EPA-450/3-85-017
Survey of Perchloroethylene
Emission Sources
Emission Standards and Engineering Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
June 1985
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This report has been reviewed by the Emission Standards and Engineering Division of the Off ice of Air Quality Planning
and Standards, EPA, and approved for publication. Mention of trade names or commercial products is not intended to
constitute endorsement or recommendation for use. Copies of this report are available through the Library Services
Office(MD-35), U.S. Environmental Protection Agency, Research Triangle Park, N.C. 27711, or from National Technical
Information Services, 5285 Port Royal Road, Springfield, Virginia 22161.
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TABLE OF CONTENTS
Page
TABLE OF CONTENTS i
LIST OF TABLES v
LIST OF FIGURES vii
1.0 INTRODUCTION AND SUMMARY 1-1
1.1 INTRODUCTION 1-1
1.2 SUMMARY 1-2
1.2.1 PCE Emission Source Categories 1-2
1.2.2 Emission Estimates 1-3
1.2.3 Regulatory Requirements 1-5
1.3 REFERENCES 1-8
2.0 PERCHLOROETHYLENE PRODUCTION 2-1
2.1 QUANTITIES PRODUCED AND MANUFACTURERS 2-1
2.2 PRODUCTION PROCESSES 2-5
2.2.1 Chlorination of Ethylene Dichloride 2-5
2.2.1.1 Process Description 2-5
2.2.1.2 Current Emission and Controls 2-5
2.2.2 Hydrocarbon Chlorinolysis 2-12
2.2.2.1 Process Description 2-12
2.2.2.2 Current Emissions and Controls 2-12
2.2.3 Oxychlorination of Ethylene Dichloride .... 2-20
2.2.3.1 Process Description 2-20
2.2.3.2 Current Emissions and Controls 2-21
2.3 REFERENCES 2-26
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TABLE OF CONTENTS
Page
3.0 CHLOROFLUOROCARBON PRODUCTION, BY-PRODUCT FORMATION,
AND MISCELLANEOUS PRODUCTION USES 3-1
3.1 QUANTITIES CONSUMED/PRODUCED AND MANUFACTURERS .... 3-1
3.2 CHLOROFLUOROCARBON PRODUCTION PROCESS 3-5
3.2.1 Chlorofluorocarbon Production 3-5
3.2.1.1 Process Description 3-5
3.2.1.2 Current Emissions and Controls 3-5
3.3 BY-PRODUCT FORMATION AND MISCELLANEOUS USES 3-9
3.3.1 By-Products From Chlorinated Hydrocarbon
Production 3-9
3.3.1.1 Process Description 3-11
3.3.1.2 Current Emissions and Controls 3-12
3.4 REFERENCES 3-22
4.0 DRY CLEANING INDUSTRY 4-1
4.1 INDUSTRY DESCRIPTION 4-1
4.1.1 Coin-Operated Cleaners 4-1
4.1.2 Commercial Cleaners 4-2
4.1.3 Industrial Cleaners 4-2
4.2 CLEANING PROCESS CHARACTERIZATION 4-4
4.3 EMISSION SOURCES 4-4
4.4 EMISSION ESTIMATES 4-5
4.5 CONTROL TECHNIQUES 4-14
4.6 REGULATORY REQUIREMENTS 4-15
4.7 REFERENCES 4-17
IV
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TABLE OF CONTENTS
Page
5.0 SOLVENT DECREASING OPERATIONS 5-1
5.1 INDUSTRY DESCRIPTION 5-1
5.2 DECREASING EQUIPMENT 5-2
5.3 EMISSIONS FROM DECREASING OPERATIONS 5-2
5.4 EMISSIONS CONTROL 5-5
5.5 REGULATORY REQUIREMENTS 5-5
5.6 REFERENCES 5-8
6.0 DISTRIBUTION FACILITIES 6-1
6.1 EMISSIONS FROM DISTRIBUTION FACILITIES 6-1
6.2 REGULATORY REQUIREMENTS 6-3
6.3 REFERENCES 6-4
7.0 MISCELLANEOUS USES OF PERCHLOROETHYLENE 7-1
7.1 EMISSION ESTIMATES 7-1
7.2 REFERENCES 7-3
8.0 PUBLICLY OWNED TREATMENT WORKS 8-1
8.1 EMISSION ESTIMATES 8-1
8.2 REFERENCES 8-2
APPENDIX A: METHODS USED FOR ESTIMATING STORAGE
TANK AND FUGITIVE EMISSIONS A-l
A.I EMISSION FACTORS FOR FIXED-ROOF STORAGE 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-3
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TABLE OF CONTENTS
A.2 EMISSION FACTORS FOR INTERNAL FLOATING ROOF
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-10
A.3 FUGITIVE EMISSIONS - SAMPLE CALCULATIONS .... A-ll
APPENDIX B: SUMMARY OF EXISTING STATE AND FEDERAL
REGULATIONS AFFECTING PERCHLOROETHYLENE
EMISSION SOURCES B-l
B.I EXISTING STATE REGULATIONS B-l
B.I.I Introduction B-l
B.I.2 General State VOC Regulations for
Solvent Use B-l
B.I.3 State RACT Regulations Affecting
Perchloroethylene-Emitting Sources B-l
B.I.4 Prevention of Significant Deterioration
Regulations B-4
B.I.5 State Regulations Affecting Chemical
Production B-4
B.2 EXISTING FEDERAL REGULATIONS B-4
APPENDIX C: MATERIAL BALANCE FOR PCE EMISSIONS FROM
DECREASING OPERATIONS C-l
C.I MATERIAL BALANCE C-l
APPENDIX D: PERCHLOROETHYLENE EMISSIONS FROM
DISTRIBUTION FACILITIES D-l
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LIST OF TABLES
NO. PAGE
1-1 EMISSIONS FROM THE PRODUCTION AND USE OF
PERCHLOROETHYLENE 1-4
2-1 PERCHLOROETHYLENE PRODUCTION FACILITIES 2-2
2-2 TOTAL EMISSIONS FROM PERCHLOROETHYLENE PRODUCTION
FACILITIES 2-3
2-3 CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITIES
PRODUCING PERCHLOROETHYLENE BY THE CHLORINATION OF
ETHYLENE DICHLORIDE 2-7
2-4 CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITIES
PRODUCING PERCHLOROETHYLENE BY THE HYDROCARBON
CHLORINOLYSIS PROCESS 2-15
2-5 CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITY
PRODUCING PERCHLOROETHYLENE BY THE OXYCHLORINATION OF
ETHYLENE DICHLORIDE 2-23
3-1 CHLOROFLUOROCARBON PRODUCTION FACILITIES USING PCE
AS AN INTERMEDIATE 3-2
3-2 TOTAL PCE EMISSIONS FROM CHLOROFLUOROCARBON PRODUCTION
FACILITIES 3-3
3-3 CURRENT CONTROLS AND ESTIMATED EMISSIONS AT
CHLOROFLUOROCARBON FACILITIES USING PCE AS AN
INTERMEDIATE 3-6
3-4 PRODUCTION FACILITIES PRODUCING PCE AS A BY-PRODUCT OR
USING PCE FOR MISCELLANEOUS PRODUCTION 3-10
3-5 TOTAL PCE EMISSIONS FROM BY-PRODUCT FORMATION AND
MISCELLANEOUS PRODUCTION USES 3-13
3-6 CURRENT CONTROLS AND ESTIMATED EMISSIONS AT FACILITIES
PRODUCING PCE AS A BY-PRODUCT OR FOR MISCELLANEOUS
PROCESSES 3-14
4-1 PARAMETERS FOR TYPICAL DRY CLEANING FACILITIES 4-3
VI 1
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LIST OF TABLES (CONCLUDED)
NO. PAGE
4-2 VARIABLES USED TO CALCULATE PCE EMISSIONS 4-6
4-3 TOTAL 1983 PCE EMISSIONS FROM COIN-OPERATED DRY CLEANERS,
BY STATE 4-7
4-4 TOTAL 1983 PCE EMISSIONS FROM COMMERCIAL DRY CLEANERS,
BY STATE 4-10
4-5 TOTAL 1983 PCE EMISSIONS FROM INDUSTRIAL DRY CLEANERS,
BY STATE 4-12
5-1 1983 PCE EMISSIONS FROM DECREASING OPERATIONS, BY
INDUSTRY 5-4
5-2 1983 PERCHLOROETHYLENE EMISSIONS FROM DECREASING OPERATIONS,
BY STATE 5-6
5-3 CONTROL TECHNIQUES FOR DEGREASERS 5-7
6-1 SUMMARY OF MAJOR PERCHLOROETHYLENE DISTRIBUTORS 6-2
7-1 MISCELLANEOUS USES OF PERCHLOROETHYLENE IN 1983 7-2
8-1 PCE EMISSION ESTIMATES FROM POTWs IN THE 10 HIGHEST-EMITTING
COUNTIES 8-1
A-l PAINT FACTORS FOR FIXED ROOF TANKS A-2
A-2 TYPICAL NUMBER OF COLUMNS AS A FUNCTION OF TANK DIAMETERS . . A-5
A-3 SUMMARY OF DECK FITTING LOSS FACTORS (Kf) AND TYPICAL
NUMBER OF FITTINGS (Nf) I A-7
B-l GENERAL STATE VOC REGULATIONS FOR PHOTOCHEMICAL SOLVENTS ... B-2
B-2 STATE RACT REGULATIONS FOR PERCHLOROETHYLENE EMISSIONS .... B-3
B-3 PSD APPLICABILITY FOR PERCHLOROETHYLENE EMISSIONS B-5
B-4 STATE REGULATIONS AFFECTING CHEMICAL PRODUCTION
FACILITIES . B-6
B-5 SUMMARY OF FEDERAL REGULATIONS AFFECTING PERCHLOROETHYLENE-
EMITTING SOURCES B-10
vm
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LIST OF FIGURES
NO. PAGE
2-1 LOCATIONS OF PERCHLOROETHYLENE PRODUCTION FACILIITES .... 2-4
2-2 PROCESS FLOW DIAGRAM FOR THE PRODUCTION OF
PERCHLOROETHYLENE BY THE CHLORINATION OF ETHYLENE
DICHLORIDE 2-6
2-3 PROCESS FLOW DIAGRAM FOR THE PRODUCTION OF
PERCHLOROETHYLENE BY HYDROCARBON CHLORINOLYSIS 2-13
2-4 PROCESS FLOW DIAGRAM FOR THE PRODUCTION OF
PERCHLOROETHYLENE BY OXYCHLORINATION 2-22
3-1 LOCATIONS OF CFC PRODUCERS USING PCE AND MISCELLANEOUS
PRODUCTION FACILITIES 3-4
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1.0 INTRODUCTION AND SUMMARY
1.1 INTRODUCTION
This document identifies the sources and locations of perchloroethylene
(PCE) emissions, estimates total production volumes and emission levels, and
identifies the applicable control technologies for each source. The informa-
tion collected in this source assessment study will also be used by the
U. S. Environmental Protection Agency (EPA) to estimate human exposure to
PCE.
Information for this document was acquired from various sources. The
approach to information gathering for each of these sources is discussed in
the following paragraphs.
Background information, such as previous EPA documents and other
published literature was reviewed in an attempt to identify the producers of
PCE and the major uses and applications. Five companies producing PCE at
eight facilities were identified. Two chlorofluorocarbon (CFC) producers
using PCE as an intermediate were also identified. Letters were sent to
these seven companies under the authority of Section 114 of the Clean Air
Act requesting information concerning PCE emissions, emission levels, and
control techniques from all possible emission sources associated with the
production, storage, and use of PCE in the calendar year 1983. General
production information such as production volumes and total sales/purchase
data were also requested in order to verify the completeness of the
information. These data are considered confidential information by the
companies and are not discussed in this report. For each process unit
making or consuming PCE, detailed information was requested on the following
emission types: fugitive emissions, process vent emissions, equipment
opening losses, raw material/product storage emissions, loading/handling
1-1
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emissions, and secondary emissions. The companies were asked only to
estimate these emissions. No testing was required to be done specifically
for this information request.
Plant trips were taken to Vulcan Chemicals in Geismar, Louisiana, and
Dow Chemical U. S. A. in Plaquemine, Louisiana, to gain familiarity with the
processes, emission sources, and emissions controls at these PCE production
facilities. Meetings were held with plant representatives to discuss
operating procedures, the process equipment used, potential emission sources,
and methods of emissions control.
The other major uses of PCE were identified to be dry cleaning and
solvent degreasing. Since there are numerous facilities using PCE in these
applications, no attempt was made to obtain any direct information from
these facilities. However, information was obtained from the Halogenated
Solvents Industrial Alliance (HSIA), a trade group representing the producers
of PCE and other chlorinated solvents, about the total amounts of PCE used
in 1983 for various applications. Using this and other available
information, 1983 emissions were estimated for each application.
1.2 SUMMARY
1.2.1 PCE Emission Source Categories
PCE is produced by eight chemical companies at eleven plants in the
United States. Five of these companies produce PCE at eight facilities as a
main product. Three other companies produce PCE as a by-product at three
other facilities. The estimated total 1983 production volume of PCE was
249,200 megagrams (Mg). Three different processes are used to produce PCE.
In 1983, 51 percent of the PCE produced was consumed by the dry cleaning
industry, 25 percent was used as an intermediate in the production of CFC's,
15 percent was used as a solvent in degreasing operations, and 9 percent was
used in miscellaneous applications. The miscellaneous applications include
the production of adhesives, aerosols, and paints and coatings. The consump-
2
tion of PCE has declined by about 30 percent since 1980, causing some
former PCE producers to halt production of the chemical.
Emission estimates have been made in this study for the following
categories: PCE production, CFC production, miscellaneous production (PCE as
1-2
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a by-product), dry cleaning, degreasing operations, distribution sources,
miscellaneous uses, and publicly-owned treatment works (POTWs).
1.2.2 Emission Estimates
The total emissions from PCE production and use in 1983 were
106,000 Mg/yr. The largest sources of emissions were dry cleaning facilities
(50,000 Mg/yr), degreasing operations (32,600 Mg/yr), and PCE production
facilities (650 Mg/yr). The emission sources and emissions are shown in
Table 1-1.
PCE emissions from production processes are estimated to be 650 Mg/yr.
This estimate was obtained from the information provided by the plants in
response to Section 114 requests. This information included emission
estimates from process vents (estimated at full plant capacity), loading/
handling operations, equipment opening losses, pressure relief valve dis-
charges, and secondary streams. The plants also provided equipment counts
for fugitive emission sources in PCE service and data on the number and
types of product/raw material storage tanks containing PCE. Total volatile
organic compound (VOC) emissions from fugitive emission sources were
calculated by applying Synthetic Organic Chemical Manufacturing Industry
o
(SOCMI) VOC fugitive emission factors to the equipment count. PCE
emissions were estimated by applying the fraction of PCE in the stream for
each piece of equipment to the calculated VOC emissions. (Actual test data
were provided by one plant for PCE fugitive emissions.) Emissions from
storage tanks were estimated by using AP-42 equations. Methods for
estimating these emissions are described in Appendix A.
It is estimated that in 1978, there were approximately 11,804 coin-
operated, 15,060 commercial, and 334 industrial dry-cleaning facilities in
the United States using PCE. No attempt was made in this study to update
the estimated number of dry cleaning facilities. The amounts of PCE consumed
by the three sectors of the dry cleaning industry in 1983 were obtained from
HSIA. Based on the consumption data and the emission factors for each of
the three sectors of the industry (obtained from previous EPA documents), it
is estimated that about 50,000 Mg of PCE was emitted from dry cleaning
facilities in 1983.
1-3
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TABLE 1-1. EMISSIONS FROM THE PRODUCTION AND USE OF PERCHLOROETHYLENE
Process
PCE Production
CFC Production
Misc. Production
Dry Cleaning
Degreasing
Distribution
MISCELLANEOUS USES
Adhesives
t Aerosols
Paints & Coatings
0 Miscellaneous
POTWs
TOTAL
Production/Consumption
(Mg/yr)
230,400
60,300
N/A
117,000
35,000
162,000a
2,800
2,530
1,660
13,700
Emissions
(Mg/yr)
650
34
245
50,000
32,600
50
2,800
2,500
1,600
13,700
2,000
106,000
N/A = Not available
aAmount of PCE estimated to be sold through distributors.
1-4
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Information was also obtained from HSIA on the 1983 consumption of PCE
in degreasing applications. The HSIA indicated that PCE 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 and total 1983 emissions of PCE from degreasing facilities
were estimated from 1983 consumption data. It is estimated that degreasing
accounted for 32,600 Mg of PCE emissions in 1983.
Miscellaneous uses of PCE include use in manufacture of adhesives,
aerosols, and paints and coatings. Essentially all PCE used in these
consumer product applications are emitted to the atmosphere. It is estimated
that approximately 21,000 Mg of PCE were emitted from these miscellaneous
uses.
Almost all of the PCE produced is sold through various chemical
distributors. The handling and storage operations at distribution facilities
located throughout the country were estimated to emit 50 Mg of PCE emissions
in 1983. Finally, information from previous EPA studies indicate that
about 2,000 Mg of PCE is emitted from POTWs annually.
1.2.3 Regulatory Requirements
The 14 plants that produce PCE or use it as an intermediate are located
in five States: Texas, California, Louisiana, Michigan, and Kansas. VOC
emissions from these existing production facilities are not controlled by
Federal regulations such as the new source performance standards (NSPS) for
volatile organic compounds in the synthetic organic chemicals manufacturing
industry. However, two plants that produce PCE as a by-product may be
controlled by the national emission standards for hazardous air pollutants
(NESHAP) for vinyl chloride (VC). In addition, the emissions at most plants
are controlled to some extent in each of these States by county, district,
or State regulations.
California is currently the only State with regulations for fugitive
emissions control. In the Bay Area Air Quality District of California,
1-5
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where the Dow Chemical U. S. A., Pittsburg facility is located, organic
compounds with vapor pressures less than 1.5 pounds per square inch absolute
(psia) are exempt from control by the regulation for fugitive emissions from
valves and flanges (Regulation 8, Rule 22). Since the vapor pressure of PCE
is 0.3 psia, this facility is not covered by this regulation. On January 20,
1984, Louisiana initiated a fugitive emissions control program. The
regulations will require a VOC leak patrol/repair program, and full
compliance will be required by December 31, 1987. The Texas Air Control
Board (TACB) has recently promulgated regulations that will require a formal
fugitive emissions monitoring program in Texas. The first round of
monitoring must be completed by the end of 1987.
PCE emissions from process vents are not controlled in any of these
states. Regulations exist in Texas for process emissions, but PCE is exempt
due to the vapor pressure cutoff limit of 0.44 psia. If the stream also
contains VOC with vapor pressures greater than 0.44 psia, the total stream
vapor pressure must be evaluated prior to ruling for an exemption.
VOC emissions from storage tanks are regulated in California, Texas,
Louisiana, and Michigan. Kansas only regulates emissions from storage tanks
containing petroleum. In the Bay Area Air Quality District of California,
PCE emissions from storage tanks are exempt from control due to a vapor
pressure cutoff of 1.5 psia. In general, a storage tank with a capacity
greater than 151,400 liters (40,000 gallons) but storing liquid with less
than 76 kilopascals (kPa) (11 psia) vapor pressure, would require a floating
roof with seals between the tank wall and roof edge, or a vapor recovery
system which returns vapor to a disposal system. For tanks smaller than
151,400 liters (40,000 gallons), use of a submerged fill pipe during loading
is considered sufficient control, and for tanks larger than 151,400 liters
(40,000 gallons) storing liquids with a vapor pressure greater than 76 kPa
(11 psia), a submerged fill pipe and vapor recovery system is required.
VOC emissions from loading/handling operations are controlled in
Louisiana, Texas, and Michigan. However, Louisiana is the only one of these
States in which PCE emissions are not exempt from control due to a vapor
pressure cutoff of 1.5 psia. Loading facilities for VOC with throughputs of
1-6
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at least 75,700 liters (20,000 gallons/day) (40,000 gallons or more for
existing facilities) must be equipped with vapor collection and disposal
systems. Barges and ships are exempt from loading/handling regulations.
There are no regulations for VOC emissions from loading/handling in Kansas
or the Bay Area Air Quality District in California.
There are no Federal regulations for PCE emissions from dry cleaners.
Control Techniques Guideline (CTG) documents have been issued by EPA estab-
lishing reasonably available control technology (RACT) guidelines that have
been used by State agencies to develop State implementation plans (SIPs).
Twenty-three States have adopted RACT for PCE dry cleaning. Twenty-six
States have not adopted any regulations. The decision to adopt RACT provisions
is pending in New York.
There are no Federal regulations for PCE 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 plus the District of Columbia have adopted
RACT for the use of PCE in degreasing operations. Eighteen States have not
adopted any regulations. Further details on State regulations are contained
in Appendix B.
1-7
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1.3 REFERENCES
1. Letter from D. L. Morgan, deary, Gottlieb, Steen, and Hamilton, to
R. E. Rosensteel, EPA/ESED. March 1, 1985. Response for Halogenated
Solvents Industrial Alliance concerning industial consumptions volumes
of PCE in 1983.
2. Mannsville Chemical Products. Chemical Products Synopsis -
Perchloroethylene. Cortland, New York. November 1984.
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, NC. January 1984,
4. Letter and attachments from Komorski, K. S., PPG, to Farmer, J. R.,
EPA/ESED. February 14, 1985. Response to PCE 114 letter.
1-8
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2.0 PERCHLOROETHYLENE PRODUCTION
This chapter presents the emissions and controls associated with the
production of PCE at the eight production facilities in the United States.
Two of these facilities use the PCE product for additional chemical
processing within the plant. Three other plants also produce PCE as a
by-product in the production of VC, trichloroethylene (TCE), and carbon
tetrachloride (CC1,). Emissions from PCE production facilities come from
process vents, equipment leaks, storage tanks, secondary sources, and truck,
rail car or barge loading.
PCE is currently produced by three processes. These are the
chlorination of ethylene dichloride (EDC), hydrocarbon chlorinolysis, and
2
the oxychlorination of EDC.
2.1 QUANTITIES PRODUCED AND MANUFACTURERS
PCE is currently produced by five companies at eight facilities. The
2
estimated total production capacity of these plants is about 410,500 Mg/yr.
In 1983, about 230,400 Mg/yr of PCE was produced.2 The total imports of PCE
in 1983 were 24,950 Mg/yr, and the total exports were 24,490 Mg/yr.2 The
producers, their capacities, and production process are listed in Table 2-1.
The types and amounts of emissions from these facilities are shown in
Table 2-2. The plant locations are shown in Figure 2-1.
Several companies, such as Stauffer Chemical Company (Louisville, KY),
Ethyl Corporation (Baton Rouge, LA) and Occidental Petroleum Company (Taft, LA)
have stopped producing PCE due to the decline in PCE consumption in recent
2
years. Dow Chemical U.S.A. has recently stopped producing PCE at its
Freeport, TX facility. The United States' capacity for PCE will be further
reduced when duPont converts its plant in Corpus Christi, TX to chloroform
and CC14 production by the end of 1985.2
2-1
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(1) Dlaifond Shamrock Corporation, Deer Park, Texas
(2) Dow Chemical U.S.A., Freeport, Texas
(3) Dow Chemical U.S.A., Pittsburg, California
(4) Dow Chemical U.S.A., Plaquemine, Louisiana
(5) E.I. duPont de Nemours and Company, Inc., Corpus Christi, Texas
(6) PPG Industries, Inc., Lake Charles, Louisiana
(7) Vulcan Materials Company, Geismar, Louisiana
(3) Vulcan Materials Company, Wichita, Kansas
Figure 2-1. Locations of perchloroethylene production facilities,
2-4
-------
Although the business slowdown of the early 1980's cut overall demand
for chlorinated solvents, the principle reason for PCE drop-off was the
continuing trend toward lower consumption for apparel dry cleaning and other
textile-related applications. This is primarily responsible for the
anticipated capacity production decrease in 1985 of 18 percent. Increased
recycling of the solvent in the dry cleaning and degreasing industries will
also limit future growth.
2.2 PRODUCTION PROCESSES
3
PCE was first prepared in 1821 by Faraday from hexachloroethane.
Different methods of PCE preparation were developed by Regnault in 1884,
Meyer in 1884, and Combes in 1887. Industrial production began in the in
United States about 1925. Acetylene was the raw material in the early
production processes, but its high cost has resulted in current PCE
production primarily from the following three processes.
2.2.1 Chlorination of Ethylene Dichloride
Two companies produced PCE in 1983 via the chlorination of EDC. These
companies are Diamond Shamrock in Deer Park, TX and Dow Chemical U.S.A. in
Freeport, TX.
2.2.1.1 Process Description. PCE and TCE are co-produced from the
chlorination of EDC. Reaction conditions control the final production
formation. Changes in the EDC/chlorine ratio determine which compound will
be formed in the greatest quantity. The chlorination process occurs
according to the noncatalytic reaction:
C1CH2CH2C1 + 3C12 _ 400-450°C _ ^ CIgC = CC12 + 4HC1
(ethylene dichloride) (perchloroethylene)
The reaction is usually carried out at about 400° to 450°C (750° to
850°F) and at a pressure slightly above one atmosphere. The process flow
diagram is shown on Figure 2-2.
2.2.1.2 Current Emissions and Controls. The primary types of emissions
from this process at the two production facilities are from process vents,
storage, fugitives, equipment openings, and handling. The emission types
and their controls are discussed below and listed in Table 2-3.
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Diamond Shamrock Corporation - Deer Park, TX
The production of PCE by EDC chlorination at this facility resulted in
total emissions of PCE of 226.2 Mg in 1983. Fugitive emissions accounted
for a majority of these emissions, totalling 138.4 Mg/yr. The largest
sources of equipment leaks were flanges, open-ended lines, and valves.
Emissions from the valves were approximately 44 Mg/yr (31 percent of total
fugitive emissions). Seventeen percent of the fugitive emissions were from
flanges. Open-ended lines in liquid service constituted 19 percent of these
emissions. Diamond Shamrock indicated that there is currently no formal
monitoring procedure for fugitive emissions. Operating personnel are
instructed to report any leaking components that they observe on their
normal rounds.
The TACB has recently promulgated regulations that will require a
formal fugitive emissions monitoring program. 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 recordkeeping of these practices.
Losses from product storage in 10 fixed-roof storage tanks were
approximately 75 Mg/yr. These tanks ranged in size from 40,000 gallons to
500,000 gallons, averaging 126,000 gallons. Storage tanks in Harris County,
Texas, with a capacity greater than 42,000 gallons (158,487 liters) but
storing liquids with a vapor pressure less than 76 kPa (11 psia), are
required to have an internal or external floating roof with primary seals
and secondary seals between the tank wall and roof edge, or a vapor recovery
system which returns vapor to a disposal system. For tanks greater than
42,000 gallons storing liquids with vapor pressure greater than 76 kPa
(11 psia), a submerged fill pipe and vapor recovery system is required.
However, Diamond Shamrock reported that there were no emission controls on
these tanks.
Fourteen process vents emitted approximately 9.0 Mg of PCE emissions in
1983. The vents were located on process equipment such as columns
(distillation, stripper) and various holding tanks. Condensation systems
2-9
-------
were used on a number of these vents for product recovery or emissions
control. The vent with the largest quantity of emissions (3.8 Mg/yr) was on
a column feed tank. There were no controls for this vent, which accounted
for 42 percent of the total PCE emissions from process vents. The next two
largest emissions sources were a column overhead decanter and a tank for dry
organics. The column vent released 2.0 Mg of PCE. A water blanket achieved
a control efficiency of 98 percent. The tank vent released 2.4 Mg/yr of PCE
emissions and achieved a control efficiency of 95 percent with a vent
chiller. Fifty-nine percent control efficiency was achieved for the
remaining 9 percent of the process vent emissions.
Regulations for emissions from vent streams in Harris County specify
that certain VOC classes, which include PCE, must be burned properly at a
temperature equal to or greater than 1,300°F (704°C) in a smokeless flare or
direct-flame incinerator before it is allowed to enter the atmosphere.
However, the vent streams at Diamond Shamrock are exempt from this
regulation. Section 115.163 specifies that vent gas streams having a
combined weight of VOC's greater than 100 Ibs (45.5 kg) in any consecutive
24-hour period but less than 250 Ibs (113.4 kg) per hour averaged over any
consecutive 24-hour period and having a true vapor pressure of less than
0.44 psia (3.0 kPa) are exempt from regulatory control. The vent with the
largest quantity of PCE emissions at Diamond Shamrock releases an average of
only 0.43 kg/hr (10.4 kg in any 24-hour period).
Losses due to handling were approximately 3.8 Mg/yr. All raw materials
for the PCE process are received by pipeline, either into surge tanks, or
directly into the reactors. The PCE product is shipped by tank cars, tank
trucks, and barges. A small fraction is drummed and shipped in 55-gallon
drums. To reduce emissions, all loading, except to drums, is done by the
submerged fill pipe method, with an estimated control efficiency of
50 percent. This facility is exempt from the handling/loading regulations
because the vapor pressure of PCE is below the cutoff limit of 1.5 psia.
Although there are four waste stream sources for secondary emissions,
Diamond Shamrock reported that no PCE was emitted to the atmosphere. Two
streams of column bottoms are incinerated or deep well injected. Spent
2-10
-------
filter cartridges are drummed (1 to 2 55-gallon drums/month) and sent to a
commercial landfill. A wastewater stream is treated biologically in a
wastewater treatment plant.
Dow Chemical U.S.A. - Freeport, TX
Fugitive emissions are the largest quantity of PCE emissions generated
by the chlorination of EDC at this facility. Approximately 80.4 Mg were
emitted in 1983. Flanges were the source of more than 70 percent of the
emissions while 25 percent were emitted from valves. Dow indicates that an
automatic sampling system continuously monitors all cooling and contaminated
process water leaving the unit and alarms the control room if the
concentrations exceed pre-set limits. An "ultrasonic leak survey" is
conducted semiannually. Six process streams are monitored internally,
continuously for water contamination that would cause accelerated corrosion.
A brief discussion on the formal fugitive emissions monitoring program
that will take effect in Texas in 1987 is contained in the previous discussion
for Diamond Shamrock, Deer Park, TX. Currently, there are no State regulations
for fugitive emissions.
Approximately 19.5 Mg of PCE were released to the atmosphere from three
process vents in 1983. There are no controls on any of the vents. A vent
on a PCE holding tank released 4.3 Mg/yr of PCE. A second vent on the
Perchlor tank emitted only 0.037 Mg/yr of PCE. The total emission duration
in 1983 was only 72 hours for this vent. The third vent emitted 15.2 Mg of
PCE in 1983. All other information concerning this vent was considered
confidential by Dow. Brazoria County is in a nonattainment area where
regulations specify that PCE emissions from vent streams must be burned
properly at a temperature equal to or greater than 1,300°F (704°C) in a
smokeless flare or direct-flame incinerator. All process vents at this
plant are exempt from regulation due to the vapor pressure cutoff of
0.44 psia.
PCE emissions from product storage in 1983 were 15.4 Mg. Storage and
emissions control information are considered confidential by Dow. Storage
control regulations in Brazoria County are identical to those in Harris
County.
2-11
-------
The PCE emissions from approximately 250 equipment openings in 1983
were 0.2 Mg. All losses were confined to evaporation from small containers
used to drain residual liquid from the equipment. These containers were
emptied into a liquid dumpster and sent off to be destroyed in a thermal
oxidizer.
Losses from loading/handling were approximately 0.07 Mg/yr. The
loading of PCE was done through the "open domes" of tank cars, tank trucks,
ships, and barges. However, this facility is exempt from loading/handling
regulations because liquids with vapor pressures of less than 1.5 psia are
exempt from regulation in Texas.
Secondary emissions from one wastewater stream were 0.125 Mg. The
stream was released into a permitted wastewater canal for disposal, but no
additional description of the stream was provided by Dow.
2.2.2 Hydrocarbon Chlorinolysis
The majority of the PCE produced in 1983 was produced by the
hydrocarbon Chlorinolysis process. Three companies use the process at five
different locations. These companies are Dow Chemical U.S.A. in Pittsburg,
CA and Plaquemine, LA, Vulcan Chemicals in Wichita, KS and Geismar, LA, and
E.I duPont de Nemours & Company in Corpus Christi, TX.
2.2.2.1 Process Description. The process involves the gas-phase
cracking of propane-propylene mixtures into C, and C? fragments along with
Chlorinolysis at 450°to 550°C. This yields a mixture of PCE, CC1,, and
hydrochloric acid (HC1), as shown below.
C3Hg + 8C12 * C12C = CC12 + CC14 + 8HC1
(propane) (perchloroethylene)
2C3Hg + 16C12 ^ C12C = CC12 + 4CC14 + 12HC1
(propylene) (perchloroethylene)
The process flow diagram is shown on Figure 2-3.
2.2.2.2 Current Emissions and Controls. Emission types, controls,
control efficiencies, and PCE emissions for each facility producing PCE by
2-12
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the hydrocarbon chlorinolysis process are shown in Table 2-4. Fugitive and
storage tank emissions account for the majority of the PCE emissions from
these facilities. Process vent, equipment opening, handling, and secondary
emissions were also reported by the five plants.
Q
Vulcan Chemicals - Geismar, LA
Fugitive emissions were the largest quantity of PCE emissions.
Approximately 60.0 Mg was emitted in 1983. All information concerning
fugitive emission sources was considered confidential by Vulcan. Effective
December 31, 1987, Louisiana regulations require a VOC leak patrol/repair
program. This includes quarterly leak check of all lines, vessels, and
equipment containing PCE with a portable gas chromatograph (GC).
The second largest source of emissions was product storage.
Approximately 23 Mg of PCE was released to the atmosphere in 1983. Vulcan
also considered all information concerning tanks and controls to be
confidential. State regulations for the storage of VOC's in storage tanks
in Louisiana are similar to those in Texas which were described previously
in this chapter. However, the minimum storage capacity (40,000 gallons) for
tanks in Louisiana is slightly lower than that for Texas.
Emissions from process vents were approximately 2.2 Mg/yr of PCE. A
"perc tower" emitted 0.0091 Mg in 1983. Vulcan reported that a pressure
tower was the control device. However, the control efficiency was reported
as not applicable (NA). The process is operating under pressure in the
tower, and vent emissions occur from pressure buildup. There is no actual
add-on control device. The PCE emissions from two solvent check tanks
(ST-6A & ST-6B) were 0.127 Mg/yr each. The emissions from another solvent
check tank (ST-6C) were 0.068 Mg/yr. Nitrogen padding is used for emissions
control for these tanks. Tanks ST-6A and ST-6B alternate service. One of
these tanks vents continuously at all times. Tank ST-6C vents only during
batch production runs of a special product. The four remaining process
vents are also on solvent check tanks. The PCE emissions from the vents on
each of these check tanks were 0.472 Mg/yr. Each tank vents 25 percent of
the time during production. Although "glycol pots" are identified by Vulcan
as the control devices for these tanks, no control efficiency is reported.
2-14
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-------
Emissions from equipment openings were approximately 0.004 Mg/yr of
PCE. Information concerning the number and types of equipment controls is
considered confidential by Vulcan. These emissions are well below the
limits which are the same as those for process vents.
o
Vulcan Chemicals - Wichita, KS
The largest quantity of emissions generated by the hydrocarbon
chlorinolysis process at this plant was from fugitive emissions. PCE
fugitive emissions in 1983 were approximately 40.1 Mg. Product storage
tanks released 15.8 Mg of PCE to the atmosphere in 1983. Emissions from
handling and equipment openings were 0.7 Mg/yr and 0.8 Mg/yr, respectively.
All information concerning equipment and controls is considered confidential
by Vulcan.
There are no regulations in Kansas for fugitive, storage, or handling
and equipment openings emissions.
Dow Chemical U.S.A. - Pittsburg, CA
The fugitive emissions from PCE production at this facility are based
on testing performed in July 1981 by Science Applications, Inc., (SAI).
The data indicated an average of 0.41 Mg/yr of fugitive emissions with a
90 percent confidence interval of 0.1 to 0.72 Mg/yr. This compares with
about 45 Mg/yr based on uncontrolled SOCMI fugitive emission factors applied
to the equipment count at the Pittsburg plant. It should be noted that
Regulation 8, Rule 22 of the Bay Area Air Quality District does not apply to
this facility due to the vapor pressure cutoff of 1.5 pisa. Dow did not
report a formal inspection and maintenance program, although it did indicate
that its operators make an hourly inspection of the plant.
Dow reported that there were no controlled pressure relief devices in
PCE service. The plant has a yearly inspection of all pressure relief
devices. The relief valves are removed, tested, adjusted if necessary, and
then put back in service.
Approximately 13.8 Mg/yr of PCE was emitted from product storage tanks.
Two 17,000-gallon fixed-roof tanks emitted 1.3 Mg/yr each, and had no
emissions controls. A 300,000-gallon and a 310,000-gallon tank are equipped
with backpressure regulators for emissions control. Dow reported that these
2-17
-------
regulators provide only "slight" control efficiency. All tanks are exempted
from the Bay Area storage tank regulations due to a vapor pressure cutoff of
1.5 psia.
Dow estimated that approximately 1.13 Mg/yr of PCE was emitted due to
loading/handling. No control devices are used when filling tank trucks,
railcars, or ships. There are no Bay Area regulations for loading/handling
operations.
Losses from 300 equipment openings were estimated by Dow to be
0.34 Mg/yr. These losses are not controlled.
The production of PCE released emissions from one process vent. Dow
indicated that the losses were minimal ("0 kg/yr"). The vent is on a
distillation column reflux drum. Nitrogen is added to maintain a constant
pressure. A back pressure regulator opens if the pressure gets too high.
The control device and control efficiency was considered confidential by
Dow.
12
Dow Chemical U.S.A. - Plaquemine, LA
The production of PCE by hydrocarbon chlorinolysis emitted 91.7 Mg of
PCE in 1983. The largest quantity of emissions was fugitive emissions,
totalling 55.8 Mg/yr. Thirty-two percent (18.0 Mg/yr) of the fugitives were
from sample connections. Thirteen percent (7.3 Mg/yr) of the fugitive
emissions were from flanges, and 37 percent (20.8 Mg/yr) from valves. Dow
indicated that preventive maintenance, inspection, and monitoring programs
have been established in Plaquemine, but did not indicate the frequencies of
these programs. Dow reported that valves and pumps are purchased primarily
on their ability to not leak.
Emissions from three fixed-roof storage tanks were estimated to be
21.4 Mg in 1983. Dow reported that two 45,300-gallon tanks used normal
American Petroleum Institute (API) padding and depadding systems for
emissions control. A control efficiency was not reported. These two tanks
emitted 38 percent (8.0 Mg/yr) of the storage emissions. Sixty-two percent
(13.3 Mg/yr) was released from a 312,800-gallon tank. Emission control was
by refrigeration (-5°F). The emission control efficiency was 90 percent.
Storage tanks in Louisiana with capacities greater than 40,000 gallons and
2-18
-------
containing organic compounds with vapor pressures less than 11 psia are
required to have a floating roof with seals between the tank wall and roof
edge, or a vapor recovery system which returns vapor to a disposal system.
However, Dow did not report these controls for these three tanks.
PCE emissions from process vents were 8.2 Mg in 1983. Ninety-eight
percent (8.0 Mg/yr) of these emissions were from an exchanger. There was no
control device for this vent. The vent on the thermal oxidizer emitted
0.3 Mg/yr of PCE. The oxidizer is a control device used for the thermal
destruction of process wastes.
Total emissions from loading/handling were 3.6 Mg/yr. Information
concerning equipment and controls are considered confidential by Dow.
Equipment opening emissions totalled 2.2 Mg in 1983. There were
255 openings in equipment for gas and liquid service. These emissions are
regulated under Louisiana's general VOC regulations for production processes.
The hourly and daily emission limits are 1.3 kg/hr and 6.8 kg/day. However,
Dow did not report if those emissions were controlled.
Secondary emissions of PCE from four waste streams totalled 0.52 Mg/yr.
Organics from the containment water and storm water waste stream are
stripped and incinerated in the thermal oxidizer. PCE losses due to
"handling" accounted for 9 percent (0.05 Mg/yr) of the secondary emissions.
One percent (0.007 Mg/yr) of the secondary emissions was from handling of
the spent filter media. Ninety percent (0.47 Mg/yr) of the secondary
emissions were from two water outfall streams. These are discharged to the
nearest POTWs.
E.I. duPont de Nemours - Corpus Christi, TX
Dupont produces PCE by hydrocarbon chlorinolysis and uses some of this
product as an intermediate in the production of CFC's. The CFC's are also
produced at their facility in Montague, MI.
The largest quantity of emissions is fugitive, totalling approximately
13.6 Mg/yr. The largest sources of fugitive emissions are valves, which
released 32 percent (4.4 Mg/yr) of the total. Twenty-nine percent
(4.0 Mg/yr) of the emissions are from pressure relief devices. Seventeen
percent (2.3 Mg/yr) of the PCE fugitives were from flanges. The remaining
2-19
-------
32 percent of the fugitive emissions were from the pump seals (1.7 Mg/yr),
sample connections (0.5 Mg/yr), and open-ended lines (0.5 Mg/yr). Dupont
did not indicate if any controls were being used for fugitive emissions.
The formal fugitive emissions monitoring program that will take effect in
1987 in Texas has been discussed previously for other plants in Texas.
Storage emissions were approximately 0.97 Mg/yr. The emissions were
from three 16,000-gallon contact internal floating-roof tanks, one
400,000-gallon contact internal floating roof tank, and one 122,000-gallon
fixed-roof tank. DuPont reported that the emission controls for each tank
were conservation vents. Control efficiencies were not reported. The use
of internal floating roofs for storage tanks is required by State regulations
in Texas.
An air exhaust system is used to collect emissions from leaks and
discharges from six continuous vents, only one of which introduces PCE into
the system. A chlorocarbon sniff scrubber is used to treat these emissions.
Approximately 0.21 Mg/yr was released. The hourly and daily emission limits
from process vents in Texas are 1.4 kg/hr and 6.8 kg/day. This scrubber
vent stream is under this limit with PCE emissions of 0.024 kg/hr and
0.57 kg/day.
Losses from 24 equipment openings in PCE service were estimated to be
0.09 Mg/yr. There are no regulations in Texas for controlling these
emissions.
Dupont indicated that negligible amounts of PCE were released to the
atmosphere as secondary emissions from waste streams from sumps, tank
sludge, and filter cartridges.
2.2.3 Oxychlorination of Ethylene Dichloride
PPG Industries developed this process and is currently the only company
14
that uses the process to produce PCE.
2.2.3.1 Process Description. This process, like the chlorination
process, produces both PCE and TCE. The product mix can be varied by
adjusting the EDC to chlorine ratio. The reaction for PCE is shown below:
CHC1 = CHC1 + Cl2/or HC1 + 02 430°C ^ CC12 = CC12 + 2H20
catalyst
2-20
-------
The build-up of a great amount of hydrogen chloride is avoided by
concomitantly-operating HC1 oxidation. The reaction involves simultaneous
oxychlorination/dehydrochlorination with chlorine or anhydrous hydrogen
chloride as the chlorine source. The process flow diagram is shown on
Figure 2-4.
2.2.3.2 Current Emissions and Controls. Emission types, controls,
control efficiencies, and PCE emissions from the production of PCE by the
oxychlorination of EDC at PPG Industries are shown in Table 2-5. The major
sources of emissions were fugitive emissions and storage tanks. PCE
emissions from process vents, loading/handling, and equipment openings were
also reported.
Fugitive emissions from equipment in PCE service totalled approximately
23.5 Mg in 1983. Valves were the largest source of emissions, releasing
42 percent (10.0 Mg/yr) of the total fugitive emissions. Twenty-seven
percent (7.4 Mg/yr) of the total fugitive emissions were released from pump
seals. Flanges were the sources of 25 percent (5.9 Mg/yr) of the fugitive
emissions. Sample connections were the sources of 4.3 percent (1.0 Mg/yr)
of the PCE emissions. Twenty-one pressure relief devices released
0.7 percent (0.2 Mg/yr) of the fugitive emissions. Thirteen of the pressure
relief valves were in liquid service and were equipped with rupture discs.
The relief valve discharges reported by PPG occurred from July 2, 1984 to
December 28, 1984, and accounted for 0.2 Mg of PCE emissions. Discharges
were due to pressure build-up, overfilled tanks, and premature failure of
the device. PPG reported that there were no formal inspection programs used
in 1983. Leaks were located by visual observations and repaired "promptly"
for economic reasons (loss of product, corrosion of equipment). Effective
December 31, 1987, Louisiana regulations will require a VOC leak
patrol/repair program. This includes quarterly leak checks of all lines,
vessels, and equipment containing PCE with a portable GC.
PCE emissions from storage tanks in 1983 were 18.5 Mg. Eighty-nine
percent (16.6 Mg/yr) of the emissions were from three fixed-roof tanks.
These are dock tanks with capacities of 430,000 gallons each. There is one
vent stack for these three tanks. No emission controls were reported.
2-21
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Storage tanks in Louisiana are exempt if they store organic chemicals with
vapor pressures less than 1.5 psia (PCE vapor pressure is about 0.3 psia).
Two fixed-roof stabilization tanks were the sources of 6.5 percent
(1.2 Mg/yr) of the storage tank emissions. The tank capacities are
65,000 gallons each. Refrigeration and vapor recovery is the method of
emissions control, achieving a control efficiency of 80 percent. Vapor loss
control devices other than internal and external floating roofs can be
approved by the Technical Secretary of Louisiana if the devices control
organic emissions as effectively as floating roofs. Four fixed-roof
degreasing stabilization tanks were the sources of 3.1 percent (0.6 Mg/yr)
of the storage emissions. The capacities of these tanks are 13,500 gallons
each. There are two vent stacks for these four tanks. Emissions control is
by refrigeration and vapor recovery with a control efficiency of 80 percent.
One fixed-roof shipping tank was the source of 0.7 percent (0.1 Mg/yr) of
the storage emissions. Emissions control on this tank is by refrigeration
and vapor recovery with a control efficiency of 80 percent.
Emissions from process vents are controlled by scrubbers and totalled
0.2 Mg/yr. Fifty-three percent (0.12 Mg/yr) of these emissions were vented
from a scrubber for a distillation column. No control efficiency was
reported. The vent on an acid sump scrubber was the source of 29 percent
(0.063 Mg/yr) of the total process vent emissions. The vent on an
emergency/startup scrubber was the source of 18 percent (0.04 Mg/yr) of the
process vent emissions. These were not continuous emissions because the
scrubber is used only during startup, shutdowns, and brief emergencies.
This scrubber was used only 44 hours in 1983. A "DH System" scrubber, which
is used only in emergency situations, was not used in 1983.
Approximately 1.3 Mg of PCE was emitted from loading/handling
operations in 1983. Louisiana regulations stipulate that loading facilities
for VOC's with throughputs of at least 20,000 gallons/day (40,000 gallons or
more for existing facilities) must be equipped with vapor collection and
disposal systems. PPG used submerged fill pipes for loading/handling rail
cars and tank trucks. Railcars were the sources of 34 percent (0.44 Mg/yr)
of the handling emissions. Tank trucks were the sources of 17.5 percent
2-24
-------
(0.22 Mg/yr) of the handling emissions. Submerged fill pipes were also the
control measures used for loading barges and ships. Thirty-two percent
(0.40 Mg/yr) of the handling/loading emissions occurred at barges; 16 percent
(0.20 Mg/yr) occurred at ships. However, barges and ships are exempt from
these loading/handling regulations.
PCE emissions from equipment openings were 0.4 Mg in 1984. The losses
were from: 12 openings on 5 reactors, 20 openings on 9 distillation columns,
and 5 openings on 5 tanks. PPG did not report equipment opening emissions
for 1983.
2-25
-------
2.3 REFERENCES
1. Letters and attachments from Gillespie, T. E., Shell Oil, to
Farmer, J. R. EPArESED. February 1985. Responses to PCE 114 letter.
2. Mannsville Chemical Products. Chemical Products Synopsis -
Perchloroethylene. Cortland, New York. 1984.
3. Wittcoff, Harold A., and Bryan G. Rueben. Industrial Organic Chemicals
in Perspective. John Wiley and Sons, Inc., New York, 1980.
4. Misenheimer, D. C., and W. H. Battye (GCA Corporation). Locating and
Estimating Air Emissions from Sources of Ethylene Dichloride. Prepared
for U.S. Environmental Protection Agency, Research Triangle Park, North
Carolina. Publication No. GCA-TR-CH-82-4. (Revised) February 1983.
p. 5.
5. Letter and attachments from Christenson, B. H., Diamond Shamrock
Company to Farmer, J. R., EPA:ESED. January 31, 1985. Response to PCE
114 letter.
6. Letter and attachments from Arnold, S. L., Dow Chemical U.S.A. to
Farmer, J. R., EPArESED. March 1985. Response to PCE 114 letter.
7. Merck and Company. The Merck Index of Chemicals and Drugs. Seventh
Edition. Rahway, New Jersey. 1960.
8. Letter and attachments from Berg, R. E., Vulcan Chemicals, to
Farmer, J. R., EPA:ESED. January 31, 1985. Response to PCE 114
letter.
9. Letter and attachments from Boyd, J. W., Vulcan Chemicals, to
Farmer, J. R., EPArESED. February 1, 1985. Response to PCE 114
letter.
10. Letter and attachments from Arnold, S. L., Dow Chemical U.S.A. to
Farmer, J. R., EPArESED. February 28, 1985. Response to PCE 114
letter.
11. Rogozen, R. A. (Science Applications, Inc.) et al. Inventory of
Carcinogenic Substances Released into the Ambient Air of California:
Phase II. Prepared for the State of California Air Resources Board.
Contract No. AO-140-31. Sacramento, California. November 1982.
12. Letter and attachments from Arnold, S. L., Dow Chemical U.S.A. to
Farmer, J. R., EPArESED. March 1985. Response to PCE 114 letter.
2-26
-------
13. Letter and attachments from Harris, J. E., E.I. duPont de Nemours, to
Farmer, J.R., EPA:ESED. February 1, 1985. Response to PCE 114 letter.
14. Letter and attachments from Komorski, K. S., PPG Industries, to
Farmer, J. R., EPA:ESED. February 14, 1985. Response to PCE 114
letter.
15. SRI International. Assessment of Human Exposure to Atmospheric
Perchloroethylene. Prepared for U.S. Environmental Protection Agency.
Project No. CRU-6780. January 1979.
2-27
-------
3.0 CHLOROFLUOROCARBON PRODUCTION, BY-PRODUCT FORMATION,
AND MISCELLANEOUS PRODUCTION USES
This chapter presents the emissions and controls associated with the use
of PCE as an intermediate in CFC production, as a by-product formed in the
production of other chlorinated hydrocarbons, and as a raw material used in
the synthesis of other chemical products. Three plants use PCE as a raw
material in the production of CFC's. One of these facilities is also a
producer of PCE. Five plants form PCE as a by-product in the manufacture of
other chlorinated hydrocarbons or use it as raw material for other processes.
PCE emissions from CFC production come from equipment leaks, raw material
storage, and loading and handling. Emissions sources in by-product formation
includes process vents, equipment openings, secondary sources, and truck,
railcar, or barge loading.
3.1 QUANTITIES CONSUMED/PRODUCED AND MANUFACTURERS
PCE is currently used as an intermediate for CFC production by two
companies at three locations. The estimated total CFC production capacity
for two of these plants is about 136,000 Mg/yr. The estimated capacity of
the third plant was not available in published literature. The producers,
their locations, and capacities are listed in Table 3-1. The types and
amounts of emissions from these facilities are shown in Table 3-2. The plant
locations are shown in Figure 3-1.
Fluorocarbons are produced in the United States by duPont, Allied,
Kaiser, Pennwalt, and Racon. Only duPont and Allied manufacture CFC's-113,
(trichlorotrifluoroethane), -114 (dichlorotetrafluoroethane), -115 (chloropenta-
fluoroethane), and -116 (hexafluoroethane), which use PCE as an intermediate.
It is estimated that duPont supplies about 70 percent of this market with
Allied selling the remainder. Although a large amount of the CFC's are sold
directly by the producers, most is reportedly sold through distributors.
3-1
-------
TABLE 3-1. CHLOROFLUOROCARBON PRODUCTION FACILITIES
USING PCE AS AN INTERMEDIATE
Capacity (Mg/yr)
Company Location (1984)
Allied Corporation Baton Rouge, LA 45,300
E.I. duPont de Nemours Montague, MI a
E.I. duPont de Nemours Corpus Christi, TX 90,600
aThe capacity for this facility could not be found in available literature.
3-2
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(1) E.I. duPont de Nemours and Company, Inc., Corpus Christi, Texas
(2) E.I. duPont de Nemours and Company, Inc., Montague, Michigan
(3) Allied Corporation, Baton Rouge, Louisiana
(4) Dow Chemical U.S.A., Midland, Michigan
(5) Dow Chemical U.S.A., Freeport, Texas
(6) Georgia Gulf, Plaquemine, Louisiana
7) Shell Oil Company, Deer Park, Texas
8} Borden Chemicals, Geismar, Louisiana
Figure 3-1. Locations of CFC producers using PCE and
miscellaneous production facilities.
3-4
-------
3.2 CHLOROFLUOROCARBON PRODUCTION PROCESS
The major consumptive use of PCE is in the manufacture of CFC's. PCE is
a chemical intermediate in the synthesis of CFC-113, CFC-114, CFC-115, and
CFC-116. These CFC's are used chiefly as refrigerants. Their use for
aerosol sprays was prohibited as of 1979 because of their potential to
contribute to stratospheric ozone depletion.
3.2.1 Chlorofluorocarbon Production
Two companies at three facilities used PCE as an intermediate in the
production of CFC's in 1983. These companies are E.I. duPont de Nemours in
Corpus Christi, TX and Montague, MI, and Allied Corporation in Baton
Rouge, LA. Dupont also produces PCE at the Corpus Christi facility.
2
3.2.1.1 Process Description. CFC-113 and CFC-114 are co-produced as
part of an integrated process within the same facility. The only commercially
important domestic process used to produce these two compounds involves the
liquid-phase catalytic reaction of anhydrous hydrogen fluoride with chlorinated
hydrocarbons (PCE and/or CCl^) and chlorine. For PCE feedstock, the net
reaction can be represented as follows:
2C12C = CC12 + 7HF + 2C12 -5 - ^ C2C13F3 + C2C12F4 + 7HC1
(PCE) catalyst (CFC_113) (CFC-114)
A portion of CFC-114 produced by this method can be isolated for consumption
in a separate reaction with anhydrous hydrogen fluoride to yield CFC-115 and
CFC-116.
3.2.1.2 Current Emissions and Controls. The major type of PCE
emissions from CFC production is from raw material storage. Fugitive
emissions and loading/handling emissions were also reported. The emission
types and their controls are discussed below and are summarized in Table 3-3.
Since all PCE produced at the duPont facility in Corpus Christi, TX is used
to manufacture CFC at the same facility and all emissions data for the plant
have been discussed in Chapter 2, this facility will not be discussed in this
chapter.
3-5
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E.I. duPont de Nemours - Montague, MI
The use of PCE as an intermediate in the production of CFC's at this
facility in 1983 resulted in total PCE emissions of 14.7 Mg. The majority of
these emissions were fugitive emissions, which accounted for 60 percent
(8.7 Mg) of PCE released to the atmosphere. The largest sources of equipment
leaks were valves, open ended lines, and mechanical pump seals. Emissions
from valves were approximately 4.4 Mg/yr (49 percent of total fugitive
emissions). Twenty-five percent of the fugitive emissions were from open
ended lines (2.2 Mg/yr) and 19 percent (1.7 Mg/yr) from mechanical pump
seals. Although operators at the facilities are trained to look for and
repair leaks, duPont did not indicate that there was a formal monitoring/
maintenance program in place for equipment leaks. There are no regulations
in Michigan requiring control of these emissions.
PCE emissions from equipment openings totalled 0.033 Mg in 1983. There
were 23 openings on a variety of tanks, reactors, filters, pumps, and pipe
flanges. There are no regulations in Michigan requiring control of these
emissions.
PCE emissions from two fixed-roof storage tanks were 6.0 Mg in 1983.
One 70,000-gallon tank released 89 percent (5.3 Mg/yr) of the total storage
emissions, and a 50,000-gallon tank was the source of the remaining storage
emissions (0.7 Mg/yr). There are no control devices for these tanks and none
are required by State regulations since storage tanks containing VOC with
vapor pressure less than 1.5 psia are exempt from control in Michigan.
Dupont reported that conservation vents (venting at 0.4 psia) are the
"control devices." No control efficiency was reported for these vents.
Dupont indicated that no working losses (due to tank filling and emptying)
occur because the tanks are vented to the rail car during PCE transfer. They
also report that no breathing losses occur during plant operation because PCE
is continuously fed to the process at volumes greater than the vapor
expansion from ambient temperature changes. If there are no breathing or
working losses, then there are no losses of PCE from storage tanks. However,
these operational procedures were not considered when calculating PCE
emissions from these storage tanks by using the AP-42 equations.
3-7
-------
PCE emissions from loading/handling procedures were 0.016 Mg in 1983.
The raw material (PCE) is received by railcar. The top of the car is opened
for sampling and connecting the liquid and vent lines. During unloading, the
storage tank is vented to the rail car. The sampling and hookup procedure is
the source of emissions. The handling of PCE is not regulated by Michigan
due to a vapor pressure cutoff of 1.5 psia.
Two sources of secondary emissions were reported by Dupont to release
"insignificant" amounts of PCE to the atmosphere. About five drums of one
unidentified waste were disposed of by incineration in 1983. Water seals
were used in the drums to help prevent PCE vapors from being emitted. The
emissions from the National Pollutant Discharge Elimination System (NPDES)
wastes were insignificant because of the small amount of PCE in the waste
water.
4
Allied Corporation - Baton Rouge, LA
The only PCE emissions from CFC production at this facility were
fugitive emissions and raw material storage emissions, which totalled
19.7 Mg/yr. Fugitive emissions accounted for 8.2 Mg of the total PCE
emissions. The largest sources of PCE fugitive emissions were valves, which
emitted 69 percent (5.5 Mg/yr) of the fugitive emissions. Two pressure
relief devices in gas service were equipped with rupture discs and, therefore,
were estimated to have no emissions. Flanges were the source of 15 percent
(1.2 Mg/yr) of the fugitive emissions, and mechanical pump seals were the
source of the remaining 16 percent (1.3 Mg/yr) of the fugitive emissions.
Effective December 31, 1987, Louisiana regulations will require VOC leak
patrol/ repair programs. This includes quarterly leak checks of all lines,
vessels, and equipment containing PCE with a portable GC.
Allied did not record the number of actual equipment openings in 1983.
They estimate that there would normally be less than five openings/year and
that the associated quantity of emissions would be negligible.
Raw material storage was the largest source of emissions. The facility
had one 172,000-gallon fixed-roof tank for PCE storage, from which about
11.5 Mg of PCE were emitted in 1983. Allied reported that the total filling
3-8
-------
and breathing losses, using AP-42 equations, was 3.1 Mg/year in 1983. This
tank is exempt from control in Louisiana because of the vapor pressure cutoff
of 1.5 psia. A submerged fill pipe was used for emissions control. The
control efficiency was not reported.
Allied's estimates for loading/handling emissions were included within
the emission losses reported for storage tanks. PCE is delivered to the
facility by railcar. After the dome has been opened for lab analysis and
approval, PCE is pumped into the storage tank through a hose. Air would be
drawn into the tank car during pumping, and loading area emissions were,
therefore, considered to be minimal. Allied included these minimal losses
with their storage tank emissions estimates. The loading of CFC into tank
trucks and rail cars is done in a closed system where vapors within the tank
trucks or cars can return to the storage tank. There is no detectable level
of PCE in the product.
The only source of secondary emissions was an outfall stream consisting
of treated process and utility wastewater and runoff from process areas.
Allied responded that the secondary emissions were "minimal." The 0.005 mg/1
concentration of PCE is well below the solubility of PCE in water of about
13 mg/1. Treatment of the stream was by equalization in ponds, monitoring,
and discharge accordance with the NPDES permit.
3.3 BY-PRODUCT FORMATION AND MISCELLANEOUS USES
PCE was produced as a by-product at four facilities in the United States
in 1983. It is produced as a by-product in the synthesis of other chlorinated
hydrocarbons such as VC, EDC, TCE, and CC1,. It was also used as a raw
material in the production of other commercially-available products at two
plants, for which all information is considered confidential by the producer.
The production facilities, their locations, processes, and total PCE emissions
are shown in Table 3-4.
3.3.1 By-products from Chlorinated Hydrocarbon Production
Four companies at five locations produced PCE as a by-product of other
chlorinated hydrocarbons in 1983. These companies were Dow Chemical U.S.A.
in Freeport, TX and Midland, MI; Borden Chemical in Geismar, LA; Shell Oil
Company in Deer Park, TX; and Georgia Gulf in Plaquemine, LA.
3-9
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3.3.1.1 Process Description. Using ethylene as a feedstock, changes
in the subsequent chlorination (oxychlorination and dehydrochlorination) and
pyrolysis stages will result in the formation of various chlorinated hydro-
carbons. The relationship between these compounds can be expressed by the
following sequences:
CH2 * CH2 + C12
(ethylene)
HC1 + CH2C1CHC12
(trichloroethylene)
\'
ru ru n j. un
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(vinylidene chloride)
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(perchforoethylene)
HC1
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(ethylene dichloride)
CH2 = CHC1 + HC1
vinyl Chloride
CHC12CHC12
(tetrachloroethane)
HC1
CHC1 = CC12
(trichloroethylene)
HC1
3-11
-------
3.3.1.2 Current Emissions and Controls. The major type of PCE
emissions from by-product formation and miscellaneous applications are
fugitive emissions and process vent emissions. The types and amounts of
emissions from these facilities are shown in Table 3-5. The emission types
and their controls are discussed below and are summarized in Table 3-6.
Dow Chemical U. S. A. - Midland. MI6
PCE is used at the Michigan Division of Dow Chemical as a raw material
and a solvent in the production of other chemicals. The three processes that
use PCE are listed below.
t Process #1 - The total PCE emissions from this process in 1983 were
approximately 49 Mg. One process vent was the largest source of
these emissions, releasing 38.9 Mg/yr (79 percent of total
emissions). These emissions were from a common vent header on a
scrubber that was also used for two other processes. The data were
based on actual sampling and flow measurement. The vent from
another scrubber in the process released 0.004 Mg/yr of PCE. All
other information concerning these process vents was considered
confidential by Dow. There are no State regulations in Michigan
controlling VOC emissions from process vents.
Twenty percent (10.2 Mg/yr) of the total emissions from this
process were fugitive emissions which are not controlled by Federal
or State regulations. Fifty-one percent (4.3 Mg/yr) of these
emissions were from valves. Forty-two percent (3.5 Mg/yr) of the
emissions were from flanges. The remaining 7 percent (0.5 Mg/yr)
were equipment leaks from mechanical pump seals (0.4 Mg/yr) and
open-ended lines in service (0.1 Mg/yr). The four pressure relief
devices were equipped with rupture discs. Preventative maintenance
inspections are scheduled for all relief devices and critical
instruments. Dow reported that a continuous air monitoring system
is used, with 20 area sampling probes for leak detection. Equipment
is monitored and inspected 24 hours per day by shift personnel.
3-12
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3-15
-------
Approximately 1 percent (0.1 Mg/yr) of the PCE emissions were
from equipment openings. There were 60 to 75 openings in PCE
service in 1983.
Less than 1 percent (0.02 Mg/yr) of the emissions were from
raw material storage according to AP-42 calculations for storage
tanks. The PCE was stored in a 750-gallon pressure vessel. Even
though State regulations do not control emissions from tanks under
40,000 gallons, pressure tanks are an accepted method of emissions
control in Michigan for tanks with capacities greater than
40,000 gallons.
Process #2 - The total PCE emitted from this process in 1983 was
95 Mg. Seventy-six percent (72.5 Mg/yrj of the emissions were
fugitive emissions, which are not controlled by Federal or State
regulations. Twenty-nine percent (20.1 Mg/yr) of the total
fugitive emissions were from flanges. Valves and open-ended lines
were the sources of 34 percent (24.5 Mg/yr) and 26 percent
(18.9 Mg/yr) of the fugitive emissions, respectively. The
remaining 11 percent (9 Mg/yr) of the PCE emissions were emitted
from mechanical pump seals, pressure relief devices in gas service,
sample connections, and open-ended lines in gas. Fugitive emission
monitoring/control involves instrumentation designed to alarm at
overflow or overpressure conditions. Annual preventative
maintenance is performed on pressure relief devices and process
equipment in PCE service.
There were seven pressure relief devices that discharged to
control equipment (a scrubber). The estimated control device
efficiency was 75 percent. This estimate was based on the ideal
gas law and scrubber solubility. The emissions from these
discharges were not reported by Dow.
Emissions from a process vent are controlled by a scrubber and
totalled 21.6 Mg/yr. Dow indicated that this was a continuous vent
stream of constant flowrate and composition. All other information
was considered confidential by Dow. Michigan does not regulate VOC
emissions from vent streams.
3-16
-------
Less than 1 percent (0.007 Mg/yr) of the total PCE emissions
were from raw material storage. Two pressure vessels with
capacities of 9,500 and 2,500, respectively, were the sources of
these emissions. Vent condensers and scrubbers control the tank
emissions, achieving a 95 percent control efficiency. These tanks
are too small to be regulated in Michigan.
Losses from equipment openings were less than 1 percent of the
total PCE emissions (0.0009 Mg/yr). There were approximately
300 equipment openings in 1983.
Process #3 - The total PCt emissions from this process in 1983 were
29.3 Mg. Ninety-seven percent (28.6 Mg/yr) of these emissions were
fugitive emissions. The largest sources of fugitive emissions were
valves, flanges, and open-end lines. Thirty-three percent
(9.0 Mg/yr) of the fugitive emissions were from valves, 30 percent
(8.0 Mg.yr) from flanges, 26 percent (7.0 Mg/yr) from open-end
lines in liquid service. The other emission sources were
mechanical pump seals (1.3 Mg/yr), pressure relief devices
(0.9 Mg/yr), open-end lines in gas service (0.8 Mg/yr), and sample
connections (0.2 Mg/yr). Routine equipment inspections are
performed on the process.
One-hundred equipment openings resulted in 2 percent
(0.7 Mg.yr) of the total PCE emissions in 1983. There are no State
or Federal regulations for the control of these emissions.
PCE emissions from storage tanks were 0.3 percent (0.1 Mg/yr)
of the total emissions. A 6,500-gallon pressure vessel was the
source of emissions. There are no add-on control devices, but the
tank is kept pressurized. This tank is smaller than the size cut-
off (40,000 gallons) in Michigan.
The emissions from a small holding tank were approximately
0.01 percent (0.003 Mg/yr) of the total emissions. The holding
tank is filled about 5 times annually. The tank only vents when it
is filled. Duration of venting is about 30 minutes.
3-17
-------
Loading and handling operations released less than 1 percent
(0.002 Mg/yr) of the total PCE emissions. PCE was lost during the
hose disconnection of the off-loading stage. The PCE was received
in 50,000 15 quantities in tank trucks. Due to the vapor pressure
cutoff limit of 1.5 psia, PCE is exempt from loading/unloading
regulations in Michigan.
There were no secondary emissions from the disposal of a
liquid waste stream. Dow reported that there were no emissions due
to complete incineration at their facility.
Borden Chemical - Geismar, LA
PCE is a by-product generated from the production of EDC at this
facility. The only PCE emissions from the facility are from by-product
storage. PCE was only 0.5 percent of the total composition stored in a
50,000-gallon pressure vessel. Approximately 0.004 Mg of PCE were emitted
from this vessel. The tank contains various other chlorinated hydrocarbon
impurities generated from the EDC process. These impurities are incinerated.
Borden reported an incinerator destruction efficiency of 99.99 percent based
on sampling data. PCE emissions from tanks of at least 40,000 gallons are
regulated in Louisiana. According to Louisiana regulations, this pressure
tank is an acceptable control device.
Shell Oil Company - Deer Park, TX
PCE is produced as a by-product in the manufacturing of vinyl chloride
monomer (VCM). All VC emissions from this facility must be controlled
according to the requirements of the NESHAP for VC. The total PCE emissions
from this process in 1983 was 0.24 Mg. Ninety-nine percent (0.236 Mg) of
these emissions were from seven fixed-roof storage tanks. Ninety-six percent
(0.233 Mg/yr) of the total emissions were from one 56,000-gallon tank which
had no emissions control. PCE was only 1 to 3 percent of the total chemical
composition in the tank. Four percent (0.001 Mg/yr) of the storage emissions
were from the other six fixed-roof tanks ranging in size from 282,000 gallons
to 424,000 gallons. Compression and incineration were the emission control
methods, achieving an estimated 98 percent control efficiency. PCE accounted
for 0.0035 to 0.005 percent of the total composition stored in each tank.
3-18
-------
The small concentrations of PCE in these tanks compared to the concentrations
in the uncontrolled tank suggests that these six tanks contain VC product and
are, therefore, subject to the NESHAP.
Shell estimated that the total handling/loading emissions in 1983 were
0.045 Mg. The heavy ends from EDC distillation were transferred to tank
trucks. The stream contained 1 to 3 percent PCE. No vapor recovery is used
as the ends are loaded into tank trucks. Shell estimated that the total
handling emissions were less than 0.045 Mg in 1983. The EDC process at the
plant is most likely not covered by the VCM NESHAP. However, in Harris
County, vapor recovery systems are required for the loading or unloading of
all VOC with vapor pressure of 1.5 psia or greater at facilities with greater
than 20,000 gallons or more throughput per day. The vapor pressure of PCE
and the additional VOC in the stream probably did not exceed the cutoff of
1.5 psia.
Process vents on two incinerator stacks were the sources of less than
1 percent (0.01 Mg/yr) of the total PCE emissions. The incinerators destroy
the impurities in the light and heavy ends recovered from the EDC
distillation stage. Shell reported that there was less than 5 percent PCE in
any equipment where PCE was used. However, no other information was provided
concerning the fugitive emissions sources in PCE service. The company
indicated that all flanges and valves on equipment in VC service are checked
annually for fugitive emissions using a portable hydrocarbon detector. The
vinyl chloride NESHAP requires that leaks from equipment in VC service must
be minimized via formal leak detection and elimination (LD&E) program,
designed by the operator and approved by the Administrator of EPA.
Shell did not indicate how many equipment openings occurred at the
facility in 1983. They only reported that there were no equipment with
greater than 10 percent PCE.
Q
Dow Chemical U. S. A. - Freeport, TX
PCE is produced as a by-product of the TCE process at this facility.
The total PCE emissions from this process in 1983 were 5.6 Mg.
Ninety-nine percent (5.5 Mg/yr) of these emissions were from equipment leaks.
Thirty-eight percent (2.0 Mg/yr) of the fugitive emissions were from valves.
3-19
-------
Eighteen percent (1.0 Mg/yr) of the emissions were from open-end lines and
16 percent (0.9 Mg/yr) were from sample connections. Mechanical pump seals
and flanges are the sources of the remaining fugitive emissions, consisting
of 15 percent (0.8 Mg/yr) and 3 percent (0.1 Mg/yr) of the total fugitive
emissions, respectively. The TACB has recently promulgated regulations that
will require a formal fugitive emissions monitoring program taking effect in
1987.
Twenty equipment openings were the sources of less than 1 percent
(0.045 Mg/yr) of the total PCE emissions from this process. Equipment is
drained of liquid which is recycled back into the system for reprocessing.
After this initial draining, vapors are evacuated with a vacuum system to
assure minimum exposure. Nitrogen is then purged through the equipment to
vacuum the system to remove vapors.
Less than 1 percent (0.1 Mg/yr) of the total PCE emissions were from
storage. All tank and emission control information was considered
confidential by Dow.
Dow indicated that there were no PCE handling emissions in 1983. The
PCE by-product is transported in rail cars which are loaded through the dome
of the car's dip tube. The cars are then vented to a scrubber to contain the
vapors. Although the sampling data were not submitted by Dow, the company
reported that the scrubber was 100 percent effective at controlling the PCE
emissions.
Two sources of secondary emissions accounted for 0.5 percent
(0.0004 Mg/yr) of the total PCE emissions from the process. These emissions
were from the disposal of the bone char and calcium chloride waste streams
by landfill.
Dow Chemical U. S. A. - Freeport, TX9
PCE was used in the production of another chemical at this facility.
All information concerning the product and the process is considered
confidential by Dow.
The total PCE emissions in 1983 were approximately 43 Mg. Fugitive
emissions accounted for 85 percent (36.2 Mg/yr) of the total emissions. The
largest source of fugitive emissions were valves, which accounted for
3-20
-------
53 percent (19 Mg/yr) of the total fugitive emissions. Pressure relief
devices and mechanical pump seals were each the sources of 13 percent
(4.6 Mg/yr) of the total fugitive emissions. The remaining emissions were
from flanges (7 Mg/yr) and sample connections (0.5 Mg/yr). The recently-
promulgated regulations by the TACB were discussed in Section 2.2.1.2 of this
report.
The process vent emissions were 14 percent (6.5 Mg/yr) of the total PCE
emissions. All other information was considered confidential by Dow. There
were no releases from pressure relief devices in 1983.
The PCE emissions from loading/handling operations and secondary sources
were less than 1 percent (0.1 Mg/yr) of the total emissions. All other
information was considered confidential by Dow.
Georgia Gulf - Plaquemine, LA
PCE is an impurity formed in the production of EDC and VCM. The total
emissions from this process were 25.2 Mg/yr. The largest source of PCE
emissions is a process vent stream which emitted 99 percent (25.1 Mg/yr) of
the total PCE emissions. All information concerning this stream was
considered confidential by Georgia Gulf. The vinyl chloride NESHAP requires
that all vent gases from process and storage vessels in VC service to be
controlled to 10 parts per million (ppm) or less VC.
Less than 1 percent (0.001 Mg/yr) of the PCE emissions were emissions
from storage. All information concerning storage tanks was considered
confidential by Georgia Gulf. Emissions from this facility must be
controlled by the vinyl chloride NESHAP, which requires that the
concentration of VC in exhaust gases discharged to the atmosphere from
storage tanks must not exceed 10 ppm.
3-21
-------
3.4 REFERENCES
1. Mannsville Chemical Products. Chemical Products Synopsis -
Perchloroethylene. Cortland, New York. November 1984.
2. Mooz, W.E., et al. Technical Options for Reducing Chlorofluorocarbon
Emissions. The Rand Corporation. Prepared for the U.S. Environmental
Protection Agency. Publication No. 2879-EPA. March 1982.
3. Letter and attachments from Coleman, J.B. Jr., E.I. duPont de Nemours
and Company, to Farmer, J.R., EPA:ESED, January 30, 1985. Response to
PCE letter.
4. Letter and attachments from Cooper, J.E., Allied Corporation, to
Farmer, J.R., EPArESED, April 2, 1985. Response to PCE Questionnaire.
5. Wittcoff, Harold, A., and Bryan G. Reuben. Industrial Organic Chemicals
in Perspective. John Wiley & Sons, Inc., New York, 1980.
6. Letter and attachments from Arnold, S.L., Dow Chemical U.S.A. to
Farmer, J.R., EPA:ESED. February 22, 1985. Response to PCE 114 letter.
7. Letter and attachments from Springer, C.R., Borden, Inc., to
Farmer, J.R., EPA:ESED. February 15, 1985. Response to PCE 114 letter.
8. Letter and attachments from Gillespie, T.E., Shell Oil, to Farmer, J.R.,
EPA:ESED. January 31, 1985. Response to PCE 114 letter.
9. Letter and attachments from Arnold, S.L., Dow Chemical U.S.A., to
Farmer, J.R., EPA:ESED. March 1985. Response to PCE 114 letter.
10. Letter amd attachments from Treetter, V.J. Jr., Georgia Gulf, to
Farmer, J.R., EPA:ESED. January 31, 1985. Response to PCE 114 letter.
3-22
-------
4.0 DRY CLEANING INDUSTRY
Fifty-one percent of the total PCE produced in 1983 was consumed as a
dry cleaning solvent. An estimated 26,000 dry cleaning facilities existed
in the United States in 1978. Due to the large number of these facilities,
no attempt was made in this study to directly contact any of these
facilities or to verify the exact number of facilities presently in
operation. Emissions from dry cleaning operations were estimated in this
study by obtaining the 1983 consumption of PCE in dry cleaning and using
previous EPA studies to estimate the fraction of PCE consumed that is
emitted to the atmosphere. It is estimated that in 1983 about 117,000 Mg of
PCE were consumed by the dry cleaning industry of which about 50,000 Mg were
emitted. The majority of the remaining PCE is recycled. The following
sections present a brief discussion of the dry cleaning industry, cleaning
operations, emission sources and levels, applicable control techniques, and
regulatory requirements for the dry cleaning industry.
4.1 INDUSTRY DESCRIPTION
The dry cleaning industry can be divided into three sectors: coin-
operated, commercial, and industrial dry cleaners. Seventy-one percent of
the PCE used for dry cleaning is used by the commercial sector. The coin-
2
operated and industrial sectors use 18 and 11 percent, respectively.
4.1.1 Coin-Operated Cleaners
Coin-operated cleaners are small self-service facilities that are
usually associated with neighborhood laundromats. They are either indepen-
dently-owned and operated facilities or operated on a franchise basis.
Available literature indicates that there were an estimated 11,804 coin-
operated dry cleaning facilities using PCE in 1978.
Only synthetic cleaning solvents (no petroleum solvents) are used at
coin-operated facilities and PCE is the solvent of choice in 97.5 percent of
the facilities. All coin-operated machines are dry-to-dry units where the
4-1
-------
clothes are washed and dried in a single unit. Machine capacities at
coin-operated cleaners range in size from 3.6 kg to 11.5 kg per load. A
typical installation has two or three machines with annual throughput
estimated at 9,050 kg. The parameters for a typical coin-operated dry
cleaner are shown in Table 4-1.
4.1.2 Commercial Cleaners
Commercial dry cleaners are typically small dry cleaning facilities
offering nonself-service cleaning. Commercial dry cleaners are represented
by small neighborhood shops that are independently owned ("Mom and Pop"
operations), franchise shops offering general dry cleaning and laundry
services, and specialty cleaners that handle leather and other fine goods.
There were an estimated 15,060 commercial cleaners using PCE in 1978.
Seventy-three percent of the commercial sector uses PCE. The remaining
commercial cleaners use either petroleum solvents (24 percent) or trichloro-
trifluoroethane (3 percent). Most machines (75 percent) used in the
commercial sector are transfer machines, where clothes are washed in one
unit and then transferred to a separate unit to be dried. Machine
capacities range from 11 kg to 23 kg per load. A typical commercial
facility has one dry cleaning system with an annual throughput of about
17,700 kg. The parameters for a typical commercial dry cleaner are shown
in Table 4-1.
4.1.3 Industrial Cleaners
Industrial dry cleaners are the largest dry cleaning plants. They are
predominantly engaged in supplying rental services for items such as
uniforms, mops, and mats to businesses, industries, and institutions.
Approximately 40 to 45 percent of all industrial laundry facilities have dry
cleaning equipment and 50 percent of these use PCE. There were an estimated
334 industrial dry cleaners using PCE in 1978.
A typical industrial dry cleaning facility has one dry cleaning system
consisting of 250 kg per load capacity washer/extractor and three to six
38-kg capacity dryers. Annual throughput for facilities in this sector
range from 240,000 to 700,000 kg and average 468,750 kg/year for a typical
source. The parameters for a typical industrial dry cleaning facility are
shown in Table 4-1.
4-2
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4.2 CLEANING PROCESS CHARACTERIZATION
The basic dry cleaning process is identical to those of ordinary
laundering practices except that a solvent such as PCE is used instead of
water. Three principle steps are involved in the process: (1) one (or more)
solvent wash cycles; (2) physical extraction of excess solvent during a spin
cycle; and (3) tumble drying. These steps are the same for both transfer
and dry-to-dry machines.
Because PCE is expensive, additional steps can be taken to ensure more
economical plant operations. These steps, used at larger dry cleaning
facilities, include solvent treatment by filtration, distillation, and
charging. Solvent treatment allows for partial recovery and reuse of
4
solvent.
Filtration removes nonsoluble soils from used solvent. Filters may
contain activated carbon to remove dye residue. The solids (called muck)
are removed from the filters on a daily basis. Muck contains solvent that
is recovered by distillation except in plants that use a disposable filter
4
system. In these plants, the filters are drained and thrown away.
Soluble nonvolatile residue also accumulates in the solvent. This
residue, composed primarily of oils, fats, and greases, is not removed by
filtration. A distillation process is used to remove this residue from the
4
solvent.
A small amount of water and detergent must be added to the solvent to
remove water-soluble residue from fabric. This step is called charging and
must be repeated after each distillation.
4.3 EMISSION SOURCES
Dry cleaning systems have several sources of emissions. The major
sources are the dryer and filter muck followed by the disposal of waste
materials, and losses from liquid and vapor leaks.
In general, the emissions can be characterized as process or fugitive
emissions. Process emissions include emissions from washers, dryers,
stills, and muck cookers. Fugitive emissions include losses from pumps,
valves, flanges, seals, storage vessels, chemical and water separators, and
losses from handling of solvent and material.
4-4
-------
4.4 EMISSION ESTIMATES
An estimated 49,740 Mg of PCE were emitted from the dry cleaning
industry, accounting for 45 percent of the total PCE emissions in 1983.
This estimate is based on the 1983 PCE consumption data and the fraction of
PCE that is emitted per kg PCE consumed by the three sectors of the dry
cleaning industry.
The HSIA indicated that in 1983, coin-operated dry cleaners used
20,960 Mg of PCE, commercial dry cleaners used 82,830 Mg, while industrial
2
dry cleaners used 13,050 Mg. Emission factors for a typical facility in
each of the three dry cleaning sectors were obtained from the background
information document (BID) for the proposed standards for PCE dry cleaners.
Since the emission factors are expressed in terms of kg PCE emitted/100 kg
clothes cleaned, an estimate had to be made of the amount of clothes cleaned
in 1983. This was done by using the ratio of PCE dry cleaning consumption
in 1976 and consumption in 1983. The ratio was applied to the amount of
clothes cleaned in 1976 to estimate the amount of clothes cleaned in 1983.
This procedure was carried out individually for the coin-operated,
commercial, and industrial dry cleaners. The appropriate emission factor
(kg PCE emitted/kg clothes cleaned) was then applied to estimate 1983
emissions from each of the three dry cleaning sectors. Table 4-2 shows the
variables used to calculate these emissions. It is estimated that in 1983
about 16,800 Mg of PCE were emitted by coin-operated dry cleaners, 25,000 Mg
by commercial dry cleaners, and about 8,000 Mg by industrial dry cleaners.
Table 4-3 shows PCE emissions from coin-operated dry cleaners in each
State. These emissions were estimated from the number of coin-operated dry
cleaners in each state and by assuming that the PCE emissions are divided
equally between each coin-operated facility.
The number of commercial dry cleaners, broken down by the number of
employees, were estimated in a previous EPA study. Since it can be
reasonably expected that a large facility (i.e., large number of employees)
would use more dry cleaning solvent than a smaller facility, an "employee-
weighted average" number of facilities was calculated for each State. The
4-5
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4-6
-------
TABLE 4-3. TOTAL 1983 PCE EMISSIONS FROM COIN-OPERATED DRY CLEANERS,
. BY STATE
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawa i i
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine *
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
# Plants,
Percent of Total
U. S. Facilities
1.55
0.12
1.49
0.68
7.60
1.60
0.93
0.068
0.72
5.04
1.24
0.39
0.23
8.83
4.02
1.22
1.32
1.21
0.96
0.18
1.35
2.31
5.50
1.25
0.52
2.49
0.20
Total 1983 Emissions
(Mg)
260.0
20.1
250.0
114.0
1,274.7
268.3
156.0
11.4
120.7
845.3
208.0
65.4
38.6
1,481.0
674.2
204.6
221.4
202.9
161.0
30.2
226.4
387.4
922.5
209.6
87.2
417.6
33.5
4-7
-------
TABLE 4-3 (CONCLUDED). TOTAL 1983 PCE EMISSIONS FROM COIN-OPERATED DRY
. CLEANERS, BY STATE
State
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
TOTAL
# Plants,
Percent of Total
U. S. Facilities
0.48
0.35
0.28
2.19
0.75
10.16
1.51
0.12
5.98
1.78
0.63
2.97
0.62
0.52
0.19
2.56
10.08
0.36
0.042
1.78
1.23
0.39
IOC
.86
0.12
Total 1983 Emissions
(Mg)
80.5
58.7
47.0
367.3
125.8
1,704.0
253.2
20.1
1,003.0
298.5
105.7
498.1
104.0
87.2
31.9
429.4
1,690.6
60 4
\J w * *T
7 n
/ * v
298.5
206.3
65 4
V -J . *t
311.9
20 1
t.U . 1
16,766.6
4-8
-------
1 - 4
67
169
5-9
28
92
10 - 19
14
51
20 - 49
9
30
50+
2
4
amount of PCE emissions in each State was estimated by allocating the total
PCE emissions for commercial dry cleaners according to the "weighted
average" number of facilities in each State. For example, consider the
following commercial dry cleaning facilities in Alabama and Michigan, listed
according to the number of employees:
Number of plants by size of operation (employees)
State
Alabama
Michigan
The mid-point of the number of employee range classification was then
multiplied by the number of facilities in that classification.
"Weighted Average" Facilities in:
Alabama = (67)(2.5) + (28)(7) + (14)(14.5) + (9)(34.5) + (2)(51) = 979
Michigan = (169)(2.5) + (92)(7) + (51)(14.5) + (30)(34.5) + (2)(51) = 3045
The total number of "weighted average" facilities in the U.S. was
similary calculated to be 65,267. The ratio of "weighted average"
facilities in each state to the "weighted average" found in the country
was used to calculate emissions. For example, PCE emissions from
commercial dry cleaners in Alabama in 1983 were:
Q7Q
y y (25,100 Mg) = 379 Mg
65,267
Table 4-4 shows the estimated emissions from commercial dry cleaners by
State.
The exact location of each of the 334 industrial dry cleaners were
3
identified in a previous EPA study. It was assumed in this study that each
industrial dry cleaner emits the same amount of PCE annually (i.e.,
7,949 r 334 = 23.8 Mg). Based on this assumption, PCE emissions were
estimated for each state and are shown in Table 4-5.
4-9
-------
TABLE 4-4. TOTAL 1983 PCE EMISSIONS FROM COMMERCIAL DRY CLEANERS,
BY STATE
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawa i i
Idaho
111 i no is
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
# Plants,
Weighted Average
By State
(*)
1.50
0.002
1.10
0.56
9.90
1.50
1.80
0.29
1.10
3.50
2.60
0.40
0.16
5.90
2.20
0.77
0.67
1.2
1.4
0.31
2.1
3.4
4.6
1.5
0.7
1.7
Total 1983 Emissions
(Mg)
379.8
0.5
278.5
141.8
2,507.0
379.8
455.8
73.4
278.5
886.3
658.4
101.3
40.5
1,494.1
557.1
195.0
169.7
303.9
354.5
78.5
531.8
861.0
1,164.9
379.8
177.3
430.5
4-10
-------
TABLE 4-4 (CONCLUDED). TOTAL 1983 PCE EMISSIONS FROM COMMERCIAL DRY
CLEANERS, BY STATE
State
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
V i rg i n i a
Washington
West Virginia
Wisconsin
Wyoming
TOTAL
# Plants,
Percent of Total
U. S. Facilities
0.19
0.68
0.92
0.18
3.00
0.36
9.00
2.50
0.27
5.60
1.20
0.54
4.90
0.58
1.20
0.10
2.10
8.60
0.065
0.03
3.00
0.93
0.44
1.50
0.059
Total 1983 Emissions
(Mg)
48.1
172.2
233.0
45.6
759.7
91.2
2,279.1
633.1
68.4
1,418.1
303.9
136.7
1,240.8
146.9
303.9
25.3
531.8
2,177.8
16.4
7.6
759.7
235.5
111.4
379.8
14.9
25,020.6
4-11
-------
TABLE 4-5. TOTAL 1983 PCE EMISSIONS FROM INDUSTRIAL DRY CLEANERS, BY STATE
State Total 1983 Emissions
(Mg)
Alabama 166.6
Arizona 4/.6
Arkansas 23.8
California 809.2
Colorado 23.8
Connecticut 142.8
Delaware 23.8
District of Columbia 47.6
Florida 214.2
Georgia 238.0
Idaho 47.6
Illinois 928.2
Indiana 309.4
Iowa 23.8
Kansas 47.6
Kentucky 23.8
Louisiana 119.0
Maine 71.4
Maryland 119.0
Massachusetts 285.6
Michigan 238.0
Minnesota ' 95.2
Mississippi 47.6
Missouri 142.8
Nebraska 214.2
Nevada 47.6
New Hampshire 23.8
New Jersey 214.2
4-12
-------
TABLE 4-5 (CONCLUDED). TOTAL 1983 PCE EMISSIONS FROM INDUSTRIAL DRY
CLEANERS, BY STATE
State
Total 1983 Emissions
(Mg)
New Mexico
New York
North Carolina
Ohio
Oklahoma
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Virginia
West Virginia
Wisconsin
TOTAL
23.8
357.0
261.8
499.8
142.8
809.2
23.8
166.6
47.6
238.0
214.2
190.4
142.8
95.2
7,949.2
4-13
-------
4.5 CONTROL TECHNIQUES
PCE emissions from dry cleaners have historically been controlled to
some extent for economic reasons even before the development of CTG
regulations. Solvent recovery dryers are used at most establishments.
This practice allows the use of PCE to be as cost competitive as the cheaper
petroleum solvents. Carbon adsorption is used at about 35 percent of all
commercial facilities, 50 percent of all industrial facilities and 5 percent
of all coin-operated facilities to capture solvent for recycle.
There are currently two methods of add-on control technology available
for controlling PCE emissions at dry cleaners. These methods, carbon
adsorption, and refrigeration/condensation, are used to control emissions
from washers, dryers, stills, and muck cookers.
Carbon adsorption is the most common form of control for PCE. In this
process, PCE-laden air is passed over activated carbon. Prior to the carbon
reaching saturation, the air stream is diverted and the carbon is desorbed
by passing steam through the adsorbent. Solvent that has been vaporized by
the steam is then recovered downstream in a condenser, separated from the
water, and then returned to the storage tank. Carbon adsorption can be used
A
to achieve 100 ppm or less outlet concentration.
Refrigeration/condensation systems provide an alternative to carbon
adsorption systems. The refrigerated condenser is normally operated as a
closed system, as opposed to the carbon adsorber that is exhausted to the
atmosphere. In the refrigeration condensation process, the solvent-laden
air is cooled below the dew point of the solvent causing it to condense and
drain into the water separator. The air thus is stripped of solvent and
recirculated to the air inlet of the dry cleaning system. Recovered solvent
from the water separator is then fed to storage. Refrigeration units,
however, are not capable of controlling emissions from the variety of
4
sources that can be ducted to a carbon adsorber.
Fugitive PCE emissions are difficult to quantify and occur at many
different points of the dry cleaning process. Significant control of
fugitive PCE emissions can be gained through the use of good housekeeping
practices. These practices include maintenance of equipment, proper
4-14
-------
operation of equipment, proper storage and disposal of waste solvent and
residue, proper storage of solvent, and avoiding spills. Emission sources
that can be controlled in this manner are:
- Equipment Maintenance (tighten loose connections or replace defective
equipment)
Hose connections
Door gaskets
Filter gaskets
Pump seals
Oivertor valves
t Air and exhaust ducts
Inefficient extraction due to loose belts
Equipment valves
- Proper Equipment Operation
9 Water separator loss
0 Filter sludge loss
Door losses (open doors only when necessary and only for short
duration)
Extraction losses (overloading or underloading dryer hinders
efficient extraction)
9 Transfer losses
Fabric loadout losses due to incomplete drying
0 Inefficient capture systems (build-up of lint in filters and on fan
and condenser surfaces adversely affects solvent capture and
recovery)
- Proper Storage and Disposal of Solvent and Waste Products
0 Cartridge filters
0 Saturated lint
9 Sludge
0 Solvent storage
4.6 REGULATORY REQUIREMENTS
There are no Federal regulations that require control of PCE emissions
from dry cleaning. However, EPA has developed RACT guidelines which have
4-15
-------
been adopted by 23 States. Two additional States plus the District of
Columbia have general VOC regulations concerning the use of photochemically
reactive solvents. A summary of State regulations appears in Appendix A.
The six States with the highest PCE emissions from dry cleaning are
New York, Ohio, Pennsylvania, California, Illinois, and Texas. These States
together account for an estimated 45 percent of the total dry cleaning
emissions of PCE. All of these States, except New York, have adopted
EPA-approved RACT regulations for dry cleaning. New York's RACT regulations
are currently being reviewed by EPA.
4-16
-------
4.7 REFERENCES
1. U. S. Environmental Protection Agency. Perchloroethylene Dry Cleaning
- Background Information for Proposed Standards. Research Triangle
Park, N. C. Publication No. EPA-450/3-79-029a. August 1979.
2. Letter from Morgan, D. L., Cleary, Gottlieb, Steen, and Hamilton, to
Rosensteel, R. E., EPA. March 1, 1985. HSIA data on perchloroethylene
production and consumption.
3. PEDCo Environmental, Inc. Directory of Volatile Organic Compound
Sources Covered by Reasonably Available Control Technology (RACT)
Requirements. Volume II: Group II RACT Categories. Prepared for the
U. S. Environmental Protection Agency. Research Triangle Park, N. C.
Publication No. EPA/450-4-81-007b. February 1981.
4. Kleeberg, C. F., J. G. Wright. Control of Volatile Organic Emissions
from Perchloroethylene Dry Cleaning Systems. U. S. Environmental
Protection Agency. Research Triangle Park, N. C. Publication
No. EPA-450/2-78-050. December 1978. 68 pp.
5. Mura, S. J., B. E. Suta, and S. S. Lee (SRI). Assessment of Human
Exposures to Atmospheric Perchloroethylene. Prepared for the U. S.
Environmental Protection Agency. Research Triangle Park, N. C.
(Contract No. 68-02-2835). January 1979. 66 pp.
4-17
-------
5.0 SOLVENT DECREASING OPERATIONS
Fifteen percent (35,000 Mg) of the total PCE produced in 1983 was
consumed as a solvent for degreasing operations. PCE was used as a solvent
for degreasing in five manufacturing industries. Due to the large number of
degreasing facilities in these industries, no attempt was made in this study
to directly contact any degreasing facilities or to verify the exact number
of facilities presently in operation. Emissions from degreasing operations
were estimated in this study by obtaining the 1983 consumption of PCE for
each and applying it to an emission factor derived for degreasing
operations. It is estimated that in 1983, about 35,000 Mg of PCE were
consumed in degreasing operations of which about 33,000 Mg were emitted.
The following sections present a brief discussion of the types of
degreasers, emissions, emissions control, and estimates of emissions from
degreasing operations in 1983.
5.1 INDUSTRY DESCRIPTION
Degreasing is an integral part of many industrial categories such as
automobile manufacturing, electronics, furniture manufacturing, appliance
manufacturing, textiles, paper, plastics, and glass manufacturing. It is a
process that is used when the surface of a part must be cleaned of all
grease, metal chips, grit, fibers, abrasives, or other debris prior to
painting, plating, or assembly. Various solvents, including petroleum
distillates, chlorinated hydrocarbons, ketones, and alcohols are used either
alone or together in degreasing operations. Fifteen percent (35,060 Mg) of
1983 PCE production volume was used for solvent degreasing. Five major
industry groups used PCE in degreasing operations. These are furniture and
fixtures, fabricated metal products, electric and electronic equipment,
2
transportation equipment, and miscellaneous industries.
5-1
-------
5.2 DECREASING EQUIPMENT
There are three basic types of degreasing machines: cold cleaners, open
top vapor degreasers, and conveyorized degreasers. Cold cleaners are
usually the simplest and least expensive type. They consist of a tank of
solvent with a cover for nonuse periods. More sophisticated cold cleaners
have solvent sumps, spray nozzels, drains, and automatic controls. In the
basic 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, brushing, or spraying. Solvents are
usually used at room temperature, although, in some processes they may be
heated (but not above the boiling point of the solvent).
Open top vapor degreasers similar in configuration to cold cleaners
clean as internally generated solvent vapors condense on relatively cold
parts. They consist of tanks equipped with heating and cooling systems.
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 parts 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 they are
nonflammable and because their heavy vapors can be easily contained within
the machine.
Conveyorized degreasers feature automated conveying systems for
continuous cleaning of parts. Conveyorized degreasers clean by either the
cold solvent process or the vaporized solvent process. 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.
5.3 EMISSIONS FROM DEGREASING OPERATIONS
National emission estimates for degreasing operations were calculated
from 1983 PCE consumption data provided by the HSIA. The consumption data
were used in conjunction with emission factors generated from available
5-2
-------
literature to estimate nationwide emissions. A brief description of the
estimating procedure follows.
Available data indicate that 24 percent of all PCE consumed in degreasing
operations is used in cold cleaning while about 76 percent is used in vapor
degreasing. Previous EPA studies estimated that for every kg of a solvent
used in cold degreasing, 0.43 kg are emitted. The corresponding emission
factors for open top vapor degreasing is 0.78 kg/kg consumed and 0.85 kg/kg
3
consumed for conveyorized degreasing. Assuming that vapor degreasing use
of PCE is divided equally between open top and conveyorized degreasing
processes, a weighted average emission factor of 0.72 kg/kg PCE consumed was
calculated. It was assumed that the remaining 0.28 kg/kg PCE consumed would
be recycled.
4
Based on information from solvent recyclers, it was estimated that
about 75 percent of all recycled solvent from degreasing (0.28 kg/kg PCE
consumed) is recovered and reused. Therefore, total PCE consumption by a
degreaser equals consumption of fresh solvent plus consumption of recycled
solvent. As before, 0.72 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 PCE used in degreasing, 0.92 kg is emitted. Appendix C
presents the details of these material balance calculations.
The total 1983 PCE emissions by each of the five industries using the
chemical in degreasing operations were estimated by applying the 0.92 kg
factor to the 1983 PCE consumption figure. Table 5-1 shows the estimated
PCE emissions from degreasing operations in these industries.
Emissions were also estimated for each State in the U. S. The total
number of employees in each of the five industries was estimated from U. S.
c
Department of Commerce data. The PCE emissions were estimated by assuming
that emissions are proportional to the fraction of employees for a given
industry in each State. For example, consider the emissions in Illinois
from the fabricated products manufacturing industry (SIC 34):
Fabricated products manufacturing consumption of PCE in 1983 =
14,976 Mg.
5-3
-------
TABLE 5-1. 1983 PCE EMISSIONS FROM DECREASING OPERATIONS,
BY INDUSTRY
Industry tmissions
(Mg/yr)
Furniture and Fixtures 170
Fabricated Products 14,000
Electrical and Electronic Equipment 2,500
Transportation Equipment 10,300
Miscellaneous Manufacturing Industries 5,700
TOTAL 33,000
5-4
-------
14,976 Mg x 0.92 Mg emitted
Mg consumed = 13,778 Mg emitted.
The number of employees within the fabricated products
manufacturing industry for Illinois = 119,005.
Total number of employees within the fabricated products
manufacturing industry = 1,497,989.
Illinois emissions = 13,778 x 119,005
1,497,989 = 1,100 Mg
This procedure was followed for each industry identified to use PCE in
degreasing operations. The results are presented for each State in
lable 5-2.
5.4 EMISSIONS CONTROL
Control methods specified in the BID'S for both RACT and NSPS standards
are summarized in Table 5-3. ' These methods include add-on equipment as
well as improved work practices.
Add-on equipment for control of degreaser emissions can be as simple as
adding covers to equipment openings, increasing freeboard area, adding
freeboard chillers, and providing part drainage racks. These 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: keep degreaser covers closed,
fully drain parts prior to removal from degreaser, maintain moderate
conveyor speeds, and keep ventilation rates moderate.
5.5 REGULATORY REQUIREMENTS
The 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 PCE from solvent
degreasing, California; Connecticut; Illinois; Indiana; Michigan; New York;
New Jersey; Ohio; Pennsylvania; and Texas, have all adopted EPA-approved
RACT. These 10 States account for about 61 percent of total degreasing
emissions of PCE. In addition, EPA has proposed (but not promulgated) an
NSPS that would control emissions from new solvent degreasers.
5-5
-------
TABLE 5-2. 1983 PERCHLOROETHYLENE EMISSIONS FROM DECREASING OPERATIONS,
BY STATE
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
District of Columbia
Florida
Georgia
Hawa i i
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Emissions
(Mg)
447.5
1.9
286.4
263.1
4086.0
327.2
1184.1
64.8
5.1
772.9
575.9
20.6
22.5
1953.2
1148.3
323.6
399.1
353.4
388.1
120.3
293.3
1039.0
2553.9
488.1
336.6
840.1
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)
9.8
117.7
46.6
124.9
1058.7
42.0
2090.9
614.4
16.2
2405.8
376.2
227.6
1734.4
143.3
539.1
258.1
19.1
639.4
1786.0
170.8
80.3
497.9
706.0
88.9
824.0
2.7
32,915.8
5-6
-------
TABLE 5-3. CONTROL TECHNIQUES FOR DEGREASERS
Degreaser Type Control Devices Operating Practices
Cold Cleaners Cover for tank Keep cover closed when
Parts drainage rack degreaser not in use
Raised freeboard Fully drain cleaned
Incinerator parts
Carbon adsorber
Vapor Degreasers Cover for tank , Keep cover closed when
Freeboard chiller degreaser not in use
Raised freeboard Fully drain cleaned
Incinerator parts
Carbon adsorber Move parts slowly into
and out of degreaser
Conveyorized Port Covers Maintain conveyor at
Degreasers Freeboard chillers moderate speed
Carbon adsorbers Keep exhaust ventilation
rates moderate
aFreeboard is the distance from the liquid solvent surface or top of the
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.
5-7
-------
5.6 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. March 1, 1985. HSIA data on perch!oroethylene
production and consumption.
3. 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.
4. Telecon. Pandullo, R.F., Radian Corporation, with Pokorng, J.,
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. 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 p.
5-8
-------
6.0 DISTRIBUTION FACILITIES
Approximately 25 to 30 percent of total PCE production sold is used in
the production of CFC's. Generally, sales of PCE to CFC producers are made
directly. The remaining 70 to 75 percent of PCE is used in applications such
as dry cleaning and solvent degreasing at numerous facilities across the
country. Most of the PCE production in these applications reach the
consumers through chemical distributors. There are an estimated 300 chemical
distributors handling chlorinated solvents. Table 6-1 presents the three
largest PCE distributors. These distributors represent approximately
20 percent of total PCE 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 estimate places the number of regional
2
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. The exact number of
distributors and distribution facilities that handle PCE is not known,
however, it is estimated that there are 270 PCE 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 D.
6.1 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.
6-1
-------
TABLE 6-1. SUMMARY OF MAJOR PERCHLOROETHYLENE DISTRIBUTORS
Company
Number of
Storage
Facilities
Number of PCE
Storage
Tanks
Typical
Size
(gal)
Typical
Turnover
Ashland
1
61
37
8,000
3 wks - 1 mo
McKesson
63
10,000
N/A
Chem-Central'
31
10
10,000
1 mo
6-2
-------
Storage and handling emissions of PCE from distribution facilities were
estimated using AP-42 emission factors and data supplied by the major
distributors. The details of those calculations are presented in Appendix D.
It is estimated that approximately 50 Mg of PCE were emitted in 1983 from
distribution facilities. Storage emissions accounted for 27 Mg, while
handling emissions were about 23 Mg.
6.2 REGULATORY REQUIREMENTS
There are currently no State or Federal regulations affecting PCE
distribution facilities. Most States have regulations for storage and
handling of volatile organic liquids, however, PCE is exempted from these
regulations due to its low vapor pressure. The vapor pressure cutoff for
most State regulations is 1.5 psia under actual storage conditions. The
vapor pressure for PCE is 0.3 psia.
6-3
-------
6.3 REFERENCES
1. Telecon. Sterett, R., Ashland Chemical Company, with Howie, R. H.,
Radian Corporation. February 7, 1985. Conversation on storage of
chlorinated solvents.
2. Telecon. Eisner, D., McKesson Chemical Company, with Howie, R. H.,
Radian Corporation. February 7, 1985. Conversation concerning storage
of chlorinated solvents.
3. Telecon. Trice, L., Chem-Central, with Howie, R. H., Radian
Corporation. February 8, 1985. Conversation concerning storage of
chlorinated solvents.
4. U. S. Environmental Protection Agency. Compilation of Air Pollutant
Emission Factors. Supplement 7. Research Triangle Park, North
Carolina. Publication No. AP-42. August 1977.
6-4
-------
7.0 MISCELLANEOUS USES OF PERCHLOROETHYLENE
Approximately 21,000 Mg of PCE were used in miscellaneous applications
in 1983. These miscellaneous uses include the manufacture of: (1) adhesives,
1 2
(2) aerosols, (3) paints and coatings; and (4) grain fumigant. ' In its use
in the manufacture of adhesives and paints and coatings, PCE acts as a
general solvent carrier. In the production of aerosols PCE has been used as
a solvent and a carrier. Another use of PCE has been as a grain fumigant,
2 5
however, one source indicates that it is no longer approved for this use. '
7.1 EMISSION ESTIMATES
Table 7-1 summarizes the 1983 consumption and emissions of PCE from
miscellaneous uses. It is assumed that 100 percent of PCE used in these
applications is emitted to the atmosphere. The known miscellaneous uses are
in consumer products that result in eventual emissions of PCE. The remaining
unidentified uses are assumed to be in similar consumer applications.
Geographically, these emissions can be expected to correlate with the general
population in the country.
7-1
-------
TABLE 7-1. MISCELLANEOUS USES OF PERCHLOROETHYLENE IN 19831
Use Consumption/Emissions (Mg/yr)
Adhesives 2,800
Aerosols 2,500
Paints & Coatings 1,700
Unidentified 13,700
Total 20,700
7-2
-------
7.2 REFERENCES
1. Letter from Morgan, D. L., Cleary, Gottlieb, Steen, and Hamilton, to
Rosensteel, R. E., EPA. March 1, 1985. HSIA data on perch!oroethylene
production and consumption.
2. Packer, K. (ed.). Nonogen Index - A Dictionary of Pesticides and
Chemical Pollutants. Freedom, California. Nanogens International.
December 1980. p. 97.
3. Chemical Products Synopsis. Cortland, New York. Mannsville Chemical
Products. March 1984.
4. Telecon. Alexander, M., Radian Corporation, with Dr. Hill, Chemical
Specialty Manufacturers Association. April 30, 1985. Uses of PCE in
aerosol production.
5. Meister, R. T., et al (eds.). Farm Chemicals Handbook. Willoughby,
Ohio. Meister Publishing Company. 1984. p. C-223.
7-3
-------
8.0 PUBLICLY OWNED TREATMENT WORKS
8.1 EMISSION ESTIMATES
Recent EPA studies have estimated emissions of PCE from POTWs. The
source of these emissions is considered to be industrial discharges of waste
streams containing PCE. The studies have estimated that about 2,000 Mg of
PCE are emitted annually from POTWs. These emission estimates were presented
for about 900 counties. Table 8-1 presents the emissions for the 10 highest
PCE emitting counties. These 10 counties account for about 35 percent of
total PCE emissions from POTWs.
TABLE 8-1. PCE EMISSION ESTIMATES FROM POTWs IN THE 10 HIGHEST-
EMITTING COUNTIES
County Emissions (Mg)
Wayne, Michigan 230.3
St. Louis City, Missouri 74.9
Los Angeles, California 73.8
Cook, Illinois 67.8
Queens, New York 65.9
Harris, Texas 49.1
Jefferson, Texas 41.1
Hamilton, Tennessee 33.8
Erie, New York 30.5
Hampden, Massachusetts 30.2
Total 697.4
8-1
-------
8.2 REFERENCES
1. Memorandum and attachments from Lahre, T., EPA:AMTB, to
Southerland, J. H., EPA:AMTB. December 5, 1983. Initial look at
available emissions data on POTWs.
8-2
-------
APPENDIX A
METHODS USED FOR ESTIMATING STORAGE TANK
AND FUGITIVE EMISSIONS
-------
APPENDIX A: METHODS USED FOR ESTIMATING STORAGE TANKS AND FUGITIVE 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:
LT = LB + LW
t LD = 1.02 x 10'5 M ( P ) °'68 D1-73H0.51T0.5F C|<
8 V 14.7-P P C
Lw = 1.09 x 10"8 MvPVNKnKc
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 PCE 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 PCE,M =
v 165.82 v
P = true vapor pressure of product, 0.3 psia
D = tank diameter (ft); dependent upon plant-specific information.
C = tank diameter factor (dimensionless):
for diameter > 30 feet, C = 1
for diameter < 30 feet, C = 0.0771 D - 0.0013(D)2 - 0.1334
A-l
-------
V = tank capacity (gal); dependent upon plant-specific information
N = number of turnovers per year (dimensionless); dependent upon
plant-specific information
T = average diurnal temperature change in °F; 20°F was assumed
for the storage tanks at these facilities
F = paint factor (dimensionless); the storage tanks were assumed
p to be in good condition and painted white; therefore, F = 1
(see Table A-l) p
TABLE A-l. PAINT FACTORS FOR FIXED-ROOF TANKS
Tank Color
Paint factors (F )
Paint condition
Roof
Shell
Good
Poor
White
Aluminum (specular)
White
Aluminum (specular)
White
Aluminum (diffuse)
White
Light gray
Medium gray
White 1.00 1.15
White 1.04 1.18
Aluminum (specular) 1.16 1.24
Aluminum (specular) 1.20 1.29
Aluminum (diffuse) 1.30 1.38
Aluminum (diffuse) 1.39 1.46
Gray 1.30 1.38
Light gray 1.33 1.44
Medium gray 1.40 1.58
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, K = 180 + N
6N
for turnovers ^ 36, K = 1
A-2
-------
A. 1.3 Sample Calculation
The following sample calculation is provided to demonstrate the
evaluation of emissions from a typical fixed-roof storage tank containing
PCE. For the general equations,
LT = Lw + LB
LD = 1.02 x 10'5 M ( p)°-68 D L73 H °'51 T °'5 F CKr
B V 14.7-P P C
LW = 1.09 x 10"8 My PVNKnKc
where, My = 165.82
P = 0.3 psia
D = 37 ft
C = 1
V = 233,000 gallons
N = 10
T = 20°F
Fp - 1.0
H = 14 ft
Kc = 1.0
The emissions from this storage tank are:
LR = 1.02 x 10'5 (165.82)( 0.3 )°'68 (37)1'73(14)°-51(20)0- 5(1) (1) (1)
14.7-0.3
= 1.075 Mg/yr
L, = 1.09 x 10"8 (165.82)(0.3)(233,000)(10)(1)(1)
w
= 1.263 Mg/yr
LT = 1.075 Mg/yr + 1.263 Mg/yr = 2.34 Mg/yr
A-3
-------
A.2 EMISSION FACTORS FOR INTERNAL FLOATING ROOF TANKS
A.2.1 Emission Equations
Emissions from internal floating roof tanks can be estimated from the
following equations: (Note that these equations apply only to freely vented
internal floating roof tanks.)
LT = Lw + Lr + Lf + Ld
where, Lj = the total loss (Mg/yr)
L = the working loss (Mg/yr) (0.943) Q C W, N,. F,.
W D [1 + ( ~eD~e" )/2205
where, D = tank diameter (ft)
N = number of columns (dimensionless)
Lr
F = effective column diameter (ft); 1.0 assumed
Lr = the rim seal loss (Mg/yr) = (KrD) P* MV Kc/2205
Lf = the fitting loss (Mg/yr) = (Ff) P* MV Kc/2205
Ld = the deck seam loss (Mg/yr) = (Fd Krf 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
C = product withdrawal clingage factor (bbl/103ft2); use
0.0015 bbl/103ft2 for VOL in a welded steel tank with light
rust (0.0075 for dense rust)
WL = density of product (lb/gal); for PCE, 13.5 Ib/gal
D = tank diameter (ft)
N,, = number of columns (dimensionless); (see Table A-2)
A-4
-------
TABLE A-2. TYPICAL NUMBER OF COLUMNS AS A
FUNCTION OF TANK DIAMETERS
Tank Diameter Range Typical Number
D (ft) Columns, N,
0 < D < 85
85 < D < 100
100 < D < 120
120 < D < 135
135 < D < 150
150 < D < 170
170 < D < 190
190 < D < 220
220 < D < 235
235 < D < 270
270 < D < 275
275 < D < 290
290 < D < 330
330 < D < 360
360 < D < 400
1
6
7
8
9
16
19
22
31
37
43
49
61
71
81
A-5
-------
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
v (Ib/lb mole). For PCE, My = 165.82
KC = the product factor (dimensionless) = 1.0 for VOL
2205 = constant (Ib/Mg)
P = the vapor pressure function (dimensionless)
P* = 0.68 P/((l + 1 - 0.068 P)°'5)2)
P = the true vapor pressure of the material stored (0.3 psia
for PCE)
K = the rim seal loss factor (Ib mole/ft yr) that for an average
fitting seal is as follows:
Seal system description Kr (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)
=1 (Nf Kf ) = [(Nf Kf ) + (Nf Kf )+...+ (Nf Kf )]
i = l Ti ri Tl Tl T2 T2 n Tn
where, N- = number of fittings of a particular type
i (dimensionless). Nf is determined for the
i
specific tank or estimated from Tables A-2 and A-3.
The values used for these emissions estimates are
designated by *.
Kf = deck fitting loss factor for a particular type
i fitting (Ib mole/yr). K. is determined for each
fitting type from Table A-3. The values used for
these emissions estimates are designated by *.
A-6
-------
Table A-3. SUMMARY OF DECK FITTING LOSS FACTORS (K ) AND
TYPICAL NUMBER OF FITTINGS (Nf)
1.
2.
3.
4.
5.
6.
7.
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 cover,
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
Deck fitting loss Typical number
factor, Kf of fittings,
(Ibmole/yr) (Nf)
1
1.6
11 *
25
1
5.1
15 *
28
(see Table A-2)
33
47
10
19 *
32
1
56 *
76
-------
SOURCE: 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.
A-8
-------
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-9
-------
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 PCE. For the general equations,
LT = Lw H- Lr + Lf + Ld
Lw = (0.94g)QCWL [ 1 + ^c/c /2205]
Lr = (KpD) P* Mv Kc/2205
Lf = (Ff) P* Mv Kc/2205
LD = (FdKdD*) P* My Kc/2205
where, My = 165.82 Ib/lb mole
P* = 0.0515
Q = 500,000 bbl/yr
C = 0.0015
WL = 13.5 Ib/gal
D = 30 ft
F_ = 1.0
\f
Kr = 6.7 Ib mole/ft yr
KC = i.o
Ff = 242 Ib mole yr
Fd = 0.20
Kd = 0
The emissions from this storage tank are:
Lw = (0.943) (500, OOP) (0.0015) (13. 5)
so [i + /22Q5]
= 0.149 Mg/yr
A-10
-------
Lr = ((6.7)(30))(0.0515)(165.82)(1.0)72205
= 0.778 Mg/yr
Lf = (242)(0.0515)(165.82)(1.0)/2205
= 0.937 Mg/yr
LD = ((0.020)(0)(30)2)(0.0515)(165.82)(1.0)72205
= 0 Mg/yr
LT = 0.149 Mg/yr + 0.778 Mg/yr + 0.937 Mg/yr
LT = 1.86 Mg/yr
EM' -SIGNS - SAMPLC CALCULATIONS
Fugitive emissions were estimated from the number of equipment leak
sources (provided by the plant), the percentage of PCE in the stream (provided
by the plant),_and the emission factors for each type of equipment (from the
SOCMI AID). ihe following sample calculations illustrate the procedure.
Source
Pump seals
Compressors
Flanges
Number
3
6
2
12
X
X
X
X
PCE
Service
7.5
50.5
87.5
100.0
X
X
X
X
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
X
X
X
X
X
X
kg/hr/source .
Emission Factorc
0.0494
0.0494
0.0494
0.0494
0.228
0.00083
0.00083
0.00083
0.00083
0.00083
0.00083
ota" Emissions
kg/hr
0.011
0.150
0.086
0.593
0.200
0.0002
0.007
0.004
0.099
0.048
0.378
A-ll
-------
Valves (gas)
Valves (liquid)
Pressure Relief
Devices
Sampling
Connections
Open Ended Lines
4
8
3
4
11
5
3
8
9
2
4
6
5
3
1
3
x
x
X
X
X
X
X
X
X
5.0
7.5
50.5
87.5
100.0
x 5.0
x 7.5
x 87.5
x 100.0
x 5.0
x 50.5
x 100.0
5.0
50,
87,
100.0
x 100.0
x
x
X
X
X
X
X
X
X
X
X
X
X
X
X
X
0.0056
0.0056
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
Annual Emissions = 2.72 kg/hr x 8760 hrs x Mg
= 23.87 Mg
year 1,000 kg
0.001
0.003
0.008
0.020
0.062
0.002
0.002
0.050
0.064
0.01
0.21
0.63
0.004
0.023
0.013
0.045
0.002
2.7252
U. S. Environmental Protection Agency. Fugitive Emission Sources of Organic
Compounds - Additional Information on Emissions, Emission Reductions, and
Costs. Research Triangle Park, NC. Publication No. EPA-450/3-82-010.
April 1982.
A-12
-------
APPENDIX B
SUMMARY OF EXISTING STATE AND FEDERAL REGULATIONS
AFFECTING PERCHLOROETHYLENE EMISSION SOURCES
-------
B.I EXISTING STATE REGULATIONS
B.I.I Introduction
PCE emissions originate at various industrial and commercial sources.
These sources include producers of PCE, sources that use PCE either as a dry
cleaning solvent, a degreasing solvent, or a chemical intermediate, and
sources that store PCE. These emissions can be characterized as either
process, process fugitive, or product storage tank emissions.
There are a number of different regulations at the State level that
limit PCE emissions. PCE emissions in nonattainment areas (areas that have
not achieved the ambient air quality standards for ozone) are normally
controlled by the States' RACT program. PCE emissions in areas designated
as attainment or unclassified for ozone are controlled by Prevention of
Significant Deterioration (PSD) regulations. In addition to the RACT and
PSD programs, 12 States (including the District of Columbia) have general
VOC regulations that limit emissions of photochemically reactive compounds.
B.I.2 General State VOC Regulations for Solvent Use
Table 8-1 presents a list of the States that have adopted a general VOC
solvent usage regulation and the emission limits established by each State.
These regulations affect volatile organic solvents found to be photochemically
reactive and usually require 85 percent reduction in VOC emissions. Sources
emitting PCE are currently covered by these regulations.
B.I.3 State RACT Regulations Affecting Perchloroethylene-Emitting Sources
Control Techniques Guideline Documents (CTG) have been issued by EPA
for the following PCE emission sources: (1) PCE dry-cleaners; (2) solvent
metal cleaners; and (3) SOCMI fugitive emissions. These documents establish
RACT guidelines to be used by State agencies in the development of SIP's.
Table B-2 presents a summarization of the State RACT regulations for each
source category that may emit PCE. While RACT is normally adopted only for
nonattainment zones, some States adopt it statewide. RACT has been adopted
statewide in Alabama; California; Connecticut; Washington, D. C.; Georgia;
Louisiana; Massachusetts; New Hampshire; New Jersey; Ohio; Rhode Island; and
South Carolina.
B-l
-------
TABLE B-l. GENERAL STATE VOC REGULATIONS FOR PHOTOCHEMICAL SOLVENTS
State Emission Reduction (%)
California 85
Colorado 85
Connecticut 85
District of Columbia 85
Illinois 85
Indiana 85
Louisiana 90
Maryland 851
North Carolina 85
North Dakota 85
Rhode Island 852
Virginia 85
Applies to sources in nonattainment areas only
2
Applies to sources emitting less than 100 tons/year, larger sources must
comply with RACT
B-2
-------
TABLE B-2. STATE RACT REGULATIONS FOR PERCHLOROETHYLENE EMISSIONS
Source Category
State
RACT Provisions
Solvent Metal Cleaning
Perch!oroethylene
Dry Cleaning
SOCMI Fugitive
Emissions
VOL Storage
CT, IN, LA, NV,
NH
AL, AZ,
DE, DC,
IL, KY,
MI, MO,
NC, OH,
RI, SC,
UT, VA,
CA, CO,
FL, GA,
MD, MA,
NO, NY,
OR, PA
TN, TX,
WA, MI
AK, AR, HI, ID,
IA, KS, ME, MN,
MS, MT, NE, NM,
ND, OK, SD, VT,
WV, WY
CA, CO, CT, DE,
FL, IL, IN, KY,
LA, MD, MA, MI,
MO, NJ, NC, OH,
OR, PA, TN, TX,
UT, VA, WA
NY
AL, AK, AZ, AR
DC, GA, HI, ID
IA, KS, ME, MN
MS, MT, NE, NV
NH, NM, ND, OK
RI, SC, SD, VT
WV, WI, WY
50% Reduction
45% Reduction
25% Reduction
65% Reduction
60% Reduction
60% Reduction
Cold Cleaners
Open Top Vapor Degreasers
Conveyorized Degreasers
Cold Cleaners
Open Top Vapor Degreasers
Conveyorized Degreasers
Have not adoped RACT regulations for
solvent metal cleaning
<100 ppm - dryer
Filter Residue <25 IDS solvent
Still Residue <60 Ibs liquid waste
Filters drained in housing
24 hours or longer
Pending
No Regulation
CTG Issued, No Regulations Adopted by
States
No CTG Issued
1
Percent reduction for solvent metal cleaning is estimated, CTG specifies equipment/work
practice as RACT.
B-3
-------
Emissions of PCE also originate at storage tanks. A CTG for storage of
volatile organic liquids is currently under development by EPA but has not
been issued.
B.I.4 Prevention of Significant Deterioration Regulations
PSD regulations control VOC emissions from major sources in areas
classified as attainment for ozone. Under PSD regulations, a source must
seek a PSD permit if it is: (1) a new source with emissions or potential
emissions considered major; (2) a major increase in emissions or potential
emissions at an existing minor source; or (3) a significant increase in
emissions or potential emissions 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. Table B-3 presents the
emission levels that determine PSD applicability.
B.I.5 State Regulations Affecting Chemical Production
In addition to the general discussion of State regulations concerning
PCE emission sources, a more indepth review was performed for States in
which PCE production facilities are located. These findings are presented
in Table B-4. While PCE emissions are not controlled under these regulations
due to the 1.5 psia vapor pressure cutoff, other VOC emissions at these
facilities may be.
B.2 EXISTING FEDERAL REGULATIONS
Several VOC NSPS and a NESHAP have been developed that could affect new
and some existing sources of PCE emissions. A summary and the current
status of each of these standards are presented in Table B-5.
B-4
-------
TABLE B-3. PSD APPLICABILITY FOR PERCHLOROETHYLENE EMISSIONS
(TONS/YEAR)
Source Category
Chemical Production Plants
Dry-Cleaning Facilities
Solvent Degreasing Facilities
New Major
Source
Emissions
100
250
250
Minor Source
Emission Increase
By Modification
100
250
250
Major Source
Emission Increase
By Modification
40
40
40
B-5
-------
TABLE B-4. STATE REGULATIONS AFFECTING CHEMICAL
PRODUCTION FACILITIES
State
Source
Regulation
California
Storage tanks >260 gal
^40,000 gal; Vapor pressure
>1.5 psia _<11.0 psia
Storage tanks >40,000
Process vessel depressur-
ization (precursor organic
compound emissions)
Valves & flanges (precursor
organic compound leaks
exceeding 10,000 ppm above
background and >_1.5 psia
vapor pressure)
Submerged fill pipe or
equivalent vapor loss control
device
- Pressure tank or
- Floating roof with primary
& secondary seals
- Internal floating roof
with primary & secondary
seals
- Vapor Recovery System with
95 percent recovery
After passing though knock-
out pot to remove the conden-
sable fraction, the organic
compounds must either be:
- Recovered & combusted
- Incinerated
- Flared
- Contained & treated
Non-essential valves or
flanges repair within
15 days
Essential valves or flanges
minimize within 15 days
Kansas
Louisiana
No regulations for control of
VOC emissions from chemical
production facilities
Storage tanks >40,000 gal
Vapor pressure _<11.0 psia
and >_1.5 psia.
- Pressure tank or
- An internal floating roof
with a closure seal & sub-
merged fill pipe
- An external floating roof
with secondary seal and
submerged fill pipe
- A vapor loss control
system & submerged fill
pipe
B-6
-------
TABLE B-4. (Continued)
State
Source
Regulation
Louisiana (cont.)
Storage tanks >250 gal
_<40,000 gal
VOC loading facilities
servicing tanks, trucks or
trailers having a capacity of
>200 gal & throughput
>20,000 gal/day (40,000 gal/
cfay for existing facilities)
Submerged fill pipe with
vapor recovery system
Vapor collection & disposal
system
Pumps, compressors, valves,
etc. (>1.5 psia vapor pressure
compounds)
Waste gas disposal containing
organic compounds from any
emission source including
process unit upsets, start-ups
and shutdowns.
Facility emitting >1.4 kq/hr
or 6.8 kg/day of VOC as solvent
Equipped with mechanical
seals & maintained to
prevent leaks
Halogenated hydrocarbons
shall be burned & the
products of combustion
subsequently controlled.
Other methods such as carbon
adsorption, refrigeration,
catalytic/thermal reaction
can be substituted. Pro-
visions may be waived if gas
stream <100 T/yr, will not
support combustion without
auxiliary fuel, or control
will cause economic hardship
- Must reduce emissions
either by incineration
(90% removal efficiency)
or by carbon adsorption
system. During process
upsets, start-ups, or shut
downs, VOC emissions must
be vented and reduced
either by an afterburner,
carbon adsorption system,
refrigeration, catalytic
and/or thermal reduction,
secondary steam stripping,
or vapor recovery system.
B-7
-------
TABLE B-4. (Continued)
State
Source
Regulation
Michigan'
Texas
Storage tanks >40,000 gal
true vapor pressure >1.5
<11.0 (existing sources)
Storage of organic compounds
having a true vapor pressure
>ll psia in existing vessels
of >40,000 gallons
VOC loading facilities
handling _>5,000,000 gal/year
of >1.5 psia VOC
Storage tanks vapor
pressure ^1.5 psia, <11 psia
<1000 gal
>1000 gal <25,000 gal
>25,000 gaT >42,000 gal
VOC loading and unloading
facilities with >20,000 gal/
day throughput of" ^1.5 psia
VOC
Vent gas control (>0.4 psia
vapor pressure)
Pressure tank or
Floating cover with closure
seal or seals
Vapor recovery system
capable of 90 percent
recovery
Pressure tank capable of
maintaining working press-
ures sufficient to prevent
organic vapor or gas loss
to atmosphere
Vapor recovery system
which recovers >90% by
weight of uncontrolled
organic vapor
All openings shall be
equipped with covers,
lids, or seals
Submerged fill pipes in
ozone attainment areas
- None
- Submerged fill pipe
- Internal or external
floating roof with primary
& secondary seal, or vapor
recovery system
Vapor recovery system
Flared or incinerated at
1300°F
B-8
-------
TABLE B-4. (Concluded)
State
Source
Regulation
Texas (cont.)
SOCMI Fugitive VOC
(Harris County)
Storage tanks containing
vinyl chloride
No compound shall be allowed
to leak with a VOC concentra-
tion >10,000 ppm (time
limits given
Concentration of exhaust
gases discharged to the
atmosphere from storage
tanks must not exceed 10 ppm
(NESHAP - Vinyl Chloride)
1
Bay Area Air Quality Management District Rules and Regulations. San Francisco, CA.
?
"Environment Reporter, State Air Laws. Washington, D.C. Bureau of National Affairs.
B-9
-------
TABLE B-5. SUMMARY OF FEDERAL REGULATIONS AFFECTING PERCHLOROETHYLENE
EMITTING SOURCES
Source
Proposed
Promulgated
Degreasers (Organic
Solvent Cleaners) NSPS
SOCMI Equipment Leaks
(Fugitive) NSPS
VOL Storage Vessels NSPS
SOCMI Air Oxidation NSPS
SOCMI Distillation
Operations NSPS
SOCMI Reactor Processes
NSPS
Vinyl Chloride
Manufacturing NESHAP
06/11/80
(applicability
date deferred)
01/05/81
10/84
10/21/83
12/30/83
04/85
12/24/75
10/18/83
10/21/76
B-10
-------
APPENDIX C
MATERIAL BALANCE FOR PCE EMISSIONS FROM
DECREASING OPERATIONS
-------
APPENDIX C: MATERIAL BALANCE FOR PCE EMISSIONS FROM DECREASING OPERATIONS
C.I MATERIAL BALANCE
(1) - Fraction of degreasing use of PCE in cold cleaning = 0.24
Fraction of degreasing use of PCE in vapor degreasing = 0.76
- 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 vapor degreasing is divided equally between open top and
conveyorized vapor degreasing, a weighted average emission factor is
calculated as follows:
(0.24)(0.43) + (0.38X0.78) + (0.38)(0.85) = 0.72 kg/kg used
(2) - For every kg of fresh PCE used, 0.72 kg is emitted. Assume all of
the remaining 0.28 kg is sent to solvent recovery.
- Estimate that 75 percent of all solvent sent to recovery is
recycled.
- Calculate emissions as follows:
0.72 kg
(emissions from
fresh PCE)
1 kg
(Fresh PCE)
0.72x
(Emissions from use of
recycled PCE)
x kg
(recycled PCE)
0.28
(to solvent
recovery)
0.28x
(to solvent
recovery)
C-l
-------
x = 0.75 (0.28 + 0.28x)
x = 0.27 (Amount of recycled PCE used per kg of fresh PCE used)
0.72x = 0.20 (Amount of recycled PCE emitted per kg of fresh PCE used)
Total PCE emitted per kg of fresh PCE used = 0.72 + 0.20
= 0.92 kg
C-2
-------
APPENDIX D
PERCHLOROETHYLENE EMISSIONS FROM DISTRIBUTION FACILITIES
-------
D-l PERCHLOROETHYLENE EMISSIONS FROM DISTRIBUTION FACILITIES
/
1) Estimate the quantity going through distribution (storage)
1983 production = 509 MMlbs
Assume 70 percent goes through distribution channels
(509 MM1bs)(0.70) = 356 MMlbs
2) Estimate the number of storage tanks' nationwide
o Assume the average tank size is 8,000 gallons
o Assume the average turnover time is 1 month
Number of tanks = 356 MMlbs gal \ / 1 tank \
x 12 j " 27°tanks
3} Estimate storage emissions (fixed roof tanks)
BreathingLoss
LB = 1.02 x 10-5 My /P_\0.68 D1.73 H0.51 T0.5 Fp ^
\i4.7-py
LB = 1.02 X 10"5 (166)/ 0.5 \0>68 (10)1'73 (7)0'51 (1.15)(0.5)(1.0)
,14.7-0.5,
LB = 0.014 Mg/yr
Working Loss
Lu = 1.09 x 10"8 MuPVNKnKr
wi v n c
Lw = 1.09 X 10"8 (166)(0.5)(8,000)(12)(1)(1)
Lw = 0.087 Mg/yr
Total Loss
LT = LB + LW = 0.10 Mg/yr per tank
Total nationwide storage emissions = (0.10)(270) = 27 Mg/yr
D-l
-------
where: M = molecular weight of product vapor (lb/lb mole)
Pv = true vapor pressure of product (psia)
D = tank diameter (ft)
H = average vapor space height (ft)
T = average diurnal temperature change (°F)
Fp = 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 - 0.0130^ - 0.1234
K = product factor (dimensionless) =1.0 for VOL
V = tank capacity (gal)
K = turnover factor (dimesionless):
n for turnovers > 36, Kn = 180 + N
for turnovers £ 36, «n = 1
4) Estimate container filling emissions
LoadingLoss
L, = 12.46 S T P
L 5
where: S = Saturation factor (0.50 for submerged fill and 1.45 for
splash fill)
P = True vapor pressure, psia
M = Molecular weight
T = Temperature, °R
Assume 50 percent splash filling (S s 1.0)
= 1.95 lb/103 gal
530
= 0.89 lb/103 gal
356 MMlb gal 0.89
D-2
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 4507/3-85-017
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Survey of Perch!oroethylene Emission Sources
5. REPORT DATE
June 1985
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
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 27711
1O. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA Contract 68-02-3816
12. SPONSORING AGENCY NAME AND ADDRESS
DAA for Air Quality Planning and Standards
Office of Air and Radiation
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/200/04
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The potential health impact of perch!oroethylene emissions is being investigated.
This document contains information on the sources of perchloroethylene emissions,
current emission levels, and State regulations applicable to the emission sources,
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Pollution Control
Synthetic Organic Chemical Manufacturing
Industry
Perchloroethylene
Tetrachloroethylene
Air Pollution Control
13B
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Unlimited
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Unclassified
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