  The final
compliance date for this regulation is December 31, 1987.  Requirements
                                     3-22
-------
include annual leak detection (greater than 10,000 ppm VOC) for pump seals
and liquid valves, monthly leak detection for compressor seals, and capping
of open-end lines.  A reasonable effort to repair identified leaking
components is required within 15 days.
     Only three of the six facilities reported CCK storage tanks.   Since
CC1» is basically a by-product in the chloromethanes process, these tanks are
relatively small, 20,000 gallons or less.  The total estimated emissions from
storage tanks is 2.7 Mg of CC1,.  Controls presently employed include
condensers on five of the six storage tanks at the Diamond Shamrock facility
in Belle, West Virginia.  Only one storage tank is located in a State with
regulations on storage tank emissions.  This tank, at Dow/Freeport  is below
the size exemption of 40,000 gallons but is still controlled.
     Two facilities reported emissions from loading product CCl^ into railcars,
LCP Chemicals in Moundsville, West Virginia, reported loading emissions of
1.9 Mg/yr and Diamond Shamrock in Belle, West Virginia, reported loading
emissions of 0.1 Mg/yr.  At all the other facilities, CCK produced in the
chloromethanes process is used as feed to the hydrocarbon chlorinolysis
process.  Therefore, there are no loading emissions.
     Other sources of emissions from facilities using the chloromethanes
process are pressure relief device discharges, opening of equipment for
maintenance and secondary emissions from handling and treatment of  waste
streams.  These sources account for only about 1.8 Mg or 2 percent  of annual
CC1, emissions from chloromethanes production facilities.  There are no
applicable State regulations governing these emission sources.

3.4  CARBON DISULFIDE PROCESS

     There is currently one CC1. facility using the carbon disulfide process.
This facility is located near LeMoyne, Alabama.  It is owned and operated by
Stauffer Chemical and accounts for 17 percent of U.S. CC1. production.  It
also accounts for 306 Mg or about 34 percent of the estimated total  annual
emissions from CC1- production facilities.  These emissions are expected to
increase when additional capacity is added in 1985.
                                     3-23
-------
3.4.1  Process Description
     In the carbon disulfide process, carbon disulfide is fed to the primary
reactor along with sulfur monochloride.  A schematic of the process is
presented in Figure 3-4.  The following reaction takes place in the primary
reactor:
        CS,
                           6S
                       CC1
 (carbon disulfide) (sulfur monochloride)     (sulfur) (carbon tetrachloride)

Unreacted carbon disulfide from the primary reactor is subsequently
chlorinated in the chlorinator reactor in the presence of divided iron
catalyst.  The following reaction occurs:
     CS,
3C1,
S Cl
au
CC1
      Jo           T   sJOIp 	»»"  OnL> I p      '          OU ' /I
 (carbon disulfide) (chlorine) (sulfur monochloride) (carbon tetrachloride)
Effluents from the chlorinator reactor are distilled to separate crude
product as overhead.  Molten sulfur containing some sulfur monochloride is
removed as bottoms.  The sulfur is separated with the "equivalent to fresh"
sulfur going to the carbon disulfide plant as feed and residual sulfur going
to the sulfur chlorinator.  The residual sulfur stream is directly chlorinated
to form sulfur monochloride for the primary reactor.  Crude CCL* from the
crude distillation column is neutralized and then further distilled to obtain
product
3.4.2  Current Controls and Emissions
     Stauffer reported process vent, fugitive, storage, loading, equipment
opening and secondary emissions.  Emission quantities from each of these
sources are summarized in Table 3-2.  Total CC1* emissions from this facility
are estimated to be 305.6 Mg/yr.
     There are three process vents at the Stauffer facility with reported
CC1. emissions.  Estimated emission quantities for each of these vents are
presented in Table 3-5.  Total process vent emissions are reportedly 138.9 Mg
                                    3-24
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3-26
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of CC1, annually accounting for 45 percent of total plant emissions.  The
majority of process vent emissions are from one vent with reported annual
emissions of 111.5 Mg of CC1, after the control device.  This emission source
is presently controlled by a refrigerated condenser with a reported efficiency
of 98 percent.  The other two process vent emissions are uncontrolled.  There
are no State or local regulations requiring control of these process vent
emissions.
     Based on equipment counts provided by Stauffer, equipment leak emissions
are estimated to be 74.2 Mg/yr.  Stauffer currently does not have any program
for control of equipment leak emissions.  Stauffer did report that area
monitoring is performed monthly which is claimed to aid in leak detection.
The control efficiency of this practice is unknown and expected to be minimal.
The State of Alabama does not have any regulations requiring control of
equipment leak emissions at this facility.
     There are six uncontrolled fixed-roof storage tanks at the Stauffer
facility.  These tanks range in size from 18,000 gallons to 460,000 gallons.
Four of the storage tanks contain greater than 99 percent pure CC1., while
two tanks are used to store an 80:20 mixture of CC14 and carbon disulfide.
Estimated emissions based on 1983 storage tank data are presented in Table 3-5
for each tank.  It should be noted that the 80:20 mixture stored in two of
the tanks was for use as a grain fumigant.  The use of CC1., in grain fumigants
                                    I Q                    ^
has recently been banned by the EPA.    These tanks are likely to be used for
storage of pure CCK, especially with current plans to boost production in
1985.  This will result in higher CCl^ storage emissions.
     Total 1983 CC1, emissions from storage tanks at the Stauffer facility
are estimated to be 66.5 Mg.  Therefore, storage emissions account for about
22 percent of total emissions from this facility.  Currently, there are no
State  regulations requiring control of these storage tanks.
     Stauffer estimated that a total of 25.8 Mg of CC14 is emitted from
loading of tank cars, tank trucks, and barges in 1983.  All of these loading
operations are presently uncontrolled.  The major sources are from tank car
and barge  loading with estimated annual emissions of 12.7 Mg and 12.9 Mg,
respectively.  There are no State regulations affecting loading emissions at
this facility.
                                     3-27
-------
     Stauffer reported 213 openings of process equipment in 1983.  The
estimated emissions from these openings is 0.04 Mg.  These emissions are
currently uncontrolled and are not subject to any State regulatory require-
ments.
     Two sources of secondary emissions were reported by Stauffer.  An
estimated 1 kg of CC1, is emitted from the effluent pit and an estimated
0.2 Mg of CC1« is emitted from the oil recovery effluent in 1983.  Neither of
these sources is controlled or subject to any regulatory requirements.

3.5  COST OF ADDITIONAL CONTROLS

     Cost estimates were developed for control of process vent, equipment
leak, storage, and loading emission sources not presently well controlled.
The cost effectiveness to control each of these emission sources at
facilities producing carbon tetrachloride are presented in Table 3-6 and
discussed in the following sections.  Methods used for estimating costs are
presented in Appendix C.
     The achievable emission reduction for different VOC cost effectiveness
ranges is presented in Table 3-7.  These emission reductions can be compared
to total estimated CC1. emissions of 898 Mg in 1983 (presented in Table 3-2).

3.5.1  Control of Process Vent Emissions
     Cost estimates were developed for controlling process emissions by
incineration for vents not presently controlled 98 percent or better.  These
estimates along with the estimated cost effectiveness are presented in
Table 3-6.  As presented in Table 3-6, the estimated cost effectiveness of
controlling process vent emissions ranges from $l,330/Mg of VOC to over
S2,000,000/Mg of VOC.  The range of estimated CC14 cost effectiveness is
$3,800/Mg of CC14 to over $2,000,000/Mg of CC14.   As shown in Tables 3-6 and
3-7, process vent emissions can be controlled for less than $5000/Mg of VOC
at only one facility, Stauffer in LeMoyne, Alabama.  This is the only facility
using the carbon disulfide process.  Control  of process vent emissions at
this facility is estimated to cost $1330/Mg of VOC and would result in a
                                     3-2S
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136 Mg/yr reduction of CC1» emissions, a 63 percent reduction in process vent
emissions from all CC1, production facilities (214.2 Mg/yr).

3.5.2  Control of Equipment Leak Emissions
     As discussed in Section 3.2, only one CC1, producer, Dow in Pittsburg,
California, has a formal leak detection program.  This facility reported very
low equipment leak emissions supported by test data.  Therefore, cost/cost
effectiveness estimates were not developed for control of equipment leak
emissions at this facility.  The costs for all other facilities are presented
in Table 3-6.  The control techniques costed for control of equipment leak
emissions are those required by the benzene fugitive national emission
standard for hazardous air pollutants (NESHAP).  This includes monthly leak
detection and repair of.pumps and valves, venting of compressor degassing
reservoirs to a combustion device, installation of 0-rings on safety relief
valves in gas service, closed purge for sample connections, and capping of
open-ended lines.
     Estimated cost effectiveness for control of equipment leak emissions
range from $300/Mg of VOC to $3500/Mg of VOC.  Estimated CC14 cost effective-
ness ranges from $500/Mg to $5100/Mg.  As shown in Table 3-7, annual equipment
leak emissions from all CC1* production facilities can be reduced by 98 Mg
(21 percent) for less than $500/Mg of VOC and by 270 Mg (57 percent) for less
than $1000/Mg of VOC.  The VOC cost effectiveness exceeds $1000/Mg for only
one facility.

3.5.3.  Control of Storage Emissions
     Cost estimates were developed for control of storage emissions from
tanks not presently controlled by floating roofs, vapor recovery (85 percent
control or better), or incineration.  Three control options were evaluated:
contact internal floating roof with primary seal only, contact internal
floating roof with primary and secondary seals, and a refrigerated condenser
for vapor recovery.  Costs/cost-effectiveness estimates are presented in
Table 3-6 for each option, if applicable.  Internal floating roofs were not
costed for tanks smaller than 2 meters in diameter or horizontal tanks.  The
                                      3-37
-------
estimated cost effectiveness ranges from $400/Mg of VOC to $228,000/Mg of VOC
for the most cost-effective option on individual tanks.  The estimated CC1.
cost effectiveness is almost identical because these tanks store product CC1.
typically greater than 99 percent pure.  There is no direct correlation
between tank size and cost effectiveness.  The cost of a floating roof is
nearly proportional to tank size.  However, the emission reduction depends
greatly of the tank throughput which is not a function of size.
     Achievable storage tank emission reductions as a function of cost
effectiveness are presented in Table 3-7.  As shown in this table, annual
storage tank emissions can be reduced by 40 Mg (30 percent) for less than
$500/Mg of VOC and by 103 Mg (77 percent) for less than $5000/Mg of VOC.

3.5.4  Control of Loading Emissions
     As discussed earlier, only two facilities presently have controls for
loading emissions.  DuPont in Corpus Christi, Texas, controls tank car
loading emissions by 86 percent with a refrigerated condenser.  Vulcan in
Geismar, Louisiana, controls railcar and tank truck loading.   The remainder
of loading operations at facilities producing CC1, are uncontrolled.  Costs
and cost-effectiveness estimates were developed for each uncontrolled land
and marine loading operation.  It was assumed that all land loading operations
can be controlled by a single incinerator and that all marine loading can be
controlled by a single incinerator.  The estimated costs of controlling each
type of loading operation at individual  facilities are presented in Table 3-6.
The range of estimated VOC and CC14 cost effectiveness is $32,600/Mg to
$4,100,000/Mg (VOC and CC14 cost effectiveness are the same).
                                     3-38
-------
3.6  REFERENCES

1.   Chloromethanes Makers Project Further Gains After Strong '84:  DuPont
     Shift to Alter the Market.  Chemical Marketing Reporter.
     227(6):5,15,17, 1984.

2.   Dow ends some solvent production.  Chemical & Engineering News.
     631(23) :7.  June 10, 1985.

3.   Stauffer Expansion Involves Two Phases.  Journal of Commerce.
     361(25,780):22b, 1984.

4.   Carbon Tetrachloride.  In:  Chemical Products Synopsis.  Cortland,
     New York, Mansville Chemical Products Corp.  May 1984 and February 1983.

5.   Khan, Z. S. and T. W. Hughes.  Source Assessment:  Chlorinated
     Hydrocarbons Manufacture.  Research Triangle Park, North Carolina.
     Publication No. EPA-600/2-79-019g.  1979.  pp. 7-27.

6.   Letter and attachments from Harris, J. E., E.I. duPont de Nemours and
     Company, to Farmer, J. R:., EPA:ESED.  January 4, 1985.  Response to
     Section 114 Letter.

 7.  Letter and attachments from Arnold, S. L., Dow Chemical, U.S.A. to
     Farmer, J. R., EPA-.ESED.  March 7, 1985.  Response to Section 114
     Letter.

 8.  Letter from Arnold, S. L., Dow Chemical, U.S.A., to Farmer, J. R.,
     EPA:ESED.  March 12,  1985.  Response to Section 114 Letter.

 9.  Letter and attachments from Arnold, S. L., Dow Chemical U.S.A. to
     Farmer, J. R., EPA:ESED.  February 1, 1985.  Response to Section 114
     Letter.

10.  Letter and attachments from Berg, R. E., Vulcan Chemicals, to
     Farmer, J. R., EPA:ESED.  January 31, 1985.  Response to Section 114
     Letter.

11.  Letter and attachments from Boyd, J. M., Vulcan Chemicals, to
     Farmer, J. R., EPA:ESED.  February 1, 1985.  Response to Section 114
     Letter.

12.  Environment Reporter, State Air Laws, Volume 3, State of Texas.  Texas
     Regulation V:  Control of Air Pollution from Volatile Organic Compounds.
     Bureau of National Affairs, Inc., Washington, D.C., September 7, 1984.
     p.  521:0621.

13.  Environment Reporter, State Air Laws, Volume-2, State of Louisiana.
     Louisiana Air  Pollution  Control Regulations.  Bureau of National
     Affairs,-Inc., Washington, D.C.,  February 22, 1985.  p. 391:0501.
                                     3-39
-------
14.  State of California, Bay Area Air Quality Management District, Rules
     and Regulations, Regulation 8 - Organic Compounds.   Bay Area Air
     Quality Management Distric, San Francisco, California, March 17, 1982.
     p. 8-1-1.

15.  Letter and attachments from Morris, A.  R., LCP Chemicals to Farmer, J.  R.,
     EPArESED.  January 3, 1985.  Response to Section 114 Letter.

16.  Letter and attachments from Christensen, B.  H., Diamond Shamrock
     Company, to Farmer, J. R., EPA:ESED.  January 31,  1985.  Response to
     Section 114 Letter.

17.  Letter and attachments from Perry, S.,  Stauffer Chemical Company, to
     Farmer, J. R., EPArESED.  January 29, 1985.   Response to Section 114
     Letter.
                                    3-40
-------
                 4.0  CHLOROFLUOROCARBON 11 & 12 PRODUCTION

     The primary and single largest use for carbon tetrachloride (CC1.) is
as feedstock for the production of dichlorodifluoromethane (CFC 12) and
trichlorofluoromethane (CFC 11).  About 254,600 Mg of domestic CC1. produced
was used as feedstock for CFC products in 1983.  Currently, CFC 11 is used
as a blowing agent in the manufacture of plastic foams and CFC 12 is used as
a refrigerant.  A list of major CFC production facilities, their locations,
and total estimated production capacities is given in Table 4-1.  The total
production capacity of these facilities is about 466,000 Mg/yr.  In 1983,
total production for these facilities was 296,000 Mg for an overall industry
capacity utilization of 64 percent.

4.1  PROCESS DESCRIPTION
     Fluorocarbons 11 and 12 are produced by bubbling anhydrous hydrogen
fluoride and carbon tetrachloride through molten antimony pentachloride
catalyst.  These reactions are slightly endothermic and take place in a
steam-jacketed atmospheric pressure reactor at 65 to 95°C.   A schematic of
the fluorocarbon production process is presented in Figure 4-1.
following chemical reactions occur in the reactor:
                           SbCl
                                                       The
HF
                               CC13F
                             (CFC 11)
                           SbCl,
CC1
                 2HF
                    -»- CC.12 F2
                      (CFC  12)
                                                    HC1
2HCL
     The gaseous mixture of fluorcarbon and unreacted chlorocarbon is
distilled to separate and recycle the chlorocarbon to the reactor while the
waste hydrogen chloride and chlorine are removed by a caustic scrubbing
tower.
                                    4-1
-------
                  TABLE 4-1.  CHLOROFLUOROCARBON PRODUCERS
Company
  Location
CFC Production Capacity3
          (Mg/Yr)
Allied
DuPont
Kaiser Aluminum
El Segundo, CA
Danville, IL
Montague, MI
Antioch, CA
Deepwater, NJ
 From chemical synopis report - August 1982.
                                                      -  140,653
                                                      -  227,860
& Chemical
Penwalt
Essex/Racon
Gramercy, LA
Calvert City, KY
Wichita, KS
36,298
40,835
20,417
                                    4-2
-------
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4.2  CURRENT CONTROLS AND EMISSIONS

     The primary types of emissions from CFC production are process vent,
equipment leak, storage, and handling losses.  In addition, a small amount
of emissions occur from equipment openings and secondary sources such as
waste stream treatment.  A summary of estimated emissions by facility and
type is presented in Table 4-2.  Total emissions from all CFC facilities is
estimated to be about 132 Mg/yr.  The emission types/sources and their
controls are listed in Table 4-3 and discussed below.
     Most CFC producers reported no CC1. process vent emissions.  For
example, all three Dupont facilities reported having no process vents while
Allied plants reported nondetectable concentrations of CC1. emissions from a
HC1 scrubber vent.  Only two producers reported CC1* process vent emissions.
They are Penwalt in Calvert City, Kentucky and Essex/Racon in Wichita,
Kansas.  Penwalt's process vents are located on a recycle tank and an air
separator.  Neither vent is controlled and reported CC1. emissions are
0.3 Mg/yr.  Essex/Racon has two CFC production units with process vents
located on recovery tanks and product purifiers for each unit.  A packed
water scrubber, with 88 percent efficiency, is used to control the recovery
tank emissions.  The product purifiers have no controls.  Total CC1, process
vent emissions from the Essex/Racon facility are estimated to be 13.7 Mg/yr.
The process vent emissions, for the two facilities reporting CC1. emissions,
accounted for approximately 10 percent of the total CC1- emissions of the
CFC industry.
     Equipment leak CC1. emissions from CFC facilities range from 4.5 Mg/yr
at Dupont in Antioch, CA to 16.3 Mg/yr at Penwalt in Calvert City, KY.
Equipment leak emissions account for 51 percent of the total emissions from
CFC facilities.
     Individual state regulations impacting equipment leak emissions vary
considerably between states.  Five facilities are currently affected by
State or local regulatory requirements for control of equipment leak
emissions.  Allied's CFC plant in El Segundo, CA is regulated by the South
Coast Air Quality Management District (SCAQMD).  Allied is required to
                                    4-4
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perform annual inspections of valves and flanges and visual inspections of
pumps and compressors every 8 hours for leak detection.  Currently, Allied
has a daily visual inspection program.  DuPont in Antioch, CA is under the
regulations set by the Bay Area Air Quality Management District (BAAQMD).
BAAQMD requires annual inspection of valves and flanges for leaks.  DuPont's
operators perform leak checks, but the frequency of the repair is unknown.
Illinois prohibits Allied's plant in Danville from discharging more than
8 pounds of organic material per hour through equipment leaks unless
controlled by a system with 85 percent efficiency.  Pumps and compressors
may not discharge over two cubic inches of liquid volatile organic material
in any 15 minute period.  Allied plant personnel perform daily visual
inspections for leaks on all process components.
     The State of Louisiana began requiring a VOC leak patrol/repair program
in January 1984.  This program has .to be implemented by December 31, 1987.
Requirements include annual leak detection (greater than 10,000 ppm VOC) for
pump seals and valves in liquid service, monthly leak detection for compressor
seals and valves in gas service, and weekly visual inspection of pump  seals.
Repair or reasonable measures to minimize identified leaks is required
within 15 days.  Also, open-ended lines are required to be capped.  Kaiser
plant operators visually checked for leaks several times a shift in 1983 and
also used a leak detector several times during a week.  The frequency  of
repair was not reported.
     The State of New Jersey does not specify inspection intervals or  repair
requirements at this time.  The DuPont plant in Deepwater, N.J. currently
makes periodic inspections for leaks, but at no set frequency.  The frequency
of repair was not reported.
     The States of Michigan, Kentucky, and Kansas have no regulatory
requirements for control of equipment leak CC1, emissions from CFC facilities.
However, two facilities in these states do have their own control programs.
Essex/Racon in Wichita, Kansas inspects all valves, flanges, pressure  safety
valves, pump seals, etc. on a monthly basis.  Liquid leaks are detected
visually and vapor leaks with a halocarbon detector.  However, no repair
program was mentioned in their response.  DuPont in Montague, Michigan has
                                   4-9
-------
trained their operators to look for and report leaks on a regular basis, but
no time table or repair program was mentioned.  Only Penwalt in Calvert
City, Kentucky did not report a program for control of equipment leak
emissions.
     Carbon tetrachloride storage emissions from CFC production facilities
range from 0 Mg/yr at Allied's plant in El Segundo, CA to 12.1 Mg/yr at the
Pennwalt facility in Calvert City, KY.  Storage emissions account for
24 percent of the total CFC industry emissions.  State regulations impacting
storage tank emissions are similar in many respects across the nation.
     The Allied CFC plant in El Segundo, California met SCAQMD requirements
by using a vapor recovery system.  Greater than 98 percent control efficiency
was reported for the system.
     DuPont's facility in Antioch, CA, presently uncontrolled, must meet
standards set by BAAQMD.  To meet state standards, DuPont plans to upgrade
their fixed roof tank with a low temperature condenser followed by a carbon
adsorber.  Calculated estimates provided by DuPont, indicate that this system
will provide greater than 98 percent control efficiency for the current CC1A
                       4
emissions of 6.8 Mg/yr.
     Illinois regulations require all volatile organic storage tanks over
40,000 gallons to be pressure tanks or to be equipped with a floating roof,
a vapor recovery system capable of 85 percent collection and a disposal
system which prevents further emissions to the atmosphere, or equipment to
provide equivalent control efficiency.  Allied's plant in Danville has one
fixed roof tank and reported no CC1, emissions.  They contend that continuous
withdrawal of CCl^ from the storage tank for CFC production reduces or
eliminates the potential for emissions.
     DuPont's facility in Montague, MI must meet state regulations which
require storage tanks over 40,000 gallons to be pressure tanks or have
either a floating roof or a vapor recovery system with 90 percent control
efficiency.  DuPont controls its emissions by using a 0.4 psig conservation
vent, a vapor recovery system, and by continuously feeding CC1. to the CFC
process at volumes greater than the vapor expansion in the storage tanks.
                                   4-10
-------
     Storage tank emissions at Essex/Racon in Wichita, Kansas and Penwalt in
Calvert City, Kentucky are not regulated.  Racon has one fixed roof tank
with reported breathing losses of 1.5 Mg/yr.  They report no working losses
because CC1» is received via pipeline.  Penwalt has 6 storage tanks (3 fixed
roof and 3 pressure types) with a condenser on one of the fixed roof tanks
providing 85 percent control of CC1, emissions.
     In the State of Louisiana, VOC storage tanks over 40,000 gallons which
are not pressure tanks must have a submerged fill pipe and one of the
following:
     (1)  internal or external floating roof,
     (2)  a vapor loss control system equivalent to floating roof, or
     (3)  other equivalent equipment or means.
Kaiser Aluminum's 250,000 gallon fixed roof tank uses a refrigerated
scrubber (90 percent efficiency) to meet these state regulations.  In the
State of Louisiana, smaller VOC storage tanks, 250 to 40,000 gallons, must
have one of the following controls:
     (1)  submerged fill pipe,
     (2)  vapor recovery system, or
     (3)  other equivalent equipment or means.
Kaiser's two smaller tanks are pressure tanks and reportedly have minimal
emissions.
     New Jersey requires that CC1. storage tanks over 300,000 gallons be
controlled with an external or internal floating roof and at least one tight
seal.  DuPont's facility in Deepwater has two 1,400,000 gallon storage tanks
with contact internal floating roofs.  It's third tank (3,700 gallons) is a
fixed roof tank which has no emission controls.
     Handling emissions range from 0 to 1.7 Mg/yr and account for
approximately 2 percent of the total CFC industry emissions.  State
regulations governing handling emissions vary from none in Kansas and
Kentucky to a limit of 8 pounds per hour in Illinois.  Most states require
at least minimal control by using submerge fill.  Allied's facility in
California uses a vapor recovery system to control loading emissions.
                                   4-11
-------
     The State of  Illinois  has  the  following unloading  regulations:
     (1)   Facilities unloading  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.
     (2)   Unloading 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.
The Allied plant in Illinois meets  these regulations by using a vapor
recovery system when unloading  CCl^.  An estimated 0.18 Mg/yr of CC1, is
emitted from the storage tank vent during the unloading operations.
     Michigan regulations require that all unloading facilities handling
over 5,000,000 gallons per year have:
     (1)   submerged unloading for facilities outside of an ozone
           nonattainment area,
     (2)  vapor recovery such that emissions are less than 0.7 pounds of
          organic vapor per 1,000 gallons of organic compound unloaded,  in
          nonattainment areas.
The DuPont plant in Montague uses vapor balance when loading CC1.  from rail
cars to their storage tanks.  The only emissions occur when the rail  car is
opened for sampling and connecting the liquid and  vent lines.
     As mentioned before, the States of Kansas  and Kentucky have no
regulations concerning loading emissions.   Essex/Racon in  Kansas receives
CCl^ shipments directly via a pipeline and has  no  unloading emissions.
Penwalt (KY) pumps CCl^ directly from either a  barge or tank car to their
storage tanks.  They report CCl^ handling  emissions  of 0.04 Mg/yr  for 1983.
     The State of Louisiana requires VOC  loading facilities with daily
throughput of 40,000 gallons or more to  have vapor collection  and  disposal,
or an equivalent control.  Spill prevention  for the  filling equipment is
also required.  Barge and ships unloading  are exempt from  these  requirements.
Kaiser Aluminum has unloading emissions of 1.1  Mg/yr.   Since  they  unload
     mostly from barges,  they are exempt  from State  unloading  regulations.
                                    4-12
-------
     Transfer operations in New Jersey require submerged filling or equivalent
control when transferring volatile organic substances into any vessel over
2,000 gallons (marine vessels exempted).  DuPont's facility has CC1. emissions
of 1.7 Mg/yr, but is exempt from state regulations because it receives
shipments by ships.
     Emissions from secondary sources, equipment openings, and relief devices
are minimal at most facilities.  Equipment opening emissions account for
eight percent and secondary emissions account for less than 0.1 percent of
the total emissions from CFC industry.  None of the plants reported relief
valve discharges in 1983.  There are no State regulations for equipment
openings or secondary emission sources.

4.3  COST OF ADDITIONAL CONTROLS

     Cost estimates were developed for control of process, fugitive and
storage emissions at each CFC facility where these emissions are presently
not well controlled.  A summary of the cost effectiveness to control these
emission sources is presented in Table 4-4 and discussed in the following
sections.
     Table 4-5 summarizes the estimated CC1, emission reductions as a
function of cost effectiveness.  The emission reductions are shown  by the
emission types as well as the total  for the entire CFC industry. A total
potential emission reduction of 63.6 Mg (48 percent)  is  technically
feasible.

4.3.1  Control of Process Vent Emissions
     The cost of controlling CC1, process  vent emissions by incineration  was
estimated for the two CFC facilities reporting process vent emissions.
Carbon tetrachloride process emissions from Penwalt in Calvert City, Kentucky
can be reduced by 0.2 Mg/yr at a cost of $63,800/Mg of VOC.  At Essex/Racon
in Wichita, Kansas CC14 emissions can be reduced  13.4 Mg/yr at a cost of
$36,800/Mg of VOC.
                                    4-13
-------






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4-14
-------
        TABLE 4-5.   ESTIMATED CC1A EMISSION REDUCTIONS AS A FUNCTION
                            OF COST EFFECTIVENESS
Cost Effectiveness
($/Mg of VOC) Range
Nationwide CCI^ Emission Reduction (Mg/yr)
                               Process  Equipment Leak   Storage
                                      Total
      Credit

      0 - 500

    500 - 1,000

  1,000 - 2,000

  2,000 - 5,000

      >5,000
                    TOTAL
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 13.6
 2.1

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3.1
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0.4
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8.8
3.3
48.4
13.5
63.6
                                    4-15
-------
4.3.2  Control of Equipment Leak Emissions
     Equipment leak emissions totaling 69.9 Mg/yr account for a majority of
the current estimated emissions from the CFC industry.   As discussed in a
previous section, several CFC facilities have inspection programs for
detection of equipment leaks, but did not mention repair programs.   For this
reason, it was assumed that no equipment leak controls  are in place.  There-
fore, costs were estimated for adding controls at all  CFC facilities.  The
control techniques costed are those required under the  benzene fugitives
NESHAP.  Costing methods are shown in Appendix C.
     The estimated cost effectiveness for controlling  equipment leak
emissions at the CFC facilities ranges from $2,400/Mg  of VOC to $7,100/Mg of
VOC.  Equipment leak carbon tetrachloride emissions could be reduced by
52 percent (36.5 Mg/yr) if additional controls were used at all CFC
facilities.

4.3.3  Controlof Storage Emissions   .
     Cost estimates were developed for control of fixed-roof tanks  emitting
33.3 Mg/yr of CC1..  Three control options were evaluated:  contact internal
roof with a primary seal (FR-PO), contact internal roof with primary and
secondary seals (FR-SS), and a refrigerated condenser.
     The estimated cost effectiveness for controlling  storage emissions at
CFC facilities ranges from $600/Mg of VOC to over $48,800/Mg of VOC.  The
additional storage controls will reduce CC1, emissions  from CFC facilities
by 41 percent (13.5 Mg/yr).
                                    4-16
-------
4.4  REFERENCES

1.   Austin, G. T., Shreve's Chemical Process Industries.  Fifth Edition.
     McGraw-Hill Book Company.  New York, 1984.

2.   Mannsville Chemical Products.  Chemical Products Synopsis -
     Fluorocarbons.  Cortland, New York.  August 1982.

3.   Letter and attachments from Cooper, J.  E., Allied Corporation, to
     Farmer, J. R., EPA:ESED, January 25, 1985.  Response to Section 114
     Letter.

4.   Letter and attachments from Coleman, J. B., E. I. DuPont De Nemours and
     Company, to Farmer, J. R., EPA:ESED, January 30, 1985.  Response to
     Section 114 Letter.

5.   Letter and attachments from Watts, R.  H., Kaiser Aluminum and Chemical
     Corporation, to Farmer, J. R., EPA:ESED, March 11, 1985.  Response to
     Section 114 Letter.

6.   Letter and attachments from Schroeder,  P. L.,  Penwalt Corporation, to
     Farmer, J. R., EPA:ESED, January 2, 1985.  Response to Section 114
     Letter.

7.   Letter and attachments from Schroeder,  P. L.,  Penwalt Corporation, to
     Farmer, J. R., EPA:ESED, February 19,  1985.  Response to Section 114
     Letter.

8.   Letter and attachments from Turner, M.  R., Racon, Inc.,  to
     Farmer, J. R., EPA:ESED, December 21,  1984.  Response to Section 114
     Letter.
                                   4-17
-------
-------
                     5.0 ETHYLENE DICHLORIDE PRODUCTION

     Carbon tetrachloride can be formed as a byproduct in the production of
ethylene dichloride (EDC).  The formation of carbon tetrachloride is
                                                           1 2
reportedly associated with the oxychlorination of ethylene. *   This process
is used in combination with direct chlorination at the majority of ethylene
dichloride facilities listed in Table 5-1.  The total estimated CC1.
emissions from the production of ethylene dichloride are 71 Mg/yr.
     Although Section 114 letters were sent to all but one EDC producer,
only two companies responded fully to the questionnaire.  A number of the
companies indicated no awareness of or reason to suspect CC1. emissions.

5.1  PROCESS DESCRIPTION

     Ethylene dichloride is generally produced in the United States by
direct chlorination of ethylene, oxychlorination of ethylene, or a
combination of the two.  The oxychlorination process is reportedly the
source of CC1, formation, and is the process of interest in this chapter.
The oxychlorination of ethylene is accomplished via the following reaction:
                                          4HC1
    (ethylene)
(oxygen)     (hydrogen chloride)
2C1CH2CH2C1
                                                 2H20
  (EDC)    (water)
The reaction is normally carried out in the vapor phase is either a fixed-
bed or fluid bed reactor.   Cupric chloride is the most common catalyst for
this reaction.  Typically, it takes place at 138 to 483 kPa gauge (20 to
70 psia) and 200° to 315°C (390° to 600°F).3  Oxygen for this reaction may
be supplied in the form of pure oxygen or air.  Since HC1  is required for
the oxychlorination process, this process is typically used in combination
with the manufacture of vinyl chloride monomer, a source of HC1  byproduct.
                                    5-1
-------
TABLE 5-1.  PRODUCERS OF ETHYLENE DICHLORIDE

Company
Atlantic Richfield Co.
Borden, Inc.
Diamond Shamrock
Dow Chemical, U.S.A.
Ethyl Corporation
Formosa Platstics Corp., U.S.A.
Georgia Gulf
BF Goodrich Company
PPG Industries
Shell Oil Company
Union Carbide Corporation
Vista Chemical
Vulcan Materials Company
Location
Port Arthur, TX
Geismar, LA
Deer Park, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Baton Rouge, LA
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
La Porte, TX
Calvert City, KY
Convent, LA
Lake Charles, LA
Deer Park, TX
Taft, LA
Texas City, TX
Lake Charles, LA
Geismar, LA
Production
Capacity
(Mg/Yr)
227,000
231,000
86,000
726,000
551,000
936,000
317,000
249,000
385,000
748,000
719,000
453,000
363,000
1,220,000
635,000
68,000
68,000
524,000
159,000
                    5-2
-------
     Carbon tetrachloride may be formed as a byproduct in oxychlorination by
the side reaction:
     H2C = CH2
    (ethylene)
   30,
8HC1
(oxygen)  (hydrogen
          chloride)
2CC1
6H20
                     '4
                  (Carbon     (water)
               tetrachloride)
This side reaction could cause the presence of CC1, in the product EDC and
result in emissions of CC'k.

5.2  CURRENT CONTROLS AND ESTIMATED EMISSIONS

     Two facilities, Shell in Deer Park, Texas and Borden in Geismar,
Louisiana, responded fully to the Section 114 request.  These two facilities
supplied estimates on process vent emissions, equipment count data, and
storage tank data.  Emission estimates for these sources are summarized in
Table 5-2.  Controls and estimated emissions for individual  sources at these
facilities are presented in Table 5-3.  Georgia Gulf also provided storage
tank data, but did not supply equipment count data or indicate process vent
emissions.  Georgia Gulf did indicate small quantities of CC1, in a number
of process streams and provided data on destruction of liquid waste
containing CCl*.  Vulcan/Geismar supplied information on one intermittent
process vent only.  The other companies responded that they  were not aware
of any CCU emissions from their facilities.  Since the oxychlorination
process is generally common to all EDC plants, it is expected that similar
CC1. emissions occur at other facilities.  For the purpose of this study,
emissions from other EDC facilities were estimated based on  received data
(from three companies) and using methods presented in the following
discussion.  The Source Assessment Document for Ethylene Dichloride Emissions
was used to identify controls at each EDC facility except the Ethyl/Baton
                                                             3
Rouge facility where the oxychlorination process is not used.   Estimated
emissions and controls at all other EDC facilities are presented in
Tables 5-2 and 5-3.
                                   5-3
-------



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     Process vent emission estimates for the Borden and Shell facilities
were obtained directly from their Section 114 responses.  Borden reported
uncontrolled process vent emissions of 60.0 Mg/yr and Shell reported
uncontrolled emissions of 14.8 Mg/yr.  These emissions are controlled
greater than 98 percent at both facilities by incineration.  Section 114
responses for the Shell and Borden facilities indicate that CC1, emissions
are from the light ends column vent in the EDC purification section of the
process.  This vent is controlled at all EDC production facilities by
                  3
thermal oxidation.
     Using the published capacity for the Shell facility and one half of the
published capacity for the Borden facility presented in Table 5-1, an
average uncontrolled process vent emission factor of 0.27 Kg CCl./Mg EDC
production was calculated.  Only one half of the Borden capacity was used
because approximately half of the Borden capacity is accounted for by the
acetylene process' which has no CC1, emissions.  The uncontrolled emission
factor was multiplied by the published capacity for each of the other
facilities to obtain estimated uncontrolled emissions.  Since thermal
oxidation with greater than 98 percent destruction is used to control all
purification section process vents in EDC production facilities, uncontrolled
emissions estimates were multiplied by 0.02 (98 percent control) to estimate
current emissions.  These estimates are presented in Table 5-3.  Estimated
process vent emissions total 40 Mg/yr for all EDC facilities accounting for
57 percent of total estimated emissions from EDC facilities.
     The B.F. Goodrich facility in Calvert City, Kentucky has one uncontrolled
process vent.  All process vents, except the oxychlorination vent, are
controlled by incineration at this facility.  Information from the Shell and
Borden responses indicate that CC1, emissions are from the light ends column
rather than the oxychlorination vent.  Therefore, this study assures that
there were no CC1, emissions from this vent.  However, it is possible that
some CC1. may be emitted from the oxychlorination vent.  Previous studies
done for EPA have estimated CC1A emissions as high as 35 Mg/yr for this vent
                              8
at the B.F. Goodrich facility.
                                    5-10
-------
     The relatively high degree of control for process vents at EDC plants
is the result of the vinyl chloride NESHAP requiring control of process vent
streams (except the oxychlorination vent) to less than 10 ppm vinyl
         Q
chloride.   Since practically all vent streams from EDC processes contain
some vinyl chloride, all process vent streams are typically incinerated to
meet regulatory requirements.  The uncontrolled vent reported by Vulcan does
not contain vinyl chloride.  The oxychlorination vent is subject to a
separate standard, 0.2 gram of vinyl chloride/kilogram of EDC production.
Incineration is used to meet this requirement at all facilities except
BF Goodrich in Calvert City, Kentucky.
     The estimated equipment leak CCK emissions from all EDC production
facilities total 18 Mg/yr, accounting for 25 percent of all EDC emissions.
Only two facilities, Borden and Shell, provided information sufficient to
estimate equipment leak emissions.  Estimated equipment leak emissions for
these two facilities are presented in Table 5-3.  Equipment leak emissions
are not a function of production., but a function of plant complexity.  Since
the complexity of individual facilities is unknown, equipment leak emissions
for all other facilities are assumed to be the average for the Borden and
Shell facilities (1 Mg/yr).
     All EDC production facilities are required to have equipment leak
control programs for vinyl chloride under the vinyl chloride NESHAP.  These
programs are to be devised by each facility and approved by the Administrator.
Therefore, the equipment leak control programs vary from plant to plant.
Recently proposed revisions to the existing vinyl chloride NESHAP will
require programs consistent with those required by the benzene fugitives
NESHAP.  Although these programs are for vinyl chloride equipment leaks, it
is likely that many of the pieces of equipment in carbon tetrachloride
service are also in vinyl chloride service.  Therefore, effective control of
vinyl chloride equipment leak emissions probably results in at least some
control of carbon tetrachloride equipment leak emissions.  However, with the
available data, it is not possible to quantitatively assess the control
level and no credit is given in equipment leak emission estimates.  Other
                                    5-11
-------
regulations that will affect carbon tetrachloride equipment leak emissions
are equipment leak VOC regulations recently enacted in Louisiana (state
wide) and Texas (Harris Co.).   '    These regulations require annual leak
detection and repair for pump seals and valves in liquid service, monthly
leak detection and repair for compressor seals and valves in gas service,
weekly visual inspection of pump seals, and capping of open ended lines.
The final compliance date for both Texas and Louisiana regulations is
December 31, 1987.
     Estimated storage emissions total about 13 Mg/yr for all  facilities,
accounting for 18 percent of EDC facility emissions.  Three facilities,
Borden, Shell, and Georgia Gulf provided data on storage tanks.  Estimated
storage emissions for these three facilities are presented in  Table 5-3.
Borden reported a storage tank containing several chlorinated  compounds with
five percent CCl^ while Shell reported less than 0.15 percent  CC1.  in the
product EDC.  Based on 2.5 percent CC14 (the average) in the storage tanks,
storage emissions were estimated for all other facilities.  Since CC1,  and
EDC have similar vapor pressures, the CCT4 emissions were estimated as
2.5 percent of VOC emissions for EDC storage tanks.   The estimates  for  VOC
emissions for EDC storage tanks were obtained from the Source  Assessment of
                              2
Ethylene Dichloride Emissions.   These estimates are presented in Table 5-3
along with present controls.
     A number of EDC storage tanks are presently controlled by incineration
or vapor recovery to meet requirements of the vinyl  chloride NESHAP. There
are also VOC storage tank regulations in Texas and Louisiana which  are
applicable.  In Texas, storage tanks larger than 25,000 gallons must be
controlled by an internal  floating roof, an external  floating  roof  (primary
and secondary seal), or vapor recovery.  In Louisiana, storage tanks larger
than 40,000 must meet the same requirements.
     The only other emission source reported was from the destruction of a
liquid waste stream at the Shell and Georgia Gulf facilities.   These
emissions are estimated to be about 0.02 Mg/yr.
                                   5-12
-------
.5.3  COSTS OF ADDITIONAL CONTROLS

     Cost estimates were developed for control of process vent, equipment
leak, and storage emissions that are not already well controlled.  These
estimates are presented in Table 5-4.  The emission reductions that can be
achieved by additional controls for different cost effective ranges are
presented in Table 5-5.  Methods used for estimating costs/cost effectiveness
are presented in Appendix C.

5.3.1  Control of Process Vent Emissions
     The costs of controlling the CC1, emitting process vent at Vulcan/Geismar
by incineration were estimated.  These costs are presented in Table 5-4.
Carbon tetrachloride emissions from this vent can be reduced by 0.02 Mg at a
cost effectiveness of $22,800,000/Mg of CCl^ and $16,500/Mg of VOC.

5.3.2  Control of Fugitive Emissions                                  .
     None of the facilities presently have equipment leak control programs
specifically for CC1,.  It is not known if any of the equipment in CCl^
service are affected by the vinyl chloride NESHAP.  Therefore, equipment
leak emission control techniques consistent with those required by the
benzene equipment leak NESHAP were costed for the Shell and Borden facilities
that supplied equipment count data.  The estimated cost effectiveness of
controlling equipment leak emissions at these two facilities are $230/Mg of
VOC and $l,900/Mg of VOC for Shell and Borden, respectively,.  The costs and
achievable emission reduction of equipment leak controls at other EDC
facilities was estimated to be the average for the Shell and Borden facili-
ties.  Using the average net annual cost and average emission reduction,
cost effectiveness for other facilities is estimated to be $260/Mg of VOC.

5.3.3  Control of Storage Emissions
     Costs of controlling storage tank emissions were estimated for each
tank not  controlled 93 percent or better.  Two options were costed:  floating
roof tanks with primary seals and floating roof tanks with primary and
secondary seals.  These cost estimates are presented in Table 5-4.  The cost
effectiveness of these controls  range from -$280/Mg of VOC to $16,600/Mg of
VOC.
                                     5-13
-------





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-------
          TABLE 5-5.   ACHIEVABLE CC14 EMISSION REDUCTION FOR EDC
                           PRODUCTION FACILITIES

Cost Effectiveness
Range, $/Mg of VOC
Credit
0 - 500
500 - 1,000
1,000 - 2,000
2,000 - 5,000
>5,000
TOTAL
Nationwide CCI^ Emission Reduction,
Process
Vent Fugitive Storage
5.8
10.1 1.7
1.0
0.3 0.5
0.2
0.02 - 0.4
0.02 10.4 9.6
Mg/Yr
Total
5.8
11.8
1.0
0.8
0.2
0.42
20.0
Emission reductions shown are for the most cost effective option.
                                   5-17
-------
5.4  REFERENCES

 1.  Telecon.  Garland, N., Ethyl Corporation with Howie, R., Radian
     Corporation.  February 25, 1985.
     from EDC production.
Conversation about CC1, emissions
 2.  Letter and attachments from Springer, C. R., Borden, Incorporated, to
     Farmer J. R., EPAiESED.  February 15, 1985.  Response to Section 114
     Letter.

 3.  Atkinson, R. D. et al.  (Midwest Research Institute.)  Source Assessment
     of Ethylene Dichloride Emissions, Final  Report.  Prepared for U.S.
     Environmental Protection Agency, Research Triangle Park, North Carolina.
     EPA Contract No. 68-02-3817.  September 1984.  pp. 2-1 through 2-7,
     2-27 through 2-30, and 2-46 through 2-63.

 4.  SRI International.  1984 Directory of Chemical  Producers - United
     States.  SRI International, Menlo Park,  California, 1984.  p. 576.

 5.  Letter and attachments from Gillespie, T. E., Shell Chemical  Company,
     to Farmer J. R., EPA:ESED.   January 4, 1985.  Response to Section 114
     Letter.

 6.  Letter and attachments from Tetter, V. J. Jr.,  Georgia Gulf,  to
     Farmer J. R., EPA.-ESED.  January 31, 1985.  Response to Section 114
     Letter.

 7.  Letter and attachments from Berg, R. E., Vulcan Chemicals, to
     Farmer J. R., EPArESED.  January 31, 1985.  Response to Section 114
     Letter.

 8.  Smith, M. G., et al.   Regulatory Options Analysis for Carbon
     Tetrachloride, Final  Report.  Prepared for U.S. Environmental Protection
     Agency, Research Triangle Park, North Carolina.  EPA Contract No.
     68-02-3599.  June 1984.  Appendix B.

 9.  U.S. Environmental Protection Agency.  Vinyl Chloride - A Review of
     National  Emission Standards.  Research Triangle Park, North Carolina.
     February 1982.  pp.  A-6 through A-ll.

10.  Environment Reporter.   State Air Laws, Volume 2.   State of Louisiana.
     Louisiana Air Pollution Control Regulations.  Bureau of National
     Affairs,  Inc., Washington,  D.C., February 22, 1985.  p. 391:0501.

11.  Environment Reporter,  State Air Laws, Volume 3.  State of Texas.   Texas
     Regulation V:  Control of Air Pollution  from Volatile Organic Compounds.
     Bureau of National Affairs, Inc., Washington, D.C., September 7,  1984.
     p. 521:0621.
                                   5-18
-------
                           6.0 CHLORINE PRODUCTION
     Carbon tetrachloride (CC1,) is used by several  chlorine producers mainly
as a scrubbing liquid to recover chlorine from a tail  gas or inert gas vent
stream following liquefaction.  Another use of CC14 is as a diluent for
nitrogen trichloride (NCI,) which is often formed in chlorine production.  In
1983, approximately 1,400 Mg of CC14 were used in chlorine production.  Of
this, about 990 Mg of CC14 were used for tail gas scrubbing and about 410 Mg
of CC14 were used as a diluent for NClg.  Use of CC14 in chlorine production
accounts for about 0.5 percent of the total 1983 use of CC14 in the United
States.  Each of the two uses of CC14 in chlorine production will be
discussed separately in the following sections.
6.1  TAIL GAS SCRUBBING

     Three chlorine producers presently use CC14 for recovery of chlorine
from tail gas at a total of seven facilities.  Five of these facilities are
owned by Diamond Shamrock.  Vulcan Materials and E.I. duPont own the other
two.  All of these facilities use a technology licensed by Diamond Shamrock.

6.1.1  Process Description
     A flow diagram for the tail gas scrubbing system is presented in
Figure 6-1.  Following compression and condensation operations in the lique-
faction of chlorine, there are small quantities of noncondensible gases often
referred to as the inert or tail gas stream.  This stream also contains
relatively small quantities of chlorine gas.  At facilities using the tail
gas scrubbing system, this' stream is sent to a scrubber which uses CC14 as
the scrubbing liquid.  The chlorine is first absorbed in the liquid CC14.
The chlorine/ CC14 mixture is then separated.  The CC14 is recycled back to
the absorber and the recovered chlorine is  liquefied to be sold as product.
Carbon tetrachloride vent emissions result  from the contact of air and other
gases with liquid CC14  in the scrubber.  The vented gas stream contains about
0.5 percent CC14-
                                      6-1
-------
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6-2
-------
6.1.2  Current Controls and Emissions
     The major source of emissions from the use of CCl^ for tail gas scrubbing
is the absorber process vent.  Emissions from this source total an estimated
292 Mg/yr for the seven facilities.  Other reported emission sources are
fugitive (equipment leaks), equipment opening losses, relief device discharges,
and handling emissions.  Total CC1. emissions from these sources is estimated
to be 64 Mg/yr.  A summary of emissions by facility and source is presented
in Table 6-1.  Emissions and controls for individual sources are presented in
Table 6-2.
     All seven facilities reported process vent emissions.  As mentioned
above, process vent emissions account for the majority of total emissions
(82 percent).  Process vent emissions are presently controlled by carbon
adsorption at three facilities.  Diamond Shamrock in Battleground, Texas,
reported greater than 98 percent control efficiency and Vulcan in Geismar,
Louisiana, reported greater than 90 percent control.  E.I. duPont also
employs a carbon adsorber, but the uncontrolled emissions and control
efficiency are unknown.   Based on Diamond Shamrock and Vulcan responses,
control efficiency of the carbon adsorber at E.I. duPont in Corpus Christi,
Texas  is estimated to be 95 percent.  From information supplied by these two
companies and published chlorine capacities, an uncontrolled emission factor
of 550 kg of CCl, emitted per gigagram (Gg) of chlorine production capacity
               ?
was calculated.   This factor was multiplied by the estimated production
capacity of the DuPont facility, 297 Gg/yr, to estimate uncontrolled emissions.
     One of the facilities, Vulcan in Geismar, is subject to process vent
requirements in Louisiana.  The State of Louisiana requires control of
process vent emissions by incineration, carbon adsorption, or refrigeration.
Process emissions at this facility are currently controlled by a carbon
adsorber.  The Diamond Shamrock facility in Battleground, Texas and the
DuPont facility in Corpus Christi, Texas are also subject to State require-
ments.  The State of Texas requires control of process vents emitting greater
than 250  Ibs/day in Harris and Neuces Counties.  Both facilities are presently
meeting this requirement by  controlling process vent emissions with a carbon
adsorber.  Other facilities  are not affected by any regulatory  requirements
for  process vents.
                                     6-3
-------



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     Equipment leaks are the second largest emission source, accounting for
17 percent (61 Mg) of estimated annual emissions.  Equipment leak emissions
were estimated for five of the facilities based on company supplied equipment
count data.  Equipment leak emissions for the remaining two facilities were
estimated as the average of estimated equipment leak emissions at all Diamond
Shamrock facilities except Battleground, Texas.  The Battleground facility
appears to be more complex than other facilities and may not be
representative.  Currently,, none of the seven facilities have practices or
controls to significantly reduce equipment leak emissions.  Several of the
facilities did report rupture discs under safety relief valves and estimated
emissions reflect this.
     Three of the seven facilities will likely be affected by recent equipment
leak regulations enacted by Texas and Louisiana.  Texas has enacted regulations
for Harris County and Louisiana has enacted regulations statewide.  One of
the facilities in Texas, Diamond Shamrock in Battleground, is located in
Harris County.  The Texas and Louisiana regulations will require annual leak
detection for pump seals and liquid valves, monthly leak detection for
compressor seals and gas valves, and weekly visual inspection of pump seals.
Reasonable attempts to repair leaks are required within 15 days.  Also,
open-ended lines are required to be capped.
     Emissions from the remaining sources are relatively small accounting for
less than 3 Mg or about 1 percent of total estimated emissions.  Storage
emissions account for 1.4 Mg. of annual emissions, relief device discharges
account for 0.4 Mg of annual emissions, equipment openings account for 0.5 Mg
of annual emissions, and handling operations account for 0.4 Mg of annual
CC1. emissions.

6.1.3  Cost of Additional Controls
     Additional controls were evaluated for control of process vent, equipment
leak,  and storage emissions not already controlled at each facility.  The
estimated costs for controlling process vent and equipment leak emissions are
presented  in  Table 6-3.  The emission reduction achievable by control of
these  emissions is presented in Table 6-4" for different VOC cost-effectiveness
                                      6-7
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       TABLE 6-4.  ACHIEVABLE CC1. EMISSION REDUCTIONS FOR CHLORINE
                           PRODUCTION FACILITIES

Cost-effectiveness
Range, $/Mg of VOC
Credit
0 - 500
500 - 1,000
1,000 - 2,000
2,000 - 5,000
>5,000
TOTAL
Nationwide
Process3
Vent
-
229.4
30.8
. -
-
-
260.2
CCT. Emission Reduction
Equipment
Leak
. . .
-
-
15.0
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1.6
30.4
Mg/Yr
Total
-
229.4
30.8
15.0
13.8
1.6
290.6
Emission reductions presented are for carbon adsorption.
                                  6-9
-------
ranges.  Cost effectiveness for control of storage tanks is estimated to
exceed $25,000/Mg of VOC for all tanks and cost/cost-effectiveness estimates
for individual tanks are not presented.
     6.1.3.1  Control of Process Vent Emissions.  Two options were evaluated
for control of process vent emissions: incineration and carbon adsorption.
The costs for each option are shown in Table 6-3.  Only one facility, Diamond
Shamrock in Battleground, Texas, presently controls process vent emissions
98 percent or greater.  Therefore, the incinerator control  was costed for all
other facilities.  The estimated cost effectiveness of controlling process
vent emissions at each of these six facilities by incineration range from
$4,300/Mg of CC14 to $81,900/Mg of CC14.  Since CC14 is the only VOC, VOC
cost effectiveness is identical.
     As discussed in Section 6.1.2, three facilities currently control CC1-
emissions by carbon adsorption.  The estimated costs for carbon adsorber
control at the remaining four facilities are presented in Table 6-3.  The
cost effectiveness of this control is significantly less than incineration
ranging from $170/Mg of CCl^ to $710/Mg of CC14.  The total emission
reduction achievable by this control is estimated at 260 Mg/yr.  This is
89 percent of current estimated process vent emissions and  73 percent of
total emissions from these chlorine production facilities.
     6.1.3.2  Controls for Equipment Leak Emissions.  The costs of
controlling equipment leak emissions with techniques required by the benzene
fugitive NESHAP were estimated for each facility.  These costs are presented
in Table 6-3.  The cost effectiveness of applying these control techniques is
estimated to range from $l,360/Mg of VOC at the Diamond Shamrock/Battleground
facility to $5,420/Mg of VOC at the Diamond Shamrock/Deer Park facility.
Equipment count data were not supplied by DuPont and Vulcan.  For these
two facilities, the costs and emission reduction were estimated to be the
average of the four similar Diamond Shamrock facilities.
                                    6-10
-------
6.2  DILUENT FOR NITROGEN TRICHLORIDE                                   -

     Another use of CC1. by chlorine producers is as^a diluent for nitrogen
trichloride (,NC1,).  Approximately 380 Mg of CC1, were used for this purpose
in 1983.  Four companies reported that CC1. is used as a NCI- diluent,at one
or more facilities.  All four companies, Dow Chemical, DuPont, FMC Corporation,
and the B.F. Goodrich Company, indicated that CC14 is used in a completely
enclosed system with no process vents. "   The used CC1. is collected for
disposal.  A list of identified users is presented in Table 6-5 along with
estimated emissions.

6.2.1  Process Description
     In the production of chlorine, salt (NaCl) is electrolytically reacted
with water to form chlorine (Cl^K sodium hydroxide, and hydrogen.  Ammonia
(NH7) is often an impurity in the salt feed and is converted to NCI, in the
   o          •  •                                                   o
electrolytic cell.  From the anodes of the electrolytic cells hot chlorine
gas containing considerable amounts of water and small quantities of NCI,
vapor is evolved.  This gas is cooled to condense out the water and then
dried with sulfuric acid.  This gas is then compressed and cooled to liquify
the chlorine.  The product or liquefied chlorine contains small quantities of
NC13.
     The chlorine to be liquefied may be passed through a bubble-cap column
countercurrent to liquid chlorine.  Liquid chlorine is evaporated causing the
NCI, to build up in recirculating liquid chlorine.  The NCI, is very unstable
even at relatively low concentrations and CC1, is added to the chlorine
column bottoms to dilute the NCI,.  Chlorine is reclaimed from the bottoms
mixture and the CC1-, NCI,, and small amounts of chlorine are disposed  of as
hazardous waste.

6.2.2  Current Controls and Estimated Emissions
     The estimated emissions for each facility are presented in Table 6-5.
As shown in Table 6-5, estimated emissions are relatively small, totalling
only 1 Mg/yr.  These estimates are based on the combined emission information
                                    6-11
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received from FMC Corporation and Dow Chemical  in Section 114 responses.
Only FMC completed the questionnaire on emissions.  However, equipment counts
for estimating equipment leak emissions were not supplied.   Dow estimated the
annual equipment leak emissions to be less than 500 pounds  and 100 pounds for
their Plaquemine and Freeport facilities, respectively.  '   The average for
these two facilities was used to estimate equipment leak emissions for other
facilities.
     A material balance of carbon tetrachloride use as a diluent is presented
in Figure 6-2.  The majority of carbon tetrachloride used for this purpose is
reclaimed for disposal.  As shown in Figure 6-2, about 0.93 Mg of CCl^ are
disposed of for every Mg used.  Most of the remaining CCl^j 0.068 Mg, ends up
in the chlorine product.  A small portion, about 1.6 kg per Mg used, may be
emitted to. the atmosphere.
     There are no applicable regulatory requirements for CC1, emissions from
these facilities.          .           .-...-
     Cost estimates for control of these emissions were not developed because
there are no process vents and fugitive and storage emissions are minimal.
                                     6-13
-------
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6.3  REFERENCES

1.   Telecon.  J. Harris, E.I. duPont, with R. H. Howie, Radian Corporation.
     February 25, 1985.  Conversation about captive uses of CC1,.

2.   SRI International.  1984 Director of Chemical Producers - United States.
     SRI International, Menlo Park, California, 1984, pp. 490-491.

3.   Letter and attachments from B. H. Christensen, Diamond Shamrock Company,
     to J.-R. Farmer, EPA.-ESED.  February 14, 1985.  Response to Section 114
     Letter.

4.   Letter and attachments from R. E. Berg, Vulcan Chemicals, to
     J. R. Farmer, EPA:ESED.  January 31, 1985.  Response to Section 114
     Letter.

5.   Letter from S. L. Arnold, Dow Chemical, U.S.A. to J. R. Farmer,
     EPA:ESED.  March 12, 1985.  Response to Section 114 Letter.

6.   Letter and attachments from S. L. Arnold, Dow Chemical, U.S.A. to
     J. R. Farmer, EPA:ESED.  March 7, 1985.  Response to Section 114 Letter.

7.   Letter and attachments from M. T. Chow, FMC.Corporation'to J. R. Farmer,
   -  EPArESED.  March 11, 1985.  Response to Section 114 Letter.

8.   Letter from W. C. Holbrook, The B.F. Goodrich Company to J. R. Farmer,
     EPA:ESED.  December 11, 1984.  Response to Section 114 Letter.
                                     6-15
-------
-------
                  7.0  HYPALON* SYNTHETIC RUBBER PRODUCTION
            R
     Hypalon'^  is the tradename for a synthetic rubber produced by
                                          R
E.I. Dupont de Nemours & Company.  Hypalon  is produced by reacting poly-
ethylene with chlorine and sulfur dioxide, transforming the thermoplastic
polyethylene into a vulcanizable elastomer.  The reaction is conducted in a
                                  The Dupont plant in Beaumont, Texas is the
                                                    D
                                                        No flow diagram for
solvent (CC1.) reaction medium.
only facility in the United States producing Hypalon
       R
Hypalon  is presented because the process is considered confidential by
Dupont.
7.1  CURRENT CONTROLS AND EMISSIONS
                                                         R
     Th'e primary types of.CCT, emissions from the Hypalon  process are -
process and fugitive emissions.  Storage, handling, relief valve discharge,
and equipment opening losses were also reported and are summarized in
Table 7-1.  Annual CC1, emissions from this facility are about 220 Mg.  The
emission types/sources and their controls are discussed below and are
summarized in Table 7-2.
                              p
     The production of Hypalon  at Dupont's plant in Beaumont, Texas result
in about 100 Mg of CC1, process vent emissions annually.  The largest
emitting process vent is controlled by a carbon adsorber.  DuPont reported
that the efficiency of the carbon absorber was greater than 98 percent.   The
controlled emissions from this vent are estimated to be about 61.1 Mg.
There are nine other dryer basement air exhaust stacks.  The emissions from
these stacks range from 3.28 to 6.9 Mg/yr.  These emissions are not
controlled.  State VOC gas stream regulations for non-attainment .areas
exempt streams emitting less than 45.4 kg (100 Ib) of VOC in any consecutive
24 hour period.  These streams are below the cut-off.
     Equipment leak emissions account for about half, 110 Mg, of the annual
CC14 emissions.  DuPont reported that the air at each of about 52 key points
                                   7-1
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in the work place at the plant is sampled and analyzed for CC1, every ten
minutes using a "Wilkes-Miran" infrared  analyzer system.  This system is
reported to be effective in maintaining average CC1, levels well below the
threshold limit value (TLV) of 5 ppm.  However, no information was provided
on an actual control program for equipment leaks.  Therefore, the equipment
leak emission estimates are based on uncontrolled emission factors.
     Carbon tetrachloride losses from product storage tanks at the DuPont
facility are estimated to be approximately 2.2 Mg/yr.  Emissions from five
fixed roof tanks ranging in size from 20,000 to 52,000 gallons accounted for
all the storage emissions.  There are also nine pressure tanks ranging in
size from 880 gallons to 15,000 gallons at this facility.  These tanks are
assumed to have minimal  emissions.  Unless VOC are stored in pressurized
tanks, the following regulations apply in Texas.
     1)   VOC storage tanks between 1,000 and 25,000 gallons must have a
          submerged fill pipe.
     2)   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.
     3)   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.
     One 20,000 gallon fixed roof storage tank at DuPont is controlled by a
brine cooled condenser and a 50,000 gallon tank is controlled by a condenser
and a carbon adsorber.  Both tanks meet State emission regulations.  A
5,200 gallon fixed roof tank has only a conservation vent, but also has a
submerged fill pipe and meets the State regulations.
     Losses due to handling of CC1, are approximately 0.4 Mg/yr.   The CC1.
raw material is received at the plant in steel railroad tank car lots of
about 200,000 Ibs. per tank car.  One tank car at a time is connected up to
an unloading spot.  The CC1, is pumped from the tank car as needed through  a
bottom unloading line to the wet CC1. storage tanks.
     Dupont does not keep records of equipment openings.   An estimate was
made by Dupont of 3,000 to 5,000 openings in 1983 of equipment containing
                                    7-6
-------
10 percent or greater CC1-.  It is standard procedure at the plant to clear
all equipment to be opened prior to opening.  The equipment is always
isolated prior to opening.  The clearing is done by pumping or draining all
process material in the equipment back to the process and then purging with
Np.  This opening procedure has allowed only trace quantities of CCl^ to be
emitted to the atmosphere.  Emissions from equipment openings in 1983 were
estimated by DuPont to be 0.02 Mg.  The state of Texas has no specific
regulations regarding equipment opening emissions.
     Secondary emissions range from 0.03 Mg/yr for off-spec reactor charge
which is landfilled, to 2.7 Mg/yr for process wastewaters treated in a
facultative pond.  Table 7-2 summarizes the rest of the secondary emission
sources and final treatment methods.  Secondary emissions are not regulated
by the state of Texas.
                                                                  R
     There were two relief valve discharges in 1983 at the Hypalon  plant.
A total of 2.1 Mg. of CC1,, were released.  Both releases occurred from the
       R '
Hypalon  reactor during pressure surges.  There are no regulations governing-
pressure relief device discharges in the State of Texas.

7.2  COST OF ADDITIONAL CONTROLS

     Costs of additional controls to reduce present CC1,, emissions at
                R
Dupont's Hypalon  facility were estimated for process, fugitive and storage
sources.  A summary of these costs and their cost effectiveness is provided
in Table 7-3 and discussed below.

7.2.1  Control of Process Vent Emissions
     Additional controls were considered only for those process vent emission
sources with no present controls or existing control efficiencies less than
98 percent.  The vents on all nine dryer basement air exhaust stacks are
presently uncontrolled.   Incineration control cost was estimated for reducing
the exhaust stack emissions.  Controlling emissions by 98 percent would reduce
the annual emissions of CCl^ by about 39.5 Mg.  Capital cost of-incinerators
(5) for control of exhaust stack emissions is $31,900,000.  The cost effec-
tiveness of incineration  for reducing CCT- emissions is $745,000/Mg of VOC.
                                    7-7
-------












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7.2.2  Control of Equipment Leak  Emissions
                                                       R
     The equipment leak emissions from Dupont's Hypalon  facility were
                                                                         2
estimated using equipment count data supplied in the Section 114 response .
Controls required by the benzene fugitive NESHAP were evaluated for
controlling equipment leak emissions.  The estimated costs and cost
effectiveness of controlling equipment leak emissions is summarized in
Table 7-3.  It is estimated that the equipment leak emissions will be
reduced by 51.6 percent at a capital cost of $38,800.  The cost effective-
ness of controlling equipment leak emissions is estimated to be $145/Mg of
VOC and $286/Mg of CC14.

7.2.3  Control of Storage Emissions
     Additional control with a condenser was costed for 1 of the 5 fixed
roof storage tanks at the Dupont facility.  Two 20,000 gallon and one
46,540 gallon fixed roof tanks are already controlled by a brine cooled
condenser with 93.9 percent efficiency.  A 50,000 gallon storage tank also
has a condenser and a carbon adsorber for a total reported control
efficiency of greater than 98 percent.  Additional controls were evaluated
for the one 5,200 gallon fixed roof tank.  It is estimated that a condenser
will provide 83.7 percent control.  The cost effectiveness of this control
is estimated to be $99,800/Mg of VOC.  Costs for a floating roof was not
estimated because a floating roof is not expected to reduce emissions due to
the small size of the tank.
                                    7-9
-------
7.3  REFERENCES

1.   Telecon.
     E.I. DuQont Beaumont Works.  General information on CC1A usage in
Howie, R., Radian Corporation, with McClure, R. L.,
                                            u
     Hypalon  Production.  December 19, 1984.

2.   Letter and Attachments from McClure, R. L., E.I. Dupont Beaumont Works
     to Farmer, J. R., EPArESED.  Response to Section 114 Letter.
     March 15, 1985.

3.   U.S. Environmental Protection Agency.  Benzene Fugitive Emissions ~
     Background Information for Promulgated Standard.  Research Triangle
     Park, North Carolina.  Publication No. EPA-450/3-80-0326.  June 1982.
                                   7-10
-------
                          8.0  PESTICIDE PRODUCTION
     Approximately 4,105 Mg of CC1. was used in the pesticide industry in
1983.  This usage accounts for 1.5 percent of the total CC1. consumed that
year.  Emissions of CC1, were reported to be associated with the production
of the following pesticides:  chlorothalonil, dacthal , and tordon acid.  The
production of these three pesticides accounts for 1,504 Mg of the total CCl^
used in the industry.  Approximately 2,601 Mg is used in other pesticide
production operations at 4 facilities.  Carbon tetrachloride is used mainly
as a solvent or reaction medium in the pesticide production processes.
     Emissions of CC1, from the three identified pesticide production
processes is approximately 420 Mg/yr.  Based on the ratio of emissions to
use  (0.28 Mg/Mg), the CC1. emissions from other pesticide production
processes is estimated to be 730 Mg/yr.  Therefore, total estimated CCl^
emissions for the pesticide industry are 1,200 Mg/yr.  The identified
pesticide production processes are discussed individually in the following
sections.            •
8.1  CHLOROTHALONIL
     Chlorothalonil is manufactured in the United States under the tradename
Daconil 2787R and Bravo  by SDS Biotech Corporation at their Greens Bayou,
TX facility.  Cited uses include agricultural and horticultural fungicide,
bactericide, and nematocide.   Chlorothalonil is made by dissolving tetra-
chloroisophthalic acid chloride in an organic solvent (CC1.) and adding
        1                                                 ^
ammonia.   A flow diagram showing the chlorothalonil process cannot be
presented because the company considers the information to be confidential.

8.1.1   Current Controls and Emissions
     The primary types of CC1, emissions from SDS Biotech's Daconil
processes are process and equipment leak.  Other minor sources of CC1.
                                     8-1
-------
emissions include relief valve discharges, storage, equipment openings, and
secondary emissions.  These emissions are summarized in Table 8-1 and
discussed below.  Total CC1. emissions from this facility are estimated to
be 377 Mg/yr.
     There are two Daconil processes at SDS Biotech's facility in Greens
Bayou, TX.  Process vent emissions are estimated to be 123.6 Mg for Daconil I
and 122.3 Mg for Daconil 2.  The two Daconil process vent emissions sources
are located on the chlorine absorber.  Both vents are controlled by freon
chillers with greater than 50 percent control efficiency.  The plant is
located in Harris county and is regulated under the State of Texas nonattain-
ment regulations for VOC's.  Emissions from vent streams in Harris County
are regulated according to certain VOC classes, which include CC1..  The
vent streams must be burned properly at a temperature equal to or greater
than 1300°F (704°C) in a direct flame incinerator before it is allowed to
enter the atmosphere.  There are exemptions to this regulation.  Alternate
means of control may be approved by the executive director.
     Equipment leak emissions for the Daconil 1 and 2 processes are estimated
to be 48.9 Mg/yr and 60.4 Mg/yr, respectively.  State regulations requiring
a formal equipment leak emissions monitoring program have recently been
promulgated.  The requirements include annual leak detection (greater than
10,000 ppm VOC) for pump seals and valves in liquid service, monthly leak
detection for compressor seals and valves in gas service, and weekly visual
inspection of pump seals.  Repair or reasonable measures to minimize identi-
fied leaks is required within 15 days.  Also, open-ended lines are required
to be capped.
     Losses from CC1- storage were estimated to be 0.015 Mg/yr for Daconil 1
and 0.043 Mg for Daconil 2 based on 1983 storage data.   Storage tanks in
Harris County with a capacity greater than 42,000 gallons (158,487 liters)
are required to have an internal floating roof, external floating roof, or
vapor recovery system which returns vapor to a disposal  system.  An external
roof must have primary and secondary seals between the tank wall  and roof
edge.
                                      8-2
-------
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     The Daconil I unit had 29 equipment openings in 1983 with estimated
CC1- emissions of 0.57 Mg.  The Daconil 2 unit also had 29 equipment openings
resulting in 0.73 Mg of CC1. emissions.  The State of Texas has no specific
regulations regarding equipment opening emissions.
     SDS Biotech reported that secondary emissions in 1983 were 0.27 Mg from
the Daconil 1 process and 0.47 Mg from Daconil 2 process.
     There were three relief valve discharges in 1983 from the Daconil 1
process.  Approximately 0.06 Mg of CC1, were released.  The Daconil 2
process had seven releases emitting approximately 0.52 Mg of CCl^.  There
are no regulations governing these pressure relief device discharge
emissions in Texas.

8.2  DACTHALR PRODUCTION

            p
     Dacthal  is manufactured under the common name of DCPA or DAC by SDS
Biotech Corporation in Greens Bayou, TX.   It is used as a selective
preemergence herbicide.   The production process and flow diagram are
considered confidential business information by the manufacturer.

8.2.1  Current Controls and Emissions
                                                                     D
     The primary sources of CC1, emissions from SDS Biotech's Dacthal
process are process and equipment leak.  Emissions from these sources are
summarized in Table 8-1 and discussed below.
     There two process emission sources from the Dachtal manufacturing
process.  The photochlorination reactor vent with estimated CC1.  emissions
of 4.2 Mg/yr and the thermal chlorination reactor vent with estimtaed CC1.
emissions of 13.2 Mg/yr.  Both vents are controlled by condensers  with
reported efficiencies of 85 percent and 79 percent, respectively.
     The SDS Biotech facility is located in Harris County, Texas  and is
covered by State emissions standards.  Both vent streams are exempt from
Harris County process emission regulations since they are under 45.4 kg/24
hour period (11.5 kg/24 hr and 36.2 Kg/24 hr).
                                    8-4
-------
     Equipment leak emissions from the Dachtal process were estimated..to be
10 Mg/yr.  State regulations have recently been promulgated requiring a
formal equipment leak control program to be completed by the end of 1987.
This program was discussed in the previous section.
     Annual emissions from CCl^ storage are estimated to be 0.80 Mg for the
Dachtal process based on 1983 storage tank data.
     The Dachtal CC1» storage emissions are minimal due to present controls.
The storage tanks emissions are within the Harris County regulation limits
for VOC.

8.3  TORDON ACID  .    •   •

     Tordon acid is manufactured in the U.S. by Dow Chemical.  Another
common name for tordon acid is pichloram.   It is a systemic herbicide
effective against a wide variety of deep-rooted herbaceous weeds and woody
plants.  It is sold for noncrop use in brush control along utility rights-
of-way, for weed and brush control in pastures and rangeland, and broadleaf
weed control in small grains production.
     Dow considers the manufacturing process for tordon acid to be  .
confidential business information and, therefore, no description or flow
diagram is provided.

8.3.1  Current Controls and Emissions
     The primary source of CC1. emissions from the manufacture of tordon
acid is equipment leaks.  Equipment leak emissions were estiamted at
33.9 Mg/yr.  Emissions from this source and other minor sources are
summarized in Table 8-1.
     Dow manufactures the tordon acid at their plant in Freeport, Texas and
is subject to Texas air regulations for Harris County.  Dow currently meets
Harris County regulations with the control equipment they have in place.
                                     8-5
-------
8.4  COST OF ADDITIONAL CONTROLS
     Cost estimates were developed for control of process vent, fugitive,
and storage emissions at the pesticide manufacturing facilities discussed
earlier.  The cost effectiveness of controlling the emissions from these
sources is summarized in Table 8-2 and discussed in the following sections.
     Table 8-3 summarizes the estimated CC1, emission reductions as a
function of cost effectiveness.  The emission reductions are separated by
type and totalled for the identified pesticide CC1, users.  If all additional
controls were put in place, a 77 percent (324 Mg/yr) reduction in
emissions would be possible from the two pesticide facilities.
8.4.1  Control of Process Vent Emissions
     Additional control by incineration was considered only for those
process vent emission sources currently not controlled greater than
98 percent.  The cost effectiveness for controlling process emissions ranged
from $3,700/Mg of VOC to $24,700/Mg of VOC.  Carbon tetrachloride process
vent emissions could be reduced by 98 percent (257.9 Mg) if the pesticide
plants implemented incinerator controls.

8.4.2  Control of Equipment Leak Emissions
     Estimated costs for controlling equipment leak emissions are based on
control techniques required by the benzene fugitive NESHAP.  The cost
effectiveness of controlling equipment leak emissions from pesticide plants
ranged from $200/Mg of VOC to $l,600/Mg of VOC.  By controlling CC14
equipment leak emissions at these two facilities, total CC14 equipment leak
emissions could be reduced by 41 percent or 63.3 Mg/yr.

8.4.3  Control of Storage Emissions
     Cost estimates were developed for control of fixed-roof storage tank
emissions which currently do not have greater than 85 percent control
efficiency.  Dow 'uses  incineration to control storage tank emissions greater
than 98 percent and SDS Biotech's Daconil process storage tanks are
                                     8-6
-------






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            TABLE 8-3.  ESTIMATED CC1A EMISSION REDUCTIONS AS A
                        FUNCTION OF COST EFFECTIVENESS

Cost-Effectiveness
Range, $/Mg of VOC
Credit
0 - 500
500 - 1,000
1,000 - 2,000
2,000 - 5,000
>5,000
TOTAL
Nationwide CC1« Emission Reduction
Process Equipment Leak Storage
_
18.1
40.4
4.8
240.9
17.0 - 0.3
257.9 63.3 0.3
(Mg/yr)
Total
-
18.1
40.4
4.8
240.9
17.3
321.5
Emission reductions presented are for carbon adsorption.
                                   8-8
-------
controlled using a confidential method.  Only the Daconil  storage tanks need
additional controls.  The three control options evaluated were:  contact
internal floating roof with primary seal (FR-PO), contact internal floating
roof with primary and secondary seal (FR-SS), and a refrigerated condenser.
The cost effectiveness ranged from $46,700/Mg of VOC using FR-SS to
$89,300/Mg of VOC with the condenser.
                                     8-9
-------
8.5  REFERENCES

1.   Farm Chemicals Magazine.  Farm Chemicals Handbook.  Meister Publishing
     Company, New York, 1984.

2.   Letter and attachments from J. E. Stansbury, SDS Biotech Corporation to
     J. R. Farmer, EPA:ESED.  April 15, 1985.  Response to Section 114
     Letter.

3.   Letter and attachments from S. L. Arnold, Dow Chemical, U.S.A. to
     J. R. Farmer, EPA:ESED.  March 1985.  Response to Section 114 Letter.
                                    8-10
-------
                    9.0  CHLORINATED PARAFFINS PRODUCTION
     Chlorinated paraffins are mainly straight-chain, saturated hydrocarbons
of the C,Q - C,Q range.  The manufacturing process consists of passing
gaseous chlorine into a paraffin hydrocarbon.   In some processes, (dry
chlorinated paraffins) chlorination is carried out by using solvents, such
as CC1., under reflux.  Paraffins of this type, containing 70 percent or
greater chlorine, contain residual amounts of CCK which may be released
into the atmosphere.
     Currently, there is only one producer of dry chlorinated paraffins
                                                             2
(resinous chlorowax) using CC1, solvent in the United States.   This Diamond
Shamrock facility is located in Deer Park, Texas.  The process by which
chlorinated paraffins are produced is considered confidential by Diamond
Shamrock.

9.1  CURRENT CONTROLS AND EMISSIONS

     The total CC1» emissions from the Diamond Shamrock chlorinated paraffins
plant is estimated to be about 9.4 Mg/yr.  Table 9-1 summarizes the emissions
of CC1. from this plant.  The emission types/sources and their controls are
discussed below and listed in Table 9-2.
     Emissions from process vents at the Diamond Shamrock plant in Deer
Park, Texas are estimated to be 0.8 Mg of CC1, at full capacity.  The vents
are located on a stripper chiller and three surge tanks.  The largest
emission source was 0.53 Mg from one of the dry CC1. surge tank vents.  The
control device on this emission source is a vent chiller with 84.5 percent
removal efficiency.  The next largest emission source resulting ;in 0.26 Mg
of CC1. emissions, is another surge tank vent.  This vent is also controlled
by a vent chiller with a 89.2 percent removal efficiency.  The remaining two
vents emit less than 0.001 Mg/yr of CC1*.  One of these vents is controlled
by a condenser, decanter and vent chiller (greater than 98 percent control
efficiency) while the other vent has a vent chiller which is intended to
control emissions in the event that the water blanket is lost.
                                    9-1
-------
    TABLE 9-1.  SUMMARY OF ESTIMATED 1983 CC1. EMISSIONS FROM THE DIAMOND
       DIAMOND SHAMROCK CHLORINATED PARAFFINS^PRODUCTION FACILITY (Mg)
Plant/Location
Process
Equipment
   Leak
Secondary
Total
Diamond   ,
  Shamrock
Deer Park, TX
 0.8
   8.3
   0.31
 9.4
                                    9-2
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     Texas regulations for vent streams in Harris County specify that
certain VOC classes, which include CC14, must be burned properly at a
temperature equal to or greater than 1300°F (704°C) in a smokeless flare or
direct flame incinerator before it is allowed to enter the atmosphere.
However, all of the vent streams at Diamond Shamrock are exempt from this
regulation.  The vent with the largest quantity of CCl^ emissions at Diamond
Shamrock releases an average of only 0.39 kg/hr (9.35 kg. in any 24 hour
period) which is well below the 45.5 kg/24 hr exemption.
     Equipment leak emissions account for 88 percent of the total CC1.
emissions from chlorinated paraffins production, totalling 8.3 Mg/yr.
Diamond Shamrock indicated that there is currently no formal, monitoring and
control program' for equipment leaks.  Operating personnel are instructed to
report any leaking components that they observe on their normal rounds.  The
Texas Air Control Board has recently promulgated regulations for Harris
County that will require a formal  equipment leak monitoring program.. ••
Requirements include annual leak detection (greater than 10,000 ppm VOC) for
pump seals and valves in liquid service, monthly leak detection for compressor
seals and valves in gas service, and weekly visual inspection of pump seals.
Repair or reasonable measures to minimize identified leaks is required
within 15 days.  Also, open-ended lines are required to be capped.
     There were no losses from storage because all CC1, is received directly
into the production system.
     All CC14 shipments are received in tank trucks.  The tank trucks are
hooked up directly to either the dry CC1, tank or the wet CC14 tank.  During
unloading, the displaced gas is vented through the respective vent chiller.
The trucks are unloaded by pressure and are kept closed.  Unloading emissions
are considered minimal by the plant because of the effectiveness of the
chillers.
     The State of Texas requires a vapor recovery system for emissions from
loading and unloading of a VOC with a true vapor pressure equal to or
greater than 1.5 psia (10.3 kPa) under actual  storage conditions.  In
addition, the facility must have 20,000 gallons (75,708 liters) or more
throughput per day (averaged over any consecutive 30-day period) to be
                                    9-5
-------
affected by this regulation.  Diamond Shamrock's total VOC throughput is not
known and therefore, it is not known if the regulation applies to their
facility.
     Diamond Shamrock does not keep records of equipment openings.  However,
the plant reported that the production process is a closed system and
equipment openings are infrequent.  Standard procedure for maintenance
opening of equipment at Diamond Shamrock is to drain all liquid and purge
with steam or nitrogen to remove the lost traces of chemicals prior to
opening.  The State of Texas has no specific regulations regarding equipment
opening emissions.
     The only source of secondary CC1, emissions at the Diamond Shamrock
facility is from wastewater treatment.  About 0.31 Mg/yr (0.86 kg/day) of
CC1, emissions occur when the chlorinated water is combined with wastewater
from the perch!oroethylene process, steam stripped, and pumped to a
biological water treatment plant for final  treatment.

9.2  COSTS OF ADDITIONAL CONTROLS

     Costs of additional controls to reduce present CC1. emissions at
Diamond Shamrock's dry chlorinated paraffins plant were estimated for
process and fugitive emission sources.  A summary of the costs and cost
effectiveness is provided in Table 9-3 and discussed below.

9.2.1  Control of Process Vent Emissions
     Additional emission controls were considered for those process sources
with no present controls or existing control efficiencies less than
98 percent.  The stripper chiller vent emissions at Diamond Shamrock's dry
chlorinated paraffins plant is reportedly controlled greater than 98 percent
by a condenser, decanter and vent chiller.   The vents on the three surge
tanks have vent chillers, with different control  efficiencies.  A control
efficiency was not reported for the first CC1. surge tank vent chiller.   The
second CC1. surge tank vent chiller has a 84.5 percent control efficiency
and the third surge tank vent chiller a 89.2 percent control  efficiency.
                                    9-6
-------















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The cost for an incinerator was estimated for all three surge tank vents.
It was assumed that the emission streams from all three tanks will be
combined and directed to one incinerator.  The cost effectiveness of this
control device is estimated at $534,000/Mg of CC1, emission reduction.
Carbon tetrachloride process vent emissions would be reduced by 98 percent
or 0.8 Mg/yr.
     Cost of controls for fugitive emissions were estimated based on control
techniques required under the benzene fugitives NESHAP.  The cost effective-
ness of fugitive emissions control at the chlorinated paraffins plant is
estimated to be $l,310/Mg of CC14 and $730 Mg of VOC.  Carbon tetrachloride
emissions would be reduced by 3.8 Mg/yr (45 percent) as a result of equipment
leak controls.
                                    9-8
-------
9.3  REFERENCES

1.   Kirk - Othmer.   Encyclopedia of Chemical  Technology:   Volume 5.
     John Wiley and  Sons Inc., New York, 1977.

2.   Telecon. Howie, R.; Radian Corporation, with Christensen,  B. H.;
     Diamond Shamrock.  General Information on Usage of Carbon  Tetrachloride
     in Production of Chlorinated Paraffins.  January 2, 1985.

3.   Letter and attachments for Christensen, B. H., Diamond Shamrock  to
     Farmer, J.R., EPA:ESED, Response to Section 114 Letter.   January 21,
     1985.
                                     9-9
-------
-------
                      10.0 PHARMACEUTICAL MANUFACTURING

     There are currently about 800 pharmaceutical plants in the United
States and its territories.  Carbon tetrachloride is sometimes used as a
solvent in the manufacturing of pharmaceutical products.  The trend,
according to several of the major pharmaceutical firms contacted, is to
reduce CC1. usage.  This is supported by information supplied by CC1»
producers.  Carbon tetrachloride consumption by pharmaceutical manufacturers
in 1983 is estimated to be 231 Mg.  This consumption can be compared to an
estimated 1,850 Mg of consumption by 26 ethical drug manufacturers in 1978.

10.1  ESTIMATED EMISSIONS

     A survey of 26 ethical drug manufacturers published in 1978 cites a
total annual CC1. 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 CC1. 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 CC1* use.  Assuming the same
disposition for 1983 consumption., estimated air emissions are 26 Mg.
     Available controls for CC1. emissions include condensers, scrubbers, and
carbon adsorbers.  Storage and transfer emissions can be controlled by vapor
return lines, conservation vents./ vent scrubbers, pressurized storage tanks,
and floating roof storage tanks.  Although control efficiencies may vary with
the specific process, overall control of 90 percent of CC1* emissions or
better is generally possible.
     The best CC14 emission control method and the one being adopted by the
pharmaceutical industry is total elimination of CCl^ as a solvent.  From
telephone discussions with various pharmaceutical manufacturers, it was
established that the industry as a whole is attempting to eliminate CC1-
usage.
                                  •  10-1
-------
10.2 REFERENCES
1.   U.S. Environmental Protection Agency.  Control of Volatile Organic
     Emissions from Manufacture of Synthesized Pharmaceutical  Products.
     Research Triangle Park, N.C.  Publication No. EPA/450/2-78-029.
     December 1978.  pp. 2-2 through 2-5 and Appendix A.

2.   Telecon.  White, T., Pharmaceutical Manufacturers Association, with
     Kowalski, 0. A., Radian Corporation, January 2, 1985.  General
     Information on Carbon Tetrachloride Usage in Pharmaceutical Production.

3.   Telecon.  Visser, M., Upjohn Co., with Howie, R., Radian  Corporation.
     April 19, 1985.  Conversation on use of CCl^.

4.   Telecon.  Robertson, B., Abbot Labs, with Howie, R., Radian
     Corporation.  April 17, 1985.  Conversation on use of
                                   10-2
-------
          11.0  MISCELLANEOUS  PRODUCTION  USES OF  CARBON  TETRACHLORIDE

     Approximately  145 Mg of  CC14 were emitted from miscellaneous  chemical
production processes  in  1983.  These miscellaneous chemical  products  are
produced  by Dow Chemical Company.  They  include  symmetrical  tetrachloro-
pyridine  and two confidential processes  which are labeled Confidential
process 1 and 2 for identification purposes.

11.1  SYMMETRICAL TETRACHLOROPYRIDINE1

     The  symmetrical  tetrachloropyridine process is currently used at Dow
facilities in Freeport, Texas and Pittsburg, California.  The symmetrical
tetrachloropyridine process is considered confidential  by Dow and will not be
discussed in any detail.

11.1.1  Current Controls and  Emissions
     The  primary types of emissions from this process are process vent,
equipment leak, and storage.  In addition, relatively small emissions occur
from equipment openings and from handling at the two facilities.  A summary
of emissions by facility and  type is presented in Table 11-1.
     Process vent emissions from the Freeport, Texas facility were 0.27 Mg in
1983.  The facility is exempt from the Brazoria County, Texas regulations for
process emissions because these emissions are below the 45.5 kg/24 hour
exemption.
     Equipment leak emissions are the largest type of CC1. emissions
generated by symmetrical tetrachloropyridine production.  Approximately 57 Mg
were emitted from the Freeport, Texas facility and 9.4 Mg from the Pittsburg,
California facility.  There are no State regulations in Brazoria County for
equipment leak emissions.
     The symmetrical tetrachlorpyridine facility located in Pittsburg,
California is regulated by the Bay Area District.  The regulations require
                                    11-1
-------


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annual inspections of all valves and flanges and repair within six months.
Dow has indicated that a formal leak detection and repair program is
currently in use.  However, the emissions reduction due to an annual leak
detection and repair program is considered minimal by EPA.
     Losses from product storage were estimated to be 0.75 Mg/yr for the
Freeport, Texas facility while the Pittsburg, California facility reported no
storage emissions.
11.2  DOW CONFIDENTIAL PROCESS 1
                                1
     Dow's Confidential process 1 is used at their facility in Midland,
Michigan.  The product and the process are both considered confidential by
Dow and will not be discussed in any detail.

11.2.1  Current Controls and Emissions
     The primary types of emissions from this process are process vent,
equipment leak, and secondary emissions.  In addition, relatively small
emissions occur from handling, equipment openings, and relief device
discharges.  A summary of the emissions is presented in Table 11-1.
     Process emissions were 9.4 Mg in 1983.   These emissions accounted for
16 percent of the total CC'I. emissions from the facility.  There are no State
regulations in Michigan requiring control of VOC emissions from process
vents.
     Sixty-eight percent (39.7 Mg) of the total emissions from this process
are fugitive emissions which are not controlled by Federal or State regula-
tions.  Secondary emissions are another major emission source accounting for
16 percent (9.1 Mg) of the total CC1. emissions in 1983.  Other emissions are
0.12 Mg/yr for relief devices, 0.01 Mg/yr for equipment openings, and
0.04 Mg/yr during handling.
                                    11-3
-------
11.3  DOW CONFIDENTIAL PROCESS 2d

     Dow's Confidential process 2 is used at five different facilities.
These facilities are located in Pittsburg, California; Midland, Michigan;
Freeport, Texas; Dalton, Georgia; and Allyn's Pt., Connecticut.  A summary of
the emissions by facility and type is presented in Table 11-1.  It should be
noted that Dow's response gave emissions for a model plant applicable to all
five facilities rather than the actual facilities.  The process and product
are considered confidential by Dow and will not be discussed in any detail.

11.3.1  Current Controls and Emissions
     The primary types of emissions from these facilities are process vent
and equipment leak emissions.  In addition, small emissions occur from relief
device discharges, equipment openings, storage, handling and secondary
sources.  A summary of the emissions by type is presented in Table 11-1.
     Process emissions were 0.54 Mg in 1983 for the model plant.  These
emissions accounted for 15 percent of the total CC1, emissions from the
facilities.  Seventy-eight percent (2.8 Mg) of the total estimated CC1,
emissions from this process are equipment leak emissions.  Storage emissions
account for less than 1.0 percent (0.032 Mg/yr) of the total CC1-  emissions
while handling emissions were estimated to make up about 3 percent
(0.13 Mg/yr) of the total model plant emissions.

11.4  COST OF ADDITIONAL CONTROLS

     Costs of additional controls to reduce present CC1. emissions at all  Dow
facilities covered in this chapter were estimated for process vent, equipment
leak, and storage sources.  A summary of the costs and their cost  effective-
ness is provided in Table 11-2 and discussed below.

11.4.1  Control of Process Vent Emissions
     The cost of controlling process vent emissions for miscellaneous
processes at Dow's facilities were developed for incineration control.
                                     11-4
-------

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-------
Control cost effectiveness ranged from $4,040/Mg of VOC for Dow's five
Confidential process 2 facilities to $l,600,000/Mg of VOC for Dow's Freeport,
Texas symmetrical tetrachloropyridine process.  A total emission reduction
12.6 Mg/yr of CC1, can be achieved by controlling the process vent emissions
by incineration.                    •

11.4.2  Control of Equipment Leak Emissions
     The cost of controlling fugitive emissions for all of Dow's miscellaneous
processes were estimated using control techniques required by the benzene
fugitives NESHAP.  The control cost effectiveness ranged from $30/Mg of VOC
for confidential process 1 to $970/Mg of VOC for the symmetrical tetrachloro-
pyridine process at Dow's plant in Pittsburg, California.  A total  emission
reduction of 63 Mg/yr of CC14 can be achieved by fugitive emissions control
at these facilities.

11.4.3  Control of Storage Emissions                     •
     Estimated costs for controlling all fixed roof storage tanks containing
CC14 are presented in Table 11-2.  Costs were estimated only for storage
tanks at Dow's Freeport, Texas symmetrical tetrachloropyridine plant.   The
other facilities were already controlled and therefore did not need
additional controls.  Three options were costed:  installation of internal
floating roof with primary seals only (FR-PO), installation of internal
floating roofs with primary and secondary seals (FR-SS), and a refrigerated
condenser system.
     The cost effectiveness of these controls ranged from $80,500/Mg of VOC
using the condenser to $l,080,000/Mg of VOC using the FR-PO control  option.
Implementation of controls for these four tanks would reduce CC1. emissions
by 0.6 Mg/yr.

11.5  SUMMARY OF COST-EFFECTIVENESS
     Table 11-3 summarizes the estimated CC1, emission reductions as a
function of cost effectiveness.  A 53 percent (76.2 Mg/yr)  reduction in CC1.
                                     11-7
-------
TABLE 11-3.  ESTIMATED CC1, EMISSION REDUCTIONS AS A
             FUNCTION OF COST EFFECTIVENESS

Cost Effectiveness
Range ($/Mg VOC)
Credit
0 - 500
500 - 1,000
1,000 - 2,000
2,000 - 5,000
>5,000
TOTAL
Nationwide
Process
-
-
-
-
2.5
10.1
12.6
CC1, Emission Reduction
Fugitive Storage
-
27.5
35.5 -
-
-
0.6
63.0 0.6
(Mg/Yr)
Total
-
27.5
35.5
-
2.5
10.7
76.2
                         11-8
-------
emissions would result if all uncontrolled emission sources at these Dow's
miscellaneous production facilities are controlled.  A 44 percent emission
reduction (63.0 Mg/yr) can be achieved, for less than $l,000/Mg CC14.
                                     11-9
-------
11.6  REFERENCES

1.   Letter and attachments from Arnold, S. L., Dow Chemical U.S.A. to
     Farmer, J. R.5 EPA:ESED.  March 1985.  Response to Section 114 Letter.

2.   Letter and attachments from Arnold, S. L., Dow Chemical U.S.A. to
     Farmer, J. R., EPA:ESED.  February 26, 1985.  Response to Section 114
     Letter.
                                    11-10
-------
                      12.0  OTHER SOURCES OF EMISSIONS

     Three additional sources of carbon tetrachloride emissions are publicly
owned treatment works, bulk terminals, and distribution facilities.  The
available emissions information on each of these is presented in the
following sections.

12.1  PUBLICLY OWNED TREATMENT WORKS

     EPA studies have estimated emissions of carbon tetrachloride (CC1.)
                                            I                         T1
from publicly owned treatment works (POTWs).   The source of these emissions
is considered to be industrial discharges of waste streams containing CC1,.
The studies have estimated that up to 220 Mg of CCl, is emitted annually
from a set of 1,600 POTWs known to handle industrial discharges.  Recent
ambient air monitoring around the Philadelphia POTW indicates that these
estimates may overstate CC1. emissions by up to a factor of 10.

12.2  BULK TERMINALS
         »                          "                                       '
     Bulk terminals operations are a source of carbon tetrachloride storage
and handling emissions.  A recent study on CCK emissions identified two
bulk terminal facilities with reported emissions of 1 Mg/yr from a 1980
                         2
Texas emission inventory. '  One tank at GATX Terminal Corp. and one loading
operation at PAK Tank Gulf Coast Inc.  were each cited as having 1 Mg/yr CC1,
emissions.
     Tanks used to store chlorinated solvents in bulk terminals range in
size from about 40,000 gallons to 200,000 gallons.   Turnover frequency
ranges from 1 to 6 turnovers per year and average about 2.5 per year for
chemical storage.   Bulk storage tanks are often switched from one chemical
to another over the period of one year depending on the length of contracts.
                                   12-1
-------
12.3  DISTRIBUTION FACILITIES

     Distribution facilities are also a potential source of CC1, storage and
handling emissions.  About 731 Mg of CC1, was sold through distributors in
1983.  The distributor typically buys CC1, in tank truck quantities and
packages it in 55 gallon drums or smaller containers.  This operation may
require storage prior to drumming which may result in storage emissions.
Emissions also result from vapor displacement in the filling of drums and
other containers.  Based on the total quantity handled by distributors and
AP-42 methods for estimating loading emissions, total emissions from all
distribution facilities are estimated to be less than 9 Mg/yr.
     Several large distributors were contacted to identify those handling
CC1«.  Only one CC1, distributor, McKesson Chemical Company, was identified.
McKesson receives a tank car of CC1. once or twice a year that is drummed
                                                                 4
directly from the tank car.  There are no storage tanks for CC1,.
                                   12-2
-------
12.4 REFERENCES

1.   Memorandum and attachments from Lahre, T., EPA:AMTB, to
     Southerland, J. H., EPA:AMTB.  December 5, 1983.  Initial look at
     available emissions data on POTWs.

2.   Smith, M.G. (GCA Corporation.)  Preliminary Study of Sources of Carbon
     Tetrachloride.  (Prepared for U.S. Environmental Protection Agency.)
     Research Triangle Park, North Carolina.  EPA Contract No. 68-02-3510.
     June 1983.  p. 10-7.

3.   Telecon.  Mesavage, C., International Liquid Terminals Association,
     with Howie, R. H., Radian Corporation.  February 26, 1985.
     Conversation about storage of chlorinated solvents.

4.   Telecon.  Eisner, D.,, McKesson Chemical Company., with Howie, R. H.,
     Radian Corporation.  February 7, 1985.  Conversation about storage of
     chlorinated solvents.                               •
                                    12-3
-------
-------
                APPENDIX A



PHYSICAL PROPERTIES OF CARBON TETRACHLORIDE
                   A-l
-------
        TABLE A-l.  PHYSICAL PROPERTIES OF CARBON TETRACHLORIDE,  CC14
     Property
 Value
Synonyms:  Tetrachloromethane, methane tetrachloride,  perch!oromethane,
           benzinoform
CAS Registry No.
Molecular weight
Melting point, °C
Boiling point, °C
Specific gravity
     20/4°C
Autoignition temperature, °C
Flash point, °C
Vapor density, air = 1
Critical temperature, °C
Critical pressure, MPa
Thermal conductivity, mW/(m«K)
     Liquid, 20°C
     Vapor, bp
Average coefficient of volume
  expansion, 0 - 40°C
Heat of combustion, liquid, at
  constant volume, 18.7°C, kJ/mol
Viscosity, 20°C, mPa s
56-23-5
153.82
-22.92
76.72

1.59472
>1,000
None
5.32
283.2
4.6

118
7.29

0.00124

365
0.965
                                    A-2
-------
                           TABLE A-l.   (Continued)

Property
Vapor pressure, kPa
C°C
20°C
40°C
60°C
150°C
200°C
Solubility of CC1A in water, 25°C
Value

4.410
11.94
28.12
58.53
607.3
1,458
0.08
  g/100 g H20

Solubility of water in CC1., 25°C,
  g/100 g CC14            4

Liquid specific gravity
0.013


1.61
                                    A-3
-------
-------
               APPENDIX B

METHODS USED FOR ESTIMATING STORAGE TANK
      AND EQUIPMENT LEAK EMISSIONS
                  B-l
-------
                                 APPENDIX B
   METHODS USED FOR ESTIMATING STORAGE TANKS AND EQUIPMENT LEAK EMISSIONS
B.I  EMISSION FACTORS FOR FIXED-ROOF STORAGE TANKS
B.I.I  Emission Equations
     The major types of emissions from fixed-roof storage tanks are breathing
and working losses.  Emission equations for breathing and working losses from
storage tanks were developed in EPA Publication No. AP-42.  The equations
used in estimating emissions rates for fixed-roof tanks storing VOL are:
      B
                     W
LD = 1.02 x 10"5 M
 D                V
                                       0.68 D1.73H0.51j0.5p
           W
where,
                    \14.7-P.
     1109 x 10"8 MvPVNKnKc
LT = total loss (Mg/yr)
Lg = breathing loss (Mg/yr)
LW = working loss (Mg/yr)
B.I.2  Parameter Values and Assumptions
     The following CC1. physical property values, plant-specific
information, and engineering assumptions were used to estimate the emission
losses:
          M  = molecular weight of product vapor (Ib/lb mole);
               for CC14, Mv = 153.82
          P  = true vapor pressure of product, 1.80 psia
          D  = tank diameter (ft); dependent upon plant-specific information.
          C  =  tank diameter factor (dimensionless):
               for diameter >, 30 feet, C = 1
               for diameter < 30 feet, C = 0.0771 D - 0.0013(D)2 - 0.1334
          V  = tank capacity (gal); dependent upon plant-specific information
                                    B-2
-------
          N  = number of turnovers per year (dimensionless); dependent upon
               plant-specific information
          T  = average diurnal temperature change in °F; 20°F was assumed
               for the storage tanks at these facilities
          F  = paint factor (dimensionless); the storage tanks were assumed
               to be in good condition and painted white; therefore, F  = 1
               (see Table B-l)
          H  = average vapor space height (ft): used tank-specific values or
               an assumed value of one-half the tank height (H/2)
          K  = product factor (dimensionless) = 1.0 for VOL
           C*                                                  -
          Kn = turnover factor (dimensionTess); dependent upon plant-specific
               information
               for turnovers > 36, K  = 180 + N
                                    n     6N
               for turnovers 4 36, K  = 1

B.I.3  Sample Calculation                                               .
     The following sample calculation is provided to demonstrate the
evaluation of emissions from a typical fixed-roof storage tank containing
CC1..  For the general equations,
where,
          L  =•
 Lw-
 My  =
  P  =
  D  =
  r*  —
  V  =
  N  =
  T  =
V
  H  =
          K  =
          c
1.02 x 10"3 M,
             V
        ,-8
                                  n  1.73',, 0.51 T 0.5
                                  U      n       I
                                14.7-Py
1.09 x 10 ° Mv PVNKnKc
153.82
1.80 psia
37 ft
1
233,000 gallons
10
20°F
1.0
14 ft
1.0
                                   B-3
-------
               TABLE B-l.  PAINT FACTORS FOR FIXED-ROOF TANKS
                                                             1
                            Tank Color
                                                    Paint factors
                     Paint condition
       Roof
     Shell
Good
Poor
White
Aluminum (specular)
White
Aluminum (specular)
White
Aluminum (diffuse)
White
Light gray
Medium gray
     White            1.00     1.15
     White            1.04     1.18
Aluminum (specular)   1.16     1.24
Aluminum (specular)   1.20     1.29
Aluminum (diffuse)    1.30     1.38
Aluminum (diffuse)    1.39     1.46
     Gray             1.30     1.38
   Light gray         1.33     1.44
  Medium gray         1.40     1.58
                                    5-4
-------
The emissions from this storage tank are:
     LD = 1.02 x 10"5 (153.82)
                     1.8  I0'68 (37)1-73(14)0V51(20)0'5(1)(1)(1)
                              J4.7-1.8J
          3.648 Mg/yr
          1,09 x 10"8 (153.82)(1.8)(233,000)(10)(1)(1)
          7.032 Mg/yr
          3.648 Mg/yr +7.032 Mg/yr = 10.68 Mg/yr
B.2  EMISSION FACTORS FOR INTERNAL FLOATING ROOF STORAGE TANKS
B.2.1  Emission Equations
     Emissions from internal floating roof tanks can be estimated from the
following equations:   (Note that these equations apply-only.to freely
vented internal floating roof tanks.)
= L.
                    L
               -w   -r   L-f   ud
where,    Lj = the total loss (Mg/yr)
          LW = the working loss (Mg/yr) = (0.943) Q C WL       NC FC
                                               D         1 +     D    /2205
where,    D  = tank diameter (ft)
          N  = number of columns (dimensionless); (see Table B-2)
          F  = effective column diameter (ft); 1.0 assumed
          Lr = the rim seal loss (Mg/yr)  = (KpD) P* MV 'Kc/2205
          Lf = the fitting loss (Mg/yr)   = (Ff)  P* My Kc/2205
          Ld = the deck seam loss (Mg/yr) = (Frf Kd D2) P* My Kc/2205

B.2.2  Parameter Values and Assumptions
     The assumptions and values used to calculate emissions from internal
floating roof tanks are:

           Q = product average throughput (bbl/yr); tank capacity
               (bbl/turnover) x turnovers/yr; dependent upon plant-specific
               information
                                    B-5
-------
 C = product withdrawal  shell  clingage factor (bbl/10  ft );  use
     0.0015 bbl/103ft2 for VOL in a welded steel  tank with light
     rust (0.0075 for dense rust)
-------
TABLE B-2.  TYPICAL NUMBER OF COLUMNS AS A FUNCTION OF TANK DIAMETERS

Tank
Greater
Than .
0
85
100
120
135
150
170
190
220
235
270
275
290
330
360
Diameter Range
D (Ft)
Less Than
And Or Equal To
85
100
120
135
150
170
190
220
235
270
275
290
330
360
400
Typical Number
Columns, N
U
1
6
7
8
9
16
19
22
31
37
43
49
61
71
81
                                B-7
-------
          where,    Nf = number of fittings of a particular type
                      i      (dimensionless).  N.p is determined for the
                         specific tank or estimated from Tables B-2 and B-3.
                         The values used for these emissions estimates are
                         designated by * in Table B-3.
                    Kp = deck fitting loss factor for a particular type
                      i  fitting (Ib mole/yr).  Kf is determined for each
                         fitting type from Table B-3.  The values used for
                         these emissions estimates are designated by *.
                    n  = number of different types of fittings
                         (dimensionless)
                    Fd = the deck seam length factor (ft/ft2)
                       = 0.15, for a deck constructed from continuous metal
                         sheets with a 7 ft spacing between seams
                       = 0.33, for a deck constructed from rectangular panels
                         5 ft by 7.5 ft
                       = 0.20, an approximate value for use when no
                         construction details are known
                    Kd = the deck seam loss factor (Ib mole/ft yr)
                       = 0.34 for nonwelded roofs
                       = 0 for welded decks
B.2.3  Sample Calculation
     The following sample calculation is provided to demonstrate the
evaluation of emissions from a typical storage tank with an internal floating
roof containing CCK.  For the general equations,

          LT = Lw + Lr + Lf + Ld
          Lw = (0.943)QCHL   l +
                    D       L
          Lr = (KrD) P* Mv Kc/2205
                                     B-8
-------
        Table B-3  SUMMARY OF DECK FITTING LOSS FACTORS (Kf)  AND

                    TYPICAL NUMBER OF FITTINGS (Nf)
        Deck fitting type
Deck fitting loss
    factor,  Kf
    (Ibmole/yr)
Typical  number
 of fittings,
     (Nf)
1. Access Hatch
   a. Bolted cover, gasketed
   b. Unbolted cover, gasketed
   c. Unbolted cover, ungasketed

2. Automatic Gauge Float Well
   a. Bolted cover, gasketed
   b. Unbolted cover, gasketed
   c. Unbolted cover, ungasketed

3. Column Well
   a. Built-up column-sliding  cover,
        gasketed
   b. Built-up column-sliding  cover,
        ungasketed
   c. Pipe column-flexible fabric
        sleeve seal
   d. Pipe column-sliding cover,
        gasketed
   e. Pipe column-sliding cover,
        ungasketed

4. Ladder Well
   a. Sliding cover, gasketed
   b. Sliding cover, ungasketed

5. Roof Leg or Hanger Well
   a. Adjustable
   b. Fixed

6. Sample Pipe or Well
   a. Slotted pipe-sliding cover,
        gasketed
   b. Slotted pipe-sliding cover,
        ungasketed
   c. Sample well-slit fabric  seal,
        10% open area

7. Stub Drain*,'1-inch diameter

8. Vacuum Breaker
   a. Weighted mechanical actuation,
        gasketed
   b. Weighted mechanical actuation,
        ungasketed
        1.6
       11
       25


        5.1
       15
       28
       33

       47

       10

       19

       32


       56
       76


        7.9
        0



       44

       57

       12

        1.2



        0.7

        0.9
                     (see  Table B-2)
    is
    ^125J

       1
 a Not used on welded, contact internal  floating decks.
 k D = tank diameter (ft).
   Values used for  estimating  internal floating  roof storage
   tank  emissions
                                   B-9
-------
          Lf = (Ff) P* Mv Kc/2205
Ld =
                        P* Mv Kc/2205
where,    My = 153.82 Ib/lb mole
          P* = 0.0326





          Q  = 500,000 bbl/yr





          C  = 0.0015





          WL = 13.4 Ib/gal





          D  = 30 ft
          Nc=l
          FC = i.o
             = 6.7 Ib mole/ft yr
          Kc = 1.0
             = 242 Ib mole yr
          Fd = 0.20
The emissions from this storage tank are:
                                   B-10
-------
L,, =|(0.943)(500,000)(0.0015)(13.4)
 w                3Q

   =0.148 Mg/yr
                                                         30
                                                              )b2205
             = .((6.7)'(30))(0.0326)(153.82)(1.0)/2205
             = 0.457 Mg/yr
          Lf = (242)(0.0326)(153.82)(1.0)/2205.
             = 0.550 Mg/yr
             = ((0.20)(0.34)(30r)(0.0326)(153.82)(1.0)/2205
             = 0.139 Mg/yr
          LT = 0.148 Mg/yr + 0.457 Mg/yr + 0.550 Mg/yr + 0.139 Mg/yr

          LT = 1.3 Mg/yr

B.3  EQUIPMENT LEAK EMISSIONS - SAMPLE CALCULATIONS

     Emissions were estimated from the number of equipment leak sources
(provided by the plant), the percentage of CC1, in the stream (provided by
the plant), and the emission factors for each type of equipment (from the
           2
SOCMI AID).   The following sample calculations illustrate the procedure.
Emissions
Source
Pump seals



•
Number
3
6
2
12


X
X
X
X
% CC1.
Service
7.5
50.5
87.5
100.0
kg/hr/source Total Emissions
Emission Factor
X
X
X
X
0.0494
0.0494
0.0494
0.0494
kg/hr
0.011
0.150
0.086
0.593
                                    B-ll
-------
Emissions
  Source

Compressors

Flanges
Number
Valves (gas)
Valves (liquid)
Pressure Relief
 Devices
Sampling
 Connections
4
112
30
235
66
456
X
X
X
X
X
X
5.0
7.5
18.0
50.5
87.5
100.0
   4
   8
   3
   4
  11

   5
   3
   8
   9

   2
   4
   6

   5
   3
   1
   3
x
x
x
x
X
X
X
X
X
  5.0
  7.5
 50.5
 87.5
100.0
Open Ended Lines    1    x  100.0
Annual Emissions =
    % CC1.       kg/hr/source  ,
   Service      Emission Factor0

    87.5     x      0.228
x      0.00083
x      0.00083
x      0.00083
x      0.00083
x      0.00083
x      0.00083

x      0.0056
x      0.0056
x      0.0056
x      0.0056
x      0.0056

x      0.0071
x      0.0071
x      0.0071
x      0.0071

x      0.1042
x      0.1042
x      0.1042

x      0.0150
x      0.0150
x      0.0150
x      0.0150

x      0.0017

       TOTAL

      <   Mg
x    5.0
x    7.5
x   87.5
x  100.0

x    5.0
x   50.5
x  100.0
  5.0
 50.5
 87.5
100.0
  2.72 kg/hr x 8760 hrs
                    year

  23.87 Mg
                                             1,000 kg
Total Emissions
	kg/hr

       0.200

       0.0002
       0.007
       0.004
       0.099
       0.048
       0.378

       0.001
       0.003
       0,008
       0.020
       0.062

       0.002
       0.002
       0.050
       0.064

       0.01
       0.21
       0.63

       0.004
       0.023
       0.013
       0.045

       0.002
                                                                    2.7252
 U. S. Environmental Protection Agency.  Fugitive Emission Sources of Organic
 Compounds - Additional Information on Emissions, Emission Reductions, and
 Costs.  Research Triangle Park, NC.  Publication No. EPA-450/3-82-010.
 April 1982.
                                    B-12
-------
B.4  REFERENCES

1.   U. S. Environmental Protection Agency.  VOC Emissions from Volatile
     Organic Liquid Storage Tanks - Background Information for Proposed
     Standards.  Research Triangle Park, North Carolina.  Publication
     No. EPA-450/3-81-003a.  July 1984.  252 pp.

2.   U.S. Environmental Protection Agency.  Fugitive Emission Sources of
     Organic Compounds - Additional Information on Emissions, Emission
     Reductions, and Costs.  Research Triangle Park, N.C.  Publication No,
     EPA-450/3-82-010.  April 1982.
                                     B-13
-------
-------
                 APPENDIX C
METHODS FOR ESTIMATING EMISSION CONTROL COSTS
                    C-l
-------
                                 APPENDIX C
                METHODS FOR ESTIMATING EMISSION CONTROL COSTS

C.I  PROCESS VENT EMISSIONS CONTROL COST ESTIMATION

     The cost estimates for process vent emission control are based on the
use of thermal incineration.  The procedure for estimating these costs uses
the methods presented in the Air Oxidation Processes Control Techniques
Guidelines (CTG) document for estimating the cost of controlling VOC
emissions through incineration.   A detailed discussion of the incinerator
costing methods may be found in Chapter 5 of the Air Oxidation CTG document.
     The total installed capital cost of control is determined using the
following equation:

Total Installed Capital Cost (10 $) = (# of incinerators) x (deescalation
factor) x (Cl - (Waste Heat Boiler Comsction Factor) + (C2 x (Flowrate per
incinerator * Design Vent Size Factor)  ) + (pipe rack cost) + (additional
ductwork cost)
where:    Cl, C2, and C3 are coefficients from Table C-l that depend upon
          heating value and halogenation status of a given vent stream;
          waste heat boiler correction factor of 40 (10 $) is used for vent
          streams with flowrates below 700 scfm, where no heat recovery in a
          waste heat boiler is assumed; deescalation factor of 0.90
          deescalates costs to 1978 dollars;
          design vent size factor of 0.95 increases vent stream flowrate for
          costing purposes;
          pipe rack cost is calculated using the equation presented in
          Table C-2;
          additional ductwork cost is calculated using the equation
          presented in Table C-3.
     A sample calculation for incinerator costing is shown in Table C-6.
The calculation is based on vent stream parameters obtained from the Stauffer
Chemical Company (Le Moyne, Alabama) Section 114 letter response.  The cost
estimate was initially calculated in 1978 dollars and then was updated to
1984 dollars using the annualized cost escalation factor shown in Table C-7.
                                     C-2
-------
           TABLE  C-l.   TOTAL INSTALLED CAPITAL COST AS A FUNCTION
                          OF VENT STREAM FLOW RATE

Category
Ala
A2a
B
C
D
Ea
Maximum
Flowrate
Rer Unit
(10 scm/min)
0.74
0.74
1.42
1.42
1.25
1.25
Minimum
Net
Heating
Value
(MJ/scm)
0.0
3.5
0.0
0.48
1.9
3.6
Maximum
Net
Heating
Value
(MJ/scm)
3.5
-
0.48
1.9
3.6
-
Fabricated
Equipment
Cost
Escalation
Factor
0.90
0.90
0.90
0.90
0.90
0.90
Cl
803.
786.
259.
297.
236.
236.

11
61
88
99
35
35.
C2
12.
12.
4.
2.
3.
.3.
C3
83
44
91
84
23
23
0
0
0
0
0
0
.88
.88
.88
.88
.88
.88
 Halogenated  vent stream.

^Dilution  flow  rate  is  used  in  capital  cost  equation.
 Dilution  flow  rate  =  (design flow rate)  x  (original  heating  value)-*
 (3.65  MJ/scm).                                           .
                                     C-3
-------
                     TABLE C-2.  ADDITIONAL DUCT COST
                                                     1,2
Additional duct cost (10  $) = (length) x (cost per unit length) x
(installation factor) x (duct deescalation factor) x (retrofit correction
 factor) v 1000
Cost per unit length = 1.37L - 1.76
     where L = duct diameter in inches
Diameter = [
                                      x 1
   Flow rate (ft /min)
Linear velocity (ft/min) A IT
Flow rate (ft3/min)     4    -, 0.5
    2000 ft/min     x 3.1412 J
           if linear velocity is assumed to be 2000 ft/min

Additional duct length = 150 ft + (additional vents x 100 ft/vent)
Installation factor = 1.087
Escalation factor (from 1977 to 1978) = 1.088
Retrofit correction factor =1.0
                                    C-4
-------
                        TABLE C-3.  PIPE RACK COST
                                                  1,2
Pipe rack cost (10  $) = (pipe rack length) x (cost per unit length) x
                         (installation factor) x (pipe rack deescalation
                         factor) x (retrofit correction factor)  * 1000
Pipe rack length = 250 ft + (# additional  vents x 100 ft/vent)
Cost per unit length = $32.045/ft
Installation factor = 1.087
Deescalation factor (1982 to 1978)  = 0.746
Retrofit correction factor =1.0
                                    C-5
-------
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C-7
-------
        TABLE C-6.  SAMPLE CALCULATION FOR INCINERATOR COSTING
1. Capital Cost (1(T $)
                                      (# incinerators) x (incinerator capital
                                      cost per unit) x (escalation factor)
                                      (# incinerators) x (803.11 - 40.0 +
                                      12.83 x (flow/0.95)0'88) x escalation
                                      factor
                                      1 x (803.11 - 40.0 + 12.83 (14.2)0'88)
                                      x 0.9
                                      806.1
2. Additional Duct Cost (10* $)
                                      (length) x (cost per unit length) x
                                      (escalation factor) x (installation
                                      factor) = 350 ft. x (((500) ft3/min)
                                      x 4 x 2000 x 3.1412))0'5 x 12 x
                                      1.37 - 1.76) x 1.088 x 1.087 * 1000
                                      3.111
3. Pipe Rack Cost
                       $)
= (length) x (cost per unit length) x
  (installation factor) x (pipe rack
  deescalation factor) x (retrofit
  correction factor) * 1000 = 250 ft. +
  (# additional vents x 100 ft./vent) x
  $32.045/ft. x 1.087 x 0.746 x * 1000
= 11.693
4. Total Installed Total Capital    = Capital cost (10  $) + extra duct
                                      cost (103 $) + pipe rack cost (103 $)
                                    = 806.1 + 3.657 + 19.00
                                    = 820.9
                              (continued)
                                    C-8
-------
                         TABLE C-6.  (Continued)
 5. Natural Gas Use (MJ/yr)
(minutes per year) x (supplemental
gas required per minute)
0.5256 106 min/yr x GO + flow x
(G: + G2 x HT)
0.5256 106 min/yr x (3.96) x (4.53
0.985 x 1.49) MJ/min)
6.37 MJ/yr
 6.  Natural  Gas Cost (10J $)
Natural gas price ($/10  J) x
natural gas use (MJ/yr)
$4.16/GJ x 6.37 MJ
26.2
 7.  Operating Labor Cost (10  $)
Wage ($/hr) x labor factor (hr/yr)
1000
$8.50/hr x 2400 hrs
20.4
 8.  Supervisory Labor Cost (103 $)    = Operating labor cost (103/yr)  x 0.15
                                     = 20.4 (103 $/yr) x 0.15
                                     = 3.06

 9.  Maintenance Labor Cost (103 $)    = Installed capital cost (103  $)  x 0.03
                                     = 820.9 (103)  $  x 0.03
                                     = 24.63

10.  Overhead Labor Cost (103 $)      = Operating labor cost (103  $) +
                                                                 3
                                       supervisory  labor cost (10  $)  +
                                                                 o
                                       maintenance  labor cost (10  $)  x 0.80
                                     = (20.40 + 3.06  + 24.63) x 0.80
                                     = 38.47
                               ("continued)
                                    C-9
-------
                         TABLE C-6.  (Continued)
11.  Total  Labor Cost (1CT $)
= Operating labor cost (10  $) +
  supervisory labor cost (10  $)
  maintenance labor cost (10  $)
                         o
  overhead labor cost (10  $)
= 20.4 + 3.06 + 24.63 + 38.47
= 86.56
12.  Electricity Cost (l(r $)
= (electricity price) x (pressure drop)
  x (flow rate) x (flue gasroffgas
  ratio) x (fan equation conversion
  factor) x (# of hours per year) * fan
  efficiency * 1000
= 0.0279 ($/KWhr) x 22 in. x 3.96 son/
  min x 2.9 x 0.004136 (KW/scmin.) *
  0.6 * 1000 ($/103 $)
= 0.426
13. Quench Water Cost (10J $)
= (quench water price) x (flow rate) x
  (flue gasroffgas ratio) x (water
  required per unit flow) x (minutes
  per year) * 1000
= 0.22 ($ 103 gal) x 3.96 (scm/min) x
  2.9 x 1.68 x 10"5 (103 gal/scm) x
  0.5256 (106 min/yr) v 1000 ($/103 $)
= 0.0223
                                 (continued)
                                    C-10
-------
                         TABLE C-6.   (Continued)
14.  Scrubbing Water Cost (1CT $)
15.  Neutralization Cost (103 $)
  (scrub water price) x (flow rate) x
  (flue gas:offgas ratio)  x (chlorine
  content of flue gas) x (water
  required per unit chlorine) x (# of
  hours per year)
  0.22 ($103 gal) x 3.96 (son/mln) x
  35.314 scf/scm x 2.9 x 0.0487
  (Ib/hr chlorine)/(scf/min flue gas) x
  0.0192 (103 gal/lb chlorine) x 8760
  (hr/yr) * 1000
  0.73

  (caustic cost) x (flow rate) x (flue
  gas:offgas ratio) x (chlorine
  content of flue gas) x (caustic
  requirement per unit chlorine) x
  (# of hours per year) *  1000
  0.0436 ($/lb NaOH) x 3.96 (scm/min) x
  35.314 scf/scm x 2.9 x 0.0487 (Ib/hr
  chlorine)/(scf/min flue  gas) x 1.14
  (Ib NaOH/lb chlorine) x  8760 (hr/yr) i
  1000 $/103 $
  8.6
16. Heat Recovery Credit
= 0 (for all streams <700 scfm)
                                 (continued)
                                    C-ll
-------
                         TABLE C-6.  (Continued)
17. Taxes, Insurance, and
    Maintenance Cost (103 $)
  (installed capital cost) x (taxes,
  insurance, and administrative
  charges factor + maintenance labor
  factor)
  820.9 (103 $) x (0.04 + 0.03)
  57.46
18. Annual Operating Cost (10  $)
19. Annualized Cost (103 $)
  (TI&M cost) + (gas cost) + total
  labor cost) + (electricity cost) +
  (quench cost) + (scrubbing cost) +
  (scrubbing cost) + (caustic cost)
  57.46 + 26.20 + 86.56 + 0.426 +
  0.0223 + 0.73 + 8.6
  180.".

  (operating cost) + (capital recovery
  factor x total installed capital
  cost)
  180.0 + (.163 x 820.9)
  313.8
20. Annual Emissions (Mg/yr)
= (hourly emissions) x 365 (days/yr) x
  24 (hrs/day) x (Mg/103 kg)
= 15.86 kg/hr x 365 (days/yr) x
  24 (hrs/day) x 1 (Mg/103 kg)
= 138.9
21. Annual Emission Reduction
    (Mg/yr)
= (annual emissions) x 0.98
= 138.9 x 0.98 (CC14) = 136.1 (CC14)
= 349.6 (VOC)
                                 (continued)
                                     C-12
-------
                         TABLE C-6.  (Continued)
22. Cost Effectiveness ($/Mg)
23. Updated Cost-Effectiveness
    Values ($/Mg)
(annual cost) * (annual emission
reduction)
313.8 (103 $•) * 136.1 Mg (CC14)
2305/Mg (CC14)
313.8 (103 $) v 349.6 Mg (VOC)
898/Mg

2305 ($/Mg) x 1.486 = $3420/Mg (CC14)
898 ($/Mg) x 1.486 = $1330/Mg (VOC)
                                    C-13
-------
TABLE C-7.  COST CONVERSION FACTORS

Original
Cost Component
Incinerator
Pipe Rack
Duct Work
Annual ized Costs
Conversion
Year
1979
1982
1977
1978
Factor
0.900
0.745
1.088
1.486
                C-14
-------
C.2  SAMPLE COST CALCULATIONS FOR CONTROL OF PROCESS EMISSIONS USING
     CARBON ADSORBERS

     Data and calculations presented; are for determining the capital costs,
annual costs, and cost effectiveness of carbon adsorption.  The total
installed capital cost is a function of the amount of carbon needed to
adsorb carbon tetrachloride (CC1»).  The adsorption isotherms for CC1, shows
that 0.1 Ibs of CCl^ is absorbed per pound of carbon.  The carbon absorber
is estimated to be 95% efficient.
     Diamond Shamrock's Delaware City, DE chlorine production facility will
be used as an example to calculate the cost effectiveness of CC1. removal  by
carbon adsorption.  (CC1, emission rate = 22.6 Ib/hr, max vent rate
= 68.5 scfm, and capacity utilization rate = 0.80)

AMOUNT OF CARBON NEEDED =
           22.6 Ib/Hr X 1 Hr
           0.1 Ib/lb Carbon
= 226 Ibs
     As the carbon reaches capacity, it will have to be regenerated.
Therefore, an additional carbon bed is needed for use when one bed is being
regenerated.

     TOTAL CARBON REQUIRED = 2 x 226 Ibs = 452 Ibs.

C.2.1  Capital Cost
     Cost curves developed by Gard, Inc. for the EPA were used to estimate
capital cost.   The cost of $22,500 (Dec. 1977) includes the adsorber,
carbon, blower or fan, controls and steam generator.  As there will  be
chlorine present in the gas stream, precautions for corrosion must be taken.
Therefore, a stainless steel carbon adsorber is recommended.  A cost
                                   2
increase of 2.3 times is estimated.

          $22,500 x 2.3 = $51,750
                                    C-15
-------
     Also, taxes, shipping, and installation costs must be included.  A cost
increase of 1.75 times is estimated.
          $51,750 x 1.75 = $90,562
     Finally, the capital costs were updated to November 1984 using Chemical
Engineering Cost Index for Fabricated Equipment.
              562 x  335.4 (Nov. 1984)  _ Sl-4 3Qf}
             ,56^ x  226.2 (Dec. 1977)  ~ 5134,300
     The fabricated equipment cost factor is used to simplify the updating
of the capital and annual ized costs.

C.2.2  Annual Cost
     The annual ized cost is based on 5800 hours of operation..  The
calculations for operating labor, maintenance, carbon replacement, steam for
regeneration, electr.icity, and cooling water are presented below.  The
operating labor ($15.00/hr) is for control device operation and is only
360 man-hours per year.  The maintenance factor is 0.05 of the total  capital
cost.  Indirect capital charges such as interest (10 percent), taxes,
insurance, and administrative charges are all grouped together under  capital
charges at 22 percent of the total installed capital cost.
  -  Operating labor ($15.00/hr):
          ($15.00/hr)(360 manhours) = $5,400
  -  Maintenance labor plus materials factor (0.05 of total  installed
     capital cost):
          0.05 x $134,300 = $6,715
  -  Carbon replacement (estimated to be every 5 years):
           452 Ibs
            5 yrs
                      x $1.75/lb = $158
                                    C-16
-------
  -  Steam for regenerating carbon dnnn ihc):
                Ibs
79 fi
22.6
          '1000 Ibs
x 5800 hrs x 4
                                          y
                                          X
                                              $5.04
                                           1QOO Ib steam
                                                                         ,,-
                                                                        »643
  -  Electricity ($0.0506/kwh):
68.5 cfm x.
            5 hp
                                 0.746kwh
                   1000 cfm A      hph
  -  Cooling Water ($0.22/1000 gallons):
                                                      x $0f0506/kwh = $75
   gal
            90.4 lb steam
                                            ,
                                            nr x
                                                  $0.22
                _
       100 Ib steam         hr                   1000 gal
  -  Capital Charges  (22 percent of installed capital cost):
          0.22 x 134,300 = $29,546
     The total operating costs are $44,550/yr.  There is a recovery credit
of $330/Mg of CC1 . which is recovered for reuse.
     Annual emissions reduction with carbon adsorber:
          89.811 x 0.95 = 85.3 Mg/yr
     Recovery Credit = $330/Mg x 85.3 Mg/yr = $28,150
     Therefore, the total annual ized cost equals
          $44,550 - $28,150 = $16,400
     Cost effectiveness = $16,400 * 85.3 Mg/yr
                        = $200/Mg
C.3  COST CALCULATIONS FOR INSTALLING INTERNAL FLOATING ROOFS IN
     FIXED ROOF TANKS

     The following equations were used to calculate the capital  and
annual ized cost for the installation of a mild steel  welded contact internal
floating roof to a fixed roof storge tank.  This internal floating roof
                                            P
utilizes both primary (constructed of Teflon ) and secondary (constructed of
VitonR) seals.
                                    C-17
-------
C.3.1  Capital Cost (4th Quarter 1982 Dollars)
     1.  Degassing Cost

                    fl ^1 "%9
     Cost = $130.8 v       or $1,000, whichever is greater where V = tank
     volume in cubic meters.
     2.  Estimated Installation Cost
                                    4
         a.  Basic cost of roof and primary seal:
             Cost = (1.91 + 2.54 x D) x $1,000 + ($204 x D)
             D = tank diameter in meters
                                                                    R
     (The $204 x D cost reflects the additional cost of using Teflon  coated
     fiberglass versus the standard polyurethane coating)
         b.  Additional cost of adding secondary seal:
                                                      4
             Cost = $580 x D
                                              R
     (The $580 x D cost reflects using a Viton  coating material for the
     secondary seal)

     3.  Door Sheet Opening Cost

         Cost = $1,300

     Total capital cost (primary seal) = degassing cost + estimated
installed cost (2a) + door sheet opening cost.

     Total capital cost (primary + secondary seals) = degassing costs +
estimated installed cost (2a,b) + door sheet opening cost.
                                     C-18
-------
C.3.2  Annual Cost (4th Quarter 1982 Dollars)

     1.  Tax, insurance, and administration — 4% of capital cost (based on
         10 percent interest rate and 10 year equipment life)       •

     2.  Maintenance — 5% of capital cost

     3.  Inspection — 1% of capital cost

     4.  Capital recovery factor — 16.275% of capital cost

     Total  annual cost = [26.275% of capital cost]

C.3.3  CCl^/VOC Reduction

     1.   Emissions calculated for fixed roof tanks using AP-42 formulas..

     2.   Emissions calculated for internal floating roof tanks using AP-42
          formulas.
          a.   Liquid mounted primary seal only
          b.   Liquid primary and secondary seal

     3.   Emissions from fixed roof tank - emissions from internal  floating
          roof tank = VOC emission reduction

          CC1, emission reduction = VOC emission  reduction x percentage of
          CC1, in stored material

C.3.4  Recovery Credits (4th Quarter 1984 Dollars)

     Credits = ($330/Mg)(Mg VOC emissions reduced)
                                    C-19
-------
C.3.5  Net Annual Cost


     Before annual cost can be calculated, all costing data is converted to

     1984 dollars using Chemical Engineering Economic Indicators)


     Cost = annual cost (4th quarter 1984 dollars) - VOC recovery credits
               (4th Quarter 1984 dollars)


C.3.6  Cost Effectiveness


     CC1, cost effectiveness = net annual cost/CC!4 emission reduction (Mg)


     VOC cost effectiveness = net annual cost/VOC emission reduction (Mg)


C.4  COST CALCULATIONS FOR INSTALLATION OF REFRIGERATED CONDENSERS

     TO CONTROL STORAGE EMISSIONS


     This section presents methods used to estimate costs for controlling
storage emission by condensation.  Based on Section 114 letter response,

85 percent control efficiency was assumed for a refrigerated condenser.
Costs were estimated using methods in Capital and Operating Costs of

Selected Air Pollution Control Systems.  Based on conversation with one CFC

producer, one CC1, producer and Section 114 response the following

assumptions were made.
   Source of
Stored Material

  Production
  Ship
  Barge
  Rail Car
  Tank Truck
 Filling
Rate (gpm)

   200
  1800
   800
   200
   200
Gas Flow Rate
to condenser
   (scfm)

      27
     240
     110
      27
      27
                                    C-20
-------
C.4.1  Capital Cost  (4th Quarter 1984 Dollars)
     Capital Cost (1977$). = [0.27 x Flow  (scfm) + 34] x  1000
          Installed Cost = Capital Cost x 1.742
          4th Quarter 84 Installed Cost = Installed Cost x
          CE Index
              December 77  = 210.3
              November 84  = 324.4
C.4.2  Annual Cost
     1.  Taxes, insurance, and administration — 4 percent of capital
     2.  Maintenance — 5 percent of capital
     3.  Inspection -- I percent of capital
     4.  Capital  Recovery Factor — 16.275 percent of capital
          Annualized capital cost = Installed capital  cost x .26275
          Electricity cost = [(0.35) x Flow (scfm) +10] x kw cost
          kw cost = $0.522/kw
C.4.3  CCl^/VOC Emission Reduction
     1.   Calculate fixed roof storage emission using  AP-42 and storage tank
          data
     2.
CC1, emission = FR emissions x % CC1. in stored material
VOC emission  = Total FR emissions
CC1, emission red = CC14 emissions x .85
VOC  emission red = VOC  emissions x .85
C.4.4  Recovery Credit
     Credits = $330/Mg x VOC emission reduction (Mg)
C.4.5  Net Annual  Cost
     Net annual cost = (total annual  cost)  - (recovery credit)
C.4.6  Cost Effectiveness
     CC1, C/E = Net annual  cost * CC1,, emission red
        ^ C/E = Net annual  cost * VOC^emission red
                                     C-21
-------
C.5  SAMPLE CALCULATIONS FOR EQUIPMENT LEAK CONTROL COSTS

     To calculate the cost for the implementation of technologies to control
equipment leak emissions, the specific control techniques, removal
efficiencies and capital/annualized costs per component are given in
Table C-8.

Capital cost per emission source:  (No. of components) x (capital cost per
component)

Total capital cost per plant:  2 [capital cost per emission source] annual
cost per emission source:  (No. of components) x (annual cost per component)

CC1, emission reduction per emission source:  (current CC1. emission) x
(percent reduction)

Total CC1, emission reduction per plant:  E [CCl^ emission reduction per
emission source]

VOC emission reduction per emission source:  (current VOC emission) x
(percent reduction)

Total VOC emission reduction per plant:  z [VOC emission reduction per
emission source]

Recovery credit per emission source:  (VOC emission reduction per plant) x
(4th Quarter 1984 VOC market value ($330/Mg)).

Recovery credit per plant:  (VOC emission reduction per plant) x
(4th Quarter 1984 VOC market value ($330/Mg)).

Net annual cost (CC1*) per, emission source:  (annual cost per emission
source) minus (recovery credits per emission source).
                                    C-22
-------
Net annual cost (CC1.) per plant:  (total annual cost per plant) minus
(total recovery credits per plant).

Net annual cost (VOC) per emission source:  (annual cost per emission
source) minus (recovery credits per emission source).         .   .  '

Net annual cost (VOC) per plant:  (total annual cost per plant) minus (total
recovery credits per plant).

Cost effectiveness for controlling CC1» emissions per emission source:  (net
annual cost (CC1.) per emission source) per (CC1» emission reduction per
emission source).

Cost effectiveness for controlling CC1» emissions per plant:  (net annual
cost (CCl^) per plant) per (CC1- emission reduction per plant).

Cost effectiveness for controlling VOC emissions per emission source:  (net
annual cost (VOC) per emission source) per (emission reduction per emission
source).                                   '

Cost effectiveness for controlling VOC emissions per plant:   (net annual
cost (VOC) per p-lant) per (emission reduction per plant).
                                    C-23
-------
          TABLE C-8.   CONTROL TECHNIQUES AND COST FOR CONTROLLING
                      EQUIPNENT LEAK EMISSION SOURCES3
                        (4th Quarter 1984 Dollars)

Equipment Type
(Emission Source)
1.




2.

3.
4.


5.



6.




7.


Pump seals
- Packed
- Mechanical
- Double
Mechanical
Compressors

Flanges
Valves
- Gas
- Liquid
Pressure Relief
devices
- Gas
- Liquid
Percent g
Control Techniques Reduction

Monthly LDAR
Monthly LDAR
N/A

Vent to combustion
device
None Available

Monthly LDAR
Monthly LDAR


0-Ring
N/A

61
61
N/A

100

N/A

73
59


100
N/A
Capital
Cost
$/Component

0
0
N/A

10,200

N/A

0
0


310
N/A
c
Annual i zed
Cost
$/Component

370
370
N/A

2,580

N/A

20 '
20


80
N/A
Sample Connections
- Gas

- Liquid

Open Ended Lines
- Gas
- Liquid
Closed-purge sampling
systems
Closed-purge sampling
systems

Caps on open ends
Caps on open ends
100

100


100
100
670

670


70
70
170

170


20
20
Updated to 4th quarter 1984 using CE index.
                                   C-24
-------
C.6  REFERENCES                                           .           .

1.   U.S. Environmental Protection Agency.  Control'of Volatile Organic
     Compound Emissions from Air Oxidation Processes in Synthetic Organic
     Chemical Manufacturing Industry.  Research Triangle Park, N.C.
     Publication No. EPA-450/3-84-015.  December 1984.  p. 510.

2.   Memo from Pandullo, R. F. and I. A. McKenzie, Radian Corporation, to
     Air Oxidation Processes and Distillation Operations Project Filtes.
     May 3, 1985.  20p.  Revision to the Incinerator Costing Procedures Used
     for the Proposed Air Oxidation and Distillation NSPS.

3.   Neveril, R. B. (GARD, Inc.).  Capital and Operating Costs of Selected
     Air Pollution Control Systems.  (Prepared for the U.S.  Environmental
     Protection Agency.)  Research Triangle Park, N.C.  Publication No.
     EPA-450/5-80-002.  December 1978.  pp. 5-39 through 5-49 and 5-65
     through 5-71.

4.   Atkinson, R. D. (MRI) et al.  Source Assessment of Ethylene Dichloride
     Emissions.  (Prepared for the U.S. Environmental  Protection Agency.)
     Research Triangle Park, N.C.  EPA Contract No. 68-02-3817.  September
     1984.

5.   U.S. Environmental Protection Agency.  Fugitive Emission Sources of
     Organic Compounds - Additional Information Document.  Research Triangle
     Park, N.C.  Publication No. EPA-450/3-82-010.  April 1982.  p. 1-4.

6.   U.S. Environmental Protection Agency.  Benzene Fugitive Emissions -
     Background Information for Promulgated Standards.  Research Triangle
     Park, N.C.  Publication No. EPA-450/3-80-032b.  June 1982.  Appendix A.
                                    C-25
-------
-------
                   APPENDIX D

SUMMARY OF EXISTING STATE AND FEDERAL REGULATIONS
 AFFECTING CARBON TETRACHLORIDE EMISSION SOURCES
                      D-l
-------
D.I  EXISTING STATE REGULATIONS

D.I.I  Introduction
     Carbon tetrachloride emissions originate from several  industrial
sources.  These sources include producers of CC1., sources  that use
as a chemical intermediate, and sources that store CC1».  These emissions
can be characterized as either process, fugitive, or product storage tank
emissions.
     There are a number of different regulations at the State level that
limit CC1, emissions.  CC1. emissions in nonattainment areas (areas that have
not achieved the ambient air quality standards for ozone) are normally
controlled by the States' RACT program.  CCl^ emissions in  areas designated
as attainment or unclassified for ozone are controlled by Prevention of
Significant Deterioration (PSD) regulations.  In addition to the RACT and
PSD programs, 12 States (including the District of Columbia) have general
VOC regulations that limit emissions of photochemically reactive compounds.

D.I.2  General State VOC Regulations for Solvent Use
     Table D-l presents a list of the States that have adopted a general VOC
solvent usage regulation and the emission limits established by each State.
These regulations affect volatile organic solvents found to be photochemically
reactive and usually require 85 percent reduction in VOC emissions.  Sources
emitting CC14 are currently covered by these regulations.

D.I.3  Prevention of Significant Deterioration Regulations
     PSD regulations control VOC emissions from major sources in areas
classified as attainment for ozone.  Under PSD regulations, a chemical
production plant must seek a PSD permit if it is:  (1) a new source and
emissions or potential emissions are considered major (100 tons/yr); (2) a
major increase in emissions or potential emissions (100 tons/yr) at an
existing minor source; or (3) a significant increase in emissions or
potential emissions  (40 tons VOC/yr) at an existing major source.  Emission
control levels for PSD are established during the State's review of the PSD
permit application prepared for the emission source.
                                   D-2
-------
D.I.4  State Regulations Affecting Chemical Production
     In addition to the general discussion of State regulations concerning
CC1. emission sources, a more indepth review was performed for States in
which CC1, production facilities are located.  These findings are presented
in Table D-2.  Other VOC emissions at these facilities may also be
controlled.

D.2  EXISTING FEDERAL REGULATIONS

     Several VOC NSPS and a NESHAP have been developed that could affect new
and some existing sources of CCl^ emissions.  A summary and the current
status of each of these standards are presented in Table D-3.
                                    D-3
-------
    TABLE D-l.  GENERAL STATE VOC REGULATIONS FOR PHOTOCHEMICAL SOLVENTS
    State
Emission Reduction (%)
California
Colorado
Connecticut
District of Columbia
Illinois
Indiana
Louisiana
Maryland
North Carolina
North Dakota
Rhode Island
Virginia
        85
        85
        85
        85
        85
        85
        90
        85
        85
        85
        85
        85
1
 Applies to sources in nonattainment areas only.
2Applies to sources emitting less than 100 tons/year, larger sources must
 comply with RACT.
                                    D-4
-------
   TABLE D-2.  STATE REGULATIONS AFFECTING CHEMICAL PRODUCTION FACILITIES
  State
          Source
         Regulation
California
(BAAQMD)
Kansas
Louisiana
Storage tanks >260 gal
_<40,000 gal; Vapor pressure
>1.5 psia £ll.O psia

Storage tanks >40,000
                Process vessel depressur-
                ization (precursor organic
                compound emissions)
Valves & flanges (precursor
organic compound leaks
exceeding 10,000 ppm VOC
above background and
>_1.5 psia vapor pressure)

No regulations for control of
VOC emissions from chemical
production facilities

Storage tanks >40,000 gal
Vapor pressure _1.5 psia.
Submerged fill pipe or
equivalent vapor loss control
device  '    .     '

- Pressure tank or
- Floating roof with primary
  & secondary seals
- Internal floating roof with
  primary & secondary seals
- Vapor Recovery System with
  95 percent recovery

After passing though knock-
out pot to remove the conden-
sable fraction, the organic
compounds must either be:

- Recovered & combusted
- Incinerated
- Flared
- Contained & treated

Non-essential valves or
  flanges repair within 15 days
Essential valves or flanges
 minimize within 15 days
  Pressure tank or
  An internal floating roof
  with a closure seal & sub-
  merged fill pipe
  An external floating roof
  with secondary seal and
  submerged fill pipe
  A vapor loss control system
  & submerged fill pipe  .
                                    D-5
-------
                           TABLE D-2.  (Continued)
  State
Source
Regulation
Louisiana       Storage tanks >250 gal
(cont.)         £40,000 gal

                VOC loading  facilities
                servicing tanks, trucks or
                trailers having a capacity of
                >200 gal & throughput
                >20,000 gal/day (40,000 gal/
                day for existing facilities)

                Pumps, compressors, valves,
                etc. (>1.5 psia vapor
                pressure compounds)
                     - Submerged fill  pipe with
                       vapor recovery  system

                     - Vapor collection & disposal
                       system
                     Equipped with mechanical
                     seals & maintained to
                     prevent leaks
                Waste gas disposal containing Halogenated hydrocarbons
                organic compounds from any    shall  be burned & the
                emission source including
                process unit upsets, start-
                ups and shutdowns.
                Facility emitting >1.4 kg/hr
                or 6.8 kg/day of VOC
                     products of combustion
                     subsequently controlled.
                     Other methods such as carbon
                     adsorption, refrigeration,
                     catalytic/thermal  reaction
                     can be substituted.  Pro-
                     visions may be waived if gas
                     stream <100 T/yr,  will not
                     support combustion without
                     auxiliary fuel, or control
                     will cause economic hardship

                     - Must reduce emissions
                       either by incineration
                       (90% removal efficiency)
                       or by carbon adsorption
                       system.  During  process
                       upsets, start-ups, or shut
                       downs, VOC emissions must
                       be vented and reduced
                       either by an afterburner,
                       carbon adsorption system,
                       refrigeration, catalytic
                       and/or thermal reduction,
                       secondary steam  stripping,
                       or vapor recovery system.
                                    D-6
-------
                           TABLE D-2.   (Continued)
  State
          Source
                          Regulation
Kentucky
Alabama
Illinois2
New Jersey*
No regulations for control
of VOC emissions from
chemical production
facilities.

No regulations for control
of VOC emissions from
chemical production
facilities.
Storage tanks
gallons
>40,000
VOC loading facilities
servicing tanks, trucks
or trailers having capacity
of >250 gal and throughput
>40,000 gal/day.

Storage tanks >300,000
gallons
                VOC transfer >2,000 gal
                (Marine vessels exempt)

                Other than storage or
                transfer
Pressure tank or
Floating roof
Vapor recovery system with
85 percent recovery
Equipment or means of equal
efficiency

Submerged loading or
Equivalent control
                - External  floating  roof with
                  at least  one tight seal
                - Internal  floating  roof with
                  at least  one tight seal

                -Submerged fill  pipe
                              Establishes a sliding scale
                              for control of VOC emissions
                              based on  concentration and
                              vapor pressure of the VOS.
                              The effective control required
                              or possible exclusion for  low
                              emission  rates must be based
                              on data for the specific
                              source in question.
                                   D-7
-------
                           TABLE D-2.  (Continued)
  State
          Source
          Regulation
New Jersey
(cont.)
West Virginia
California
(SCAQMD)
No regulations for control
of VOC emissions from
chemical production
facilities.

Storage tanks >39,630 gal
                Pumps and compressors
                (leaks exceeding 10,000
                ppm VOC)
                Valves and flanges
                Relief valves  (pressures
                over 760 mm Hg absolute)
                                Discharge >12.2 meters above
                                grade
                                Discharge >6.1 meters above
                                human use area within 15.2m
                                Direct discharge vertically
                                upward at velocity >1097m/min
- Pressure tanks or
- External floating roof or
- Internal floating roof or
- Vapor recovery system with
  95 percent recovery
- Other equipment with
  95 percent recovery ,

Repair or replace at next
scheduled process turnaround.
Visual inspections every
8 hours.  Annual inspections
using detection equipment for
all  pumps and quarterly for
compressors.

Annual inspection and repair
of leaks immediately exceeding
10,000 ppm of gaseous VOC.
Seal all open lines when not
in use.

- Vent to vapor recovery or
- Disposal system
- Rupture disc protection or
- Maintained by approved
  inspection system
                                     D-8
-------
                           TABLE D-2.   (Continued)
  State
          Source
        Regulation
Michigan"
Texas'
Storage tanks >40,000 gal
true vapor pressure >1.5
<11.0 psia (existing sources)
                Storage of organic compounds
                having a true vapor pressure
                >_!! psia in existing vessels
                of >40,000 gallons
                VOC loading facilities
                handling >5, 000,000 gal/year
                of >1.5 ps'ia VOC
Storage tanks vapor
pressure >1.5 psia,
                                        psia
                  <_1000 gal
                  >1000 gal  <25,000 gal
                  > 25, 000 gaT^42,000 gal
Pressure tank or
Floating cover with closure
seal or seals
Vapor recovery system
capable of 90 percent
recovery

Pressure tank capable of
maintaining working press-
ures sufficient to prevent
organic vapor or gas loss
to atmosphere
Vapor recovery system
which recovers >90% by
weight of uncontrolled
organic vapor
All openings shall  be
equipped with covers,
lids, or seals

Submerged fill pipes in
ozone attainment areas
                                None
                                Submerged fill  pipe
                                Internal  or external
                                floating  roof with  primary
                                & secondary seal,  or  vapor
                                recovery  system
                VOC loading and unloading     Vapor recovery system
                (facilities with ^20,000 gal/
                day throughput of >1.5 psia
                VOC)
                Vent gas control  (>0.4 psia
                and emissions >100 Ibs/
                24hr or >250 Ib/hr averaged
                over 24 hours)
                              Flared  or  incinerated  at
                              1300°F
                                   D-9
-------
                           TABLE D-2.  (Continued)
  State
          Source
          Regulation
Texas (cont.)
SOCMI Fugitive VOC
(Harris County)
                Storage tanks containing
                vinyl chloride
No compound shall  be allowed
to leak with a VOC concentra-
tion >10,000 ppm (time
limits given

Concentration of exhaust
gases discharged to the
atmosphere from storage
tanks must not exceed 10 ppm
(NESHAP - Vinyl Chloride)
 Bay Area Air Quality Management District Rules and Regulations.
 San Francisco, CA.
Environment Reporter, State Air Laws.  Washington, D.C.  Bureau of National
 Affairs.
3South Coast Air Quality Management District Rules and Regulations.
 El Monte, CA.
                                     D-10
-------
            TABLE D-3.  SUMMARY OF FEDERAL REGULATIONS AFFECTING
                        CARBON'TETRACHLORIDE EMITTING SOURCES
         Source
Proposed
                                                              Promulgated
SOCMI Equipment Leaks
  (Fugitive) NSPS
01/05/81
10/18/83
VOL Storage Vessels NSPS
SOCMI Air Oxidation NSPS
SOCMI Distillation Operations
  NSPS
10/84


10/21/83


12/30/83
SOCMI Reactor Processes NSPS
04/85
                                   D-ll
-------
-------
                                    TECHNICAL REPORT DATA
                             (Please read Instructions on the reverse before completing)
  REPORT NO.
  EPA-450/3-85-018
                                                             3. RECIPIENT'S ACCESSION NO.
 I. TITLE AND SUBTITLE

  Survey of Carbon Tetrachloride Emission Sources
              5. REPORT DATE
                July 1985
                                                             6. PERFORMING ORGANIZATION CODE
 '.AUTHORS  K. H.  Howie,  S.  A. Shareef,  J.  A. Kowalski	
            Radian  Corporation - Post Office Box 13000
 	Research  Triangle Park. North Carolina  27709
              8. PERFORMING ORGANIZATION REPORT NO
 . PERFORMING ORGANIZATION NAME AND ADDRESS
 Office of Air Quality  Planning and  Standards
 Environmental Protection Agency
 Research Triangle  Park,  North Carolina   27711
              10. PROGRAM ELEMENT NO.
              11. CONTRACT/GRANT NO.

                EPA Contract  68-02-3816
 12. SPONSORING AGENCY NAME AND ADDRESS
 DAA  for Air Quality  Planning and Standards
 Office of Air and Radiation
 U.S.  Environmental Protection Agency
 Research Triangle Park,  North Carolina   27711
              13. TYPE OF REPORT AND PERIOD COVERED
                Final
              14. SPONSORING AGENCY CODE


                EPA/200/04
 15. SUPPLEMENTARY NOTES
 Emission Standards and  Engineering Division Lead Engineer:   Robert B. Lucas
 This  document contains  information on sources,  current emission rates, current
 emission  controls, and  cost estimates for  additional emission  reductions.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                               b.lDENTIFIERS/OPEN ENDED TERMS  C.  COSATI Field/Group
 Air Pollution
 Pollution  Control
 Organic Chemical  Industry
 Carbon Tetrachloride
Air Pollution Control
   13B
 8. DISTRIBUTION STATEMENT


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                                               Unclassified
                                                                          22. PRICE
EPA Form 2220—} (Rev. 4—77)   PREVIOUS EDITION is OBSOLETE
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