United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-450/3-85-015
June 1 985
Air
vvEPA
Survey of
Methylene
Chloride Emission
Sources
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EPA-450/3-85-015
Survey of Methylene Chloride
Emission Sources
Emission Standards and Engineering Division
, . -, v-^p'i /vjency
U.S. Environmcr. <• •
Region 5, Libr.:.' • _,,. RQQf
77 WestJack^,-' ;•
Chicago, IL U/—
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, NC 27711
June 1985
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This report has been reviewed by the Emisson 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 221 61.
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TABLE OF CONTENTS
TABLE OF CONTENTS iii
LIST OF TABLES viii
LIST OF FIGURES x
Chapter Page
1.0 INTRODUCTION AND SUMMARY 1-1
1.1 INTRODUCTION 1-1
1.2 SUMMARY 1-2
1.2.1 MC Emission Source Categories 1-2
1.2.2 Emission Estimates 1-3
1.2.3 Additional Control of MC Emissions 1-6
1.2.4 Regulatory Requirements 1-7
1.3 REFERENCES 1-10
2.0 METHYLENE CHLORIDE PRODUCTION 2-1
2.1 QUANTITIES PRODUCED AND MANUFACTURERS 2-1
2.2 PRODUCTION PROCESSES 2-3
2.2.1 Direct Chlorination of Methane 2-3
2.2.2 Hydrochlorination of Methanol 2-4
2.3 CURRENT EMISSIONS AND CONTROLS 2-4
2.4 COST OF ADDITIONAL CONTROLS 2-19
2.4.1 Control of Process Vent Emissions 2-19
2.4.2 Control of Equipment Leak Emissions 2-23
2.4.3 Control of Storage Emissions 2-23
2.4.4 Control of Loading Emissions 2-24
2.5 REFERENCES 2-25
3.0 OTHER CHEMICAL PLANTS 3-1
3.1 PROCESS DESCRIPTIONS, EMISSIONS, AND CURRENT CONTROLS 3-1
3.1.1 TRIACETATE FIBER PRODUCTION 3-1
3.1.1.1 Process Description 3-1
3.1.1.2 Current Emissions and Controls 3-3
3.1.2 POLYCARBONATE RESIN 3-13
3.1.2.1 Process Description 3-13
3.1.2.2 Current Controls and Emissions 3-13
3.1.3 RUBBER CEMENT MANUFACTURING 3-19
3.1.3.1 Current Emissions and Controls 3-19
3.1.4 RUBBER ACCELERATOR MANUFACTURING 3-20
3.1.4.1 Current Emissions and Controls 3-20
i i i
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TABLE OF CONTENTS (Continued)
Chapter Page
3.1.5 INSULATING MATERIALS MANUFACTURE 3-22
3.1.5.1 Current Emissions and Controls 3-22
3.1.6 BAYGONR 1.5 MANUFACTURING 3-22
3.1.6.1 Current Emissions and Controls 3-23
3.1.7 SPECIALTY CHEMICALS 3-23
3.1.7.1 Process Description 3-23
3.1.7.2 Current Emissions and Controls 3-24
3.1.8 UNIDENTIFIED PRODUCTION PROCESSES 3-24
3.1.8.1 -Current Emissions and Controls 3-25
3.1.9 VINYL CHLORIDE MONOMER 3-28
3.1.9.1 Process Description 3-28
3.1.9.2 Current Emissions and Controls 3-28
3.1.10 PLASTICS PRODUCTION 3-28
3.1.10.1 Current Emissions and Controls 3-28
3.2 COST OF ADDITIONAL CONTROL 3-30
3.2.1 Control of Process Vent Emissions 3-31
3.2.2 Control of Equipment Leaks 3-31
3.2.3 Control of Storage Emissions 3-36
3.3 REFERENCES 3-37
4.0 SOLVENT DECREASING OPERATIONS 4-1
4.1 INDUSTRY DESCRIPTION 4-1
4.2 DECREASING EQUIPMENT . 4-2
4.3 EMISSIONS FROM DECREASING OPERATIONS . 4-3
4.4 EMISSIONS CONTROL 4-5
4.5 COST OF EMISSIONS CONTROL 4-8
4.6 REGULATORY REQUIREMENTS 4-14
4.7 REFERENCES 4-15
5.0 PHOTORESIST STRIPPING OPERATIONS 5-1
IV
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TABLE OF CONTENTS (Continued)
Chanter Page
5.1 INDUSTRY DESCRIPTION 5-1
5.2 EMISSIONS AND CONTROL TECHNIQUES 5-2
5.3 REGULATORY REQUIREMENTS 5-3
5.4 REFERENCES 5-5
6.0 FOAM MANUFACTURING 6-1
6.1 INDUSTRY DESCRIPTION 6-1
6.2 CURRENT EMISSIONS AND CONTROLS 6-2
6.3 REFERENCES 6-4
7.0 PHARMACEUTICAL MANUFACTURING 7-1
7.1 INDUSTRY DESCRIPTION 7-1
7.2 CURRENT EMISSIONS AND CONTROLS 7-2
7.3 REFERENCES 7-4
8.0 PESTICIDE MANUFACTURING 8-1
8.1 INDUSTRY DESCRIPTION 8-1
8.2 EMISSIONS AND CONTROLS 8-3
8.3 REFERENCES 8-4
9.0 DISTRIBUTION FACILITIES 9-1
9.1 EMISSIONS FROM DISTRIBUTION FACILITIES 9-1
9.2 REGULATORY REQUIREMENTS 9-2
9.3 REFERENCES 9-4
10.0 ADDITIONAL EMISSION SOURCES OF MC 10-1
10.1 AEROSOLS 10-1
10.2 PAINT REMOVERS 10-3
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TABLE OF CONTENTS (Continued)
Chapter Page
10.3 PHOTOGRAPHIC FILM PROCESSING 10-3
10.4 FOOD PROCESSING INDUSTRY 10-3
10.5 GENERAL MISCELLANEOUS 10-4
10.6 REFERENCES 10-5
APPENDIX A: METHODS USED FOR ESTIMATING STORAGE TANK AND
EQUIPMENT LEAK EMISSIONS A-l
A.I EMISSION FACTORS FOR FIXED-ROOF TANKS A-l
A.1.1 Emission Equations A-l
A.1.2 Parameter Values and Assumptions .... A-l
A.1.3 Sample Calculation A-2
A.2 EMISSION FACTORS FOR INTERNAL FLOATING
ROOF STORAGE TANKS A-4
A.2.1 Emission Equations A-4
A.2.2 Parameter Values and Assumptions .... A-4
A.2.3 Sample Calculation A-7
A.3 EQUIPMENT LEAK EMISSIONS-SAMPLE CALCULATIONS. . A-10
A.4 REFERENCES A-12
APPENDIX B: METHODS FOR ESTIMATING EMISSION CONTROL COSTS. ... B-l
B.I PROCESS VENT EMISSIONS CONTROL COST ESTIMATION. B-l
B.2 COST CALCULATIONS FOR INSTALLING INTERNAL
FLOATING ROOFS IN FIXED ROOF TANKS. . . .
B.2.1 Capital Cost
B.2.2 Annual Cost
B.2.3 MC/VOC Reduction
B.2.4 Recovery Credits
B.2.5 Net Annual Cost
Cost Effectiveness
B.2.6
B.3
COST CALCULATIONS FOR INSTALLATION OF
REFRIGERATED CONDENSERS TO CONTROL STORAGE AND
LOADING EMISSIONS
B.3.1 Capital Cost
B.3.2 Annual Cost
B.3.3 MC/VOC Emission Reduction
B.3.4. Recovery Credit
B-14
B-14
B-15
B-15
B-16
B-16
B-16
B-16
B-17
B-17
B-17
B-18
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TABLE OF CONTENTS (Continued)
Chapter
Page
B.3.5 Net Annual Cost B-18
B.3.6 Cost Effectiveness B-18
B.4 SAMPLE CALCULATIONS FOR EQUIPMENT LEAK
CONTROL COSTS B-18
B.5 REFERENCES B-22
APPENDIX C: SUMMARY OF EXISTING STATE AND FEDERAL REGULATIONS
AFFECTING METHYLENE CHLORIDE EMISSION SOURCES .... C-l
C.I EXISTING STATE REGULATIONS C-l
C.I.I Introduction C-l
C.I.2 General State VOC Regulations for
Solvent Use C-l
C.I.3 Prevention of Significant Deterioration
Regulations C-3
C.I.4 State Regulations Affecting Chemical
Production C-3
C.2 EXISTING FEDERAL REGULATIONS C-3
APPENDIX D: MATERIAL BALANCE FOR MC EMISSIONS OPERATIONS D-l
D.I MATERIAL BALANCE D-l
D.2 NATIONAL EMISSION REDUCTION CALCULATIONS .... D-3
D.3 PHOTORESIST STRIPPING EMISSION FACTOR D-6
D.4 REFERENCES D-7
APPENDIX E: EMISSIONS FROM DISTRIBUTIONS FACILITIES E-l
vn
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LIST OF TABLES
Table Page
1-1 EMISSIONS FROM THE PRODUCTION AND USE OF
METHYLENE CHLORIDE 1-4
1-2 ACHIEVABLE MC EMISSION REDUCTION FOR ALL
CHEMICAL PLANTS AND DEGREASERS AS A FUNCTION OF COST
EFFECTIVENESS 1-8
2-1 METHYLENE CHLORIDE PRODUCERS AND PRODUCTION CAPACITIES. . 2-2
2-2 TOTAL EMISSIONS FROM METHYLENE CHLORIDE PRODUCTION
FACILITIES 2-7
2-3 CURRENT CONTROLS AND ESTIMATED EMISSIONS AT
FACILITIES PRODUCING METHYLENE CHLORIDE 2-9
2-4 COST OF ADDITIONAL CONTROLS AT MC PRODUCTION FACILITIES . 2-20
2-5 ESTIMATED MC EMISSION REDUCTIONS FOR MC PRODUCTION
FACILITIES AS A FUNCTION OF COST EFFECTIVENESS 2-22
3-1 TOTAL EMISSIONS FROM CHEMICAL PLANTS USING METHYLENE
CHLORIDE PRODUCTION FACILITIES 3-2
3-2 ESTIMATED EMISSIONS AND CURRENT CONTROLS AT FACILITIES
USING METHYLENE CHORIDE IN PRODUCTION 3-5
3-3 COST OF ADDITIONAL CONTROLS AT CHEMICAL PLANTS USING MC
IN PRODUCTION 3-32
3-4 ESTIMATED MC EMISSION REDUCTIONS FOR OTHER CHEMICAL PLANTS
AS A FUNCTION OF COST EFFECTIVENESS 3-35
4-1 1983 MC EMISSIONS FROM DECREASING OPERATIONS, BY INDUSTRY 4-4
4-2 1983 METHYLENE CHLORIDE EMISSIONS FROM DECREASING
OPERATIONS, BY STATE 4-6
4-3 EXAMPLE CONTROL TECHNIQUES FOR DEGREASERS 4-7
4-4 RETROFIT CONTROL COSTS FOR COLD CLEANERS 4-9
4-5 RETROFIT CONTROL COSTS FOR OPEN TOP
VAPOR DEGREASERS 4-10
4-6 RETROFIT CONTROL COSTS FOR CONVEYORIZED DEGREASERS .... 4-12
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LIST OF TABLES (Continued)
Table Page
5-1 1983 METHYLENE CHLORIDE EMISSIONS FROM PHOTORESIST
STRIPPING OPERATIONS, BY STATE 5-4
6-1 1983 MC EMISSIONS FROM FOAM MANUFACTURING, BY STATE ... 6-3
8-1 1983 CONSUMPTION OF METHYLENE CHLORIDE IN PESTICIDE
MANUFACTURING 8-2
9-1 SUMMARY OF MAJOR METHYLENE CHLORIDE DISTRIBUTORS 9-3
10-1 ADDITIONAL USES OF METHYLENE CHLORIDE IN 1983 10-2
A-l PAINT FACTORS FOR FIXED-ROOF TANKS A-3
A-2 TYPICAL NUMBER OF COLUMNS AS A FUNCTION OF TANK DIAMETERS A-5
A-3 SUMMARY OF DECK FITTING LOSS FACTORS (K.) AND
TYPICAL NUMBER OF FITTINGS (Nf) . . .f A-8
B-l TOTAL INSTALLED CAPITAL COST AS A FUNCTION OF VENT
STREAM FLOW RATE B-2
B-2 ADDITIONAL DUCT COST B-3
B-3 PIPE RACK COST. B-4
B-4 OPERATING FACTORS FOR EACH DESIGN CATEGORY B-5
B-5 ANNUALIZED COST FACTORS B-6
B-6 SAMPLE CALCULATION FOR INCINERATOR COSTING B-7
B-7 COST CONVERSION FACTORS B-13
B-8 CONTROL TECHNIQUES AND COST FOR CONTROLLING EQUIPMENT LEAK
EMISSION SOURCES B-19
C-l GENERAL STATE VOC REGULATIONS FOR PHOTOCHEMICAL SOLVENTS. C-2
C-2 STATE REGULATIONS AFFECTING CHEMICAL PRODUCTION FACILITIES
EMITTING METHYLENE CHLORIDE C-4
C-3 SUMMARY OF FEDERAL REGULATIONS AFFECTING VOLATILE ORGANIC
COMPOUND EMITTING SOURCES C-5
IX
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LIST OF FIGURES
Figure Page
2-1 Process flow diagram for the production of methylene
chloride and co-products by the direct chlorination
of methane 2-5
2-2 Process flow diagram for the production of methylene
chloride and co-products by the hydrochlorination
of methanol 2-6
3-1 Process flow diagram for the production of triacetate
fiber 3-4
3-2 Process flow diagram for the production of polycarbonate
resin 3-14
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1.0 INTRODUCTION AND SUMMARY
1.1 INTRODUCTION
This document identifies the sources and locations of methylene
chloride (MC) emissions, estimates total 1983 production and consumption
volumes, estimates emission levels, identifies applicable control
techniques for each source, and estimates the cost effectiveness of
controlling emissions for selected sources. The information collected
in this source assessment study will also be used by the U.S.
Environmental Protection Agency (EPA) to estimate human exposure to MC.
Information for this document was acquired from various sources.
Background information, such as previous EPA documents and other
published literature, was reviewed in an attempt to identify the
producers of MC and the major applications. Four companies producing MC
at six facilities were identified. Also, two companies producing
polycarbonate resins and one company producing triacetate fibers were
identified. Letters were sent to these seven companies under the
authority of Section 114 of the Clean Air Act requesting information
concerning MC emissions, emission levels, and control techniques for all
possible emission sources associated with the production, storage, and
use of MC in the calendar year 1983. General information such as
production volumes and total sales/purchase data were also requested in
order to verify the completeness of the submitted information. The
production and sales/purchase information was requested to be treated as
confidential and is not discussed in this report. For each process unit
making or consuming MC, detailed information was requested on the
following emission types: process vent emissions, equipment leaks,
equipment opening losses, raw material/product storage emissions,
loading/handling emissions, and secondary emissions (i.e. emissions as a
result of treating or disposing of plant waste streams). The companies
were asked only to estimate these emissions. No testing was required
specifically for this information request.
1-1
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Plant trips were taken to Vulcan Chemicals in Geismar, Louisiana;
Dow Chemical U.S.A. in Plaquemine, Louisiana; and General Electric in
Mt. Vernon, Indiana to gain familiarity with the processes, emission
sources, and emission controls at these facilites. Meetings were held
with plant representatives to discuss operating procedures, the process
equipment used, potential emission sources, and methods of emissions
control.
The predominant uses of MC are as a constituent in aerosols and
paint removers. Since aerosols and paint removers are largely consumer
products, it was assumed that associated emissions are proportional to
general population distribution in the U.S. Other significant uses of
MC that were identified include solvent degreasing, chemical production,
foam manufacturing, pharmaceutical manufacturing, pesticide manufacturing
and photoresist stripping. Information for chemical plants was obtained
directly through Section 114 requests. For the other significant MC use
categories, no attempt was made to identify the locations of all
facilities using MC. However, information was obtained from the
Halogenated Solvents Industry Alliance (HSIA), a trade group representing
the producers of MC and other halogentated solvents, regarding the total
amount of MC used in 1983 for all known applications. Using HSIA and
other available information, emission levels in 1983 were estimated for
each application.
1.2 SUMMARY
1.2.1 MC Emission Source Categories
Methylene chloride is produced by four companies at six plants in
the United States. The estimated total 1983 production volume of MC was
240,000 Mg . Two processes are used to produce MC: (1) hydrochlorination
of methanol, and (2) chlorination of methane. In 1983, the disposition
of MC was as follows: aerosols (22 percent), paint removers
(28 percent), degreasing operations (9 percent), foam manufacturing
(7 percent), pharmaceutical manufacturing (6 percent), photoresist
stripping operations (5 percent), film processing (3 percent), food
processing (1 percent), and pesticide manufacturing (1 percent).
1-2
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Additional applications include general miscellaneous uses such as a
solvent in the printing industry, as a thinning agent for adhesives, as
a solvent in cleaning solutions, and as a solvent or reactant in the
chemical processing industry. Individual consumption levels are not
known for these general uses. Their combined consumption was 5 percent
of total use.
Emission estimates have been made in this study for the following
categories: MC production facilities, chemical plants, degreasing
operations, photoresist stripping operations, foam manufacturing,
pharmaceutical manufacturing, pesticide manufacturing, distribution
facilities, aerosols, paint removers, photographic film processing, food
processing, and the general miscellaneous applications.
1.2.2 Emission Estimates
The total emissions from MC production and use in 1983 are
estimated to be 197,500 Mg/yr. The largest sources of MC emissions were
paint removers (62,000 Mg/yr), aerosols (52,900 Mg/yr), degreasing
operations (17,700 Mg/yr), foam manufacturing (14,200 Mg/yr), and
photoresist stripping operations (6,800 Mg/yr). The source categories
and emissions are presented in Table 1-1.
Methylene chloride emissions from MC production processes are
estimated to be 770 Mg/yr. MC emissions from miscellaneous chemical
production processes using MC are estimated to be 10,700 Mg/yr. The
chemical products of these processes include triacetate fibers,
polycarbonate resins, plastics, rubber cement, rubber accelerators,
insulating materials, specialty chemicals, vinyl chloride, and BAYGONR
1.5 (pesticide). The estimate of total emissions from MC producing
plants and other chemical plants was obtained from information provided
by these facilities in response to Section 114 requests. These plants
provided emission estimates from process vents (estimated at full
capacity), loading/handling operations, equipment opening losses,
pressure relief valve discharges, and secondary streams. The chemical
plants also provided counts of all equipment (such as pumps, valves, and
flanges) in MC service and data on the number and types of product/raw
1-3
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TABLE 1-1. EMISSIONS IN 1983 FROM THE PRODUCTION AND USE
OF METHYLENE CHLORIDE
Production/Consumption
Emission Source (Mg/yr)
MC Production
Other Chemical Production
Degreasing Operations
Photoresist Stripping
Operations
Foam Manufacturing
Pharmaceutical Manufacturing
Pesticide Manufacturing
Distribution Facilities
Aerosols
Paint Removers
Photographic (film processing)
Food Processing
Miscellaneous
TOTAL
240,000
N/A
21,300
11,900
14,200
13,200
2,700
218,000a
52,900
62,000
8,100
3,330
12,100
-
Emissions
(Mg/yr)
770
10,700b
17,700
6,800
14,200
5,700
2,700
500
52,900
62,000
8,100
3,300
12,100
197,500
bEstimated amount of MC sold through distribution.
Based on update of preliminary information provided by chemical plants
N/A = Not Available
1-4
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material storage tanks containing MC. Total volatile organic compound
(VOC) emissions from equipment leaks were calculated by applying the
Synthetic Organic Chemical Manufacturing Industry (SOCMI) VOC equipment
leak emission factors to the equipment counts. MC emissions were
estimated in a similar manner except that the fraction of MC in the
stream for each piece of equipment was applied to the calculated VOC
emissions. Emissions from storage tanks were estimated by using AP-42
equations and storage tank data supplied by each company.3 Methods for
estimating these emissions are described in Appendix A.
Methylene chloride emissions from degreasing operations were
estimated to be 17,700 Mg in 1983. Degreasing emission estimates were
made using HSIA information on 1983 MC consumption in various degreasing
applications and available emission factors. The HSIA indicated that MC
was used as a degreasing solvent in five major industry groups in 1983.
These are: furniture and fixtures (Standard Industrial Classification
(SIC)25), fabricated metal products (SIC 34), electric and electronic
equipment (SIC 36), transportation equipment (SIC 37), and miscellaneous
industries (SIC 39). Emission factors for degreasing operations were
obtained from previous EPA studies.
MC emissions from photoresist stripping operations were estimated
to be 6,800 Mg in 1983. Emissions were estimated using 1983 consumption
data provided by HSIA and emissions factors derived for the printed
circuit board manufacturing industry, in which photoresist stripping
operations occur.
Almost all of the MC produced is sold through various chemical
distributors. The handling and storage operations at distribution
facilities located throughout the country were estimated to account for
500 Mg of TCE emissions in 1983.
Emissions of MC from foam manufacturing were estimated to be
14,200 Mg in 1983. Emission estimates were made using 1983 consumption
data for foam manufacturing provided by the HSIA. It was assumed that
all the MC used in foam manufacturing is emitted.
1-5
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Emissions of MC from pharmaceutical manufacturing were estimated to
be 5,700 Mg in 1983. Emissions were estimated using 1983 consumption
data for pharmaceutical manufacturing provided by HSIA and an emission
factor for pharmaceutical manufacturing obtained in a previous EPA
study.
Emissions of MC from pesticide manufacturing were estimated to be
2,700 Mg in 1983. Emissions were estimated from 1983 consumption data
for pesticide manufacturing provided by HSIA. It was assumed that all
the MC consumed in pesticide manufacturing during 1983 was emitted.
Emissions of MC from photographic film processing were estimated to
be 8,100 Mg in 1983. Emissions were estimated from 1983 consumption
data for film processing provided by HSIA. It was assumed that all the
MC consumed in photographic film processing during 1983 was emitted.
Emissions of MC from food processing were estimated to be 3,300 Mg
in 1983. This estimate was based as 1983 consumption data for food
processing provided by HSIA, assuming all MC consuming in food
processing during 1983 was emitted.
Emissions of MC from the aggregated general miscellaneous source
category were estimated to be 12,100 Mg in 1983. HSIA indicated
12,100 Mg was the consumption level of MC for the combined miscellaneous
sources. It was assumed that all MC consumed in those applications is
emitted.
1.2.3 Additional Control of MC Emissions
The cost associated with additional control of MC emissions was
estimated for MC production plants, other chemical plants and
degreasers. Due to the large number of degreasers, no attempt was made
to develop cost estimates for each degreaser actually in use. Instead,
cost estimates were developed for model degreasers. National costs and
national emission reductions associated with controlling degreasers were
based on model degreaser data. Specific information was provided for MC
production and other chemical production facilities. This information
was used to develop national costs and emission reduction estimates were
made for these production facilities. The methodology for estimating
control costs is presented in Appendix B.
1-6
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Emissions of MC from chemical plants producing or using MC can be
reduced by various technically feasible controls. Process vent
emissions can be controlled by incineration. Equipment leak emissions
can be reduced through a combination of leak detection and repair
programs and application of equipment control 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 a
refrigerated condenser.
Emissions of MC from degreasers can be reduced by using covers for
degreasers openings, increasing degreaser freeboard area, adding
freeboard chillers, providing drainage racks for parts, and installing
carbon adsorbers. The methodology for estimating cost effectiveness of
degreaser emission control is presented in Chapter 4.
Costs were estimated for the above control techniques for all
emission sources from chemical plants and degreasers which are not
presently well controlled. These costs estimates are based on the
information provided in the company Section 114 responses on the
emission stream and process equipment parameters and also on the data
for model degreasers. It is estimated that about 11,300 Mg/yr MC
emissions can be controlled by the application of control techniques on
process vent, fugitive, storage tanks, and handling emissions and by
application of control techniques on uncontrolled degreasers. This
represents an overall emission reduction of about 39 percent over
current estimated emissions from chemical production and degreasing.
Table 1-2 shows the emission reduction for each emission type for
various ranges of cost effectiveness.
1.2.4 Regulatory Requirements
The plants that produce MC or use it in production processes are
located in 13 States: West Virginia, Texas, Louisiana, Kansas,
Massachusetts, Indiana, New York, South Carolina, Pennsylvania,
California Ohio, Missouri, and Michigan. Emissions from these existing
chemical production facilities are not controlled by Federal regulations
1-7
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TABLE 1-2. ACHIEVABLE MC EMISSION REDUCTION FOR
ALL CHEMICAL PLANTS AND DEGREASERS AS A FUNCTION
OF COST EFFECTIVENESS
I
oo
Nationwide MC Emission Reduction* Ma/Yr
Cost Effectiveness
Range, S/Mg of VOC
Credit
0-500
501-1000
1001-2000
2001-5000
> 5000
Process
Vents
864
1,940
-
82.4
132
851
Equipment
Leak
339
69.7
25.4
1.2
-
Storage
Tanks Loading
182
47.8
10.9
33.6 51.9
18.3 73.2
13.8 16.9
Degreasing Total
1,050
4,130 6,460
81
2,460 2,650
225
882
TOTAL
3,870
435
307
142
6,590
11,300
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such as the new source performance standards (NSPS) for volatile organic
compounds (VOC) in the synthetic organic chemical manufacturing industry
(SOCMI) because these regulations are designed to cover new, modified,
or reconstructed sources.
The emissions of MC from chemical plants are controlled in only two
(Pennsylvania, and Michigan) of the 11 States where MC is produced or
used in production processes. MC is exempt from VOC regulations in the
other States because of its negligible photochemical reactivity with the
exception of Massachusetts where MC emissions from specific sources
such as metal coating are regulated. However, Massachusetts regulations
do not impact chemical plants.
Michigan has adopted regulations controlling storage of organic
compounds having a true vapor pressure between 1.5 psia and 11 psia in
existing stationary vessels of more than 40,000 gallon capacity. The
vapor pressure of MC at 20°C (68°F) is approximately 6.75 psia. The
regulations require that the storage tank is a pressure tank, be
equipped with a floating cover with closure seal or seals, or be
equipped with a vapor recovery system capable of 90 percent recovery.
Pennsylvania regulations require storage tanks with a volume below
40,000 gallons to be equipped with pressure relief devices; for tanks
above 40,000 gallons the regulations require a floating roof and vapor
recovery system.
VOC emissions from loading/handling emissions are regulated by
Michigan. The state regulation requires loading facilities handling
5,000 gal/year or more of VOC (with a true vapor pressure equal to
1.5 psia) to have submerged fill pipes.
There are no Federal regulations for MC emissions from degreasing
operations. A CTG for organic solvent cleaners has been issued by EPA
establishing RACT guidelines that have been used by State agencies to
develop SIPs. Thirty-two States and the District of Columbia have
adopted RACT for use of MC in degreasing operations. Eighteen States
have not adopted any regulations. Further details on State regulations
are presented in Appendix C.
1-9
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1.3 REFERENCES
1. Mannsville Chemical Products. Chemical Products Synopsis -
Methylene chloride. Cortland, New York. November 1984.
2. U. S. Environmental Protection Agency. Benzene Fugitive
Emissions-Background Information Document. Research Triangle
Park, North Carolina. Publication No. EPA-450/3-80-0326.
June 1982. Appendix A. 1982.
3- Compilation of Air Pollutant Emission Factors. 3rd Edition.
U. S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, Monitoring and Data Analysis Division
Research Triangle Park, N.C. January 1984.
1-10
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2.0 METHYLENE CHLORIDE PRODUCTION
This chapter presents the emissions and controls associated with
the production of methylene chloride (MC) at the six production
facilities in the United States. Methylene chloride is produced by
the hydrochlorination of methanol at all six of these plants and by the
direct chlorination of methane at one of these plants. Emission sources
in MC production facilities are process vents, equipment leaks,
equipment openings, relief devices, storage tanks, secondary sources,
and truck, rail-car, drum, or barge loading.
2.1 QUANTITIES PRODUCED AND MANUFACTURERS
Methylene Chloride is currently produced by four companies at
six plants. The estimated total production capacity of these plants is
358,000 Mg/yr.1 In 1983 about 240,000 Mg of methylene chloride was
produced. The total imports of methylene chloride in 1983 were
20,000 Mg, and the total exports were 32,700 Mg indicating a domestic
United States demand of about 228,000 Mg in 1983.1 The producers, their
capacities, and production processes are listed in Table 2-1.
Methylene Chloride consumption declined approximately 14 percent
from 1979 to 1983. This is because several MC end uses such as paint
stripping, aerosols, and metal and plastic processing consumption levels
decreased during the economic downturn. However, in 1984 MC demand
level was 252,000 Mg, showing a 10.5 percent growth over 1983.2 Also in
1984, imports increased to 30,000 Mg, 50 percent higher than in 1983.2
The import surge upset the traditional trade surplus of U.S. MC but
tightening chlorine availability in Europe is expected to drop imports
in 1985. Current predictions for future growth are in the 2 to 3
i ?
percent range. '
2-1
-------
TABLE 2-1. METHYLENE CHLORIDE PRODUCERS AND PRODUCTION CAPACITIES
fXJ
I
ro
Company
Diamond Shamrock
Corporation
Dow Chemical U.S.A.
LCP Chemicals
Vulcan Materials Co.
TOTAL
^Estimated capacities
Location
Belle, WV
Freeport, TX
Plaquem1ne» LA
Moundsvllle, WV
Ge1smar» LA
Wichita, KS
Capacity3 (Mg/yr)
Process (1984)
Hydrochlorlnatlon of methanol
Hydrochlor1nat1on of methanol
Hydrochlorlnatlon of methanol
Hydrochlorlnatlon of methanol
Hydrochlorlnatlon of methanol
Hydrochlorlnatlon of methanol
Chlor1nat1on of methane
50,000
91,000
86,000
36,000
36,000
59,000b
358,000
from Mannsvllle Chemical Products Corporation.
-------
2.2 PRODUCTION PROCESSES
The two basic methods of methylene chloride production, direct
chlorination of methane and hydrochlorination of methanol, differ
primarily in the initial feedstock. Both processes produce methyl
chloride as an intermediate. Methylene chloride is then produced by the
direct chlorination of methyl chloride.
All six plants produce MC by the hydrochlorination of methanol. In
addition, Vulcan/Wichita uses the direct chlorination of methane to
produce about 33 percent of their MC output.
2.2.1 Direct Chlorination of Methane.4
Methyl chloride, methylene chloride, chloroform, and carbon
tetrachloride are co-produced via the direct chlorination of methane.
Methane is mixed with chlorine and fed to a chlorination reactor where
all four co-products are produced. The co-products are then separated
by distillation. After separation the methyl chloride can be recycled to
the chlorinator. The reaction conditions and the amount of methyl
chloride recycled to the chlorination reactor can be controlled to yield
predominantly methylene chloride. The chlorination process occurs
according to the reactions:
Cl,
CH3C1
(methane) (chlorine) (methyl chloride)
CH3C1
Cl,
HC1
(hydrogen chloride)
HC1
(methyl chloride)(chlorine) (methylene chloride) (hydrogen chloride)
CHC1.
«o "" 7 "•** ^nv^i«
(methylene chloride) (chlorine) (chloroform)
CHC13 + C12
-^ CCL
HC1
(hydrogen chloride)
HC1
(chloroform) (chlorine) (carbon tetrachloride) (hydrogen chloride)
2-3
-------
The reactions are usually carried out at about 350°C to 370°C
(660°F to 700°F) and at a pressure slightly above one atmosphere. The
process flow diagram is shown in Figure 2-1.
2.2.2 Hvdrochlorination of Methanol4
Methyl chloride is produced via the hydrochlorination of methanol,
the reaction of hydrochloric acid with methanol in the liquid phase and
in the presence of a catalyst at about 340°C (644°F). The direct
chlorination of methyl chloride then produces methylene chloride and
chloroform as co-products, and carbon tetrachloride as a by-product.
The chlorination processes occur according to the reactions:
CH3OH + HC1 catalyst > CH3C1 + H20
(methanol) (hydrochloric acid) liquid phase (methyl chloride) (water)
CH3C1 + C12 > CH2C12 + HC1
(methyl chloride) (chlorine) (methylene chloride) (hydrochloric acid)
CH2C12 + C12 => CHC13 + Ha
(methylene chloride)(chlorine) (chloroform) (hydrogen chloride)
CHC13 + C12 > CC14 + HC1
(chloroform) (chlorine) (carbon tetrachloride)(hydrogen chloride)
Cuprous chloride, activated charcoal, or zinc chloride on pumice is used
as catalyst in the hydrochlorination reaction. A process flow diagram
is shown in Figure 2-2.
2.3 CURRENT EMISSIONS AND CONTROLS
Emission sources and emission levels for each facility producing
methylene chloride are summarized in Table 2-2. A more detailed
discussion of emission sources including controls, and control
2-4
-------
ro
i
en
••Heavy Ends
Methyl
Chloride
Methylene
Chloride
Chloroform
Carbon
Tetrachlorlde
Figure 2-1. Process flow diagram for the production of methylene chloride
and co-products by the direct chlorination of methane.
-------
METHYL CHLORIDE
CATALYST
METHANOL
HCL
O <
<
HI
cc
\
z £
IU $
3 O
O H
HCL
WATER
CAUSTIC
SODA
cc
u
ca
m
a
cc
U
u>
O CC
-2
ac O
O H
H2SO4
I SPENT
f CAUSTIC
SPENT
ACID
ro
i
en
tc
IU
a.
a
cc
u
_i a.
U a
z a:
i-
u>
I O
- i
u
CHLORINE
J
METHYLENE
CHLORIDE
CHLOROFORM
u
z u
u Q cc
s
E
O
If.
0
CC
O
_1
X
u
cc
u
$
O
t-
•CARBON TETRACHLORIDE
AND HEAVY ENDS
Figure 2-2. Process flow diagram for the production of methylene
chloride and co-products by the hydrochlorination of methanol
-------
TABLE 2-2 TOTAL EMISSIONS FROM METHYLENE CHLORIDE
PRODUCTION FACILITIES
ro
i
1963 Methvlene Chloride Fmlsslons (Mq/yr)
Equipment
Plant/Location Process Leaks Relief Devices Storage" Handling Equipment Openings Secondary TOTAL
Diamond Shamrock 5.7 75.2
Belle, WV
Dow Chemical - 87.3
Freeport, TX
Dow Chemical - 27.5
Plaquemine. LA
LCP Chemicals 84.4 28.5
Moundsville, WV
Vulcan Materials 0.7 35.5
Geismar. LA
Vulcan Materials 12.3 38.1
Wichita. KS
TOTAL 103 292
3.4
.05
0.5
.01
4.0
26.1
18.3
73.5
21.1
19.3
32.2
190
4.2
4.2
115
23.7
8.2
6.2
162
aBased on equipment count provided by plants and SOCHI fugitive emission factors.
Based on storage tank information provided by plants and AP-42 equations.
1.1
.05
0.6
0.9
0.6
0.8
4.1
0.7
0.8
.02
6.4
3.9
11.8
116
111
217
165
68.2
89.6
770
-------
efficiencies is presented below and shown in Table 2-3. Equipment leak,
storage tank, and handling emissions account for the majority of the
methylene chloride emissions from these facilities. Process vent,
equipment opening, relief device, and secondary emissions were also
reported by the six plants.
Dow Chemicals U.S.A. - Freeport. TX5
The production of methylene chloride by hydrochlorination of
methanol at this facility resulted in total emissions of methylene
chloride of 111 Mg in 1983. Equipment leaks accounted for a majority of
these emissions, totalling 87.3 Mg/yr. The largest sources of equipment
leaks were valves, flanges, and pressure relief devices. Emissions from
valves were approximately 42 Mg/yr (48 percent of total equipment
leaks). Seventeen percent of the equipment leaks were from flanges.
Pressure relief devices constituted 19 percent of these emissions. Dow
reported that inspection programs were in place for monitoring equipment
leaks. These programs include routine inspection of equipment during
each shift, a pressure vessel inspection program, an annual leak survey,
and continuous corrosion rate monitoring. Since no repair frequency was
reported, no control efficiency could be estimated for Dow's inspection
program. Therefore, equipment leak emission estimates assume no
control. This may overstate somewhat Dow's equipment leak emissions.
The Texas Air Control Board has recently promulgated regulations
that will require a formal monitoring and repair program for volatile
organic compound equipment leaks. The first round of monitoring must be
completed by the end of 1987. The regulation will require the periodic
testing of all valves in VOC service with a portable hydrocarbon meter,
capping of open-ended lines and valves, monitoring of pump seals, and
detailed record keeping of these practices. Methylene Chloride is
excluded from these regulations and from other regulations governing
volatile organic compounds in Texas because of its low photochemical
reactivity. However, Dow would be covered by Texas regulations where MC
streams are mixed with regulated volatile organic compounds (such as
methyl chloride, chloroform, and carbon tetrachloride).
2-8
-------
TABLE 2-3. CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITIES
PRODUCING METHYLENE CHLORIDE
Company/Location
Diamond Shamrock
Belle, M
Type of Emission/
Source
Process
o Regeneration Vent
o Vent Recovery
System 1
o Vent Recovery
System 2
Equipment Leaks
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
Equipment Opening
Handling
o Tank cars, tank
trucks
o Barges
Present Controls
Reported
Control Efficiency
None
Condenser
Condenser
None
Conservation Vent
Water Cooled Condenser
Conservation Vent
Hater Cooled Condenser
Conservation Vent
Water Cooled Condenser
Conservation Vent
Water Cooled Condenser
None
None
Conservation Vent
Water Cooled Condenser
Conservation Vent
Water Cooled Condenser
None
None
None
None
None
None
Conservation Vent
Water Cooled Condenser
Refrigerator Condenser
Conservation Vent
Water Cooled Condenser
None
None
None
0
68.5
26.7
0
62.4
86.7
86.7
86.7
0
0
41.9
41.9
0
0
0
0
0
0
90.7
62.4
0
0
0
Present
MC Emissions
(Hg/yr)
3.8
1.1
0.8
75.2
1.8
0.8
0.8
0.4
0.4
2.9
5.3
5.3
0.1
0.04
0.04
0.08
0.9
1.0
4.4
1.8
1.1
0.3
3.9
Comments
Visual Inspection
15,000 gallons
20,000 gallons
20,000 gallons
17,000 gallons
15,000 gallons
15,000 gallons
20,000 gallons
20,000 gallons
900 gallons
2,350 gallons
250 gallons
550 gallons
20,000 gallons
20,000 gallons
500,000 gallons
15,000 gallons
12 major
150 minor
Dome loading
Bottom loading
(Continued)
-------
TABLE 2-3 CONTINUED.
CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITIES
PRODUCING METHYLENE CHLORIDE
ro
i
Company/Local ton
Dow Chemical
Freeporti TX
Type of Emission/
Source
Secondary
o Waste»ater
Treatment
Influent
o Solid Waste
Drumming
o Sludge Disposal
Relief Devices
Equipment Leaks
Storage
0 »
Equipment Opening
Present Controls Reported
Control Efficiency
Steam Strip/Carbon Adsorp. N/R
Landfill N/R
Off-site Treatment N/R
N/A
None 0
« *
None 0
Present
MC Emissions Comments
(Mg/yr)
0.05
0.43
0.24
3.4 Relief Valve
87.3 Routine Freeport.
Inspection
programs
18.3
0.05 216 openlngs> large
vessels cleared to
200 ppm oryantes
Dow Chemical
Plaquumtne. LA
Handling
o Tank trucks, tank
cars, ships.
barges
o Drums
Secondary
o Mastewater rain
and washdonn
o Spent Filter
Elements
Equipment Leaks
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
None
Flume vacuum system
Nonblologlcal Treatment
Material and Energy
Recovery Unit
None
None
None
0
N/R
0
N/R
0
0
0
4.2 Open dome
loading
N/R
0.8
27.5 Continuous A1r
Monitoring
6.3 126,500 gallons
2.7 56.000 gallons
(Continued)
-------
TABLE 2-3 CONTINUED.
CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITIES
PRODUCING METHYLENE CHLORIDE
• . ,
Company/Location
LCP Chemicals
Moundsvtlle. WV
Type of Emission/
Source
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Contact Internal
Floating-Roof
Equipment Opening
Handl Ing
o tank truck >tank
car, barges
Secondary
o Not Identified
Relief Devices
Process
o Purge Condenser
o Recovery Tank
Equipment Leaks
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
Handl Ing
o Rail cars, truck
Secondary
o Not Identified
o Not Identified
o Not Identified
Relief Devices
Present Controls
None
None
None
N/A
None
None
None
N/A
Compression and
Condensation
None
Nono
None
None
None
None
None
None
None
None
Distillation and
Recovery
Neutralization and
Carbon Adsorp.
Off-site
N/A
Reported
Control Efficiency
0
0
0
N/A
0
0
0
0
0
N/R
0
0
0
0
0
0
0
0
N/R
N/R
N/R
MC Emissions
(Mg/yr)
12.0
23.4
23.4
5.7
0.6
115
0.02
0.05
84.3
0.05
28.5
1.3
1.3
1.3
4.3
10.7
1.7
0.5
23.7
1.3
0.6
4.5
0.5
Comments
187,900 gallons
48,000 gallons
48,000 gallons
507,600 gallons
54 Openings
Dip pipe loading
Reactor Discharge
Sampling Program
13,600 gallons
13,600 gallons
13,600 gallons
51,456 gallons
100,455 gallons
18.260 gallons
4,750 gallons
Splash Fill
Reactor
Overpressurlzatlon
(7 times)
(Continued)
-------
TABLE 2-3 CONCLUDED. CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITIES
PRODUCING METHYLENE CHLORIDE
t\5
I
Company/Location
Vulcan Chemicals
Gelsmar* LA
Vulcan Chemicals*
Wichita. KS
Type of Emission/ Present Controls Reported
Source Control Efficiency
Process Vent
o » » »
Equipment Leaks * "
Storage * *
Equipment Opening * *
Handling » «
Secondary * *
Relief Devices « »
Process Vent
0 « « «
Equipment Leaks * *
Storage
0 » « »
Equipment Opening " *
Handling * *
Present
MC Emissions Comments
(Mg/yr)
0.7
35.5
19.3
0.6
8.2
3.9
0.01
12.3
38.1
32.2
0.8
6.2
"This Information Is considered by the company to be confidential.
Company reported greater than 98 percent control, but 93 percent was used 1n
the absence of supporting test data.
N/A = Not applicable.
N/R = Not reported.
-------
Losses from product storage were approximately 18.3 Mg/yr. All
information concerning storage facilities and controls is considered
confidential by Dow. Since methylene chloride is excluded from regulation
in Texas, no state storage tank regulations are applicable to the Dow
plant.
Losses due to handling were approximately 4.2 Mg/yr. Methylene
chloride product is currently loaded and transported in tank trucks,
tank cars, barges and ships using open dome loading. It is also shipped
in 55 gallon drums which are loaded using a flume vacuum system.
Emission levels were calculated by Dow from air samples taken during
tank truck and rail car loading.
Dow reported two process waste emission sources. These are a
wastewater stream and spent filter elements. The two sources emit
approximately 0.8 Mg/yr of methylene chloride. The wastewater stream is
treated in a nonbiological treatment system, and the spent filter
elements are treated in a material and energy recovery unit. The
wastewater stream accounts for 99% of the secondary emissions. Dow
indicated a formal wastewater monitoring procedure is followed where a
sample is taken every fifteen minutes and analyzed in a gas
chromatograph. Dow reported the wastewater monitoring system as a means
of monitoring MC secondary emissions.
The methylene chloride emissions from 216 process equipment
openings in 1983 were 0.05 Mg/yr. Ninety-five percent of the equipment
openings were for pump seal replacement. The remaining five percent of
equipment openings were on larger pieces of equipment during routine
cleaning and inspection. Dow reported that the vessels are cleared to a
concentration of 200 ppm organics before being opened. Dow did not
describe the procedure followed to clear vessels of organics.
There were no emissions from process vents at the Freeport facility.
Dow reported that there are no process vents and all vapor streams are
recycled within the process.
2-13
-------
Vulcan Materials - Geismar. LA
Total emissions generated by the hydrochlorination process at this
plant were 68.2 Mg in 1983. The largest quantity of emissions was from
equipment leaks. Methylene chloride equipment leak emissions in 1983
were approximately 35.5 Mg. Product storage tanks released 19.3 Mg of
methylene chloride to the atmosphere in 1983. Secondary emissions from
waste treatment or disposal were 3.9 Mg. Emissions from process vents,
handling, and equipment openings were 0.7 Mg/yr, 8.2 Mg/yr and
0.6 Mg/yr, respectively. Relief device discharges emitted .01 Mg of
methylene chloride in 1983. All information concerning equipment (such
as process vents, process components including valves and flanges, and
storage facilities) and controls is considered confidential by Vulcan.
The State of Louisiana has adopted regulations for control of
emissions of volatile organic compounds from storage facilities, loading
facilities, process components and specific MC end uses such as surface
coating and solvent metal cleaning. Methylene chloride is excluded from
these regulations. However, mixed streams containing methylene chloride
may be controlled under these regulations.
Vulcan Materials - Wichita. KS7
Emissions from MC production by the direct chlorination of methane
and the hydrochlorination of methanol were 89.6 Mg at this facility in
1983. Vulcan did not distinguish equipment leaks, storage emissions,
handling losses, and equipment opening losses by production process.
Process vent emissions were reported only for the hydrochlorination
process.
The largest quantity of emissions was from equipment leaks.
Methylene chloride equipment leak emissions in 1983 were approximately
38.1 Mg. Product storage tanks released 32.2 Mg of MC to the atmosphere
in 1983. Process vents emitted 12.3 Mg of MC. Emissions from handling
and equipment openings were 6.2 Mg and 0.8 Mg, respectively. All
information concerning equipment and controls is considered confidential
by Vulcan.
There are no regulations in Kansas for control of organic compound
emissions from chemical production facilities.
2-14
-------
g
Diamond Shamrock - Belle. WV
This plant emitted 116 Mg of MC in 1983. The largest quantity of
emissions was from equipment leaks, totalling 75.2 Mg. Fifty-five
percent (41.5 Mg) of the equipment leaks were from valves. Nineteen
percent (14.6 Mg/yr) were from flanges and fifteen percent (11.3 Mg/yr)
from pump seals. Diamond Shamrock has equipped 52 percent (13 of 25) of
their pressure relief devices with rupture disks. The plant indicated
that operators make hourly checks of the operating equipment to check
for leaks. Also, all employees are required to wear sample pumps on
their person several times per year. Exposure levels are used to
identify potential problems. Since no leak repair frequency was
reported by Diamond Shamrock, no control efficiency could be estimated
for their inspection program and equipment leak emission estimates are
for uncontrolled sources. Therefore, actual equipment leak emissions
may be somewhat lower.
Emissions from sixteen fixed roof storage tanks are estimated to
have been 26.1 Mg in 1983. Tanks range in volume from 250 gallons to
500,000 gallons. The 500,000 gallon fixed roof tank had 1983 emissions
of 4.4 Mg and is equipped with a conservation vent, a water cooled
condenser, and a freon cooled condenser for a combined estimated control
efficiency of 90.7 percent. Seven other storage tanks (with volumes
between 15,000 and 20,000 gallons) are equipped with conservation vents
and water cooled condensers. Control efficiencies range from 41.9
percent to 86.7 percent. The remaining eight storage tanks are not
equipped with emission control devices.
MC emissions from process vents were 5.7 Mg. Sixty-seven percent
(3.8 Mg/yr) of these emissions were from a regeneration vent. There was
no methylene chloride control device for this vent. Two vent recovery
systems emitted 19 percent and 14 percent of total process vent emissions.
Both vents are equipped with condensers with control efficiencies of
68.5 percent and 26.7 percent, respectively.
Total emissions from loading/handling were 4.2 Mg/yr. Methylene
chloride is loaded into tank cars, tank trucks, and barges. Tank cars
and tank trucks are loaded through the domes. Barges are loaded from
the bottom and are vented through a four inch header on either end of
the barge.
2-15
-------
A pressure relief valve malfunction resulted in a discharge of
3.4 Mg of MC in 1983. The relief valve was on a methyl separation
column reboiler. This was the only emission from relief devices in 1983,
Equipment opening losses totalled 1.1 Mg in 1983. There were
12 major equipment openings and 150 minor equipment openings.
Secondary emissions of MC from three waste streams totalled about
0.7 Mg/yr. Emissions from the waste treatment plant influent
contributed only 7 percent (.05 Mg/yr) of the total. The waste is
treated by steam stripping and carbon adsorption. Disposal and related
activities accounted for the major portion of secondary emissions.
Sixty percent (0.43 Mg/yr) of MC emissions were from drumming solid
waste for off-site landfilling. Loading sludge from the waste treatment
plant into bulk tank trucks for off-site treatment contributed
approximately 33 percent (.24 Mg/yr) of emissions.
West Virginia does not have regulations requiring control of MC
emissions from this plant.
Dow Chemical - Plaquemine.. LA9
Dow - Plaquemine produces MC by the hydrochlorination of methanol.
Total emissions of MC at the facility were 217 Mg in 1983.
The largest source of air emissions reported at the Dow facility
was from loading and handling practices. Dow calculated losses to be
115 Mg (53% of total emissions). Methylene chloride is shipped by tank
truck, tank car, and barge. Submerged fill pipe loading is used to
reduce emissions from what would occur with splash fill loading.
Louisiana regulates loading facilities for VOC with throughputs of
20,000 gallons/day or more (40,000 gallons or more for existing
facilities), but methylene chloride is excluded from this regulation.
Emissions from storage facilities contributed 34 percent (73.5 Mg)
of total 1983 MC emissions. Dow has five fixed roof storage tanks and
one contact internal floating roof storage tank with a mechanical shoe
floating roof seal (primary only). None of the storage tanks are
equipped with control devices. Louisiana regulations on VOC storage
tanks are not applicable to MC.
2-16
-------
Emissions from equipment leaks totalled 27.5 Mg in 1983.
Twenty-five pressure relief devices were the largest source of
emissions, releasing 8.7 Mg (32%) of the total equipment leaks
emissions. One pressure relief device in gas service was equipped with
a rupture disc. Emissions from valves were 8.5 Mg (31 percent) of
equipment leak emissions. Nineteen percent (5.2 Mg) of the total
equipment leaks emissions were released from mechanical pump seals.
Liquid and gas sample connections were the sources of 15 percent of
equipment leaks emissions, contributing 1.6 Mg and 2.4 Mg respectively.
A compressor was the next largest source, emitting five percent (1.0 Mg)
of total equipment leaks emissions. To monitor equipment for leaks, Dow
has installed two process vapor phase chromatographs each capable of
analyzing 10 streams. Twenty points in the process area are monitored
and an alarm is set at 100 ppm. In addition, Dow requires operators to
make a minimum of 12 rounds through the process, storage area per 24
hour day. Other formal division-wide programs include preventative
maintenance, a pressure valve program, pressure safety valve, critical
instrument, equipment thickness check, and visual internal inspections.
In January, 1985 an equipment leaks emissions test conducted at Dow
indicated 1.6 percent of the valves and 0.91 percent of the flanges were
leaking. Calculated emission estimates incorporate this test data.
Louisiana regulations requiring a VOC leak patrol/repair program do not
apply to MC.
Losses from equipment openings were 0.6 Mg in 1983. The emissions
were from 24 pump openings, 10 vessel openings, and 20 piping openings.
Dow reported one discharge from pressure relief devices in 1983. A
reactor instrument malfunction resulted in the discharge of .05 Mg of
MC. A waste stream from the plant emitted approximately 0.02 Mg of MC.
Dow reported no process vents emitting MC.
LCP Chemicals - Moundsville. WV10
The production of MC at this facility resulted in total emissions
of 165 Mg MC in 1983. Emissions from two process vents were about 84.9
Mg, or 51 percent of total emissions. An unidentified process vent
emitted more than 99 percent (84.3 Mg) of those emissions. LCP reported
2-17
-------
that the process vent is controlled by a chloromethanes purge condenser
that is operating at 100 percent pollutant removal efficiency. However,
the purge condenser is only in operation for 50 percent of the plant
operating hours. Therefore, the process vent emissions reported are for
when the purge condenser is inoperative and the process vent is
uncontrolled. The remaining process vent emissions (.05 Mg) were from a
chloromethanes recovery tank.
Emissions from equipment leaks accounted for 17 percent of total
emissions, or 28.5 Mg. The largest sources of equipment leaks were
valves, flanges, and pressure relief devices. Emissions from the valves
were approximately 12.4 Mg (44 percent of total equipment leaks
emissions). Twenty-two percent (6.2 Mg) of the emissions were from
flanges. Pressure relief devices constituted 12 percent of these
emissions. LCP indicated that five areas are manually sampled once per
shift for contaminants. The samples are transported to the plant
laboratory and analyzed by gas chromatograph. Since no leak repair
frequency was reported no control efficiency could
be estimated for LCPs inspection program. Therefore, all emission
estimates are for uncontrolled sources. This may overstate LCP's
equipment leak emissions.
Losses from product loading and handling were approximately 23.7 Mg
MC in 1983. Methylene chloride is loaded into rail cars and trucks by
the top splash fill method at a rate of approximately 75 gpm.
Approximately 30 percent of the MC is transported by rail cars with the
remaining 70 percent transported by truck.
Seven fixed roof storage tanks emitted 21.1 Mg of MC in 1983. None
of the storage tanks are equipped with control devices.
Secondary emissions from three waste streams totalled 6.4 Mg in
1983. A waste stream sent to off-site treatment and disposal contributes
70 percent of the secondary emissions. Twenty-one percent of the
secondary emissions were from distillation and recovery. Emissions from
treatment by neutralization and carbon adsorption accounted for
9 percent of secondary emissions. LCP reported a fourth waste stream
treated by neutralization. However, no information was given regarding
MC concentration in this stream.
2-18
-------
LCP reported 8 discharges from pressure relief devices in 1983.
All of the discharges were due to overpressurization of a thermal
reactor. Estimated emissions were 0.5 Mg.
There were 104 changeouts of liquid driers in 1983. A changeout is
accomplished by opening the drier and removing the spent drier residue.
LCP indicated that emissions from drier changeouts were 0.9 Mg.
West Virginia has no regulations governing volatile organic
compounds.
2.4 COST OF ADDITIONAL CONTROLS
Cost estimates were developed for control of process vent, fugitive,
storage, and loading emission sources not presently well controlled.
The cost effectiveness to control each of these emission sources at
facilities producing methylene chloride are presented in Table 2-4 and
discussed in the following sections. Methods used for estimating costs
are presented in Appendix B.
The achievable emission reduction for different VOC cost
effectiveness ranges is presented in Table 2-5. The achievable MC
emission reduction is 552 Mg. This emission reduction can be compared
to total estimated MC emissions of 770 Mg in 1983 (presented in Table
2-2).
2.4.1 Control of Process Vent Emissions
Incinerator cost estimates were developed for process vents not
presently controlled by 98 percent or better. These estimates along
with the estimated cost effectiveness are presented in Table 2-4. Three
facilities, Diamond Shamrock in Belle, WV, LCP Chemicals in Moundsville,
WV, and Vulcan Chemical, in Wichita, KS reported process vents not
presently controlled 98 percent or better. The cost effectiveness of
controlling process vent emissions at LCP, Diamond Shamrock and Vulcan
is $l,220/Mg of VOC, $16,200/Mg of VOC and $17,100/Mg of VOC
respectively. The combined MC emission reduction is 88.7 Mg, an
86 percent reduction in process vent emissions from all MC production
facilities.
2-19
-------
TABLE 2-4. COST OF ADDITIONAL CONTROLS
AT MC PRODUCTION FACILITIES
ro
i
ro
o
Company/Location
Diamond Shamrock
Belle, WV
Dow Chemical
Freeport, TX
Don Chemical
Plaquemlnet LA
Emission Type
Process
Equipment Leak
Storage
Storage
Storage
Storage
Storage
Storage
Storage
Storage
Loading
Equipment Leak
Storage
Storage
Storage
Loading
Equipment Leak
Storage
Storage
Storage
Storage
Loading
Loading
Control"
Incineration
LDAR
CO NO
FR-PO
FR-SS
FR-SS
CONO
CONO
FR-PO
FR-SS
CONO
LDAR
FR-SS
FR-SS
FR-SS
CONO
condenser
LDAR
FR-SS
FR-SS
FR-SS
FR-SS
CONO
CO NO
Control
Efficiency
(X)
98
53
85
94
97
97
85
85
94
97
90
60
97
97
97
90
68
97
97
97
97
90
90
HC/VOC Emission
Reduction
(Mg/yr)
5.6/25.8
40.C/81.6
l.l/ 1.4
0.4/ 0.4
2.8/ 2.8
10.3/12.5
O.I/ 0.1
O.I/ 0.1
1.8/ 1.8
1.7/ 2.2
3.5/ 3.5
52.4/72.0
1.9/ 1.9
3.8/ 3.9
3.8/ 3.9
3.8/ 3.8
18.6/31.3
6.2/ 6.2
2.6/ 2.6
11.7/11.7
45.4/45.4
51.9/51.9
51.9/51.9
Capital
Cost
(lO^S)
1,220
58.0
111
14.7
16.9
35.3
111
111
32.7
16.9
247
56.0
19.0
18.8
18.8
247
60.6
39.1
26.9
50.6
53.5
247
380
Recovery
Credit
(103$)
0.0
33.1
1.0
0.2
2.3
9.1
0.1
0.1
0.9
1.6
1.5
31.9
1.5
3.1
3.1
1.7
13.2
5.0
2.1
9.5
37.0
22.8
22.8
Net
Annual
Cost
(103J)
418.5
29.5
28.1
3.7
2.1
0.2
29.0
29.1
7.7
2.9
108
16.8
3.4
1.8
1.8
108
27.1
5.2
4.9
3.8
-22.9
88.1
145
Cost Effectiveness
MC VOC
($/Mg) ($/Mg)
74,900
737
26,100
10,500
753
16
286,000
402,000
4,220
1,650
30,800
321
1,820
477
477
28,500
1,460
852
1.890
324
-505
1,700
2,800
16,200
361
20,700
10,500
753
13
284,000
318,000
4,220
1,310
30,800
234
1,820
463
463
28,500
866
852
1,890
324
-505
1,700
2,800
(Continued)
-------
TABLE 2-4 CONCLUDED.
COST OF ADDITIONAL CONTROLS
AT MC PRODUCTION FACILITIES
ro
i
ro
Company/Location
LCP Chemicals
Moundsvllle, WV
Vulcan Chemical
Geismar, LA
Vulcan Chemical
Wichita. KS
Emission Type
Process
Equipment Leak
Storage
Storage
Storage
Storage
Storage
Loading
Equipment Leak
Storage
Storage
Loading
Process
Equipment Leak
Storage
Storage
Storage
Storage
Storage
Storage
Storage
Loading
Control
Efficiency
Control" (X)
Inc Ineratlon
LDAR
COND
FR-SS
FR-SS
COND
FR-PO
COND
LDAR
FR-SS
FR-PO
COND
Incineration
LDAR
CONO
COND
COND
COND
COND
COND
COND
COND
98
59
65
97
97
85
94
90
49
97
94
90
98
58
85
85
85
85
85
85
85
90
MC/VOC Emission
Reduction
(Mg/yr)
82.
16.
3.
4.
10.
1.
0.
21.
17.
14.
4.
4.
0.
22.
0.
0.
0.
0.
11.
8.
0.
5.
4/329
7/56.6
2/3.2
2/ 4.2
4/10.4
5/ 1.5
5/ 0.5
3/21.3
4/33.2
5/14.5
2/4.2
0/4.0
7/24.1
0/50.5
4/ 0.4
6/ 0.6
4/ 0.4
8/ 0.8
9/11.9
1/16.2
5/ 9.5
6/ 5.6
Capital
Cost
(103$)
1,190
133
333
18.4
35.1
111
12.5
219
27.6
105
77.1
83.6
1.210
47.5
111
111
111
333
222
in
111
247
Recovery
Credit
(1CP$)
0.0
21.3
2.6
3.4
8.5
1.2
0.2
9.4
13.6
11.8
2.0
1.7
0.0
20.1
0.3
0.5
0.3
0.6
9.7
9.2
3.4
2.5
Net
Annual
Cost
(103$)
403
27
84
1
0
27
3
88
20
15
18
166
410
21
28
28
28
86
485
19
25
107
.0
.8
.4
.7
.9
.1
.5
.1
.7
.2
.0
.8
.6
.8
.7
.9
.8
Cost Effectiveness
MC VOC
(I/My) (t/Mg)
4,900
1,620
26,500
344
69
18,900
6,690
4,200
1,150
1.080
4,370
41,400
585,000
954
80.200
49,100
80,900
112,000
4,060
2.460
54,300
19,100
1,220
478
26,500
344
69
18,900
6,690
4,200
605
1,080
4,370
41,400
17,100
416
80,200
49,100
80,900
112,000
4,060
1,230
2,710
19,100
"Abbreviations
FR-SS: Floating roof »1th primary and secondary seals.
FR-PO: Floating roof with primary seals only.
COND: Refrigerated condenser.
LDAR: leak Detection and Repair.
Product storage tank: emissions previously described as process vent emissions.
-------
TABLE 2-5. ESTIMATED MC EMISSION REDUCTIONS FOR
MC PRODUCTION FACILITIES AS A FUNCTION
OF COST EFFECTIVENESS
Nationwide MC Emission Reduction (Ma/vrl
Cost Effectiveness
Range ($/Mg VOC)
Credit
0 - 500
501 - 1000
1001 - 2000
2001 - 5000
> 5000
Process Equipment
Leaks
-
131
36.0
82.4
-
6.3
Storage
45.4
44.2
9.0
28.8
18.1
9.1
Loading Total
45.4
175
45.0
51.9 163
73.2 91.3
16.9 32.3
TOTAL 88.7 167 155 142 552
2-22
-------
2.4.2 Control of Equipment Leak Emissions
The costs for additional control of equipment leak emissions from
process components were estimated based on the requirements of the
benzene equipment leaks NESHAP and the equipment count data supplied by
the production facilities. The potential reduction in emissions from
equipment leaks is estimated to be 167 Mg MC, 57 percent of total
emissions from equipment leaks. Control efficiencies associated with
controlling equipment leak sources range from 49 percent at the Vulcan-
Geismar facility to 68 percent at the Dow-Piaquemine plant. MC emission
reductions range from 16.7 Mg at the LCP plant (control efficiency
58 percent) to 52.4 Mg at Dow-Freeport (control efficiency 60 percent).
The cost effectiveness of controlling equipment leaks ranges from
$234/Mg VOC at Dow-Freeport to $866/Mg VOC at the Dow-Piaquemine plant.
2.4.3 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. Internal floating roofs were
not costed for tanks smaller than 2 meters in diameter or horizontal
tanks. Costs/cost-effectiveness estimates are presented in Table 2-4
for the most cost effective option. Using the most cost-effective
option, storage emissions may be reduced by 155 Mg of MC (82 percent).
The estimated cost effectiveness ranges from a net credit of $505/Mg of
VOC to $573,000/Mg of VOC for the most cost-effective option on
individual tanks. The estimated MC cost effectiveness is almost
identical because these tanks store product MC typically greater than 99
percent pure. Since emissions are a function of throughput as well as
size, there is no direct correlation between tank size and cost
effectiveness. Achievable storage tank emission reduction as a function
of cost effectiveness is presented in Table 2-5.
2-23
-------
2.4.4 Control of Loading Emissions
Costs and cost-effectiveness estimates were developed for each
uncontrolled land and marine loading operation. A refrigerated vapor
recovery system operating at 90 percent MC removal efficiency was used
as the control technique. The estimated costs of controlling each type
of loading operation at individual facilities are presented in Table
2-4. The range of estimated cost effectiveness is $l,700/Mg VOC to
$41,400/Mg of VOC. Using refrigerated vapor recovery as the control
technique, total loading emissions may be reduced by 142 Mg
(88 percent).
2-24
-------
2.5 REFERENCES
1. Mannsville Chemical Products. Chemical Products Synopsis-Methylene
chloride. Cortland, New York. 1984.
2. Chloromethanes Makers Project Further Gains After Strong '84:
DuPont Shift to Alter the Market. Chemical Marketing Reporter.
227(6):5,15,17, 1984.
3. SRI International. 1984 Directory of Chemical Producers. Stanford
Research Institute International. Menlo Park, California.
4. Organic Chemical Manufacturing, Volume 8: Selected Processes,
U. S. Environmental Protection Agency, Office of Air Quality
Planning and Standards, Research Triangle Park, North Carolina,
Publication No. EPA-450/3-80-028C. December, 1980.
5. Letter and attachments from Arnold, S.L., Dow Chemical U.S.A., to
Farmer, J.R., EPA:ESED. March 7, 1985. Response to MC 114
Questionnaire.
6. Letter and attachments from Berg, R.E., Vulcan Chemicals, to
Farmer, J.R., EPA:ESED. January 31, 1985. Response to MC 114
Questionnaire.
7. Letter and attachments from Boyd, J.M., Vulcan Chemicals, to
Farmer, J.R., EPA:ESED. February 1, 1985. Response to MC 114
Questionnaire.
8. Letter and attachments from Christensen, B.H., Diamond Shamrock
Company, to Farmer, J.R., EPA:ESED. January 31, 1985. Response to
MC 114 Questionnaire.
9. Letter and attachments from Arnold, S.L., Dow Chemical U.S.A to
Farmer, J.R., EPA:ESED. March 12, 1985. Response to MC 114
Questionnaire.
10. Letter and attachments from Morris, A.R., LCP Chemicals, to Farmer,
J.R., EPA:ESED. February 28, 1985. Response to MC 114
Questionnaire.
2-25
-------
3.0 OTHER CHEMICAL PLANTS
3.1 PROCESS DESCRIPTIONS, EMISSIONS, AND CURRENT CONTROLS
This chapter presents the emissions and controls associated with
the use of methylene chloride (MC) as a raw material used in the
synthesis of other chemical products. Eleven plants use MC in
production processes. These processes include: triacetate fibers,
polycarbonate resin, plastics, rubber cement, rubber accelerator,
insulating materials, specialty chemicals, vinyl chloride monomer, and
production of BAYGONR 1.5, a pesticide. Emissions from BAYGONR 1.5
production are duscussed in this chapter since detailed emission
estimates were received from the company for this facility. The chapter
on Pesticide Manufacturing (Ch. 8) presents only generalized consumption
and emissions information for the pesticide industry. MC is also used
in other chemical production processes which are not identified because
the company either considers production process descriptions as
proprietary information, or the company did not provide sufficient
information on the type of operation."
Methylene chloride emissions from these chemical plants are from
equipment leaks, raw material storage, process vents, equipment
openings, loading and handling, and secondary sources. The plants using
MC in production and the types and amounts of emissions from these
plants are presented in Table 3-1.
3-1-1 Triacetate Fiber Production
Triacetate fiber is manufactured by Celanese Fibers Operation in
Rock Hill, South Carolina. Methylene chloride is used by Celanese to
dissolve triacetate polymer flake and form a liquid polymer (referred to
as "dope") that is suitable for extruding.
3.1.1.1 Process Description . A solution of methylene chloride
and methanol is fed into a batch mixer containing triacetate polymer
flakes and other dry ingredients.
3-1
-------
TABLE 3-1. TOTAL EMISSIONS FROM CHEMICAL PLANTS USING METHYLENE CHLORIDE IN PRODUCTION
Plant/Location
B.F. Goodrich, Plant I
Cleveland, OH
B.F. Goodrich, Plant II
Cleveland, OH
Burden Chemical
Fremont, CA
Borden Chemical
Norrlstown, PA
Celanese
Rock Hill, SC
Dow Chemical
Midland. MI
General Electric
Mount Vernon, IN
General Electric
Plttsfleld, MA
General Electric
Scnenectady. NY
Mobay Chemicals
Baytown, TX
Mobay Chemicals
Kansas City. MO
Shell
Deer Park, TX
Process
65. 6C
7.5
2.2
—
5150
1120
2680
64.9
0.01
0.4
9090
Equipment Leaks
4.6
10.1
0.003
2.1
22.0
207
247
6.1
0.001
51.2
0.02
550
1983 Methvlene Chloride Emissions (Mg/Yr)
Relief Oovlces Storage Handling Equipment Openings Secondary Total
0.2 169 239
0.5 18.1
0.3 2.S
0.8 0.3 3.2
2.7 0.5 5180
0.1 29.0 2.7 4.3 88.5 1450
63.7 584 3570
0.3 0.2 2.3 0.2 74.0
0.2 0.2
0.2 0.6 16.5 74.4 143
0.4 0.4
0.06 0.06
2.8 31.0 4.3 86.8 917 10,700
Based on equipment count provided by plants and SOCMI fugitive emission factors.
Based on storage tank Information provided by plants and AP-42 equations.
Combined emissions from process vents, equipment openings, and loading and handling.
-------
The solvents are slowly mixed with the solids until the solids are
completely dissolved, forming the liquid polymer dope. The dope is then
filtered and pumped to the extrusion area, where it is preheated, and
then extruded and dried. The dried fibers are spun onto bobbins until
further processing including twisting, coning, and beaming. A process
flow diagram is shown in Figure 3-1.
2
3.1.1.2 Current Emissions and Controls . Methylene chloride
emissions totalled 5180 Mg at the Celanese facility in 1983. Emission
sources, current controls, control efficiencies, and emission amounts
are given in Table 3-2. The major emission source from triacetate fiber
production is from solvent recovery. Carbon adsorption units operating
at a reported control efficiency of greater than 98 percent are used to
recover spent solvent. Emissions from the units were 5150 Mg in 1983.
Celanese did not report any other process vent emission points.
Equipment leaks were the source of 22.0 Mg of MC emissions. Valves
contributed 51 percent (11.2 Mg) of those emissions. Flanges and pumps
seals emitted 22 percent (4.9 Mg) and 21 percent (4.6 Mg), respectively.
To monitor for equipment leaks, Celanese operates four infra-red gas
analyzers in different process areas. The analyzers measure room
concentrations and are equipped with recorders and alarms. These
instruments are useful in detecting process upsets and spills, but not
for determining individual equipment leaks. Celanese did not report a
leak repair program, therefore no control efficiency could be estimated
for their inspection program and emission estimates are for uncontrolled
sources. This may overstate somewhat Celanese's equipment leak
emissions.
Handling emissions accounted for about 0.5 Mg of MC emissions at
the Celanese facility. Methylene chloride is received by tank truck and
tank car. The tank truck or tank car compartments are pressurized with
inert gas and the MC is pumped to storage tanks. The storage tanks are
tied into the solvent recovery ducting. Therefore, losses occur only
when the tank truck or car is empty and the compartment is depressurized
into the atmosphere. Celanese indicated that there are no emissions
from MC storage since storage tanks are vented into the solvent recovery
ducting.
3-3
-------
METHYLENE
CHLORIDE
CO
-p-
TRIACETATE
POLYMER
FLAKE
FILTER
EXTRUSION
BOBBIN
BOBBIN
TRANSPORT
BOBBIN
STORAGE
TEXTILE DEPT
TWISTING
CONING
BEAMING
'-STORAGE
Figure 3-1. Process flow diagram for the production of triacetate
fiber.
-------
TABLE 3-2 ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
CO
I
en
Company/Location
B.F. Goodrich
Cleveland, OH
Plant I
B.F. Goodrich
Cleveland. OH
Plant II
Borden Chemical
Fremont. CA
Borden Chemical
Norrlstown, PA
Product Type of Emissions
Rubber
Accelerator Miscellaneous
Equipment Leaks
Storage
o Fixed-Roof lank
Secondary
o Product water wash
Rubber
Accelerator Process
o Vacuum Jet pump
Equipment Leaks
Storage
o Pressure vessel
o Pressure vessel
o Pressure vessel
Rubber Cement Process
o Adhestves fume
collection
Equipment Leaks
Secondary
o Waste product drums
Liquid Chemical Equipment Leaks
Specialty
Products
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
Reported Control
Present Controls Efficiency (*)
None
None
To POTW
Water cooled condenser.
refrigerated condenser
None
Back pressure relief valve
Back pressure relief valve
Back pressure relief valve
None
None
To solvent reclaimer
None
None
None
None
None
0
0
NR
94
0
NR
NR
NR
0
NR
0
0
0
0
0
Present MC
Emissions (Mg/yr) Comments
65.6
4.6
0.2
169
7.5
10.1
0.06
0.1
0.4
2.2
0.003
0.3
2.1
0.4
0.2
0.1
0.06
From mass balance-
See discussion
Visual Inspection
No monitoring
750 gallons
750 gallons
750 gallons
4 process
components
Visual Inspection
5.000 gallons
10.000 gallons
5.000 gallons
3.000 gallons
(Continued)
-------
TABLE 3-2 CONTINUED. ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
CO
I
Company/Location
Borden Chemical
Norrlstown. PA
(Cont'd)
Celanese
Rock Htll, SC
Dow Chemical (IS)
Midland. MI
Dow Chemical (/6)
Midland. MI
Product Type of Emissions
Handling
o Tank trucks
o Product handl 1ng
Triacetate Process
Fibers o Solvent Recovery
Equipment Leaks
Handl Ing
o Tank truck.
tank car
Relief Devices
Unidentified Process
0 »
Equipment Leaks
Storage
o Fixed-Roof Tank
Equipment opening
Handling
o Tank truck
Unidentified Process
o »
Equipment Leaks
Storage
o Pressure vessel
o Pressure vessel
Equipment opening
Reported Control
Present Controls Efficiency (X)
None 0
Carbon Adsorption 98b
Infra-red gas analyzers 0
Vent to solvent recovery NR
NA
* K
Pressure relief device
controls 0
Vapor Return
Conservation vent 98
None 0
Vapor balance line 95
« «
Pressure relief device
controls 0
None 0
None 0
None 0
Present MC
Emissions (Mg/yr) Comments
0.3
5150
22.0
0.5
2.7
1.7
8.2
0.003
0.02
0.03
67.1
16.6
.01
.02
0.04
Mixer Rupture
Dtsharge
3 vents
Visual Inspection
preventive
maintenance
17 openings
1 vent
Visual Inspection
preventive
maintenance
30 gallons
100 gallons
200 openings
(Experimental pro-
cess-small lines)
(Continued)
-------
TABLE 3-2 CONTINUED. ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
CO
I
Company/Location
Dow Chemical (17)
Midland. HI
Oow Chemical (16)
Midland. MI
Dow Chemical (t9)
Midland. MI
Product Type of Emissions
Unidentified Process
o »
Equipment Leaks
Equipment opening
Secondary
o Liquid waste stream
Unidentified Process
0 »
Equipment Leaks
Equipment opening
Secondary
o Liquid waste stream
o Liquid waste stream
o Liquid waste stream
o Liquid waste stream
o Liquid waste stream
Unidentified Process
0 «
Equipment Leaks
Storage
o Pressure vessel
o Pressure vessel
o Pressure vessel
Handling
o Tank cars
Reported Control Present MC
Present Controls Efficiency (X) Emissions (Mg/yr> Comments
*
None
None
Biological Treatment
*
Chroma tographlc Air
Monitoring Pressure
Relief device controls
None
Blotreatment
Blotreatment
Process Recovery
Process Recovery
Incinerator
*
Pressure relief device
controls
Pressure Relief Device
Pressure Relief Device
Pressure Relief Device
None
«
0
0
NR
*
NR
0
NR
NR
NR
NR
NR
*
NR
NR
NR
0
54. S
5.5
0.2
40.2
52.5
60.1
0.3
0.006
1.0
12.8
0.01
0
135
13.3
0.5
0.1
1.0
1.4
1 vent
Visual Inspection
preventive main-
tenance
2 openings
4 vents
54 openings
2 vents
Visual Inspection
Preventive main-
tenance
10,000 gallons
500 gallons
8.000 gallons
(Continued)
-------
TABLE 3-2 CONTINUED. ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
CO
I
co
Company/Location
Dow Chemical (110)
Midland. MI
Dow Chemical (111)
Midland. MI
Dow Chemical (/12>
Midland. HI
Product Type of Emissions
Unidentified Process
o «
Equipment Leaks
Storage
o Pressure vessel
Equipment openings
Handling
o Rail car
Secondary
o Liquid Waste Stream
Unidentified Equipment Leaks
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
Equipment opening
Unidentified Process
0 «
Equipment Leaks
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
o Pressure vessel
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
Equipment opening
Secondary
o Liquid waste stream
Relief devices
Reported Control Present MC
Present Controls Efficiency (X) Emissions (Mg/yr) Comments
*
Quarterly air monitoring
pressure relief device
control s
None
None
None
Olotreatment
Continuous Air Monitor
Relief Valve
Relief Valve
Relief Valve
Relief Valve
Relief Valve
None
*
Continuous Air Monitor
Relief Valve
Vented to Scrubber
Water seal and relief valve
Vented to Scrubber
Vented to Scrubber
None
None
Biological Treatment
NA
•
NR
0
0
0
NR
NR
NR
NR
NR
NR
NR
0
«
NR
NR
NR
NR
NR
NR
0
0
S
0.7
27.6
1.0
0.7
1.3
1.2
6.7
0.4
0.4
0.08
0.08
0.02
0.5
810.8
68.7
12.0
3.7
4.7
1.8
1.9
1.0
2.5
33.3
0.1
2 vents
Visual Inspection
32.000 gallons
100 openings
20 sampling probes
2,650 gallons
2,850 gallons
1,900 gallons
2,000 gallons
2,850 gallons
115 openings
3 vents
20 sampling probes
47,000 gallons
5,900 gallons
12.900 gallons
5.900 gallons
4.300 gallons
12,900 gallons
234 openings
Storage tank
corrosion failure
(Continued)
-------
TABLE 3-2 CONTINUED. ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
CO
I
UD
Company/Location Product Type of Emissions
General Electric Polycarbonate Process
Mount Vernon. IN Resin o Moppor Oryors
o Ikippor Oryors
o Extruder Die Moods
o Extruder Die Hood
o Extruder Die Hood
o Extruder Die Hood
o Extruder Die Hood
o Extruder Die Hood
o Molding Machine
Vents
o Q.A. Hood Vent
o Extruder Die Vents
o Extruder Vacuum
Pump
o Extruder/Die Vent
o Extruder/Ole Vent
o Molding Machine
o Vacuum Stripping
Blowers
o Vent Gas Absorber
o Vent Gas Absorber
o Carbon Adsorption
System
o Fl Her Receiver
o Filter Receiver
o Height Hopper Vent
o Feed Hopper
o Surge Hopper
o MC Storage Tank
o Storage Silo
o Solvent Recovery
o MC Dryer System
o Tar/lsomer Storage
Equipment Leaks
o Building 14/16
o Building 15/31
Reported Control Present MC
Present Controls Efficiency <*) Emissions (Mg/yr) Comments
None
Nonn
None
Mono
None
None
Hone
None
None
None
None
None
None
None
None
None
Hater Scrubber
Water Scrubber
Carbon Bod
None
None
None
None
None
Conservation Vent
None
Carbon Bed
Knock Out Pot/Domlster
None
Photo lontzatlon
detection system
Photo lonlzatlon
detection system
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
87
87
87
0
0
0
0
0
10
0
87
50
0
0
0
17.0
18.6
224.6
4.5
2.5
8.6
13.4
0.2
4.8
6.4
391
86.4
11.2
93.8
3.2
0.6
477.3
477.3
46.2
85.6
85.6
0.6
0.3
7.6
17.6
170
347
79.6
0.4
175
71.8
41 dryers
45 dryers
7 hoods
hood
hood
hood
hood
hood
2 vonts
4 vents
17 vents
6 pumps
3 vents
8 vents
2 units
4 units
1 vent
1 vent
2 units
2 units
2 units
1 unit
2 units
Monitors 40 points
Monitors 10 points
(Continued)
-------
TABLE 3-2 CONTINUED. ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
Reported Control Present MC
Company/Location Product Type of Emissions Present Controls Efficiency (I) Emissions (Hg/yr) Comments
General Electric
Mount Vornon, IN
(Cont'd)
Storage
o 44 process and
storage vessels Vent gas absorbers 87
o Pressure Vessel Conservation Vent 10
Equipment Opening None 0
Secondary
o Biological
Treatment None 0
0.1 Bldg 14/16
1.5 Bldg 15/31
63.7
564
CO
I
General Electric Plastics Process
PHtsfleld, MA Manufacture o Reactor Vent None
o Phosgenatlon
Reactor None
o Predp.Room Vent None
o Work-up Room Vent None
o Stripper Room Vent None
o Stripper Room Vent None
o Perclp. Condenser
Vent Condenser
o MC Still Water-tank None
o Area Vent None
o MC Still Vent Condenser
o MC/Water Separator None
o Still Decant Tank None
o Dryer Vacuum Pump Condenser
Equipment leaks None
0
0
0
0
0
50
0
0
97
0
0
50
4.6
2.4
1.8
1.3
1.8
1.8
27.2
0.9
2.7
8.2
1.8
0.5
9.8
6.1
Leaks detected by
observation and
weekly mass balance
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
To Condenser
None
None
To Condenser
To Condenser
None
50
0
0
50
50
0
0.09
0.06
0.06
0.007
0.1
0.005
4100 gallons
500 gallons
500 gallons
1500 gallons
1250 gallons
250 gallons
(Continued)
-------
TABLE 3-2 CONTINUED. ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
OJ
I
Company/ Location
General Electric
PHtsfleld. MA
(Cont'd)
General Electric
Schenectady. NY
Mobay Chemicals
Baytown. TX
Product Type of Emissions
Equipment Opening
Handling
o Drums
Secondary
o Aqueous waste
stream
o Drums
Insulating Process
Materials o «
Secondary
0 •
Polycarbonate Process
Resin o Vent
o Reactor Vent
o Reactor Vent
Equipment Leaks
Equipment opening
Storage
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
o Fixed-Roof Tank
Secondary
o Wastewater stream
o Contained solvent
o Process Water
Trench
o Leaks and spills
Reported Control
Present Controls Efficiency (X)
None
None
To Sewage Treatment
To Maz. Waste Disposal
*
M
Scrubber
None
None
Monthly Portable Gas
Chromatograph Check,
Pressure Relief Device
Controls
None
Vent to Scrubber
Vent to Scrubber
Vent to Scrubber
Vent to Scrubber
Vent to Scrubber
Biological 4 Carbon
Treatment
Incineration
Biological & Carbon
Treatment
None
0
0
8°b
98°
«
N
98
0
0
NR
0
98
98
98
98
98
NR
NR
80
0
Present MC
Emissions (Mg/yr) Comments
2.3
0.2
0.1
0.01
0.01
0.2
0.3
0.07
0.05
51.2
16.5
0.006
0.006
0.1
0.1
0.003
22.0
0
11.0
41.4
2000 openings
Present delivery via
tank trucks.
Primarily sampling
openings
27.100 gallons
150,000 gallons
85,200 gallons
85,200 gallons
27,100 gallons
(Continued)
-------
TABLE 3-2 CONCLUDED. ESTIMATED EMISSIONS AND CURRENT CONTROLS
AT FACILITIES USING METHYLENE CHLORIDE IN PRODUCTION
CO
I
Company/ Location
Mobay Chemicals
Kansas City. MO
Shell
Deer Park, TX
Product Type of Emissions Present Controls
Handling
o Rail car, tank
truck None
BAYGON 1.5 Equipment Leaks None
Storage
o Fixed-Roof Tank None
Vtnyl Chloride Secondary
Monomer o Waste stream one Blotreatment
Reported Control
Efficiency <*>
0
0
0
NR
Present MC
Emissions (Mg/yr) Comments
0.6
0.02 No monitoring
0.4 No longer uses on-
slte storage
0.06
"The company considers this confidential Information.
Combined emissions from process vents, equipment openings, and loading and handling.
Company reported greater than 98 percent control, but only 98 percent Is accepted xlthout supporting test data.
NR = Not reported.
NA = Not applicable.
-------
Celanese reported one discharge from a pressure relief device on a
mixer. The discharge resulted in 2.7 Mg of MC emissions.
South Carolina has developed regulations pertaining to emissions of
volatile organic compounds (VOC) from specific sources, such as solvent
metal cleaning and storage tanks. However, methylene chloride is
excluded from these regulations in South Carolina due to its negligible
photochemical reactivity.
3.1.2 Polycarbonate Resin
Polycarbonate resins were manufactured by two producers in 1983.
These are General Electric in Mount Vernon, Indiana, and Mobay Chemical
in Baytown, Texas. Methylene chloride is used by both plants as a
solvent in the polymerization reaction.
3.1.2.1 Process Description . Bisphenol-A is reacted with
phosgene in the presence of pyridine to form a polycarbonate. MC is
used as a solvent in the polymerization reaction. The reaction is
carried out at a temperature below 40°C (104°F) with a residence time of
1 to 3 hours. The polycarbonate production process occurs according to
the reaction:
pyridine
HOgH4C(CH3)2C6H4H + COC12 ^ polycarbonate resin
(Bisphenol-A) (phosgene) MC
Following reaction, reactor contents are washed to remove excess
pyridine from the polymer/methylene chloride stream. This stream is
treated with an organic compound, such as aliphatic hydrocarbon, to
effect precipitation of the polymer. After the polycarbonate
precipitates, it is filtered and dried. Methylene chloride is present
in all process steps. A process flow diagram is shown in Figure 3-2.
3.1.2.2 Current Controls and Emissions. The types of emissions
from this process at the two production facilities are from process
vents, equipment leaks, storage, handling, equipment openings, and
secondary sources. The emission types and their controls are discussed
below.
3-13
-------
METHYLENE
CHLORIDE
STORAGE
COOLING-
WATER
WATER +HCI
PRECIPITANT-
I
BISPHENOL-A
PYRIOINE
STORAGE
REACTOR
•COOLING
WATER
WASH TANK
PHOSGENE
AQUEUOS PHASE
N»OH
PYRIDINE
RECYCLE
AZEOTROPIC
DISTILLATION
POLYCARBONATE
METHYLENE CHLORIDE
PRECIPITATION
METHYLENE CHLORIDE
RECYCLE
METHYLENE CHLORIDE
RECYCLE
NaCI
CRYSTALLINE
POLYCARBONATE
DRYER
-HOT AIR
POLYCARBONATE
PRODUCT
PREPARATION
PRODUCT
Figure 3-2. Process How diagram for the Production
of polycarbonate resin.
3-14
-------
General Electric - Mount Vernon. Indiana
The. production of polycarbonate resins and proprietary associated
processes at this facility resulted in 3,570 Mg of MC emissions in 1983.
General Electric indicated that emissions reported for individual
sources were either rough estimates or maximum allowable permitted
levels and that they could not give exact values for each emission
source. Actual emissions in 1983 were much lower than the reported
levels. General Electric reported 4 process areas emitting MC. Two of
the process areas use methylene chloride in polycarbonate synthesis.
Therefore emissions result from process vents as well as equipment leaks
and equipment openings. The other two areas are used in polycarbonate
processing and MC emissions result from residual in materials processed.
Emission sources, current controls, control efficiencies, and emission
quantities are presented in Table 3-2. Process vents were the source of
2,680 Mg of those emissions. Seventeen extruder die vents emitted
about 391 Mg MC (27 percent of total process vent emissions). Seven
extruder die hoods emitted approximately 225 Mg MC (15 percent of
process vent emissions). Neither the extruder die vents nor the
extruder die hoods are equipped with MC control devices! Other major
uncontrolled contributors include six extruder vacuum pumps 86.4 Mg/year
emissions), eight more extruder die vents (93.8 Mg/year emissions), two
filter receivers emitting 85.6 Mg of MC each, and two storage silos
emitting 85.0 Mg of MC each.
General Electric reported control devices on 6 process vents.
Two vent gas absorbers are controlled by water scrubbers at an estimated
87 percent MC control efficiency. Emissions from the vent gas absorbers
were 477 Mg each. Two carbon adsorbers control various process vents.
The adsorbers achieve 87 percent pollutant removal giving final emission
levels of 46.3 Mg and 348 Mg. A MC dryer system is equipped with a
knock-out Pot/Demister that reduced emissions by 50 percent, to 79.5 Mg.
General Electric also reported a conservation vent on a MC storage tank
with 10 percent control efficiency. The storage tank emissions were
17.6 Mg of MC. This tank was reported as a process vent by General
Electric.
3-15
-------
Current estimates for emissions from secondary sources are
584 Mg/year. General Electric estimates that approximately 1,818 kg/day
MC is discharged to the site sewer system. Approximately 218 kg/day
reaches the wastewater treatment plant for on-site biological treatment.
The remaining 1,600 kg/day is lost to the atmosphere in three areas:
(1) the Brine Recovery Operation,( 2) the sewer system, and (3) the
wastewater treatment plant prior to biological treatment.
Equipment leaks were the next largest source of emissions generated
at the General Electric facility, totalling 247 Mg of MC. General
Electric reported equipment counts for two of four process areas. The
other two process areas do not have equipment in MC service and
emissions result from residual in materials processed. Equipment leaks
in one process building resulted in emissions of 176 Mg MC with flanges
being the major contributor (42 percent). General Electric reported
that multipoint programmable sequence area monitoring is performed to
detect MC leaks using a photo ionization detection HNu system.
Forty points are monitored throughout the process area. According to
General Electric, the monitoring has proven effective in identifying
major leak occurrences and the instrumentation can detect MC in the low
ppm range. However, sample system limitations with 40 sample points can
inhibit detection of minor leaks and spillage. No information was
reported about the frequency of repair of leaks. Therefore,
uncontrolled emission factors were used to estimate equipment leak
emissions, possibly resulting in an overestimate of these emissions.
Equipment opening losses in this process area were reported as 5.1 Mg in
1983. The number of equipment openings was not provided, but this
emissions estimate was based on scheduled maintenance activities
assuming 100 percent loss of estimated quantities in the system at the
time of opening.
Equipment leak losses in a second process building totalled 71 Mg
MC. General Electric also utilizes a HNu system in and around the
primary potential leak areas in this building. Continuous area
monitoring is performed at 10 points in the operation. General Electric
did not report the frequency of leak repair for this area. Therefore,
uncontrolled emission factors were used to estimate equipment leak
emissions and these emission levels may be overstated.
3-16
-------
Equipment opening losses in this area were 58.6 Mg, as a result of
weekly recorded activities for several hundred pieces of equipment.
General Electric based this emission figure on field estimates of
quantities in the system at the time of opening, and extrapolated
emissions out using 100 percent loss and number of occurrences.
There are 45 process and storage vessels for MC at this facility.
All but one of these vessels vent to gas absorbers, with an estimated
87 percent control efficiency. The remaining vessel is equipped with a
conservation vent with an estimated 10 percent control efficiency.
Emissions from storage facilities were 1.6 Mg in 1983.
Indiana has adopted regulations limiting the allowable emissions of
volatile organic compounds to 100 tons per year or an 85 percent
reduction of emissions. However, the regulations exclude non-photo-
chemically reactive hydrocarbons and organic compounds that are not
liquid at standard conditions. Methylene chloride is excluded from
these regulations due to its negligible photochemical reactivity.
Mobay Chemical - Bavtown. Texas
The polycarbonate resin process generated 143 Mg MC emissions at
this facility in 1983. Table 3-2 documents emission sources, current
controls, control efficiencies, and emission amounts for this facility.
Emissions from secondary sources were the largest source of MC
emitters at 74.4 Mg. Mobay listed three sources for these emissions:
1) a wastewater stream going to biological and carbon treatment
(22.1 Mg), 2) a process water trench also going to biological and carbon
treatment (10.9 Mg), and 3) other leaks and losses prior to maintenance
work (41,4 Mg).
Emissions from equipment leaks were 51.2 Mg in 1983. Valves
emitted 55 percent (28.4 Mg). Flanges accounted for 19 percent (9.5 Mg)
and pump seals emitted 15 percent (7.6 Mg). Mobay has 33 pressure
relief devices protected by rupture disks. Twenty more relief valves
are vented to a scrubber to control emissions. Five pressure relief
valves are unprotected.
3-17
-------
Mobay records process variables each shift to detect obvious leaks.
Also, a daily walkthrough is performed to spot leaks. A solvent
inventory is taken each week to account for any unusual loss. All pump
seals and vent locations are checked monthly with a portable gas
chromatograph. In addition, one technician devotes half-time to solvent
loss prevention. Mobay believes this monitoring system is reasonably
effective for obvious losses. Mobay did not report the frequency of
leak repairs and emissions from equipment leaks were calculated using
uncontrolled emission factors. Therefore, these emissions may be
overstated.
Losses from equipment openings were 16.5 Mg in 1983. Forty-four
percent (7.3 Mg) of equipment openings losses were due to daily
sampling. Mobay reports that approximately 50 samples are taken a day.
Filter replacement contributed about 6.1 Mg (37 percent) of MC
emissions. Replacement of an 80,000 gallon product tank emitted 1.6 Mg.
Other equipment opening losses were due to routine maintenance of
purification equipment, pump seal replacement, heat exchanger
replacement, and from opening open solvent lines to remove pluggage.
Solvent handling losses were 0.6 Mg. MC is delivered by rail car
and/or tank truck. No control equipment is used to reduce emissions
during unloading.
Emissions from three process vents totalled 0.4 Mg in 1983. A
process vent scrubber operating at 98 percent MC removal efficiency
emits 0.3 Mg MC. The emission level was determined from inlet and
outlet sampling and gas chromatograph analysis of the samples for
composition. Two reactor vents that emit MC only when the reactor is
being filled have a combined annual loss rate of about 0.1 Mg/year.
Emissions occur from these vents for only about 10 minutes per month.
Losses from five fixed roof storage tanks were about 0.2 Mg in
1983. All storage tank conservation vents are vented to a scrubber.
Mobay reported that sampling indicated that this control technique
reduces emissions by 98 percent.
Texas has adopted regulations to control emissions from volatile
organic compounds. However, methylene chloride is excluded from these
regulations due to its negligible photochemical reactivity.
3-18
-------
3.1.3 Rubber Cement Manufacturing
Methylene chloride is used in the production of rubber cement at
Borden Chemical, Fremont, California. Borden considers process
description information confidential.
3.1.3.1 Current Emissions and Controls. Emissions from rubber
cement manufacturing at this facility are primarily from process vents,
and secondary sources. In addition, some emissions result from
equipment leaks. Emission levels and controls at these facilities are
discussed below and are presented in Table 3-2.
The estimated methylene chloride emissions from this plant are
2.5 Mg/year. Emissions are from a process vent, waste product disposal,
and equipment leaks. There were no relief device discharges or
equipment openings during 1983. Methylene chloride and product
containing MC are handled and stored in 5-gallon pails and 55-gallon
drums. Emissions were estimated by the plant to be negligible from
these sources.
An adhesives fume collection system was the primary emission source
at the Borden facility with about 2.2 Mg MC emissions (Borden estimated
this figure from 1984 production). MC emissions occur intermittently
during the 6-hour batch cycle as the mixer lid is opened to add batch
ingredients and to take product samples. The ventilation system serving
the rubber cement mixers also serves several other mixers not using MC.
The combined flow from all mixers discharges through one stack.
Waste product is packed in drums and sent to a solvent reclaimer
for solvent recovery and/or disposal. Emissions during packing are
estimated to be 0.3 Mg/year.
Equipment leaks from process components in MC service were 3 kg
(.003 Mg) in 1983. Borden has only four components in MC service, used
less than 0.1 percent of the time. They have no monitoring or repair
program for equipment leaks.
Fremont is in the Bay Area Air Quality Management District
(BAAQMD). The BAAQMD has adopted a series of rules for the regulation
of precursor organic compounds. However, in the BAAQMD, methylene
chloride is defined as a non-precursor organic compound and is therefore
excluded from regulation.
3-19
-------
3.1.4 Rubber Accelerator Manufacturing
B.F. Goodrich uses MC in the production of rubber accelerator at
two plants in Cleveland, Ohio. Rubber accelerator is a compound that
greatly reduces the time required for vulcanization of natural and
synthetic rubbers, while improving the aging and other physical
properties at the same time.
3.1.4.1 Current Emissions and Controls. Emission sources from
rubber accelerator manufacture at the two B.F. Goodrich plants are
process vents, equipment leaks, storage, and secondary sources.
Emission levels and controls at these facilities are discussed below and
are presented in Table 3-2.
B.F. Goodrich - Cleveland. Ohio; Plant I6
B.F. Goodrich did not supply emission estimates for process vents,
equipment openings, or loading and handling losses at this facility.
However, a material balance was provided indicating that 70.4 Mg MC are
emitted directly to the air. This figure does not include a product
water wash stream containing MC that is discharged to an industrial
sewer for pretreatment, and then to a publicly owned treatment works
(POTW) facility. This secondary source emits 169 Mg MC. B.F. Goodrich
did not indicate what fraction of MC is emitted in pretreatment prior to
discharge to the POTW facility. Therefore, it was assumed all MC is
emitted at the B.F. Goodrich facility.
Emission estimates were calculated for equipment leaks for process
components in MC service and for storage facilities. Equipment leaks
resulted in MC emissions of 4.6 Mg in 1983. Valves were the largest
source of equipment leak emissions emitting 2.4 Mg MC. Sample
connections were the next largest contributor with 1.1 Mg MC. Pressure
relief devices emitted 0.5 Mg. B.F. Goodrich reported that process
components are monitored for leaks through routine visual inspection and
equipment maintenance. Since a leak repair program was not reported,
emissions from equipment leaks were calculated using uncontrolled
emission factors.
3-20
-------
One fixed roof underground storage tank was the source of 0.2 Mg of
MC emissions. The tank is not equipped with a control device.
B.F. Goodrich reported no other storage tanks in MC service.
Equipment leaks and storage tanks result in total MC emissions of
4.8 Mg. From the material balance, if 70.4 Mg MC are emitted directly
to the air, then the remaining 65.6 Mg may be assumed to be from process
vents, equipment openings and loading and handling losses. B.F. Goodrich
reported six process vent emission points. Four of those emission
points were equipped with brine cooled shell and tube condensers
operating at more than 98 percent MC removal efficiency. The remaining
two process vents, a wash tank and a centrifuge blower were uncontrolled.
There were seven equipment openings at this facility in 1983. No
estimate can be made on specific emission levels from these openings
since B.F. Goodrich gave no indication of solvent purging procedures
prior to opening. No estimate can be made on loading and handling
emissions either, since no information was given on loading and handling
techniques (i.e., splashfill versus dip pipe loading).
The State of Ohio has adopted regulations controlling
photochemically reactive materials, hydrocarbons, and related materials.
However, MC is excluded from these regulations due to its negligible
photochemical reactivity.
B.F. Goodrich - Cleveland. Ohio; Plant II6
Emissions from process vents, equipment leaks, and storage
facilities are approximately 18.1 Mg/year at this facility. The rubber
accelerator manufacturing process was not in operation in 1983, so this
emission level represents current conditions. However, the MC emissions
were incorporated in the 1983 total MC emission estimates. Emission
sources, current controls, control efficiencies, and emission quantities
are reported in Table 3-2. B.F. Goodrich did not supply information
concerning emissions from pressure relief devices and equipment
openings.
3-21
-------
Equipment leaks from process components are the largest source of
MC emissions at 10.1 Mg/year. Valves emit 4.3 Mg (43 percent), pump
seals emit 3.0 Mg (30 percent), and pressure relief devices emit 1.6 Mg.
Sample connections are also minor contributors. B.F. Goodrich does not
have a formal process component leak monitoring and repair program.
A vacuum jet/pump is the only process vent emitting MC. The
emission rate for this vent is 7.5 Mg/year following control by a water
cooled condenser and a refrigerated condenser operating at -9°C (16°F).
The estimated MC removal efficiency is 94 percent.
B.F. Goodrich stores MC in three pressure vessels ranging in volume
from 750 gallons to 2,000 gallons. Emissions from these storage vessels
are approximately 0.5 Mg/year. These tanks are N2 blanketed. During
filling operations, the N2/MC headspace is vented through back pressure
relief valves (approximately 7 inches H20) in ratio to the volume of
liquid being filled. No estimate was provided for loading emissions.
3.1.5 Insulating Materials Manufacture
General Electric in Schenectady, New York, uses MC in the
manufacture of insulating materials. General Electric considers all
information concerning their process description and equipment and
controls confidential.
3.1.5.1 Current Emissions and Controls . Methylene chloride
emissions at this facility are from a process vent and a secondary
source. Total MC emissions were about 0.2 Mg in 1983. The process vent
emits 0.01 Mg, while the secondary source emits 0.2 Mg. Equipment leak
emissions are negligible (less than 1 kg/year). General Electric
reported no discharges from pressure relief devices, no equipment
opening losses, and no MC storage tanks. Methylene chloride is
purchased and stored in drums. Emission sources, current controls,
control efficiencies, and emission amounts are presented in Table 3-2.
3.1.6 BAYGON^ 1.5 Manufacturing
Mobay Chemicals in Kansas City, Missouri, uses MC in their
Agricultural Chemicals Division as a diluent in the formulation of
D
BAYGON 1.5, a pesticide. Mobay considers the process description and
product packaging information confidential.
3-22
-------
3.1.6.1 Current Emissions and Controls . Total MC emissions at
this facility are about 0.4 Mg/year. Emission sources, current
controls, control efficiencies, and emission quantities are reported in
Table 3-2.
One fixed roof storage tank emitted 0.4 Mg in 1983. However, Mobay
indicated that MC is currently pumped directly from tank trucks to the
process with no on-site storage. In the past, the MC was shipped to the
plant in tank trucks and pumped into fixed roof storage tanks with no
control devices in use.
Equipment leaks from process component leaks were 0.02 Mg in 1983.
Mobay reported that 8AYGONR 1.5 is only formulated 4 or 5 days per year
for 8 hours per day, and the formulation process is a closed system with
a minimum of production steps. Therefore, no monitoring or repair
program is conducted for MC leaks.
Mobay reported no process vent emissions, no pressure relief device
discharges, no equipment opening losses, and no emissions from secondary
sources. Although Mobay indicated no controls were used for unloading
MC in 1983, no handling emission estimates were given.
Missouri air laws are distinguished by metropolitan area. There
are regulations controlling VOC emissions from specific sources (such as
solvent metal cleaning) in the Kansas City metropolitan area. However,
MC is excluded from these regulations due to its negligible
photochemical reactivity.
3.1.7 Specialty Chemicals
Borden Chemical, in Norristown, PA uses MC in liquid chemical
specialty product mixes. Borden indicated that the rate of MC
consumption at their facility has been declining and is expected to
continue to decline. No explanation was given for the consumption
decrease.
3-l-7.1 Process Description. At Borden, MC is pumped from storage
to three liquid chemical specialty mixing tanks. Following mixing, the
liquid chemical specialty product, containing 30 percent MC, is sent to
a "filler" where pint size cans are filled at the rate of 18 gpm. The
cans are then sealed and sent to packing, warehousing and marketing.
3-23
-------
3.1.7.2 Current Emissions and Controls . Emissions from equipment
leaks, storage, and handling were 3.2 Mg at this facility in 1983. The
emission levels and controls are presented in Table 3-2. Equipment
leaks were the largest source of emissions, contributing 2.1 Mg. Pump
seals contributed 51 percent of those emissions while valves contributed
47 percent. Borden reported the entire system is readily subject to
visual inspection for liquid leaks which are obvious and that these
leaks are repaired "promptly". However, since Borden did not report a
definitive leak repair program, equipment leak emissions were calculated
assuming uncontrolled sources. Therefore, equipment leaks at this plant
may be overstated. Storage facilities emitted 0.8 Mg MC. These
emissions were from four fixed roof tanks including the three specialty
chemical mixing tanks. Handling losses were 0.3 Mg in 1983. These
losses result from the uncontrolled loading of raw MC from tank
trucks to storage tanks and from evaporation of the 30 percent MC
specialty chemical solution as it passes through the "filler" which puts
the product into sealed cans. There are no controls for the filler
process.
Pennsylvania has adopted regulations controlling emissions from
storage tanks containing volatile organic compounds. MC is not
specifically excluded from these regulations. Storage tanks with
capacity less than or equal to 40,000 gallons which contain VOC with
vapor pressure greater than 1.5 psia under actual storage conditions
must be equipped with pressure relief valves. Storage tanks with
capacity greater than 40,000 gallons which contain VOC with vapor
pressure greater than 1.5 psia must be equipped with an external or
internal floating roof or a vapor recovery system capable of recovering
at least 80 percent of the vapors emitted by the tank.
Borden storage tanks range in capacity from 3,000 to 10,000
gallons. Borden did not report any conservation vents on these tanks.
3.1.8 Unidentified Production Processes
Dow Chemical, in Midland, MI operates 8 process units using MC in
production. These processes are identified as processes #5 through #12.
Dow indicated that all information concerning process flowcharts and end
3-24
-------
products is confidential business information. Therefore, this
discussion is limited to emissions and controls used at the Dow
facility.
P
3.1.8.1 Current Emissions and Controls . Process vents and
equipment leaks were the major emission sources at the Dow facility.
Emissions were also reported from secondary sources, storage facilities,
equipment openings, and loading and handling. In addition, Dow reported
one discharge from a pressure relief device. Emissions, current
controls, and control efficiencies for this facility are presented in
Table 3-2.
Combined emissions from the eight process units were 1450 Mg in
1983. Emissions from process vents were 1120 Mg (77 percent of total
emissions). Three process vents in process #12 emitted 811 Mg of total
process vent emissions. Dow considers information on process
vents and controls confidential for all processes except for an
uncontrolled overheads receiver emitting 0.2 Mg/yr in process #5 and an
uncontrolled storage tank emitting 129 Mg/yr in process #9. Dow
reported the storage tank as a process vent. It is filled almost
continuously and pumped out in batches. There are sixteen process vent
emission points in the eight processes. Michigan has no regulations
controlling VOC emissions from process vents.
Equipment leaks from process component leaks were 207 Mg at the
Midland facility. Process components for processes #8, #10, and #12
emitted 60.1 Mg (29 percent), 27.6 Mg (13 percent), and 68.7 Mg
(33 percent) respectively. Overall, the greatest sources of equipment
leaks were valves (90.6 Mg, 44 percent), flanges (75.6 Mg, 37 percent),
and pressure relief devices (27.2 Mg, 13 percent).
Equipment leaks are not controlled by Michigan state regulations.
Monitoring programs vary widely in the degree of sophistication for
different process units at this facility. Processes #11 and #12 are
equipped with a continuous air monitor with 20 area sampling probes
located throughout the process areas. The monitors are regularly
standardized and calibrated and provide continuous sampling with time
weighted average composition data. In addition to continuous air
monitoring, shift personnel are responsible for 24 hour per day coverage
3-25
-------
and equipment inspection. There are also scheduled preventive
maintenance inspections for all pressure relief devices and critical
instruments. Shift inspection and preventive maintenance inspections
are also practiced at processes #5, #7, and #9, and are the only
fugitive monitoring practices at these process areas.
Process area #8 is equipped with a chromatographic air monitoring
device in addition to shift inspection and annual preventive
maintenance. The system is alarmed and operators have been instructed
on how to respond to this alarm by finding and correcting problems.
A MC air monitoring program is conducted quarterly in the process
#10 area. Dow reported a $40,000 cost plus $10,000 for maintenance.
This process area is also subjected to shift inspections and an annual
preventive maintenance program.
Dow indicated process #6 is experimental in nature. Therefore,
equipment leak monitoring is limited to inspection by operating
technicians.
Although Dow reported several monitoring and inspection programs
for equipment leaks, they did not report a repair program. Therefore,
equipment leak emissions were calculated using uncontrolled emission
factors, and emission levels may be overstated somewhat.
Emissions from secondary sources were 88.5 Mg at the Dow facility.
Dow uses biological treatment or incineration to treat or dispose of
process waste streams. Emissions from incineration are negligible,
therefore all secondary emissions are a result of biological treatment.
Michigan does not regulate VOC emissions from secondary sources.
Storage facility emissions were 29.0 Mg in 1983. Storage tanks
range in volume from 30 gallons to 47,000 gallons and include pressure
vessels and fixed roof tanks. Control techniques employed include vapor
return, scrubbers, carbon adsorption systems, pressure relief devices,
and conservation vents. The only reported control efficiency was for
vapor return, estimated by Dow as 100 percent. However, only 98 percent
control efficiency is accepted without supporting test data. Michigan
has adopted regulations controlling storage of organic compounds having
a true vapor pressure of more than 1.5 psia, but less than 11 psia, in
existing stationary vessels of more than 40,000 gallon capacity. The
3-26
-------
vapor pressure of MC at 20°C (68°F) is approximately 6.75 psia, and MC
is not specifically excluded from regulation in Michigan. The
regulations require that the storage tank be a pressure tank, or be
equipped with a floating cover with closure seal or seals, or be
equipped with a vapor recovery system capable of 90 percent recovery.
Dow has one fixed roof storage tank with capacity exceeding
40,000 gallons (a 47,000 gallon tank). The tank is only equipped with a
pressure relief device.
Losses from equipment openings were 4.3 Mg in 1983. Losses were
reported for all processes except for process #9 where Dow indicated all
equipment is drained or pumped out before maintenance work. According
to Dow, the equipment is empty when opened and estimated losses are
minimal. Process #12 was the largest source of equipment opening losses
where 2.5 Mg MC were emitted. There are no regulations in Michigan
requiring control of these emissions.
Loading and handling emissions were 2.7 Mg in 1983. Methylene
chloride is received by tank truck, rail car, in drums, or through
direct pipeline transfer from other processes within the Dow facility.
Additionally, product containing MC from process #9 is loaded into tank
cars and tank trucks. At process #5, a vapor balance line is used
between tank trucks and storage tanks to prevent filling losses during
transfer. At process #9, connection lines are blown empty with inert
gas before disconnecting to prevent spills. Process #10 receives MC by
rail car; the car is pressurized with nitrogen to help the transfer.
Following transfer the rail car is vented to the atmosphere. MC is
unloaded via pump at process #12. Dow reported that since pressure
transfer is not used there are no loading losses. Other processes
either receive MC in drums or from other processes or have "negligible"
handling losses. Michigan requires submerged fill pipes in ozone
attainment areas for VOC loading facilities handling 5,000,000 gal/year
or more of VOC with a true vapor pressure greater than or equal to
1.5 psia.
A corrosion failure of a storage tank neck resulted in a discharge
of 0.1 Mg MC to the air in 1983. Dow reported the spilled material was
contained in a dike. Dow reported this corrosion failure as a pressure
relief device discharge.
3-27
-------
3.1.9 Vinyl Chloride Monomer
Methylene chloride is produced as a by-product of Vinyl Chloride
Monomer (VCM) manufacturing by Shell Oil Company in Deer Park, TX. This
MC is sold as light ends.
3.1.9.1 Process Description . Vinyl chloride (VC) is produced by
the thermal dehydrochlorination (cracking) of ethylene dichloride (EDC).
The cracking of EDC occurs according to the non-catalytic reaction:
CH2C1CH2C1 * C2CHC1 + HC1
(ethylene dichloride) (vinyl chloride) (hydrogen chloride)
Operating the process at high pressures results in higher yield, fewer
by-products, and allows easier separation of the VCM product from
unreacted EDC and by-products.
3.1.9.2 Current Emissions and Controls10. Total MC emissions were
0.06 Mg at this facility. Emissions are low because Shell did not
report a MC concentration greater than 0.6 percent in its process
streams and 0.004 percent in its storage tanks. Therefore, process
emissions, equipment leaks, and equipment opening losses were reported
as minimal prior to control. In addition, Shell operates two organic
chloride incinerators at the Deer Park facility. Therefore, process
emissions following incineration are
insignificant. Four fixed roof storage tanks are controlled by
compression and incineration and have negligible emissions. The total
MC emissions of 0.06 Mg resulted from an unidentified waste stream being
sent to a biotreatment process. These secondary source emissions are
reported in Table 3-2.
3.1.10 Plastics Production
General Electric in Pittsfield, MA, uses MC in a plastics
production operation. General Electric considers information concerning
process description and end products confidential.
3-1-10.1 Current Emissions and Controls . Process vents and
process component leaks were the major emission sources at the General
Electric facility. Emissions were also reported for secondary sources,
3-28
-------
storage facilities, equipment openings, and loading and handling.
Emission sources, current controls, control efficiencies, and emission
levels are presented in Table 3-2.
Total methylene chloride emissions at this facility were 74.0 Mg in
1983. Emissions from process vents were 64.9 Mg MC (88 percent of total
MC emissions). General Electric reported thirteen process vents with
three vents controlled by condensers. A precipitation condenser vent
and a dryer vacuum pump are both controlled by condensers operating at
50 percent MC removal efficiency. Emissions from these vents after
control were 27.2 Mg and 9.8 Mg respectively. The precipitation
condenser vent is the largest single MC emission point at the facility.
A methylene chloride still vent is controlled by a condenser operating
at 97 percent MC removal efficiency. Emissions from this vent were
8.2 Mg. The ten remaining process vents are uncontrolled. Emissions
range from 4.6 Mg for reactor area ventilation to 0.9 Mg for the
methylene chloride still water tank.
Equipment leaks resulted in MC emissions of 6.1 Mg. Valves emitted
approximately 3.1 Mg MC (51 percent). Pump seals and flanges emitted
1.0 Mg (16 percent) and 0.8 Mg (13 percent), respectively. General
Electric reported that there is no automated leak detection system for
MC. Any significant MC leaks are generally determined by operator
observation. Also, a weekly mass balance inventory is maintained for MC
usage. Substantial increases over the normal process usage requirements
initiates a full system investigation to determine if any leakages are
occurring. Since General Electric did not report a leak repair program,
uncontrolled emission factors were used to calculate equipment leak
emissions, possibly resulting in an overestimate of these emissions.
Equipment opening losses were approximately 2.3 Mg in 1983.
General Electric estimated this loss for approximately 2000 openings,
1300 of which were an end cap reactor nozzle opened each batch to add
reactants. In addition, another reactor nozzle is opened 650 times per
year. Other equipment openings involved work-up tanks, Westfalia
centrifuges, filter feed tanks, filters, methylene chloride stills and
separator/decant tank. General Electric provided on overall equipment
opening loss estimate and did not identify emissions by specific
sources.
3-29
-------
General Electric maintains five fixed roof storage tanks containing
MC. The emissions from these tanks totalled 0.3 Mg. The tanks range in
volume from 250 gallons to 4100 gallons. Three of the tanks are vented
to a vent condenser with 50 percent control efficiency. Two other tanks
emissions are piped to a controlled tank, while one tank is
uncontrolled.
Through September, 1983, MC was delivered in 55 gallon drums. The
MC was pumped from the drums into dry MC tanks for process use. General
Electric estimated that emissions from this operation were 0.2 Mg. In
September 1983, a bulk handling system became operational. Tank truck
deliveries are now made to a fixed roof 4100 gallon storage tank. The
tank car feed line is connected to a pump at the storage tank base and
delivered into the storage tank. Vapors are piped to the plant vent
system, which condenses most of the MC vapors. General Electric
reported air intake is through a cannister and a vacuum relief valve.
Two waste streams emitted about 0.2 Mg MC in 1983. The major
secondary emission source is a liquid stream to a sewage treatment plant
which emits 0.15 Mg of MC. A second waste stream was unidentified.
This stream is contained in drums which are sent to a licensed hazardous
waste disposal company. Emissions (0.01 Mg) occur when the waste stream
is transferred to drums.
Massachusetts has adopted regulations for control of VOC emissions
from specific sources such as surface coating operations. Methylene
chloride is not specifically excluded from these regulations. However,
none of the regulations are applicable to chemical production
facilities.
3.2 COST OF ADDITIONAL CONTROL
Cost estimates were developed for control of process, equipment
leak and storage emissions at each chemical production facility where
these emissions are presently not well controlled. The cost of
controlling loading and handling emissions at these facilities was not
calculated since these emissions were low (4.4 Mg from all 12
facilities) and control would not be cost effective. The methodology
used for
3-30
-------
estimating costs is presented in Appendix D. A summary of the cost
effectiveness to control these emission sources in presented in
Table 3-3 and discussed in the following sections.
Table 3-4 summarizes the estimated MC 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 miscellaneous
production category. A total emission reduction of 4200 Mg (40 percent)
is technically feasible.
3.2.1 Control of Process Vent Emissions
The cost of controlling MC process vent emissions by incineration
was estimated for the miscellaneous production facilities reporting
process vent emissions. MC emissions can be reduced by 3780 Mg
(94 percent) by incineration. The cost effectiveness of controlling MC
process vent emissions ranges from a net credit of $64,800/Mg VOC at the
General Electric/Mount Vernon facility to a cost of $33,000,000/Mg VOC
at the General Electric/Schenectady facility where process vent
emissions are only 0.012 Mg of VOC.
3.2.2 Control of Equipment Leaks
Emissions from equipment leaks totalled 550 Mg MC at the chemical
plants using MC in production. As discussed in previous sections,
several chemical plants have inspection programs for detection of
equipment leaks, but do not mention or define repair programs. For this
reason, it was assumed that no equipment leak controls were in place.
Therefore, costs were estimated for adding controls at all miscellaneous
production facilities except for Mobay/Kansas City, where emissions from
equipment leaks were only 0.02 Mg MC. The control techniques costed are
those required under the benzene fugitives NESHAP and are shown in
Appendix C.
The estimated costs effectiveness for controlling equipment leak
emissions range from $142/Mg of VOC to $4,320/Mg of VOC. Methylene
chloride equipment leak emissions could be reduced by 49 percent
(268 Mg/yr) if additional controls were used at all of the chemical
production facilities.
3-31
-------
TABLE 3-3 COST OF ADDITIONAL CONTROLS AT CHEMICAL PLANTS
USING MC IN PRODUCTION
CO
I
CO
f\i
Company/Location
Genera] Electric
Plttsfteld, MA
General Clectrlc
Mount Vernon, IN
Btdg. 4
General Electric
Mount Vernon, IN
Bldg. 13
General Electric
Mount Vornon, IN
Bldg. 14/16
General Electric
Mount Vernon, IN
Bldg. 15/31
General Electric
Schenectady, NY
Celanese
Rock Hill, SC
Borden Chemical
Norrlstoxn, PA
Borden Chemical
Fremont, CA
Emission Type Control*
Process
Equipment
Storage
Storage
Storage
Process
Process
Process
Equipment
Process
Equipment
Storage
Process
Equipment
Equipment
Storage
Storage
Storage
Storage
Process
Incineration
leaks
FR-PO
COND
COND
Incineration
Incineration
Incineration
leaks
Incineration
leaks
FR-SS
Incineration
leaks
leaks
FR-PO
FR-PO
FR-PO
FR-PO
Incineration
Control
Efficiency
(X)
98
59
94
85
70
98
98
98
41
98
74
97
98
49
59
94
94
94
94
98
MC/VOC Emission
Reduction (Mg/yr)
63. 3/ 63.3
3.6/ 6.6
O.I/ 0.1
O.I/ 0.1
O.I/ 0.1
282/282
582/582
1150/H50
72.3/124
600/600
53. 4/ 80.
2.0/ 2.
0.01/ 0.
10. 8/ 17.
1.2/ 2.
0.4/ 0.
0.2/ 0.
O.I/ 0.
O.I/ 0.
2.2/ 2.
8
0
01
0
0
4
7
3
2
2
CapltaJ Cost Recovery..
(10J$) Credit (10J
4,430
17.6
11.5
222
111
74,300
73,300
2,220
122
5,760
156.5
16.7
1.180
30.1
12.7
11.5
11.5
11.5
11.5
5,210
1,270
2
.7
0.0
0.1
0.1
71,220
81,700
1170
52.
5,910
34.
1.
0.
7.
0.
0.
0.
0.
0.
708
1
9
6
0
3
9
2
1
Q
0
Net Cost Effectiveness
Annual, MC VOC
t) Cost (lO^t) ($/Mg) (t/Mg)
2,190
9.9
3.0
58.2
29.0
-18,300
-24,500
40.500
17.6
3,220
26.1
2.8
402
15.4
8.7
2.8
2.9
3.0
3.0
1,160
34,600
2,750
37,100
573.000
348.000
-64 ,800
-42,100
35.2
244
5,370
490
1.360
33.000,000
1,430
6,960
7,130
13.600
30,300
53,300
533 ,000
34,600
1.490
37.100
573 .000
348,000
- 64,800
- 42.100
35.2
142
5,370
323
1,360
33,000,000
904
4,320
7,130
4,100
9.100
16,000
533.000
(Continued)
-------
TABLE 3-3 CONTINUED.
COST OF ADDITIONAL CONTROLS AT CHEMICAL PLANTS
USING MC IN PRODUCTION
GO
I
00
CO
Company/Location
B.F. Goodrich
Cleveland. OH
Plant I
B.F. Goodrich
Cleveland. OH
Plant II
Dow Chemical (15)
Midland, MI
Do» Chemical (16)
Midland. MI
Do* ChemfcaK/7)
Midland'. MI
Dow Chemical (18)
Midland. MI
Dow Chemical (19)
Midland. MI
Dow Chemlcal(llO)
Midland, MI
Dow Chemical (III)
Midland, MI
Emission Type Control"
Equipment
Storage
Process
Equipment
Storage
Storage
Storage
Process
Equipment
Process
Equipment
Process
Equipment
Process
Equipment
Process
Equipment
Storage
Storage
Storage
Storage3
Process
Equipment
Storage
Equipment
Storage
Storage
Storage
leaks
FR-PO
Incineration
leaks
COND
COND
COND
Incineration
leaks
Incineration
leaks
Incineration
leaks
Incineration
leaks
Incineration
leaks
CONO
COND
COND
FR-SS
Incineration
leaks
COND
leaks
FR-PO
FR-PO
FR-PO
Control
Efficiency
<*>
68
94
98
68
85
85
85
98
58
98
66
98
75
98
37
98
56
85
85
85
97
98
56
85
44
94
94
94
MC/VOC Emission
Reduction (Mg/yr)
3. 1/
O.I/
7.3/
6.8/
O.I/
O.I/
0.3/
I.7/
4.8/
65. 3/
10. 9/
53. 0/
4. 1/
51. 5/
22. 4/
7.8
0.1
7.3
8.0
0.1
O.I
0.3
2.1
7.1
65.3
18.4
53.2
4.7
53.1
41.6
1J2/132
7.4/ 8.9
0.4/
0.4
O.I/ 0.1
0.9/ 1.5
125/125
0.7/
15. S/
O.B/
3.0/
0.8/
O.I/
O.I/
0.7
21.3
0.8
8.7
1.0
0.3
0.3
CapltaJ Cost
UO3*)
26.6
11.6
1,210
18.7
111
111
111
1,220
16.
1,210
19.
1.180
19.
2.480
67.
1,210
16.
Ill
111
111
39.
1,210
41.
Ill
18.
21.
10.
11.
,9
6
2
7
3
4
2
8
2
6
5
Recovery
Credit (lO^t)
3.0
0.1
0.0
3.7
0.0
0.1
0.2
0.0
3.1
0.0
7.8
0.0
2.2
1,490
17.2
0.0
4.1
0.4
0.1
0.9
102
0.0
9.4
0.7
3.3
0.4
0.0
0.0
Net
Annual.
Cost (lO^J)
10.1
3.0
3,420
10.0
29.1
29.0
28.9
412
8.9
421
7.2
402
7.9
1,700
19.7
412
8.6
28.8
29.0
28.2
-91.7
415
19.1
28.4
11.1
5.2
2.7
3.0
Cost Effectiveness
MC VOC
(S/Mg) (S/Mg)
3,270
21,100
56 ,800
1,470
542.000
257,000
95,000
244.000
1.860
6,430
660
7,580
1,910
33.000
879
3.140
1.160
65,000
289,000
31,600
-733
623 ,000
1.240
34,300
3,720
6,820
36,900
38,000
1,310
21,100
56,800
1,250
542,000
257,000
95,000
196,000
1,250
6,430
393
7,550
1,670
32,100
474
3,140
965
65 ,000
289,000
19,000
-733
623 ,000
899
34,300
1,270
5,120
9,200
9,490
(Continued)
-------
TABLE 3-3 CONCLUDED. COST OF ADDITIONAL CONTROLS AT CHEMICAL
PLANTS USING MC IN PRODUCTION
OJ
-f=>
Company/L ocatlon
Dow Chemical (112)
Midland.
MI
Mobay Chemicals
Emission Type Control*
Process
Equipment
Storage
Storage
Storage
Storage
Storage
Storage
Storage
Incineration
leaks
FR-SS
FR-SS
COND
FR-SS
FR-SS
FR-SS
FR-PO
Control
Efficiency
<*>
98
31
97
97
85
97
97
97
94
MC/VOC Emission
Reduction (Mg/yr)
795/885
21. 1/
11. 7/
3.67
4.0/
1.8/
1.9/
l.O/
0.4/
44.0
11.7
4.0
4.5
1.8
2.5
2.0
0.4
CapHaJ Cost
(lO^S)
1,190
22.1
27.0
15.3
111
15.3
12.6
16.1
14.4
Recovery-
Credit <103$)
0.0
17.8
9.5
3.1
3.4
1.4
1.7
1.1
0.2
Nat
Annual.
Cost (103$)
424.8
16.3
-2.4
0.9
25.7
2.6
1.6
3.1
3.6
Cost Effectiveness
MC
(l/Mg)
532
770
-209
255
6,390
1,460
837
3,120
9.660
VOC
(S/Mg)
480
370
-209
229
5,750
1,460
628
1,560
9,660
Kansas City. MO
Mobay Chemicals
Baytown.
TX
Process
Equipment
Incineration
leaks
98
54
0.12/
0.12
27.4 /74.4
1,190
72.3
0.0
36.5
403
43.0
3,420,000
1,570
3,420,000
578
* Ab.brfiv1a.t1o.ns
FR-SS: Floating roof with primary and secondary seals.
FR-PO: Floating roof with primary seals only.
COND: Refrigerated condenser.
aStorage tank discussed previously under process vent emissions.
-------
TABLE 3-4. ESTIMATED MC EMISSION REDUCTIONS FOR
OTHER CHEMICAL PLANTS AS A FUNCTION
OF COST EFFECTIVENESS
Cost Effectiveness
Range ($/Mg VOC)
Nationwide MC Emission Reduction (Mo/YH
Equipment
Process Leak Storage Total
Credit
0 - 500
501 - 1000
1001 - 2000
2001 - 5000
>5000
TOTAL
864
1940
132
845
3780
208
33.7
25.4
1.2
268
137
3.6
1.9
4.8
0.2
4.7
152
1000
2150
35.6
30.2
133.4
850
4200
3-35
-------
3.2.3 Control of Storage Emissions
Cost estimates were developed for control of storage tanks
containing MC. In 1983, emissions from these storage tanks were
estimated to be 31.0 Mg/yr of MC. Three control options were evaluated:
contact internal roof with a primary seal (FR-PO), contact internal roof
with a secondary seal (FR-SS), and a refrigerated condenser. The most
cost effective option is presented in Table 3-3.
The estimated cost effectiveness of controlling storage emissions
at CFC facilities ranges from a net credit of $209/Mg of VOC to
$573,000/Mg of VOC. The additional storage controls costing less than
$2,000/Mg of VOC would reduce MC emissions by 27.6 Mg (85 percent).
3-36
-------
3.3 REFERENCES
1. PEI Associates, Inc. Occupational Exposure and Environmental
Release Assessment of Methylene Chloride. Prepared for the U.S.
Environmental Protection Agency. Washington, D.C. (Contract
No. 68-02-3935). April 1985.
2. Letter and attachments from Pullen, J.C., Celanese, to
Farmer, J.R., EPA/ESED. April 3, 1985. Response to MC 114
questionnaire.
3. Letter and attachments from Perkins, O.K., General Electric, to
Farmer, J.R., EPA/ESED. April 4, 1985. Response to MC 114
questionnaire.
4. Letter and attachments from Granger, L.S., Mobay Chemicals, to
Farmer, J.R., EPA/ESED. April 9, 1985. Response to MC 114
questionnaire.
5. Letter and attachments from Springer, C.R., Borden Chemical, to
Farmer, J.R., EPA/ESED. February 15, 1985. Response to MC 114
questionnaire.
6. Letter and attachments from Holbrock, W.C., B.F. Goodrich, to
Farmer, J.R., EPA/ESED. February 5, 1985. Response to MC 114
questionnaire.
7. Letter and attachments from Drake, A.L., General Electric, to
Farmer, J.R., EPA/ESED. April 9, 1985. Response to MC 114
questionnaire.
8. Letter and attachments from Arnold, S.L., Dow Chemicals, to Farmer,
J.R., EPA/ESED. February 22, 1985. Response to MC 114
questionnaire.
9. TRW, Inc. Vinyl Chloride - A Review of National Emission
Standards. Prepared for the U.S. Environmental Protection Agency.
Research Triangle Park, North Carolina. EPA-450-3-82-003.
February 1982.
10. Letter and attachments from Gillespie, T.E., Shell Oil, to
Farmer, J.R., EPA/ESED. January 31, 1985. Response to MC 114
questionnaire.
11. Letter and attachments from Thayer, J.H., General Electric, to
Farmer, J.R., EPA/ESED. April 3, 1985. Response to MC 114
questionnaire.
3-37
-------
4.0 SOLVENT DECREASING OPERATIONS
About 10 percent (21,300 Mg) of the total methylene chloride (MC)
produced in 1983 was consumed in degreasing operations. It is estimated
that of this amount about 17,700 Mg were emitted to the atmosphere.
Methylene chloride was used as a solvent for degreasing in a variety of
industries, primarily within five distinct Standard Industrial
Classifications (SIC). Emissions from degreasing operations were
estimated in this study by obtaining the 1983 consumption of MC for each
user industry and applying it to an emission factor derived for
degreasing operations. The following sections present a brief
discussion of the types of degreasers, emissions, emissions control,
estimates of emissions from degreasing operations in 1983, and estimates
of the costs associated with emissions control. Due to the large number
of degreasing facilities in these industries, no attempt was made in
this study to identify locations of individual degreasers.
4.1 INDUSTRY DESCRIPTION
Degreasing is an integral part of many industrial processes such as
the manufacture of automobiles, electronics, furniture, appliances,
jewelry, and plumbing fixtures. It is also used to a minor extent in
the textiles, paper, plastics, and glass manufacturing industries. The
degreasing process makes use of nonaqueous or aqueous solvents to clean
and remove debris from a surface prior to painting, plating, assembly,
repair, inspection, or other treatment. Various solvents, including
petroleum distillates, chlorinated hydrocarbons, ketones, and alcohols
are used either alone or in blends for degreasing purposes. Five major
industry groups used MC in degreasing operations. These are furniture
and fixtures (SIC 25), fabricated metal products (SIC 34), electric and
electronic equipment (SIC 36), transportation equipment (SIC 37), and
o
miscellaneous manufacturing industries (SIC 39).
4-1
-------
4.2 DECREASING EQUIPMENT
There are three basic types of degreasing equipment: cold cleaners,
open top vapor degreasers, and conveyorized degreasers. Cold cleaners
are usually the simplest and least expensive type of degreaser.
Individual cold cleaners consist of a tank of solvent with a cover for
nonuse periods. More sophisticated cold cleaners may have solvent
sumps, spray nozzles, drains, and automatic controls. In the typical
cold cleaning process, soiled objects are dipped into the solvent bath
until the soils are dissolved from the surface. The cleaning process
can be enhanced by agitating the solvent, and brushing or spraying
soiled parts. Solvents are normally used at room temperature, but in
some applications may be heated to a temperature below the boiling point
of the solvent.
Open top vapor degreasers are similar in configuration to cold
cleaners but are operated in a different manner. Open top vapor
degreasers are operated at an elevated temperature to boil the solvent.
The vapors from the boiling solvent condense on and clean soiled objects.
A typical open top vapor degreaser consists of a tank equipped with a
heating and cooling system. The heating coils on the inside bottom of
the tank boil the solvent, thereby generating the vapors needed for
cleaning. Cooling coils located near the top and on the inside
perimeter of the tank condense solvent vapors, preventing them from
diffusing out of the tank. Thus, a controlled vapor zone is created
within the tank. Soiled objects are lowered into the vapor zone where
solvent condenses on their surfaces and dissolves the soils. When
condensation ceases, the cleaned objects are withdrawn. Only
halogenated solvents are used for vapor degreasing because, in addition
to their excellent cleaning properties, they are nonflammable and
because their heavy vapors can be easily contained within the machine.1
Conveyorized degreasers feature automated conveying systems for
continuous cleaning of parts. Conveyorized degreasers clean either by
cold cleaning or vapor degreasing, although most clean using vaporized
4-2
-------
solvent. While these units tend to be the largest degreasers, they are
enclosed systems and actually produce less emissions per part cleaned
than other types of degreasers.
4.3 EMISSIONS FROM DEGREASING OPERATIONS
National emission estimates for degreasing operations were
calculated from 1983 MC consumption data provided by the Halogenated
o
Solvents Industry Alliance (HSIA). The consumption data were used in
conjunction with emission factors generated from available literature to
estimate nationwide emissions. A brief description of the estimation
procedure follows.
Available data indicate that 67 percent of all MC consumed in
degreasing operations is used in cold cleaning while about 33 percent is
used in vapor degreasing. Previous EPA studies estimated that for
every kg of a solvent used in cold cleaning, 0.43 kg are emitted. The
corresponding emission factor for open top vapor degreasing is
0.785 kg/kg consumed and for conveyorized degreasing is 0.85 kg/kg
consumed. Assuming that vapor degreasing use of MC is divided equally
between open top and conveyorized degreasing processes, a weighted
average emission factor of 0.56 kg/kg MC consumed was calculated. It
was assumed that the remaining 0.44 kg/kg MC consumed would be recycled.
Based on information from solvent recyclers, it was estimated that
about 75 percent of all waste solvent from degreasing (0.44 kg/kg MC
consumed) is recovered and reused. Therefore, total MC consumption by a
degreaser equals consumption of fresh solvent plus consumption of
recycled solvent. As before, 0.56 kg/kg of the recycled solvent is
emitted. Taking into account the emission of recycled solvent, it is
estimated that for every kg of fresh MC used in degreasing, 0.83 kg is
emitted. The remaining 0.17 kg is assumed to be either incinerated or
disposed of in a landfill according to applicable regulations.
Appendix C presents the details of these material balance calculations.
The total 1983 MC emissions for each of the five SICs were
estimated by applying the 0.83 kg factor to the 1983 MC consumption
figure. Table 4-1 shows the estimated MC emissions from degreasing
operations in these industries.
4-3
-------
TABLE 4-1. 1983 MC EMISSIONS FROM DECREASING OPERATIONS, BY INDUSTRY
Emissions
Industry (SIC Code) (Mg/yr)
Furniture and Fixtures (25) 1,140
Fabricated Products (34) 4,130
Electrical and Electronic Equipment (36) 4,910
Transportation Equipment (37) 2,170
Miscellaneous Manufacturing Industries (39) 5,360
TOTAL 17,700
4-4
-------
Emissions were also estimated for each State in the U.S. The MC
emissions were estimated by assuming that emissions are proportional to
the number of employees for a given industry in each State. The total
number of employees in each of the five industry groups was estimated
from U.S. Department of Commerce data. For example, the emissions
in Illinois from the fabricated products manufacturing industry (SIC 25)
were estimated as follows:
Funriture and fixtures manufacturing consumption of MC in
1983 = 1,370 Mg.
- l>™ ^ x °'83 Mg'consumed = ^ M9 emitted'
The number of employees within the furniture and fixtures
manufacturing industry for Illinois = 18,700.
Total number of employees within the furniture and fixtures
manufacturing industry = 438,000.
Illinois emissions = 1,140 x 433^^ = 50 Mg
This procedure was followed for each industry identified to use MC in
degreasing operations. The totals for industry groups were then
aggregated for each state. The results are presented in Table 4-2.
4.4 EMISSIONS CONTROL
Control methods specified in the CTG and BID for degreasing are
summarized in Table 4-3. ' These methods include add-on equipment as
well as improved work practices.
Add-on equipment for control of degreaser emissions includes adding
covers to equipment openings, increasing freeboard area, adding
freeboard chillers, and providing drainage racks for parts. These
4-5
-------
TABLE 4-2. 1983 METHYLENE CHLORIDE EMISSIONS FROM
DECREASING OPERATIONS, BY STATE
State
Al abama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Del aware
District of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Emissions
(Mg)
240
1
180
140
2,320
190
500
20
3
490
280
10
10
1,180
610
230
130
200
140
60
200
700
810
280
200
370
State
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto Rico
Rhode Island
South Carol ina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
TOTAL
Emissions
(Mg)
5
70
30
100
760
30
1,470
550
10
930
160
70
940
140
400
160
20
410
880
60
50
260
250
40
440
1
17,700
4-6
-------
TABLE 4-3. EXAMPLE CONTROL TECHNIQUES FOR DEGREASERS
Degreaser Type
Control Devices
Operating Practices
Cold Cleaners
Vapor Degreasers
Conveyorized
Degreasers
Cover for tank
Parts drainage rack
Raised freeboard
Cover for tank .
Freeboard chiller
Raised freeboard
Carbon adsorber
Port Covers
Freeboard chillers
Carbon adsorbers
Keep cover closed when
degreaser not in use
Fully drain cleaned
parts
Keep cover closed when
degreaser not in use
Fully drain cleaned
parts
Move parts slowly into
and out of degreaser
Maintain conveyor at
moderate speed
Keep exhaust ventila-
tion rates moderate
Freeboard is the distance from the liquid solvent surface or top of the
solvent vapor to the lip of the tank. "Raised freeboard" is a physical
extension of the freeboard to reduce drafts, and thereby solvent
evaporation, within the degreaser.
Additional cooling coils above the primary coils to further inhibit the
diffusion of solvent vapors to the atmosphere.
4-7
-------
devices limit evaporation losses from solvent baths and solvent
carry-out. More sophisticated control techniques include carbon
adsorption to recover solvent vapors.
Work practices can be improved to limit solvent emissions from
degreasing. These improvements, characterized by practices that reduce
solvent exposure to the atmosphere, include: keeping degreaser covers
closed, fully draining parts prior to removal from degreaser,
maintaining moderate conveyor speeds, and keeping ventilation rates
moderate.
4.5 COST OF EMISSIONS CONTROL
The costs for controlling emissions from model degreasing
facilities have been estimated in previous EPA-sponsored studies.7'8'9
The purpose of the cost evaluation effort for this document is to update
the costs presented in the earlier EPA studies. Costs are presented for
a representative size degreaser for each of three degreaser types:
(1) cold cleaners, (2) open top vapor degreasers, and (3) conveyorized
vapor degreasers. The cost estimates are for retrofitting existing
degreasing facilities. Tables 4-4, 4-5, and 4-6 present the retrofit
cost estimates for cold cleaners, open top vapor degreasers, and
conveyorized vapor degreasers, respectively. The costs estimated in the
previous EPA study.are in fourth quarter 1980 dollars. These costs were
updated to fourth quarter 1984 dollars using the plant cost indexes
(323.6/269.7=1.2).10'n
Several assumptions concerning degreaser operating parameters were
made in developing costs for controlling emissions from the three types
of degreasers. It was necessary to assume operating parameters for
typical uncontrolled and controlled degreasers so that average emission
reductions for each type of degreaser could be determined.
In developing cold cleaner control costs the degreaser size was
o
assumed to be 0.4 m and the annual period of operation was assumed to
be 500 hours (2 hrs/day, 5 days/week, 50 wks per year). The
uncontrolled emissions were based on a cold cleaner with a 0.3 freeboard
ratio and a manual cover. Total emissions from this uncontrolled cold
4-8
-------
TABLE 4-4. RETROFIT CONTROL COSTS FOR COLD CLEANERS
(FOURTH QUARTER 1984 DOLLARS)
0.7 F8R,a Manual Cover
Cost Component and Drain
Capital Costs, ($)
Freeboard (installed) 357
Drain 25
Installation Costs, $
Freeboard (in purchase cost)
Drain 13
Annual Operating Costs, #/yr
Capital Charges 47
Administration, Insurance, and Taxes0 14
Added Labor° 285
Maintenance 11
Utilities 0
Total Annualized Cash, $/Yr
Emission Reduction, Mg/Yr 0.4
Recovered Solvent Credit, $/Yr 194
Net Annualized Cost, $/Yr 163
Cost Effectiveness, $/Mg 410
aFreeboard ratio.
Total Installed Capital Cost annualized over 15 years at a 10 percent
interest rate.
cFour percent of total installed capital cost.
Labor due to drain time requirement, based on 20 loads per day,
15 second drain time per load.
eThree percent of total installed capital cost.
Based on solvent price of $0.485 per kilogram.
4-9
-------
TABLE 4-5. RETROFIT CONTROLS COSTS FOR OPEN TOP VAPOR DEGREASERS
(FOURTH QUARTER 1984 DOLLARS)
I
I—»
o
Capital Costs, $
Cover
0.76 Freeboard
Refrig. Freeboard
Carbon Adsorber
Auxiliary Equipment
Added Plant Space
Installation Costs, $
Cover
0.75 Freeboard
Refrig. Freeboard
Carbon Adsorber
Auxiliary Equipment
Total Capital Costs, $
Operating Costs, $/yr
Capital Charges $/yr.d
Administration, Ins., Taxes6
Maintenance
Added Labor
Utilities
Electricity
Steam
Water
Cover
0.75 FBRa
1,238
1,012
-
-
595
—
136
136
-
-
136
3,253
427
130
98
570
-
-
™
Automatic
Cover
0.75 FBR
3,832
268
-
-
595
—
203
136
-
-
, 136
5,170
679
207
155
-
-
-
~"
Cover
Above
Freezing
FBCb,c
1,238
1,012
-
-
595
—
136
136
-
-
136
8,499
1,117
45
34
570
71
-
_
Cover
Below
F reez i ng
FBCC
1,238
1,012
-
-
595
-
136
136
-
-
136
13,021
1,711
68
51
570
98
-
—
Cover,
Carbon
Adsorber
1,238
1,012
-
-
595
—
136
136
-
5,950
136
18,366
2,413
97
72
570
208
201
26
(continued)
-------
-p"
I
TABLE 4-5 CONCLUDED. RETROFIT CONTROLS COSTS FOR OPEN TOP VAPOR DEGREASERS
(FOURTH QUARTER 1984 DOLLARS)
Total Annual ized Costs, $/Yr
Emission reduction
Recovered solvent
Net annual control
Cost Effectiveness
, Mg/yr
credit, $/yrs
cost, $/yr
, $/Mg
Cover
0.75 FBRa
1,225
1.84
892
333
180
Automatic
Cover
0.75 FBR
1,041
2.86
1,387
-346
10
Cover
Above
Freezing
FBCb,c
1,837
3.19
1,547
290
90
Cover
Below
Freezing
FBCC
2,498
3.19
1,547
951
300
Cover,
Carbon
Adsorber
3,587
3.89
1,887
1,700
440
Freeboard Ratio.
Refrigerated freeboard chiller.
°Also require 0.75 freeboard ratio.
dTotal installed capital cost annualized over 15 years at a 10 percent interest rate.
eFour percent of total Installed capital cost.
Three percent of total installed capital cost.
9Based on solvent price of $0.485 per kilogram.
-------
TABLE 4-6. RETROFIT CONTROL COSTS FOR CONVEYORIZED DEGREASERS
(FOURTH QUARTER 1984 DOLLARS)
Capital Costs, $
Refrig. Freeboard
Carbon Adsorber
Auxiliary
Installation Costs, $
Refrig. Freeboard
Carbon Adsorber
Auxil iary Equipment
Additional Plant Space
Total Capital Costs, $
Operating Costs, $/Yr
Capital Charges
Adm. , Ins. , & Taxes0
Operating Labor
Maintenance
Utilities
Electricity
Steam
Cool ing Water
Total Annual ized Cost, S/Yr
Emission Reduction, Mg/Yr
Recovered Solvent Credit, $/Yre
Net Annual ized Costs, $/Yr
Cost of Control , $/Mg
RFCa
14,994
0
0
407
0
0
175
15,576
2,047
623
0
467
195
3,332
9.84
4,772
-1,440
-150
Carbon
Adsorber
0
58,310
0
0
11,900
0
4,998
75,208
9,882
3,008
0
2,256
277
626
62
16,111
10.9
5,287
10,824
990
Adsorber
Drying
Tunnel
0
58,310
11,900
0
11,900
2,380
5,998
90,488
11,890
3,620
0
2,715
277
626
62
19,190
12.4
6,014
13,176
1,060
Refrigerated freeboard chiller.
3Total installed capital cost annualized over 5 years at a 10 percent
interest rate.
'Four percent of total installed capital cost.
Three percent of total isntalled capital cost.
"Based on solvent price of $0.485 per kilogram.
4-12
-------
cleaner were estimated to be 1,140 kg/yr. The controlled emissions were
based on a cold cleaner with a 0.75 freeboard ratio, a manual cover and
a drainage rack. Total emissions from this cold cleaner were estimated
to be 740 kg/yr. It is estimated that a 35 percent emissions reduction
can be achieved with a raised freeboard, a manual cover, and a drainage
rack.9'12'13
For open top vapor degreaser (OTVD) control cost development
2
degreaser size was assumed to be 1.5 m and an operating schedule of
1,500 hours (6 hrs/day, 5 days/wk, 50 wks/yr) was used. The
uncontrolled emissions were based on an OTVD with a freeboard ratio of
0.5 and were estimated to be 8,770 kg/yr. This estimate assumes an
8-hour working day during which the degreaser is uncovered for 6 of
these hours; the degreaser is idle for the remaining 2 hours.
Five control options for OTVDs were investigated, including covers and
raised freeboards, automated covers and raised freeboards, above-
freezing refrigerated chillers, below freezing refrigerated chillers,
and carbon adsorption systems. The control costs are presented in Table
4-5, and are based on the following: (1) utilization of a cover with a
control efficiency of 90 percent during idle time; (2) reduction of 15
percent in vaporization losses by increasing the freeboard ratio from
0.5 to 0.75; (3) reduction of 40 percent in vaporization losses by use
of either above- or below-freezing chillers; (4) reduction of 40 percent
in vaporization losses due to the use of an automated cover; (5)
reduction of 65 percent in vaporization losses due to the use of a
carbon adsorber; and (6) a 10 percent reduction in carry out losses due
to use of a refrigerated freeboard device. Overall achievable emission
reductions with these techniques were estimated to range from 21 percent
Q 1 7 1 ^
to 44 percent. '1£>1
Conveyorized degreaser control cost estimates were based on a
2
degreaser 3.0 m in size with an operating schedule of 2,000 hours.
(8 hrs/day, 5 days/wk, 50 wks/yr) Uncontrolled emissions for a typical
conveyorized degreaser were estimated to be about 21,800 kg/yr.
Three control options were examined for costing purposes, including
refrigerated freeboard chillers, carbon adsorbers, and carbon adsorbers
along with a drying tunnel. Control costs are presented in
4-13
-------
Table 4-6 and are based on the following: (1) a 45 percent reduction in
solvent loss due to the use of refrigerated freeboard chillers; (2) a
50 percent reduction in solvent loss due to the use of a carbon
adsorber; and (3) a 15 percent reduction in carry-out emissions only,
due to the use of a drying tunnel. Achievable emission reductions
using these techniques are estimated to range from 45 percent to
57 percent.9'12'13
Estimates of the national emission reduction associated with
controlling MC emissions from degreasers were made using: (1) emission
factors developed for uncontrolled cold cleaners, open top vapor
degreasers, and conveyorized vapor degreasers; and (2) the estimated
total number of uncontrolled degreasers in MC service in 1983. It is
estimated that about 6,590 Mg/yr MC emissions can be reduced by the
application of control techniques on uncontrolled cold cleaners, open
top vapor degreasers, and conveyorized vapor degreasers. This represents
a 37 percent reduction in MC emissions from degreasers. Potential MC
emission reductions for each type of degreaser are 2,360 Mg/yr (cold
cleaners), 1,770 Mg/yr (open top vapor degreasers), and 2,460 Mg/yr
(conveyorized vapor degreasers). The details of the calculations for
estimating national emission reduction are presented in Appendix D.
4.6 REGULATORY REQUIREMENTS
EPA has approved RACT guidelines for solvent degreasing operations
that have been adopted by 32 States and the District of Columbia. The
10 States that have the highest estimated emissions of MC from solvent
degreasing, California, Ohio, New York, Michigan, Illinois, Pennsylvania,
Indiana, Texas, Massachusetts, and New Jersey, have all adopted EPA-
approved RACT. These 10 States account for about 59 percent of total
degreasing emissions of MC. In addition, EPA has proposed (but not
promulgated) an NSPS that would control emissions from new solvent
degreasers.
4-14
-------
4.7 REFERENCES
1. Bellinger, J.C., and J.L. Shumaker. Control of Volatile Organic
Emissions from Solvent Metal Cleaning. U.S. Environmental
Protection Agency. Research Triangle Park, N.C. Publication No.
EPA-450/2-77-022. November 1977. 203 p.
2. Letter from Morgan, D.L., Cleary, Gottlieb, Steen, and Hamilton, to
Rosensteel, R.E., EPA. February 22, 1985. HSIA data on methylene
chloride production and consumption.
3. Tang, J.L. Industrial Survey of Halogenated Solvent Producers and
Degreaser Manufacturers. GCA/Technology Division, Chapel Hill,
North Carolina. July 1981.
4. Hoogheem, T.J., D.A. Horn, T.W. Hughes, and P.J. Marn (Monsanto
Research Corporation). Source Assessment: Solvent Evaporation -
Degreasing Operations. Prepared for U.S. Environmental Protection
Agency. Cincinnati, OH. Publication No. EPA-600/2-79-019f.
August 1979. 133 p.
5. Telecon. Pandullo, R.F., Radian Corporation, with Pokorny, J.,
Baron-Blakeslee, Inc. March 19, 1985. General information on
solvent recycling.
6. Bureau of the Census. County Business Patterns 1982. U.S.
Department of Commerce. Washington, D.C. Publication No. CBP-82.
October 1984.
7. GCA Corporation. Organic Solvent Cleaners - Background Information
for Proposed Standards. Prepared for U.S. Environmental Protection
Agency. Research Triangle Park, N.C. Publication No.
EPA-450/2-78-045a. October 1979. 282 pp.
8. Memo from O'Brian, T., GCA, to D.A. Beck, EPA/CPB. March 2, 1982.
Estimation of Solvent-Specific Control Costs.
9. Memo from Smith, M., GCA, to D.A. Beck, EPA/CPB. August 20, 1981.
Background Information on Cost Analysis for Emission Guideline
Document for Organic Solvent Cleaners.
10. Chemical Engineering plant cost index. Chemical Engineering.
Volume 88, Number 8.
11. Chemical Engineering plant cost index. Chemical Engineering.
Volume 92, Number 6.
12. West!in, P.R., and J.W. Brown, Test Report-Solvent Drainage and
Evaporation from Cold Cleaner Usage. U. S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Research Triangle Park, North Carolina, January 1978.
4-15
-------
13. Suprenant, K.S. and D.W. Richards. Study to Support New Source
Performance Standards for Solvent Metal Cleaning Operations.
Prepared by the Dow Chemical Company for the U. S. Environmental
Protection Agency, Contract No. 68-02-1329. April 1976.
4-16
-------
5.0 PHOTORESIST STRIPPING OPERATIONS
About five percent of the methylene chloride (MC) produced in 1983
was used as a photoresist stripping solvent in the electronics industry
during the production of printed circuit boards. It was not within the
scope of this study to make direct contact with all manufacturers of
printed circuit boards or to verify the exact number of facilities
presently in operation. Emissions from photoresist stripping operations
in printed circuit board manufacturing were estimated in this study by
obtaining the 1983 MC consumption for printed circuit board
manufacturing and applying an emission factor derived for photoresist
stripping operations. It is estimated that in 1983, about 11,900 Mg of
MC were consumed in photoresist stripping operations and about 6,800 Mg
were emitted to the atmosphere.
5.1 INDUSTRY DESCRIPTION
Photoresist stripping is an operation used in the electronics
industry during the production of printed circuit boards. The
processing of copper-clad laminated circuit boards into printed circuit
boards occurs in several basic steps. First, a polymer-based
photoresist chemical is applied to the entire circuit board surface and
is masked with the appropriate design. Next, the photoresist is exposed
to light. Further, the photoresist is developed using a solvent to
remove unwanted resist. Finally, the exposed copper is etched with
acid and the remaining resist is stripped away with methylene chloride.
Three types of systems are employed in the production of printed
circuit boards. These are (a) solvent systems, which use methylene
chloride as the stripper solvent and 1,1,1-trichloroethane as the
developer solvent; (b) semi-aqueous systems; and (c) aqueous systems.
The semi-aqueous system and aqueous systems do not use methylene
chloride as a stripper solvent. Solvent systems may use pure methylene
chloride or a blend of methylene chloride, with an alcohol (usually
methanol) as the stripper solvent.
5-1
-------
Overall, there is a trend away from solvent stripping systems
toward semi-aqueous or aqueous systems. This has been due primarily to
the growing concern for minimizing exposure to halogenated hydrocarbon
solvents. Further, solvent systems have higher operating costs because
of high solvent costs, solvent recovery equipment costs, and waste
disposal expenses.1 However, despite the fact that there is a trend
away from solvent systems, there is indication that for printed circuit
boards requiring high resolution, solvent systems will continue to be
used.
5.2 EMISSIONS AND CONTROL TECHNIQUES
National emission estimates for photoresist stripping operations
were calculated from 1983 MC consumption data provided by the
Halogenated Solvents Industry Alliance (HSIA).3 The consumption data
were used in conjunction with an emission factor generated from industry
contacts.
Based on information from an industry representative, it was
estimated that for every kg of methylene chloride consumed in
photoresist stripping 0.25 kg is emitted directly to the atmosphere.4
It was assumed that the remaining 0.75 kg/kg of methylene chloride goes
to recycling. Further, information from solvent recyclers indicates
that about 75 percent of all recycled solvent from photoresist stripping
is recovered and reused. Therefore, total MC consumption in photoresist
stripping equals consumption of fresh solvent plus consumption of
recycled solvent. As before 0.25 kg/kg of the recycled solvent is
emitted. Taking into account the emission of recycled solvent, it is
estimated that for every kg of fresh solvent used in photoresist
stripping, 0.57 kg is emitted. Appendix C presents the details of these
material balance calculations. The remaining 0.43 kg is assumed to be
either incinerated or disposed of in a landfill according to applicable
regulations.
The total 1983 MC emissions for photoresist stripping were
estimated for each State in the U.S. The MC emissions were estimated by
assuming that emissions are proportional to the number of employees for
5-2
-------
the printed circuit board manufacturing industry in each State. The
total number of employees in printed circuit board manufacturing was
estimated from U.S. Department of Commerce data. For example the
emissions in Illinois were estimated as follows:
- Printed circuit board manufacturing nationwide consumption
of MC in 1983 = 11,900 Mg
- 11,900 Mg x 0.57 Mq emitted = 6,800 Mg nationwide emissions
Mg consumed
- The number of employees within printed circuit
board manufacturing in Illinois = 11,600
- Total number of employees within printed circuit
board manufacturing industry = 215,000
- Illinois emissions = 6,800 Mg x Ill60° = 370 Mg
215,000
This procedure, was followed for each State and the results are presented
in Table 5-1.
A broad survey of individual facilities using MC was not conducted
regarding controls commonly applied within the industry. Consequently,
the current status of control technology could not be ascertained.
However, one printed circuit board manufacturer indicated that carbon
adsorption was being used to control MC emissions from photoresist
stripping operations.
5.3 REGULATORY REQUIREMENTS
Currently only California has regulations affecting photoresist
stripping operations in printed circuit board manufacturing. However,
MC is exempt from these regulations because it is not considered to be
an ozone precursor.
5-3
-------
TABLE 5-1. 1983 METHYLENE CHLORIDE EMISSIONS FROM
PHOTORESIST STRIPPING OPERATIONS, BY STATE
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawaii
Idaho
111 i no is
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Emissions
(Mg)
130
1
70
5
1,910
70
250
20
5
260
20
20
5
370
40
30
20
10
0
30
50
570
50
200
5
60
State
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto Rico
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
TOTAL
Emissions
(Mg)
0
5
5
130
340
10
1,020
30
5
140
60
50
290
120
40
15
5
30
160
0
5
50
0
0
40
0
6,800
5-4
-------
5.4 REFERENCES
1. PEI Associates, Inc., 1985. Occupational Exposure and Environmental
Release Assessment of Methylene Chloride. Prepared for Office of
Pesticides and Toxic Substances. U.S. Environmental Protection
Agency. Washington, D.C. April 12, 1985.
2. Telecon. R. H. Howie, Radian with D. Berdman, Institute for
Interconnecting and Packaging Electronic Circuits. April 23, 1985.
Emissions of methylene chloride from photoresist stripping.
3. Letter from Morgan, D.L. of Cleary, Gottlieb, Steen and Hamilton to
R.E. Rosensteel, EPA/ESED, March 8, 1985. Halogenated Solvents
Industry Alliance (HSIA) information on consumption of methylene
chloride.
4. Telecon. Pandullo, R.F., Radian Corporation with J. Pokorny,
Baron-Blakeslee, Inc. March 19, 1985. General information on
solvent recycling.
5. Bureau of the Census. County Business Patterns. 1982. U.S.
Department of Commerce. Washington, D.C. Publication No. CBP-82
October 1984.
6. Telecon. R.H. Howie, Radian with R. Jensen, AT&T. April 23, 1985.
Emissions of methylene chloride from photoresist stripping.
5-5
-------
6.0 FOAM MANUFACTURING
The foam manufacturing industry consumed about 7 percent (14,200 Mg)
of the methylene chloride (MC) produced in 1983. It is estimated that
100 percent of the MC consumed in foam manufacturing was emitted to the
atmosphere.
There have been 85 foam manufacturing plants in the United States
identified by this study. The States having the most manufacturers are
California (12 plants), Texas (10 plants), North Carolina (7 plants),
Indiana (6 plants), and Mississippi (6 plants).1 It is unlikely that
all of these foam plants consume, and thus, emit MC. However, it was
not within the scope of this study to identify the locations of all foam
manufacturing plants using MC.
6.1 INDUSTRY DESCRIPTION
Methylene chloride is used as an auxiliary blowing agent in the
production of flexible urethane foam slabstock. The primary blowing
agent is carbon dioxide which forms from the reaction of two basic
formulation ingredients of the foam. Auxiliary blowing agents are used
when softer foams are required. The cushioning nature of the foam is
due to minute foam cells that are formed by the gaseous blowing agents.
It has been reported that most foam manufacturing facilities have
traditionally used CFC-11 as the auxiliary blowing agent.2 MC is also
used often because it is a relatively inexpensive agent compared to
CFC-11. However, its higher boiling point requires more heat to initiate
reaction than do chlorofluorocarbons and thus the reaction is more
difficult to control-1
Methylene chloride and other ingredients are pumped to a mixing
head and discharge nozzle positioned at the opening of a foam tunnel.
The material is then expelled onto a conveyor belt within the foam
tunnel. The exothermic reaction of materials in the tunnel vaporizes
the blowing agent, forming cells in the foam. This curing process
continues as the material passes through the tunnel, exiting as formed
slabstock ready to be sawed into slabs and later packaged for shipment.1
6-1
-------
6.2 CURRENT EMISSIONS AND CONTROLS
Methylene Chloride emissions result from vaporization in the foam
tunnel primarily, but also may result from storage tanks, equipment
leaks and vaporization of residual MC in the foam curing area. Based on
information from an industry representative it is estimated that well
over 50 percent of MC emissions from foam manufacturing processes are
from the foam tunnel itself, with the remainder emitted during storage,
transfer, or use. Industry contacts have indicated the foam plants are
typically uncontrolled.3'4
The Halogenated Solvents Industry Alliance reported that the foam
blowing industry consumed approximately 14,200 Mg of MC in 1983.5 It
was assumed for the purposes of this study that all MC consumed is
eventually emitted to the atmosphere. Emissions from foam manufacturing
are presented by State in Table 6-1. These emission estimates are
estimated by State according to the consumption distribution provided by
HSIA.
6-2
-------
Table 6-1. 1983 MC EMISSIONS FROM
FOAM MANUFACTURING, BY STATE
STATES
Arkansas
California
Colorodo
Florida
Georgia
Hawaii
Illinois
Indiana
Kentucky
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Ohio
Oregon
Pennsylvania
New Jersey
New York
North Carolina
Rhode Island
South Carolina
Tennessee
Texas
Virginia
Washington
TOTAL
ANNUAL EMISSIONS (Mg)
340
3,060
120
350
670
120
370
690
120
230
230
540
120
960
230
300
580
230
120
1,970
780
120
610
1,130
110
100
14,200
6-3
-------
6.3 REFERENCES
1. Thomas Register of American Manufacturers and Thomas Register
Catalogue File. 69th Edition. Thomas Register Publishing Company,
New York, New York, 1979 and 1985.
2. Mooz, W.E., S.H. Dole, O.L. Jaquette, W.H. Krase, P.F. Morrison,
S.L. Salem, R.G. Salter, and K.A. Wolf, Rand Corporation, 1982.
Technical Options for Reducing Chiorof1uorocarbon Emissions.
Prepared for U.S. Environmental Protection Agency. R-2879-EPA.
3. Telecon. Pandullo, R.F., Radian with H. Stone, General Foam.
April 22, 1985. Information on operating parameters for foam
manufacturing.
4. Telecon. Pandullo, R.F., Radian with A. Pereira, Foamex Products.
April 22, 1985. Information on use of methylene chloride on
foam manufacturing.
5. Letter from Morgan, D.L. of deary, Gottlieb, Steen and Hamilton to
R.E. Resensteel, EPArESED. March 8, 1985. Halogenated Solvents
Industry Alliance information on consumption of methylene chloride.
6-4
-------
7.0 PHARMACEUTICAL MANUFACTURING
The pharmaceutical industry used approximately 6 percent (13,200 Mg)
of total methylene chloride (MC) production in 1983. Methylene chloride
is used in pharmaceutical manufacturing as a general solvent, as an
extraction solvent, and in tablet coatings. Previous EPA studies
indicate that there are over 800 pharmaceutical plants in the United
States and its territories , although only a fraction of these plants
likely use MC. Prior EPA reports indicate that in addition to its use
in tablet coatings, MC is used in the manufacture of antibiotics,
steroids, and vitamins, and specifically in the production of reserpine,
cephalothin, cephaliride, cepharin, tolbutamide, and estrone.2'3 The
exact locations of all pharmaceutical plants using MC have not been
identified in this study.
7.1 INDUSTRY DESCRIPTION
Pharmaceuticals typically are manufactured in a series of batch
operations. The following description represents a likely sequence of
operations. The solvent is received and stored in tanks ranging from
20,000 to 110,000 liters (5,280 to 29,100 gallons) capacity. From
storage the solvent is piped directly to a glass - or stainless
steel-lined reactor. A typical batch reactor has a capacity of 2,000 to
11,000 liters (500-3000 gallons). To begin a production cycle, the
reactor is washed and dried with the solvent. After washing occurs, air
or nitrogen is commonly used to purge the reactor. Solid reactants and
solvent are then charged to the reactor which is equipped with a
condenser. After the reaction cycle is finished, the unreacted volatile
compounds and remaining solvent are cleared from the reactor through
distillation and condensation. The crude product is then transferred to
a holding tank where it is washed with water or solvent to remove any
remaining reactants or by-products. Next, the crude product undergoes
one of several separation processes.
7-1
-------
Typical separation processes include distillation, extraction, and
filtering. The crude product may then be dissolved in another solvent
and transferred to a crystal!izer for purification. After crystalli-
zation, the solid material may be separated from the remaining solvent
by centrifugation. While in the centrifuge, the product may be washed
again with water or solvent. Tray, rotary, or fluid-bed dryers are then
used for final product finishing.
7.2 CURRENT EMISSIONS AND CONTROLS
At pharmaceutical plants where MC is used as a solvent, each
operation within the manufacturing process, as well as the storage and
handling steps, may be sources of MC emissions. The level of emissions
varies significantly among different operations and depends on the
quantity of solvent used, the type of equipment performing the
operation, and the frequency of performing the operation. Dryers are
potentially large emission sources. Emission rates from dryers vary
depending on the size of the unit, the number and duration of drying
cycles per year, and the amount of MC evaporated during a given drying
cycle. Emissions from reactors result from the displacement of MC-laden
air during reactor charging, as well as from solvent evaporation during
the reaction cycle, the venting of uncondensed MC from overhead
condensers during refluxing, from the purging of vaporized MC following
solvent wash, and from the opening of reactors during the cycle for
sampling. Distillation columns emit MC as uncondensed solvent. Storage
and handling emissions result from displacement of vapors during storage
tank filling and from displacement of vapors within the storage tank
when temperature or atmospheric pressure changes occur.
A survey of 17 ethical drug manufacturers in 1982 indicated a total
annual MC purchase of about 11,400 Mg by these manufacturers. The
responding firms were estimated to represent approximately one-half of
the production of ethical domestic Pharmaceuticals in 1982. The
estimated final disposition of the above total MC usage was the
following: 4,900 Mg air emissions (43 percent); 570 Mg sewer disposal
(5 percent); 4,330 Mg incinerated (38 percent); 1,250 Mg contract hauled
7-2
-------
(11 percent); and 340 Mg disposed of off-site (3 percent).4 Assuming
the same disposition for 1983 consumption provided by the Halogenated
Solvents Industry Alliance, estimated air emissions are 5,700 Mg.5
Individual facilities using MC were not contacted regarding the
control techniques commonly used within the industry. Consequently, the
current status of control technology for pharmaceutical manufacturing
could not be ascertained. However, the controls available to the
industry include condensers, absorbers, carbon adsorbers and, in some
cases, incinerators. Storage and transfer emissions can be controlled
by vapor return lines, conservation vents, vent scrubbers, pressurized
storage tanks, and floating roof storage tanks.1
7-3
-------
7.3 REFERENCES
1. U.S. Environmental Protection Agency. Control of Volatile Organic
Emissions From Manufacture of Synthesized Pharmaceutical Products.
Office of Air Quality Planning and Standards. EPA-450/2-78-029.
December 1978.
2. PEI Associates, Inc., 1985. Occupational Exposure and Environmental
Release Assessment of Methylene Chloride. Prepared for Office of
Pesticides and Toxic Substances. U.S. Environmental Protection
Agency. Washington, D.C. April 12, 1985.
3. Memorandum and attachments from M.A. Callahan, TSPC Solvents Work
Group #2 to M.C. Bracken, Toxic Substances Priorities Committee.
February 1, 1982. Summary of data collection and analysis efforts
of the TSPC Sources and Exposure Work Group.
4. Letter and attachment from T.X. White, Pharmaceutical Manufacturers
Association (PMA) to D.A. Beck, EPA.-ESED. June 1984. Emissions of
selected organic compounds in the pharmaceutical industry.
5. Letter from Morgan, D.L. of deary, Gottlieb, Steen and Hamilton to
R.E. Rosensteel, EPA:ESED. April 11, 1985. Halogenated Solvents
Industry Alliance information on consumption of methylene chloride.
6. Letter from Morgan, D.L. of deary, Gottlieb, Steen and Hamilton to
R.E. Rosensteel, EPA:ESED. June 28, 1985. Clarification of
Halogenated Solvents Industry Alliance information on consumption
of methylene chloride.
7-4
-------
8.0 PESTICIDE MANUFACTURING
Pesticide manufacturing accounted for about one percent (2,700 Mg)
of total methylene chloride (MC) consumption in 1983. Methylene
chloride has several applications in the pesticide industry. It is used
for extraction, phase separations, purifications, crystallization, and
O O /[
as a general transport solvent. '' Previous studies indicate that
there are about 140 individual pesticide facilities in the United States
manufacturing one or more pesticides. Of these, a fraction are users
of MC.
According to information provided by the Halogenated Solvents
Industry Alliance (HSIA), pesticide facilities in three cities accounted
for about 77 percent of total 1983 use of MC in pesticide production.1
The facilities in these cities were identified from a list of pesticide
manufacturers in the available literature.6 No attempt was made in this
study to verify the amount of MC used by these facilities.
Three additional pesticide facilities accounting for about 2 percent
of total MC production in 1983 were identified directly through a
telephone survey.2'3 The identified pesticide facilities and associated
1983 methylene chloride consumption volumes are presented in Table 8-1.
8.1 INDUSTRY DESCRIPTION
The methods and exact technology for manufacturing pesticides
varies considerably depending on the type of pesticide. The pesticide
industry employs the same unit processes and operations used in the
chemical processing industry. These include chemical reactions,
filtering, separation operations, condensation, and drying. Production
processes are usually carried out at ambient or slightly above ambient
temperatures. Elemental chlorine is the raw material common to most
pesticide production and is also frequently used to prepare other raw
material used for pesticide production. The raw materials,
intermediates, by-products, and products may be highly toxic to certain
plants and animals, including man.
8-1
-------
TABLE 8-1. 1983 CONSUMPTION OF METHYLENE CHLORIDE
IN PESTICIDE MANUFACTURING
Company/Location
Consumption/Emissions (Mg/yr)
Chevron Chemical Company
Richmond, CA
Union Carbide
Woodbine, GA
Great Lakes Chemical Company
El Dorado, AR
Buckman Laboratories
Memphis, TN
Buckman Laboratories
Cadet, MO
Rhone-Poulenc Chemical Company
Mt. Pleasant, TN
Unidentified
TOTAL
740
1060
265
26
7
12
590
2,700
8-2
-------
8.2 EMISSIONS AND CONTROLS
Air emissions from pesticide facilities include particulates,
gases, and vapors which may emanate from process equipment at each step
of the manufacturing process. There is indication that evaporation of
wastewater from holding ponds may be a significant source, although few
quantitative data are available. The limited data gathered in this
source assessment study indicate that primary MC emission sources are
equipment leaks, and waste treatment facilities as well as emissions
from control devices such as condensers and scrubbers.2'3'4 It is
likely that most of the MC consumption in pesticide manufacturing is
emitted to the atmoshpere. In this study it was assumed that all the MC
consumed in pesticide manufacturing during 1983 was emitted.
It was not within the scope of this study to undertake a
comprehensive survey of the control techniques commonly used within the
industry. Consequently, typical control levels for pesticide
manufacturing could not be ascertained. However, the control techniques
employed by two pesticide facilities using MC that were contacted
include condensers, recycling systems, refrigerated condensers, and
incinerators. '
8-3
-------
8.3 REFERENCES
1. Letter from Morgan, D.L., Cleary, Gottlieb, Steen and Hamilton.
March 8, 1985. HSIA information on methylene chloride consumption.
2. Letter from Hentschel, M.K., Buckman Laboratories, to J.A. Kowalski,
Radian. March 22, 1985. Information on methylene chloride use.
3. Letter from Embry, W.A., Rhone-Poulenc, to J.A. Kowalski, Radian.
March 14, 1985. Information on methylene chloride use.
4. Letter from Nevin, J.B., Chevron, to J.A. Kowalski, Radian.
May 1, 1985. Information on methylene chloride use.
5. Archer, S.R., W.R. McCurley, and G.S. Raw!ings. 1978 Source
Assessment: Pesticide Manufacturing Air Emissions - Overview and
Prioritization. EPA-600/2-78-004d Prepared for U.S. Environmental
Protection Agency. Office of Research and Development.
Washington, D.C.
6. SRI Directory of Chemical Producers-1983. SRI International.
Menlo Park, California.
8-4
-------
9.0 DISTRIBUTION FACILITIES
Virtually all methylene chloride (MC) produced is sold through chemical
distributors. There are an estimated 300 chemical distributors handling
chlorinated solvents. Table 9-1 presents the five largest MC distributors.
These distributors handle about 40 percent of the total MC sold through
distributors. In general, distributors maintain as few as three to as many
as 65 regional distribution facilities spread out across the nation. One
chemical distributor estimated the number of regional distribution
facilities at 500 nationwide. Each district distributor receives chemicals
directly from the producer by tank truck or railcar. Transportation is
provided by the distributor. The received chemicals are stored by district
distributors in 8,000 to 20,000 gallon fixed-roof storage tanks. The
storage tanks used by district distributors include vertical, horizontal,
and underground tanks. Turnover times for storage tanks typically range
from 2 weeks to a little over a month. Although the exact number of
distributors and distribution facilities that handle MC is not known, it is
estimated that there are 109 MC storage tanks owned by distributors,
the majority of which are fixed roof tanks. The procedure used to
estimate the number of tanks is given in Appendix E.
9.1 EMISSIONS FROM DISTRIBUTION FACILITIES
Emissions from distribution facilities can be categorized as two types,
storage and handling. Storage emissions include breathing and working
losses from tanks. Handling emissions result from vapor displacement when
drums and tank trucks are filled.
Storage and handling emissions of MC from distribution facilities were
estimated using AP-42 emission factors4 and data supplied by the major
distributors. The details of those calculations are presented in
Appendix E. It is estimated that approximately 490 Mg of MC were
emitted in 1983 from distribution facilities. Storage emissions
accounted for 280 Mg, while handling emissions were about 210 Mg.
9-1
-------
9.2 REGULATORY REQUIREMENTS
There are State and Federal regulations that may affect methylene
chloride distribution facilities. Most States have regulations for
storage and handling of volatile organic liquids (VOL). However, many
of these States exclude MC from their VOL regulations due to its low
photochemical reactivity. Also, a Federal regulation for volatile
organic liquid storage has been proposed. However, these regulations
generally apply to storage tanks with a volume of 25,000 gallons or
greater. According to the major distributors of MC, the size of MC
storage tanks is typically 15,000 gallons or less.5
9-2
-------
TABLE 9-1. SUMMARY OF MAJOR METHYLENE CHLORIDE DISTRIBUTORS
Company
Number Of
Distribution
Facilities
Number
Of MC
Storage
Tanks
Typical Typical
Size Size
(Gal) Turnover
Ashland
1
McKesson
2
61
63
46
32
8,000 3 wks - 1 mo
10,000
N/A
Chem-CentraV
Detrex5
31
25
10,000
25 Drum Directly 15,000
1 mo
Thompson-
Hayward
26
10,000 2 - 3 months
9-3
-------
9.3
1.
REFERENCES
Telecon. Sterett, R., Ashland Chemical Company, with Howie, R. H.,
Radian Corporation. February 7, 1985. Conversation on storage of
chlorinated solvents.
Telecon. Eisner, D., McKesson Chemical Company, with Howie, R. H.,
Radian Corporation. February 7, 1985. Conversation on storage of
chlorinated solvents.
Telecon. Trice, L., Chem-Central, with Howie, R. H., Radian
Corporation. February 8, 1985. Conversation on storage of chlorinated
solvents.
U.S. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors. Supplement 7. Research Triangle Park, North
Carolina. Publication No. AP-42. August 1977.
Memorandum from Howie, R. to D. A. Beck, EPA. February 19, 1985.
Distribution of Methylene Chloride, Trichloroethylene, and
Perchloroethylene.
Telecon. Roberts, M., Detrex Chemical Industries, Inc. with
Howie, R. H., Radian Corporation. February 12, 1985. Conversation on
storage of halogenated solvents.
Telecon. Hart, W., Thompson-Hayward, with Howie, R. H.,
Radian Corporation. February 18, 1985. Conversation on storage of
halogenated solvents.
9-4
-------
10.0 ADDITIONAL EMISSION SOURCES OF MC
About 138,000 Mg of methylene chloride (MC) were consumed in 1983
in various uses including aerosol products, paint removers, photographic
film processing, the food processing industry, and general miscellaneous
applications. No attempt was made in this study to identify individual
emission points for each use. However, several of these uses of MC
result in emissions from the industrial point sources as well as from
end use by the consumer. In general, the entire amount of MC used in
these applications is emitted to the atmosphere. Table 10-1 identifies
the amount of MC consumed and emitted in these additional source
categories.
10.1 AEROSOLS
Methylene chloride is used as a solvent in aerosol products
including finishes and coatings, hair sprays, cleaners, room deodorants,
and various household and personal products. Approximately 52,900 Mg of
MC were consumed in aerosol products in 1983.1
Aerosols are largely consumer products, although they are also used
in industrial applications. Methylene chloride emissions from
consumption of aerosol products result from the volatilization of
suspended droplets or by evaporation from sprayed surfaces. Due to the
nature of the use of aerosol products all MC in aerosol products
(52,900 Mg in 1983) is emitted.
Emissions also occur at aerosol packaging plants due to spills and
from evaporation during mixing and aerosol can charging.2 It was
outside of the scope of this study to investigate the amount of MC
emitted at aerosol packaging facilities. However, those emissions are
believed to be small relative to the total amount emitted nationwide
from aerosol consumption.
10-1
-------
TABLE 10-1. ADDITIONAL USES OF METHYLENE CHLORIDE IN 1983
Source
Consumption/
Emissions
(Mg/Yr)
Aerosols
Paint Removers
Photographic (film processing)
Food Processing
Miscellaneous
52,900
62,000
8,100
3,300
12,100
10-2
-------
10.2 PAINT REMOVERS
Methylene chloride is used as a solvent in paint removers. The
solvent is the primary ingredient in stripping formulations and acts to
penetrate, soften, or dissolve the paint, film, or coating.
Approximately 62,000 Mg of MC were consumed in paint removers in 1983.*
Paint removers, like aerosols, are used by both industry and
consumers. The stripping formulation is applied to a painted surface
and allowed to penetrate or dissolve the coating. The surface is then
cleaned and the paint remnants are disposed. Emissions occur during
application, use, and disposal of the removed coating. Due to the
nature of the use of paint removers, all MC used in paint removers is
eventually emitted to the atmosphere.
Methylene chloride is also emitted at paint remover formulation
facilities. Emissions result from evaporation during mixing, packaging,
and storage. These emission levels are believed to be low relative to
the total amount of MC emitted nationwide from use of paint removers.2
10.3 PHOTOGRAPHIC FILM PROCESSING
Methylene chloride serves as a solvent in the glue used to splice
film. Since the MC evaporates soon after application, emissions are
assumed to be 100 percent of consumption. Total consumption and
therefore emissions, of MC from splicing glue was 8,100 Mg in 1983.1
10.4 FOOD PROCESSING INDUSTRY
Methylene chloride consumption in the food processing industry was
3,300 Mg in 1983. It is used as an extraction solvent in the extraction
of heat sensitive substances such as caffeine, cocoa, and edible fats.3
Specific emission sources were not identified in this study. However,
major emission sources would most likely be in the extraction process
and storage and handling facilities. In this study it was assumed that
the entire 3,300 Mg consumed in the food processing industry in 1983 was
emitted.
10-3
-------
10.5 GENERAL MISCELLANEOUS
Approximately 12,100 Mg/yr of MC are consumed through miscellaneous
end uses. Examples of miscellaneous methylene chloride uses include
use in the printing industry as a solvent for cleaning ink from printing
equipment and as a thinning agent in some ink formations. It is also
used to bond pieces of plastic together by dissolving the plastic at the
interface of two pieces. After MC evaporation the pieces are "welded"
together. Other uses for methylene chloride include use as a thinning
agent for adhesives, and as a cleaner or in cleaning solutions.
Emissions from these general miscellaneous categories are from
evaporation during use. Additionally, MC may be used as a solvent or
reactant in the chemical processing industry by companies not discussed
in the chapter discussing chemical plants using MC in production
(Chapter 3). The magnitude of MC use in these individual miscellaneous
applications is not known at present. In addition, other small unknown
uses of MC may also exist.
10-4
-------
10.6 REFERENCES
1. Letter from D. L. Morgan, Cleary, Gottlieb, Steen, and Hamilton, to
R. E. Rosensteel, EPArESED. March 8, 1985. Response for
Halogenated Solvents Industry Alliance (HSIA).
2. PEI Associates, Inc. Occupational Exposure and Environmental
Release Assessment of Methylene chloride. Prepared for the U. S.
Environmental Protection Agency. Washington, D. C. (Contract
No. 68-02-3935). April 1985.
3. Mannsville Chemical Products. Chemical Products Synopsis -
Methylene chloride. Cortland, New York. 1984.
10-5
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APPENDIX A
METHODS USED FOR ESTIMATING STORAGE TANKS AND EQUIPMENT LEAK EMISSIONS
A.I EMISSION FACTORS FOR FIXED-ROOF STORAGE TANKS
A. 1.1 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:
'
14.7-P
LW = 1.09 x 10"8 MyPVNKnKc
where, LT = total loss (Mg/yr)
LB = breathing loss (Mg/yr)
LW = working loss (Mg/yr)
A. 1.2 Parameter Values and Assumptions
The following MC 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 MC, My = 84.93
P = true vapor pressure of product, function of temperature.
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
N = number of turnovers per year (dimensionless); dependent upon
plant-specific information
A-l
-------
T = average diurnal temperature change in °F; diurnal
temperature change assumptions were plant specific
according to location
F = paint factor (dimensionless); the storage tanks were
assumed to be in good condition and painted white;
therefore, F = 1 (see Table A-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
\*
K = turnover factor (dimensionless); dependent upon plant-specific
information
for turnovers > 36,
-------
TABLE A-l. PAINT FACTORS FOR FIXED-ROOF TANKS
1
Tank Color
Paint factors (F )
Paint condition
Roof
Shell
Good
Poor
White
Aluminum (specular)
White
Aluminum (specular)
White
Aluminum (diffuse)
Wh i te
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
\-3
-------
the emissions from this storage tank are:
LB - 1.02 x 10-5 (84.93)( 6.75 )0.68 (37)1'73(14)0'51(20)°-5(1)(1)(1)
14.7-6.75
= 6.877 Mg/yr
Lw = 1.09 x 10'8 (84.93)(6.75)(233,000)(10)(1)(1)
w
= 14.560 Mg/yr
LT = 6.877 Mg/yr + 14.560 Mg/yr = 21.44 Mg/yr
A. 2 EMISSION FACTORS FOR INTERNAL FLOATING ROOF STORAGE TANKS
A. 2.1 Emission Equations
Emissions from internal floating roof tanks can be estimated from the
wing equations: (Note that the
vented internal floating roof tanks.)
LT = Lw + Lr + Lf + Ld
where, L = the total loss (Mg/yr)
following equations: (Note that these equations apply only to freely
L = the working loss (Mg/yr) = (0.943) Q C
F
\
w
1 + \ D / /2205
where, D = tank diameter (ft)
N = number of columns (dimensionless); (see Table A-2)
F = effective column diameter (ft); 1.0 assumed
Lr = the rim seal loss (Mg/yr) = (y)) P* My 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
A.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
A-4
-------
TABLE A-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
1
6
7
8
9
16
19
22
31
37
43
49
61
71
81
A-5
-------
3 2
C = product withdrawal shell clingage factor (bbl/10 ft );
use 0.0015 bbl/103 ft2 for VOL in a welded steel tank with
light rust (0.0075 for dense rust)
WL = density of product (Ib/gal); for MC, 11.1 Ib/gal
D = tank diameter (ft)
N = number of columns (dimensionless); (see Table A-2)
F = effective column diameter (ft); 1.0 assumed
D = the tank diameter (ft); dependent upon plant-specific
information
M = the average molecular weight of the product vapor
(Ib/lb mole). For MC, MV = 84.93
KC = the product factor (dimensionless) = 1.0 for VOL
2205 = constant (Ib/Mg)
P = the vapor pressure function (dimensionless)
P* = 0.068 P/((l f (1 - 0.068 P)0'5)2)
P = the true vapor pressure of the material stored (6.75 psia
for MC)
K = the rim seal loss factor (Ib mole/ft yr) that for an
average fitting seal is as follows:
Seal system description Kp (Ib mole/ft yr)
Vapor-mounted primary seal only 6.7
Liquid-mounted primary seal only 3.0
Vapor-mounted primary seal plus
secondary seal 2.5
Liquid-mounted primary seal plus
secondary seal 1.6
Ff = the total deck fitting loss factor (Ib mole/yr)
= S (Nf Kf ) = [(Nf Kf ) + (Nf Kf )+...+ (Nf Kf )]
1=1 i i 11 22 n n
A-6
-------
where, Nf = number of fittings of a particular type
i (dimensionless). Nf is determined for the
specific tank or estimated from Tables A-2 and A-3.
The values used for these emissions estimates are
designated by * in Table A-3.
IC = deck fitting loss factor for a particular type
i fitting (Ib mole/yr). Kf is determined for each
fitting type from Table A-3. The values used for
these emissions estimates are designated by *.
n = number of different types of fittings
(dimensionless)
F, = 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
K, = the deck seam loss factor (Ib mole/ft yr)
=0.34 for nonwelded roofs
= 0 for welded decks
A.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 MC. For the general equations,
Lw = (0.943)QCWL 1 + ^c-^ /2205
D L D
Lf = (KpD) P* MV Kc/2205
A-7
-------
TABLE A-3. SUMMARY OF DECK FITTING LOSS FACTORS (K-) AND
TYPICAL NUMBER OF FITTINGS (Nf) T
1.
2.
3.
4.
5.
6.
7.
8.
Deck Fitting Type
Access Hatch
A. Bolted cover, gasketed
B. Unbolted cover, gasketed
C. Unbolted cover, ungasketed
Automatic Gauge Float Well
A. Bolted cover, gasketed
B. Unbolted cover, gasketed
C. Unbolted cover, ungasketed
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 fabric
gasketed
E. Pipe column-sliding cover,
ungasketed
Ladder Well
A. Sliding cover, gasketed
B. Sliding cover, ungasketed
Roof Leg or Hanger Well
A. Adjustable
B. Fixed
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
Stub Drain, 1-inch diameter
Vacuum Breaker
A. Weighted mechanical actuation,
gasketed
B. Weighted mechanical actuation,
Deck
Fitting Loss Typical Number
Factor, Kf Of Fittings
(Ib mole/yr) (Nf)
1.6 1
11 *
25
5.1 1
15 *
28
(see Table A-2)
33
47
10
19 *
32
1
56 *
76
? a
7.9 * ,5 + D + D .
0 l 10 600'
I
44 *
57
12
9 k
1.2 * , D2 b
U25'
1
0.7 *
0.9
ungasketed
A-8
-------
Lf = (Ff) P* My Kc/2205
LD = {FdKdD) P* Mv Kc/2205
where, My = 84.93 Ib/lb mole
P* = 0.152
Q = 500,000 bbl/yr
C = 0.0015
WL = 11.1 Ib/gal
D = 30 ft
= 1.0
= 6.7 Ib mole/ft yr
K = 1.0
\*
Ff = 242 Ib mole yr
F, = 0.20
K, = 0.34
d
A-9
-------
the emissions from this storage tank are:
(0.943)(500,OOP)(0.0015)(12.3)
30
= 0.123 Mg/yr
30
/2205
= ((6.7)(30))(0.152)(84.93}(1.0)/2205
= 1.177 Mg/yr
= (242)(0.152)(84.93)(1.OJ/2205
= 1.417 Mg/yr
= ((0.20)(0.34)(30r)(0.152)(84.93)(1.0)/2205
= 0.358 Mg/yr
LT = 0.123 Mg/yr + 1.177 Mg/yr + 0.417 Mg/yr + 0.358Mg/yr
LT = 3.08 Mg/yr
A.3 EQUIPMENT LEAK EMISSIONS - SAMPLE CALCULATIONS
Emissions were estimated from the number of equipment leak sources
(provided by the plant), the percentage of MC 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
% MC
Service
7.5
50.5
87.5
100.0
Mg/yr source Total Emissions
Emission Factor
X
X
X
X
0.0494
0.0494
0.0494
0.0494
Mg/yr
0.011
0.150
0.086
0.593
A-in
-------
Emissions
Source
Compressors
Flanges
Number
Valves (gas)
Valves (liquid)
Pressure Relief
Devices
Sampling
Connections
4
8
3
4
11
5
3
8
9
2
4
5
5
3
1
3
x
x
X
X
X
% MC
Service
87.5
4
112
30
235
66
456
x
x
X
X
X
X
5.0
7.5
18.0
50.5
87.5
100.0
5.0
7.5
50.5
87.5
100.0
x 5.0
x 7.5
x 87.5
x 100.0
x 5.0
x 50.5
x 100.0
x 5.0
x 50.5
x 87.5
x 100.0
Open Ended Lines 1 x 100.0
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Mg/yr source
Emission Factorc
0.228
0.00083
0.00083
0.00083
0.00083
0.00083
0.00083
0.
0.
.0056
.0056
0.0056
0.0056
0.0056
0.0071
0.0071
0.0071
0.0071
0.1042
0.1042
0.1042
0.0150
0.0150
0.0150
0.0150
0.0017
TOTAL
Total Emissions
Mg/yr
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
Annual Emissions = 2.72 kg/hr x 8760 hrs/year x Mg/1,000 kg
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.
A-ll
-------
A.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.
A-12
-------
APPENDIX B
METHODS FOR ESTIMATING EMISSION CONTROL COSTS
B.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. A detailed discussion of the incinerator
costing methods may be found in Chapter 5 of this document. It should be
noted that these incinerator costing procedures are designed for vent
streams having high flowrates. Since the vent streams containing MC
generally have lower flowrates, the cost estimates for process vent emission
control may be somewhat overstated. Further work will be performed to
develop incinerator costing procedures for lower flowrate vent streams if
regulatory development proceeds.
The total installed capital cost of control is determined using the
following equation:
Total Installed Capital Cost (103$) = (# of incinerators) x (escalation
factor) x (Cl - (Waste Heat Boiler Correction 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 B-l that depend upon
heating value and halogenation status of a given vent stream;
waste heat boiler correction factor of 40 (1CT$) is used for vent
streams with flowrates below 700 scfm, where no heat recovery in a
waste heat boiler is assumed; escalation 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 B-2;
additional ductwork cost is calculated using the equation - "
presented in Table B-3.
-------
TABLE B-l. TOTAL INSTALLED CAPITAL COST AS A FUNCTION
OF VENT STREAM FLOW RATE
Minimum
Maximum Net
Flowrate Heating
r Unit Value
Maximum Fabricated
Net Equipment
Heating Cost
Value Escalation
Category (10 scm/min) (MJ/scm) (MJ/scm)
Ala
A2a
B
C
D
Ea
0
0
1
1
1
1
.74
.74
.42
.42
.25
.25
0
3
0
0
1
3
.0
.5
.0
.48
.9
.6
3
0
1
3
.5
-
.48
.9
.6
-
Factor
0
0
0
0
0
0
.90
.90
.90
.90
.90
.90
Cl
803.11
786.61
259.88
297.99
236.35
236.35
C2
12.83
12.44
4.91
2.84
3.23
3.23
C3
0.88
0.88
0.88
0.88
0.88
0.88
Halogenated vent stream.
Dilution flow rate is used in capital cost equation;
Dilution flow rate = (design flow rate) x (original heating value) f
(3.65 MJ/scm).
5-2
-------
TABLE B-2. ADDITIONAL DUCT COST1'2
Additional duct cost (10 $) = (length) x (cost per unit length) x
(installation factor) x (duct escalation factor) x (retrofit correction
factor) 7 1000
Cost per unit length = 1.37L - 1.76
where L = duct diameter in inches
Diameter - r Flow rate fft3/min) 4 , 0.5
Diameter - L Linear Ve1ocity (ft/min) x T J
r How rate (ft /min) 4 , 0.5
L 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
3-3
-------
TABLE B-3. PIPE RACK COST1'2
Pipe rack cost (103 $) = (pipe rack length) x (cost per unit length) x
(installation factor) x (pipe rack escalation
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
B-4
-------
TABLE B-4. OPERATING FACTORS FOR EACH DESIGN CATEGORY
DO
I
Category
A.b
A2b
B
C
0
E
'Both it
Minim*
Net
Heating
Value
(MJ/sca)
0
3.5
0.
0.48
1.9
3.6
standard conditions.
Off gas contains halogen* ted
Includes
Includes
6 inches across the
6 inches across the
Maximum
Net
Heating
Value
(MJ/scm)
3.5
-
0.48
1.9
3.6
-
conpounds .
combustion
combustion
Ratio of Heat
Flue Gas Recovery
flow to Factor
Off gas flow* (HJ/sc«)
2.9 3.38
2.9 3.38
1.9 0
2.3 0
2.5 0
2.5 0
chamber, 4 inches across the
chamber and 4 Inches across
Pressure
Drop
(Inches.
H20)f
22C
22C
10"
10"
6e
6e
Natural Gas Use Coefficients
<* G1 G2 G3
0
0
0.425
0
0
0
4.56 -0.985 0
0.329 0 0
0.666 -1.29 0.015
2.39 -1.22 0
0.183 0 0
0. 183 0 0
waste heat boiler, and 12 inches across the scrubber
the recuperative heat exchanger.
-------
TABLE B-5. ANNUAL IZED COST FACTORS
CO
I
CTl
Direct
Operating Labor: $8.50/hr (Includes Overhead)
Operating Labor Factor: 2400 Man-hr/yr (Categories
A1-A2)
2133 Man-hr/yr (Categories B-C)
1200 Man-hr/yr (Categories D-E)
Supervisory Labor: $8.50/hr x (0.15)
Total Labor: [($8.50/hr x 1.15) + (0.03 of Total
Installed Capital)]
All Factors are Based on June 1980
Indirect ("Capital Charges")
Interest Rate = i = 10%
Incinerator Lifetime = 10 Years = N
Capital Recovery Factor = i (1 + i)
(1 + i)
= 0.163 of Total Installed Capital
N
Overhead Labor: 0.80 of Total Labor
Electricity: $0.0279/kWh
Natural Gas: $4.16/GJ =
Heat Recovery Credit: $4.16/GJ =
Quench Water Price: $0.22/Thousand Gallons
Scrubbing Water Price: $0A22/Thousand Gallons
Caustic Price: $0.0436/lba
Maintenance Labor Plus Materials Factor = 0.06
of Total Installed Capital
Overall Taxes and Maintenance Factor = 0.10 of Total
Installed Capital
aFifty percent liquid solution of caustic soda.
Memo to Hurley, E., EEA, from Galloway, J., EEA. January 13, 1981. Average capacity utilization
for the air oxidation industry.
Taxes, Insurance and Administrative Charges
Factor = 0.04 of Total Installed Capital
Overall Capital Charges Factor = 0.203 of
Total Installed Capital
-------
TABLE B-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 (10J $)
(length) x (cost per unit length) x
(escalation factor) x (installation
L3
factor) = 350 ft. x ((((500 fr/min)
x 4 f 2000 f 3.1412))0'5 x 12 x
1.37 * 1.76) x 1.088 x 1.087 * 1000
3.111
3. Pipe Rack Cost (10 $)
(length) x (cost per unit length) x
(installation factor) x (pipe rack
escalation factor) x (retrofit
correction factor) * 1000 = 250 ft. +
(2 additional vents x 100 ft./vent) x
$32.045/ft. x 1.087 x 0.746 x 1.0
f 1000
11.693
4. Total Installed Total Capital = Capital cost (103 $) + extra duct
cost (103 $) + pipe rack cost (103 $)
= 806.1 + 3.111 + 11.693
- 820.9
(continued)
l-l
-------
TABLE 8-6. (Continued)
5. Natural Gas Use (MJ/yr)
(minutes per year) x (supplemental
gas required per minute)
0.5256 106 min/yr x GQ + flow x
(Gj + G2 x HT)
0.5256 105 min/yr x (3.96) x (4.53
0.985 x 1.49) MJ/min)
6.37 MJ/yr
6. Natural Gas Cost (10* $)
Natural gas price ($/10 J) x
natural gas use (MJ/yr)
S4.16/GJ x 6.37 MJ
26.2
7. Operating Labor Cost (103 $) = Wage (S/hr) x labor factor (hr/yr) t
1000
= $8.50/hr x 2400 hrs
= 20.4
8. Supervisory Labor Cost (10 $)
Operating labor cost (10 /yr) x 0.15
20.4 (103 $/yr) x 0.15
3.06
9. Maintenance Labor Cost (10 $)
Installed capital cost (10 $) x 0.03
820.9 (103) $ x 0.03
24.63
10. Overhead Labor Cost (10 $)
= Operating labor cost (10 $) +
supervisory labor cost (10 $) +
maintenance labor cost (10 S) x 0.80
- (20.40 + 3.06 + 24.63) x 0.80
= 38.47
(continued)
B-8
-------
TABLE B-6. (Continued)
11. Total Labor Cost (1(T $)
= Operating labor cost (10 $) +
supervisory labor cost (103 $) +
maintenance labor cost (10 $) +
overhead labor cost (103 $)
= 20.4 + 3.06 + 24.63 + 38.47
- 86.56
12. Electricity Cost (10J $)
(electricity price) x (pressure drop)
x (flow rate) x (flue gasroffgas
ratio) x (fan equation conversion
factor) x (# of hours per year) * fan
efficiency * 1000
0.0279 ($/KWhr) x 22 in. x 3.96 son/
min x 2.9 x 0.004136 (KW/scmin.) ?
0.6 t 1000 ($/103 $)
0.426
13. Quench Water Cost (103 $)
= (quench water price) x (flow rate) x
(flue gasroffgas ratio) x (water
required per unit flow) x (minutes
per year) t 1000
= 0.22 ($ 103 gal) x 3.96 (scm/min) x
2.9 x 1.68 x 10"5 (103 gal/scm) x
0.5256 (105 min/yr) f 1000 ($/103 $)
= 0.0223
(continued)
B-9
-------
TABLE B-6. (Continued)
14. Scrubbing Water Cost (1CT $)
(scrub water price) x (flow rate) x
(flue gasroffgas 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 (scm/min) 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) t 1000
0.73
15. Neutralization Cost (l(T $)
(caustic cost) x (flow rate) x (flue
gasroffgas ratio) x (chlorine
content of flue gas) x (caustic
requirement per unit chlorine) x
(# of hours per year) t 1000
0.0436 ($/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)
f 1000
8.6
16. Heat Recovery Credit
= 0 (for all streams <700 scfm)
(continued)
B-10
-------
TABLE B-6. (Continued)
17. Taxes, Insurance, and
Maintenance Cost (10 $)
(installed capital cost) x (taxes,
insurance, and administrative
charges factor + maintenance labor
factor)
820.9 (10*
57.46
$) x (0.04 + 0.03)
18. Annual Operating Cost (10 $)
(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
180.90
19. Annualized Cost
$)
(operating cost) + (capital recovery
factor x total installed capital
cost)
180.0 + (.163 x 820.9)
313.8
20. Annual Emissions (Mg/yr)
(hourly emissions) x 365 (days/yr) x
24 (hrs/day) x (Mg/103 kg)
15.86 kg/hr x 365 (days/yr) x
24 (hrs/day) x 1 (Mg/103 kg)
138.9
21. Annual Emission Reduction
(Mg/yr)
= (annual emissions) x 0.98
= 138.9 x 0.98 (MC) = 136.1 (MC)
= 349.6 (VOC)
(continued)
B-n
-------
TABLE B-6. (Continued)
22. Cost Effectiveness ($/Mg)
= (annual cost) t (annual emission
reduction)
= 313.8 (103 $) f 136.1 Mg (MC
= 2305/Mg (MC)
= 313.8 (103 $) f 349.6 Mg (VOC)
= $898/Mg
23. Updated Cost-Effectiveness
Values ($/Mg)
2305 ($/Mg) x 1.486 = $3420/Mg (MC)
898 ($/Mg) x 1.486 = $1330/Mg (VOC)
B-12
-------
TABLE B-7. COST CONVERSION FACTORS
FOR INCINERATOR COMPONENTS
Original
Cost Component
Incinerator
Pipe Rack
Duct Work
Annual ized Costs
Original
Conversion
Year
1979
1982
1977
1978
Conversion
Year
1978
1978
1978
1984
Conversion
Factor
0.900
0.745
1.088
1.486
B-13
-------
A sample calculation for incinerator costing is shown in Table B-6.
The calculation is based on representative vent stream parameters for a
typical MC production facility. 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 B-7.
B.2 COST CALCULATIONS FOR INSTALLING INTERNAL FLOATING ROOFS IN
FIXED ROOF TANKS
The following equations were used to calculate the capital and
annualized cost for the installation of a mild steel welded contact internal
floating roof to a fixed roof storge tank. This internal floating roof
utilizes both primary (constructed of Teflon ) and secondary (constructed of
VitonR) seals.
B.2.1 Capital Cost (4th Quarter 1982 Dollars)
A
I. Degassing Cost
Cost = $130.8 v°t5132 or $1,000, whichever is greater where V = tank
volume in cubic meters.
2. Estimated Installation Cost
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
(The $204 x D cost reflects the additional cost of using TeflonR coated
fiberglass to protect against MC attack versus the standard
polyurethane coating)
b. Additional cost of adding secondary seal:
Cost = $580 x D
B-14
-------
(The $580 x D cost reflects using a VitonR coating material for the
secondary seal)
3. Door Sheet Opening Cost6
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.
B.2.2 Annual Cost (4th Quarter 1982 Dollars)
1. Taxes, 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]
B.2.3 MC/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
R-15
-------
3. Emissions from fixed roof tank - emissions from internal floating
roof tank = VOC emission reduction
MC emission reduction = VOC emission reduction x percentage of
MC in stored material
B.2.4 Recovery Credits (4th Quarter 1984 Dollars)
Credits = (MC emission reduction) x (4th Quarter 1984 MC market value
($485/Mg)) + [(VOC emission reduction-MC emission reduction) x
(4th Quarter 1984 VOC market value ($330/Mg))].
B.2.5 Net Annual Cost
Before annual cost can be calculated, all costing data is converted to
1984 dollars using Chemical Engineering Economic Indicators)
Cost = annual cost (4th quarter 1984 dollars) - VOC recovery credits
(4th Quarter 1984 dollars)
B.2.6 Cost Effectiveness
MC cost effectiveness = net annual cost/MC emission reduction (Mg)
VOC cost effectiveness = net annual cost/VOC emission reduction (Mg)
B.3 COST CALCULATIONS FOR INSTALLATION OF REFRIGERATED CONDENSERS
TO CONTROL STORAGE AND LOADING EMISSIONS
This section presents methods used to estimate costs for controlling
storage dnd loading emission by condensation. Based on Section 114 letter
responses, 85* control efficiency was assumed for storage applications and
90% control efficiency was assumed for loading applications.
B-16
-------
Costs were estimated using methods in Capital and Operating Costs of
Selected Air Pollution Control Systems. Based on conversation with one
chloroflorocarbon producer, one carbon tetrachloride producer and Section
114 response the following assumptions were made.
Gas Flow Rate
Source of Filling to condenser
Stored Material Rate (qpm) (scfm)
Production 200 27
Ship 1800 240
Barge 800 110
Rail Car 200 27
Tank Truck 200 27
B.3.1 Capital Cost (4th Quarter 1984 Dollars)
Capital Cost (1977$) = [0.27 x Flow (scfm) + 34] x 10003
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
B.3.2 Annual Cost
1. Taxes, insurance, and administration -- 4 percent of capital
2. Maintenance -- 5 percent of capital
3. Inspection -- 1 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
B.3.3 MC/VOC Emission Reduction
1. Calculate fixed roof storage emission using AP-42 and storaqe tank
data
MC emission = FR emissions x % MC in stored material
VOC emission = Total FR emissions
B-17
-------
2. MC emission red = MC emissions x .85
VOC emission red = VOC emissions x .85
B.3.4 Recovery Credit
Credits - (MC emission reduction) x (4th Quarter 1984 MC market value
($485/MG)) + [(VOC emission reduction-MC emission reduction) x
(4th '
Quarter 1984 VOC market value (S330/MG))].
B.3.5 Net Annual Cost
Net annual cost = (total annual cost) - (recovery credit)
B.3.6 Cost Effectiveness
MC C/E = Net annual cost 4 MC emission red
VOC C/E = Net annual cost T VOC emission red
8.4 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 B-8. The equipment leak emission sources costed are pump seals,
compressors, flanges, valves, pressure relief devices, sample connections,
and open ended lines.
Capital cost per emission source: (No. of components) x (capital cost per
component)
Total capital cost per plant: * [capital cost per emission source] annual
cost per emission source: (No. of components) x (annual cost per component)
MC emission reduction per emission source: (current MC emission) x
(percent reduction)
Total MC emission reduction per plant: * [MC emission reduction per
emission source]
B-18
-------
TABLE B-8. CONTROL TECHNIQUES AND COST FOR CONTROLLING
EQUIPMENT 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 Rel i
devices
- Gas
- Liquid
Percent ,-
Control Techniques Reduction
Monthly LDAR
Monthly LDAR
N/A
Vent to combustion
device
None Available
Monthly LDAR
Monthly LDAR
ef
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
Annual i zed
Cost
$/Component
370
370
N/A
2,580
N/A
20
20
80
N/A
Sample Connections
- Gas
Liquid
Open Ended Li
- Gas
- Liquid
Closed-purge sampling
systems
Closed-purge sampling
systems
nes
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.
B-19
-------
VOC emission reduction per emission source: (current VOC emission) x
(percent reduction)
Total VOC emission reduction per plant: f [VOC emission reduction per
emission source i]
Recovery credit per emission source: (MC emission reduction per source i) x
(4th Quarter 1984 MC market value ($485/Mg)) + [(VOC emission reduction per
source i - MC emission reduction per source i) x (4th Quarter 1984 VOC
market value ($330/Mg))].
Recovery credit per plant: The summation of recovery credits per emission
source.
Net annual cost (MC) per emission source: (annual cost per emission source)
minus (recovery credits per emission source).
Net annual cost (MC) 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 MC emissions per emission source: (net
annual cost (MC) per emission source) i (MC emission reduction per emission
source).
Cost effectiveness for controlling MC emissions per plant: (net annual cost
(MC) per plant) t (MC emission reduction per plant).
B-20
-------
Cost effectiveness for controlling VOC emissions per emission source: (net
annual cost (VOC) per emission source) t (emission reduction per emission
source).
Cost effectiveness for controlling VOC emissions per plant: (net annual
cost (VOC) per plant) t (emission reduction per plant).
E-21
-------
B-5 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.
B-22
-------
APPENDIX C
SUMMARY OF EXISTING STATE AND FEDERAL REGULATIONS
AFFECTING METHYLENE CHLORIDE EMISSION SOURCES
C.I EXISTING STATE REGULATIONS
C.I.I Introduction
Methylene chloride (MC) emissions originate from several industrial
sources. These sources include producers of MC, sources that use MC as
a chemical intermediate, and sources that store MC. These emissions can
be characterized as either process, equipment leak, product storage
tank, or loading and handling emissions.
There are a number of different regulations at the State level that
limit volatile organic compound (VOC) emissions. VOC emissions in
nonattainment areas (areas that have not achieved the ambient air
quality standards for ozone) are normally controlled by the States' RACT
program. VOC emissions in areas designated as attainment or
unclassified for ozone are controlled by Prevention of Significant
Deterioration (PSD) regulations. MC is excluded from many of these
state regulations due to its low photochemical reactivity. However,
eleven States that have regulations controlling VOC emissions do not
specifically exclude MC from the applicable regulations. These States
are Alabama, Kentucky, Massachusetts, Maryland, Michigan, Nevada, New
Jersey, Pennsylvania, Rhode Island, Tennessee, and Wisconsin.
C.I.2 General State VOC Regulations for Solvent Use
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 solvents. Table C-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. Methylene
chloride is excluded from regulation by all of these States with the
exception of Maryland and Rhode Island.
C-l
-------
TABLE 0-1. GENERAL STATE VOC REGULATIONS FOR PHOTOCHEMICAL SOLVENTS1
State Emission Reduction (56)
California 85
Colorado 85
Connecticut 85
District of Columbia 85
Illinois 85
Indiana 85
Louisiana 90
Maryland 852
North Carolina 85
North Dakota 85
Rhode Island 853
Virginia 85
These regulations exclude MC with the exception of Maryland and Rhode
-Island.
gApplies to sources in nonattainment areas only.
Applies to sources emitting less than 100 tons/year, larger sources
must comply with RACT.
C-2
-------
C.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 with
emissions or potential emissions 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/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.
C.I.4 State Regulations Affecting Chemical Production
In addition to the general discussion of State regulations
concerning MC emission sources, a more indepth review was performed for
States in which MC production facilities and facilities using MC in
production are located. Only two States, Michigan and Pennsylvania, had
regulations controlling MC emissions from chemical production
facilities. These regulations are presented in Table C-2. All
applicable MC emissions must be controlled under these regulations due
to the 6.75 psia vapor pressure of MC. Other VOC emissions at these
facilities may also be controlled.
C.2 EXISTING FEDERAL REGULATIONS
Several VOC NSPS and a NESHAP have been developed that could affect
new and some existing sources of MC emissions. A summary and the
current status of each of these standards are presented in Table C-3.
C-3
-------
TABLE C-2. STATE REGULATIONS AFFECTING CHEMICAL
PRODUCTION FACILITIES EMITTING METHYLENE CHLORIDE
State
Source
Regulation
Michigan
Pennsylvania
Storage tanks >40,QOO gal
true vapor pressure >1.5
<11.0 (existing sources)
Storage of organic compounds
having a true vapor pressure
>.!! psla in existing vessels
of >40,000 gallons
VOC loading facilities
handling >.5,000,000 gal/year
of >1.5 psla VOC
Above ground storage tanks
<40,000 gal and >2,000 gal
true vapor pressure
>1.5 psia
Storage tanks 140,000 gal
true vapor pressure
>1.5 psia
Pressure tank or
Floating cover with closure
seal or seals
Vapor recovery system
capable of 90 percent
recovery
Pressure tank capable of
maintaining working pres-
sures 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,
1 ids, or seals
submerged fill pipes in
ozone attainment areas
- Pressure tank or
- External or internal
floating roof is true
vapor pressure <.11.0 psia or
- Vapor recovery system
capable of 80 percent
recovery
- Pressure relief valves
Environment Reporter, State A1r Laws. Washington, D. C. Bureau of National
Affairs.
C-4
-------
TABLE C-3. SUMMARY OF FEDERAL REGULATIONS AFFECTING
VOLATILE ORGANIC COMPOUND EMITTING SOURCES
Source Proposed Promulgated
SOCMI Equipment Leaks (Fugitive) NSPS 01/05/81 10/18/83
VOL Storage Vessels NSPS 10/84
SOCMI Air Oxidation NSPS 10/21/83
SXMI Distillation Operations NSPS 12/30/83
SOCMI Reactor Processes NSPS draft
05
-------
APPENDIX D
MATERIAL BALANCE FOR MC EMISSIONS OPERATIONS
D.I MATERIAL BALANCE
(1) - Fraction of degreasing use of MC in cold cleaning = 0.67
Fraction of degreasing use of MC in vapor degreasing = 0.33
Emission factors:
- cold cleaning: 0.43 kg/kg used
- open top degreasing: 0.78 kg/kg used
- conveyorized degreasing: 0.85 kg/kg used
Assuming methylene chloride usage in vapor degreasing is
divided equally between open top and conveyorized vapor
degreasing, a weighted average emission factor is calculated as
follows:
(0.67)(0.43) + (0.165)(0.78) + (0.165)(0.85) = 0.56 kg/kg used
(2) - For every kg of fresh MC used, 0.56 kg is emitted. Assume all of
the remaining 0.44 kg is sent to solvent recovery.
- Estimate that 75 percent of all solvent sent to recovery is
recycled.
- Calculate emissions as follows:
0.56 kg
(Emissions from
fresh MC)
1 kg
(Fresh MC )
0.56x
(Emissions from use
of recycled MC)
x kg
(Recycled MC)
0.44
(To solvent
recovery)
0.44x
(To solvent
recovery)
D-l
-------
x = 0.75 (0.44 + 0.44x)
x = 0.49 (Amount of recycled MC used per kg of fresh MC used)
0.56x = 0.27 (Amount of recycled MC emitted per kg of fresh MC used)
Total MC emitted per kg of fresh MC used = 0.56 + 0.27
= 0.83 kg
D-2
-------
D.2 NATIONAL EMISSION REDUCTION CALCULATIONS
National emission reduction can be calculated by estimating the amount of
solvent emitted by the degreasers that are presently uncontrolled and applying
a control efficiency to these emissions. The emission factors presented in
Section D.I for cold cleaners, open top vapor degreasers, and conveyorized
vapor degreasers are overall emission factors representing the average
emission factor from controlled and uncontrolled degreasers. An uncontrolled
degreaser emission factor was developed for the three types of degreasers so
that the national emissions from uncontrolled degreasers could be calculated.
An uncontrolled degreaser is considered to be one that does not have the most
stringent control techniques for its degreaser type. These control techniques
were described in Chapter 4. For example, the most stringent control
technique for an open top vapor degreaser is a carbon adsorber. Therefore, an
uncontrolled open top vapor degreaser is one that does not control emissions
with a carbon adsorber. In reality, degreasers have levels of controls
ranging from no control techniques to the most stringent control techniques
available. Therefore, defining an uncontrolled degreaser as one that does not
have the most stringent control techniques for its degreaser type results in
an overestimate of the achievable emission reduction.
Information on the number of uncontrolled versus controlled degreasers
I o
was obtained from industry contacts. ' These are as follows:
Ratio of uncontrolled/controlled cold cleaners
= 0.65/0.35
Ratio of uncontrolled/controlled open top vapor degreasers
= 0.99/0.01
Ratio of uncontrolled/controlled conveyorized vapor degreasers
= 0.95/0.05
The uncontrolled degreaser emission factors were then calculated
according to the following equation:
D-3
-------
(a)x + (b)(c)x - y
where:
y = overall degreaser emission factor, kg/kg solvent consumed
a = fraction of uncontrolled degreasers
x = uncontrolled degreaser emission factor, kg/kg solvent consumed
b = fraction of controlled degreasers
c = 1 - achievable emission reduction
Since emission reduction is calculated only for presently uncontrolled
degreasers, the total solvent consumption must be adjusted to include only the
solvent used in uncontrolled degreasers. The adjusted solvent consumption
levels were calculated according to the equation:
(1) z = (s)(t)(u)
where:
z = total solvent consumed by uncontrolled degreasers by
degreaser type, Mg/yr
s = total solvent consumption by all degreasers (fresh solvent
plus recycled solvent = total emissions divided by
emission factor for fresh MC), Mg/yr
t = fraction of consumption by degreaser type
u = fraction of uncontrolled degreasers by degreaser type
The uncontrolled emission factors were applied to the total amount
consumed by uncontrolled sources within each degreaser type to yield the
national uncontrolled emissions for the degreaser type. Applying the control
efficiency to the national uncontrolled emissions gives the emission
reduction for the degreaser type. These calculations proceed according to the
equation:
(2) r = (z)(x)(v)
where:
D-4
-------
r = emission reduction for degreaser type, Mg/yr
z = total solvent consumed by uncontrolled degreasers by
degreaser type, Mg/yr
x = uncontrolled degreaser emission factor (kg/kg solvent
consumed)
v = achievable emission reduction
Calculations:
I. Cold Cleaners
(1) y = (a)x + (b)(c)x
0.43 = (0.65)x + (0.35)(l-0.35)x
x = 0.49
(2) z = (s)(t)(u)
Z = ^Q
z = 13,800 Mg/yr
(3) r = (z)(x)(v)
r = 13,800 (0.49)(0.35)
r = 2,360 Mg/yr
II. Open Top Vapor Degreasers
(1) y = (a)x + (b)(c)x
0.78 = (0.99)x + (0.01)(l-0.44)x
x = 0.78
(2) z = (s)(t)(u)
Z = 10?5eP (0-165)(0.99)
z = 5,160 Mg/yr
(3) r = (z)(x)(v)
r = (5,160)(0.78)(0.44)
r = 1,770 Mg/yr
D-5
-------
III. Conveyorized Vapor Degreasers
(1) y = (a)x + (b)(c)x
0.85 = (0.95)x + (0.05)(l-0.57)x
x = 0.87
(2) z = (s)(t)(u)
Z = 10?56fl (0-165K0.95)
z = 4,950 Mg/yr
(3) r = (z)(x)(v)
r = (4,950)(0.87)(0.57)
r = 2,460 Mg/yr
D.3 PHOTORESIST STRIPPING EMISSION FACTOR
1. Emission factor = 0.25 kg/kg used
2. For every kg of fresh MC used, 0.25 is emitted. Assume remaining .75
is sent to solvent recovery.
Estimate that 75 percent of all solvent sent to recovery is
recycled
x = 0.75 (0.75 + 0.75x)
where x = recycled solvent
x = 1.29 (amount recycled MC used per kg of fresh MC used)
0.25x = 0.32 (amount recycled MC emitted per kg fresh MC used)
3. Total MC emitted per kg fresh MC used
0.25 + 0.32
0.57
D-6
-------
D.4 REFERENCES
1. Telecon. Murphy, P.V., Radian Corporation, with Pokorng, J.,
Baron-Blakeslee, Inc. August 9, 1985. Information on control devices
for degreasers.
2. Telecon. Murphy, P.V., Radian Corporation, with Barr, F., Graymills
Corp. August 9, 1985. Information on control devices for cold cleaners
D-7
-------
APPENDIX E
EMISSIONS FROM DISTRIBUTION FACILITIES
(1) Estimate the quantity going through distribution (storage)
1983 production = 530 MM Ibs
Assume 100 percent goes through distribution channels
(2) Estimate the number of storage tanks nationwide
- Assume the average tanks size is 10,000 gallons
- Assume the average turnover time is 3 weeks
of tanks . 356 MM Its
(3) Estimate storage emissions (fixed roof tanks)
Breathing Loss
! - 1 0? x in'5 M 1 _ P_)0.68n1.73 R0.51 T0.5
LB - 1.02 x 10 Ml--- I D H T
LB = 1.02 x 10"5 (85 I0'68 (10)1'73 (9)0'51 ( 1. 15) (0.5) (1.0)
LB = 0.23 Mg/yr
Working Loss
LW = 1.09 x 10'8 MyPVNKnKc
LW = 1.09 x 10"8 (85)(5)(10,000)(17)(1)(1)
Lw = 0.79 Mg/yr
Total Loss
LT = LB + LW = 1.0 Mg/yr per tank
Total nationwide storage emissions = (1.0) (280) = 280 Mg/yr
£-1
-------
where:
M = molecular weight of product vapor (Ib/lb mole)
P = true vapor pressure of product (psia)
D = tank diameter (ft)
H = average vapor space height (ft)
T = average diurnal temperature change (°F)
F = paint factor (dimensionless); 1.0 for clean white paint
C = tank diameter factor (dimensionless):
for diameter >_ 30 feet, C = 1
for diameter < 30 feet, C = 0.771D - 0.013D2 - 0.1334
K = product factor (dimensionless) = 1.0 for VOL
V = tank capacity (gal )
K = turnover factor (dimensionless):
for turnovers > 36, K = 18°* N
6
for turnovers ;< 36, K = 1
(4) Estimate container filling emissions
Loading Loss
where: S = saturation factor (0.50 for submerged fill and
1.45 for splash fill)
T = True vapor pressure, psia
M = Molecular weight
R = Temperature, °R
E-2
-------
Assume 50 percent splash filling (S = 1.0)
S = (0.5)(0.5) + (0.5)(1.45) = 1.0
LL = 12.46/(1'0)^(85)V 10.0 lb/103 gal
= 4.5 lb/103 gal
530 106 1b( *°' )( •*•" ^)= 210 Mg/yr
\11.1 lb/\103 gal>
E-3
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
. REPORT NO.
EPA-450/3-85-U15
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Survey of Methylene Chloride Emission Sources
5. REPORT DATE
June 1985
6. PERFORMING ORGANIZATION CODE
7. AUTHQR(S)
R.F, Pandullo, I.E. Kincaid, P-v- Murph
adian Corporationn- Post Office Box "
esearch Triangle Park, North CaroTi
ina
.S.A.
!7709
Shareef
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Office of Air Quality Planning and Standards
Environmental Protection Agency
Research Triangle Park, North Carolina
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 Aqency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/2UO/U4
15. SUPPLEMENTARY NOTES
16, ABSTRACT
The potential health impact of methylene chloride emissions is being investigated.
This document contains information on tne sources of methylene chloride emissions,
current emission levels, control methods that could be used to reduce methylene
chloride emissions, and cost estimates for emolovinc controls.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Pollution Control
Synthetic Organic Chemical Manufacturing
Industry
Methylene Chloride
Dichloromethane
Air Pollution Control
13B
8. DISTRIBUTION STATEMENT
Unlimited
19 SECURITY CLASS (This Report)
Unclassified
21 NO OF PAGES
117
20. SECURITY CLASS (Tins page)
Unclassified
22. PRICE
EPA Form 2220—1 (Rev. 4—77) PREVIOUS EDITION is OBSOLETE
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