-------
The manufacture of EHEC involves the treatment of a'lkalai cellulose
with ethyl chloride and ethylene oxide, and js produced by the same
process as the previously mentioned ethylation procedures. They find
application as additives in silkscreen and gravure inks. They are also
used as thickeners in emulsion paints and paint removers, as binders, and
also as pastes (e.g. wallpaper).8
3.3 FOAMED PLASTICS
Foamed plastics, also referred to as cellular plastics or cellular
polymers, have found commercial application since the iy40's. A foamed
plastic is a plastic with an apparent density substantially decreased by
the presence of numerous cells throughout -its mass. The term most often
refers to a two-phase gas-solid system where the continuous solid phase
is a synthetic plastic or rubber and the gas phase is distributed in
voids or pockets referred to as cells. If the cells are discrete and
independent of each other, the material is termed "closed cell." If the
cells are interconnected such that gas may travel from one.to.another, it
is termed "open cell." Rigi.d foams are closed-cell plastics; flexible
foams are open-cell plastics. Common foamed plastics include polyurethane,
cellular rubber, latex foam rubber, polyvinyl chloride, polystyrene and
phenolic resin. Phenolics, polystyrene and polyurethanes are used mainly
for rigid foams while vinyls and linear polyurethanes are used in flexible
foams.14,15
Foamed plastics may be manufactured by a variety of methods and take
forms such as slabs, blocks, boards, beads, sheet, film, molded shapes
and extruded insulation. The most distinctive step is the expansion
of the fluid polymer phase to the low-density cellular state. This step
is known as foaming or expanding. 14,15
3-11
-------
Most thermosetting and thermo-plastic polymers can be foamed
(expanded) by the addition of blowing agents.1^ The selection of these
agents is critical to the formation of the cellular structure and in
imparting the desired and necessary properties to the final product.!6
The agents are mixed with the polymer. They react or volatilize to form
a gaseous phase. The aggregation of these gaseous molecules creates tne
cellular structure.17
Blowing agents can be classified into two groups: physical and
chemical. Physical blowing agents are gases or low boiling liquids that
do not react chemically in the foam blowing process. Examples of these
physical, agents are nitrogen, air, methylene chloride, and ethyl chloride.
These agents are combined with the polymer and released, or volatilized,
by process heat or by heat of polymerization.
Chemical agents generally are finely powdered and easily mixed with
resin for processing. Examples of chemical blowing agents are: hydrazine
derivatives, sodium bicarbonate, isocyanates, and other organic and inorganic
chemicals. These compounds decompose to gases, such as nitrogen, carbon
dioxide, carbon monoxide, ammonia', and others. The released gases then form
the cellular structure. Chemical blowing agents can be used for foam
densities of 2b Ib/cu ft. or higher and, when accompanied by a physical
blowing agent, they can also be used as nucleating agents. Nucleating agents,
such as talc or finely divided fillers, facilitate bubble formation, or
clustering, of the gas molecules.17
3-12
-------
Dow Chemical, U.S.A., uses ethyl chloride and methylene chloride and
CFC-12 as blowing agents in the manufacture of Styrofoam.ฎ Styrofoamฎ is
the brand name of a closed cell, extended polystyrene foam product.
Dow uses ethyl chloride because of its dimensional stability, moisture
resistance, compressive strength, ease of handling, and other good physical
characteristics. Some blowing agent selection criteria are given below:15
1. Any replacement product should have high solubility in
polystyrene at high temperature for acceptable processing.
2. Low solubility in polystyrene at low temperature for high
compressive strength and dimensional stability.
3. Relatively high diffusivity of primary blowing agent through
the polymer for dimensional stability and low diffusivity
of secondary blowing agent for high insulation value.
4. Capability of producing large cells in order to produce
whole product mix with cell size ranging from 0.1 mm to 2.4- mm.
5. Sufficient vapor pressure (or blowing power) to produce
thick products.
6. High latent heat of vaporization for dimensional stability.
7. Low reactivity with formulations.
8. Low toxicity (acute and chronic).
9. Low flammability in the process and the product.
10. Stratospheric ozone acceptability.
11. Cost.
N-pentane is a blowing agent for expandable polystyrene beads.19 The
chloroflurocarbon, CFC-12, is also a blowing agent for extruded polystyrene
foam. These products differ in some ways from the Styrofoamฎ products
but they are considered competitive in some markets.1^
3-13
-------
Due to, the availability of specific information on the use of ethyl
chloride as a blowing agent in the Styrofoamฎ extrusion process, the
focus in this section will be placed on the manufacture of this brand of
extruded polystyrene foam. Currently, Styrofoamฎ is the only polystyrene
foam known to use ethyl chloride as a blowing agent.
There are two major types of expanded polystyrene products: extruded
polystyrene foam and expandable polystyrene beads. The expandable beads
are manufactured by a variety of processes. The beads are used as loose
fill or molded into cups, boards, and other end products.
Extruded polystyrene foam, such as Styrofoamฎ, is used in construction,
packaging, and other end uses. Polystyrene foam is usually manufactured
as boards which are then cut in desired sizes. The board is used as
insulating material in buildings and in cold storage compartments.
Polystyrene foam is also used in insulation board for roofing and as
laminates for sheathing products.*9
The extrusion of styrene polymers is one of the most convenient and
least expensive methods for, fabricating sheet, pipes and film. The
function of the extruder is to plasticate the resin to the proper viscosity
for absorption of the blowing agent, to mix all components, and to cool
the mixture to a temperature that will provide optimum properties for-foam
applications. The type and amount of blowing agent, the extrusion process
conditions, and the cooling and stretching techniques affect density and
other foam properties. "Extruded polystyrene foam planks and boards, with
densities near 29 kg/m^, are often used for low temperature thermal insulation,
buoyancy, floral displays, novelty items, packaging and construction.
Extruded polystyrene sheet 1-7 mm thick, with densities in the range of
64-160 kg/m3, are often used in packaging.17,18
3-14
-------
Three extrusion systems are used to extrude thermoplastic foam: single-screw,
twin-screw, tandem. The single-screw extruders have been used more frequently
with medium to high density foam applications (320-80U kg/m3) where blowing
agents are used. These systems operate under very high pressures, which
are necessary to assure formation of fine, discrete cells. They have been
most widely used in extruding foam profiles for use as wood molding and
trim replacements, although they are becoming more popular for the production
of high density foam sheet. The twin-screw systems are most suited to
medium density foam applications. Lower melt temperatures in the cooling zone
are possible with this system due to a lower input of mechanical work for
mixing the resin and the blowing agent. They operate essentially as positive
displacement pumps and only offer one screw speed for melting, mixing and
cooling.
The tandem or two-extruder system is the most popular extrusion
system in the United States. It offers direct injection of physical blowing
agents and is especially well suited to extrusion of low to medium density
foams. Their principle application is in extruded foam sheet in gages of
0.25 to 3.8 mm wide or. less. The resin and nucleating agent are fed into
the first stage of.the primary extruder and melted. A liquified blowing . -
agent is metered through the barrel into the second stage of the primary
extruder, where it is thoroughly mixed with resin and nucleating agent.
This mixture is pumped into the secondary extruder where it is gently
stirred, cooled, and advanced to the die. As the gaseous polymer melt
exits the die, the pressure falls below the vaporization pressure of the
blowing agent. The vaporization of the blowing agent forms the foam
cells.17,18
3-15
-------
3.4 ANESTHETICS
Ethyl chloride is currently marketed in the U.S. as a topical
anesthetic. It is available in 100 gram unbreakable metal tubes with a
fingertip-control, adjustable valve. It is also available in a light
resistant, 4-oz amber glass bottle with a spring cap. The cap is available
in four calibrations: fine (under 0.005-inch spray width), medium (O.OOb-
to 0.008-inch spray width), coarse (0.008- to 0.011-inch spray width), and
in a mist spray. The ethyl chloride used in this service is approximately
99 percent pure, but may be diluted for bottling. Further information
regarding this use is available from:20
GeBauer Chemical Company
Cleveland, Ohio 44104
(800) 321-9348
3.5 ETHYLBENZENE
It nas been reported that ethyl chloride is used as an ethylating
agent in the production of dyestuffs and specialty chemicals. One such
use is in the Freidel-Crafts alkylation of benzene to ethyl benzene.
Ethyl chloride or hydrogen chloride may be used as an initiator in this
liquid phase, reaction.5,21,22
. Although this use has 'been documented, more specific information on
the extent of its use has not been found in the literature.
3.6 OTHER USES
Some other very limited uses of ethyl chloride include use as a
feedstock in the production of 1,1,1-trichloroethane, as a solvent and
refrigerant, and as an aerosol propellant. Ethyl chloride has been used
for a number of years as the wo.rking fluid at an electric power plant on
the Island of Ischia in the Bay of Naples. A temperature difference of
o
over 30 C exists between the local thermal streams and the surrounding
sea water; ethyl chloride is used to "extract" power from the geothermally
heated water.^ Ethyl chloride was included in the emissions inventory for
a Rhone Poulenc ethyl vanillin facility in Freeport, Texas.^ However, more
extensive or descriptive information on the process was not available.
3-16
-------
3.7 References
1. SRI International, Chemical Economics Handbook, Ethyl Chloride,
CEH Data Summary. SRI International, Menlo Park, CA., February 1988.
p.646.5030A',C,D,F.
2. Federal Register, Vol 50, Mo.45, March 7, 1985 (40 CFR Part 80).
3. SRI International, Chemical Economics Handbook, Gasoline Octane
Improvers. SRI International, Menlo Park, CA., September 1986, p.543.7051
C,0,P.
4. Markets Newsletter, "Ethyl will close more lead antiknock capacity,"
Chemical Week, January 1-8, 1986, p.IB.
5. Mannsville Chemical Products Corporation, Chemical Products Synopsis:
Ethyl Chloride, Cortland, NY, September 1981.
6. Lowenheim, FA, and M K Moran, eds. Faith Keyes, and Clark's Industrial
Chemicals, 4th edition. John Wiley & Sons. New York. 1975. p 502-506.
7. Grayson, M., Ed., Kirk Othmer Encyclopedia of Chemical Technology:
2nd edition, Vol. 14. Interscience, 1981, p.186, 187.
8. Standen, A., ed., Kirk Othmer Encyclopedia of Chemical Technology:
Cellulose Derivatives, 2nd edition, Vol 4, Interscience, 1964. p.638-
642,650.
9. Austin, G.T., ed., Manufacturing Processes: Ethyl Cellulose Plastics,
Shreve's Chemical. Process Industries, McGraw Hill, New York. p.663.
10. Considine, 0. M., ed. Chemical and Process Technology Encyclopedia, .
McGraw-Hill Book Company, New York. 1974. p.427-429.
11. SRI International, Chemical Economics Handbook, Cellulose Ethers,
Menlo Park, CA, March 1977, p.581.5021 C,D, 581.5022 C,D,H,J.
3-17
-------
12. SRI International, Chemical Economics Handbook., Cellulose Ethers.
Menlo Park, CA. December 1984. p. 584.5022 D,I,L,X.
13. Library Search, Ethyl Cellulose, Toxinet Database, U.S. Environmental
Protection Agency, Research Triangle Park, NC.
14.- Kirk-Othmer Encyclopedia of Chemical Technology, 2nd edition,
Volume 9. John Wiley and Sons, New York, p. 847-850.
15. Dertsch, M. and V. Kollonitsch, eds. The Kline Guide to the Plastics
Industry, 2nd edition. Charles H Kline & Co., Fairfield, NJ. p.191.
16. Testimony of Kyung W. Suh of Dow Chemical U.S.A.: Generic Rule,
Illinois Pollution Control Board, Springfield, Illinois,
February 10, 1987.
17. Dean, A.F. and W.S. McCormick, Extruding Thermoplastic Foams, Modern
Plastics Encyclopedia 1978-1979, Vol. 55, p. 288, 289.
18. Kirk Othmer Encyclopedia of Chemical Technology: Styrene Plastics,
3rd Edition, Vol. 21, John Wiley & Sons Interscience, N.Y., N.Y.,
1983. p. 830, 837.
19. SRI International Chemical Economics Handbook, Polystyrene
SRI International, Menlo Park, CA., August 1985, p. 580.1502 L,S.
20. Information on Ethyl Chloride and Use as an Anesthetic, Product
Information Brochure, GeBauer Chemical Company, Cleveland, Ohio.
21. Kirk Othmer Encyclopedia of Chemical Technology: Styrene,
2nd Edition, Vol 19, John Wiley & Sons, Interscience, NY, NY, p.61.
22. Ibid. Vol. 5, p.720.
23. Austin, G.T., "Industrially Significant Organic Chemicals: Part 5,"
Chemical Engineering, April 29, 1974, p.145.
24. Emissions Inventory: Rhone Poulenc (Ethyl Vanillin) Texas Air
Control Board, Austin, TX. September 1986.
3-18
-------
4. INDUSTRIAL PERSPECTIVE
4.1 HISTORICAL TRENDS
Between 1965 and 1975, ethyl chloride production increased at an
average growth rate of 0.5 percent per year. Between 197b and 1979, this
rate averaged 1.61 percent: 16.3 percent from 1975-76, -19.3 percent from
1976-78, 7.82 percent from 1978-79. Refer to Table 4.1-1 for yearly produc-
tion figures. The economic history of ethyl chloride has been
Table 4.1-1 Yearly Ethyl Chloride Production*
Producti
Year
1955
1956
1957
1958
1959
1960
1961
1962
1963
1964
1965
1966
. 1967
1968
1969
on
106 Ibs
541.6
645.5
604.4
535.7
550.8
545.4
496.8
536.8
591.8 '
666.1
685.8
677.0
618.2
573.1
678.8
Producti
Year
1970
1971
1972
1973
1974 '
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986**
1987**
on
106 Ibs
678.0
620.3
575.5
660.1
662.5
575.2
669.2
612.5
539.8
582.0
396.4
324.3
339.2
281.7
290.2
170.5
156.9
164.4 (projected)
*SRI International, Chemical Economics Handbook. Menlo Park, CA.
February 1988. p.646.5030 C
**SRI International, Chemical Economics Handbook, Manual of Current
Indicators. April 1988. p.646.5030 B
4-1
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4.1.1 Imports
Over the past ten years, ethyl chloride imports have been significant
only in 1980, 1981, and 1982. During those years, imported quantities were
3, 11, and 5 million pounds, respectively. Before 1980 and since 1983,
ethyl chloride has been imported either in negligible quantities or not at
all. In 1986, the last year for which import data are available, no ethyl-
chloride was imported into the United States.6
4.1.2 Exports
Domestically produced ethyl chloride is exported in significant
quantities. Mexico has been a major importer of domestic ethyl chloride.
Its use in these cases is primarily in tetraethyl lead manufacture. In
1986, of the 31 million Ibs of ethyl chloride exported, 92 percent was sent
to Mexico for TEL production.5
4.2 OUTLOOK
Only four ethyl chloride production companies are currently operating.
Hercules closed its-.Hopewell, Virginia facility in 1980. Although the
manufacture of TEL has been.the primary end use of ethyl chloride, federal
regulations(40 CFR Part'80) on the allowable lead content in gasoline
continue to decrease the demand for this antiknock additive.
The new regulation has reduced, by approximately 90 percent, the
previously existing regulation of 1.1 grams of lead per leaded gallon
(yplg) to 0.10 gplg. As a result, manufacturers must rely
4-2
-------
upon an overseas market in order to keep TEL production active. However,
members of the European Economic Community (EEC) were required, as of
January 1, 1981, to limit the lead content to 0.4 and 0.15 grams per litre
for premium and regular grade gasoline, respectively.6 Some have voluntarily
reduced to levels below those required. In 1982, Japanese lead levels in
gasoline were 0.3 and 0.0 mi 1M litres per litre premium and regular, respec-
tively. Their TEL consumption peaked in 1969 and has declined 24 percent
annually to a 1981 level of 600 tons (100 percent basis).7 According to
this 1982 source, the Japanese were expected to halt consumption altogether
by 1986.
Domestic ethyl chloride production and consumption continue to decline.
Leaded gasoline currently comprises 40 percent of the gasoline market and
is expected to continue decreasing.5 if TEL foreign markets expand, this
may offset the decline in domestic demand and the parallel decline in ethyl
chloride production.^ The other minor end uses of ethyl chloride, manufacture
of cellulose ethers and some pharmaceutical application, have not seen a
significant increase in activity in the recent past, and no significant
increases in demand are anticipated in the near future.2
4-3
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4.3 REFERENCES
1. Khan, Z.S., T.W. Hughes, Source Assessment: Chlorinated Hydrocarbons
Manufacture, Office of Energy,, Minerals, and Industry, U.S. Environmental
Protection Agency, Research Triangle Park, N.C., EPA-600/2-79-019,
August 1979.
2. Grayson, M., ed., Kirk Othmer Encyclopedia of Chemical Technology:
Ethyl Chloride, 3rd edition, Vol. 5, John Wiley & Sons, Interscience, New York,
N.Y., 1982, p.719.
3. Mannsville Chemical Products Corporation, Chemical Product Synopsis:
Ethyl Chloride, Cortland, N.Y., September 1981.
4. SRI International, Chemical Economics Handbook, Menlo Park, CA, October
1987, p.646.50308
5. SRI International, Chemical Economics Handbook, Menlo Park, CA.
February 1988. p.646.5030 B-E.
6. SRI International, Chemical Economics Handbook, Menlo Park, CA, April
1973, p.646.5030E.
9. SRI, International, Chemical Economics Handbook, Gasoline Octane
Improvers, Menlo Park, CA, June 1982, p.583.0400F.
4-4
-------
b. EMISSIONS
Emissions from identified sources are listed below according to process,
5.1 INDUSTRIAL
5.1.1 Production
5.1.1.1 Hydrochlorination of Ethylene. Emission rates were estimated
for each production site using current data on operations at the Ethyl
Corporation Pasadena, Texas facility as a basis for calculation of emission
factors.1 These rates may be found in Table 5.1-1. These estimates, in
addition to emission parameters, and other site specific information have
been included as input to the Human Exposure Model (HEM), and are provided
in Appendix H. Calculations on ethyl chloride emissions from production
(process, equipment leaks, transportation, storage) are provided in
Appendix C. .'
5.1.1.2 Other Production Processes
Although only two of the ethyl chloride production facilities use
the hydrochlorination process, emission data for the other processes
were not available. The"emission estimates for all processes were based
upon the data for ethylene hydrochlorination2
5-1
-------
Table 5.1-1 Estimated Emissions from Ethyl Chloride Production
Company,
Location
1987
Capacity
- (Gg/yr)
Emission
Type
Estimated
Emissions3'13
(kg/yr)
Dow Chemical
Freeport, TX 4.54
DuPont 45.4
Deepwater, NJ
Ethyl Chloride
Pasadena, TX 72.6
PPG Industries
Lake Charles, LA 56.7
TOTAL
process
process
equipment leaks
proce
process
equipment leaks
process
process
equipment leaks
process
process
equipment leaks
2,180
2,180
29,600
21,800
21,800
29,600
34,800
34,800
29,600
27,200
27,200
29,600
210 Mg/yr
a". Process emissions were assumed to come equally from two vents. Emission,
factor per process vent = 480 kg/Gg capacity.
b. Equipment leaks based on Model A plant, 100 percent ethyl chloride service.
See appendicies for calculations and assumptions.
5-2
-------
5.1.2.1. Tetraethyl Lead (TEL)
The process emissions for the only remaining TEL production facility
were obtained from the permitting records of the State of New Jersey.4
These emissions were given for ethyl chloride emissions from process
units at Du Pont's facility at Deepwater/ Pennsville, New Jersey. The
appendicies D and H list the complete data (including stream characteristics)
which were necessary for dispersion modeling.
The available data did not contain emissions information for equipment
leaks at the Deepwater facility. Equipment leak emissions were calculated
using model plant processes, and average Synthetic Organic Chemical
Manufacturing Industry (SOCMI) values.3'9 The emission rates for the Deepwater
facility are given in Table 5.1-2. The calculations and data for the equipment
leaks can also be found in appendicies C and D.
5-3
-------
Table 5.1-2 Emissions of Ethyl Chloride fromTetraethyl Lead Production3
Du Pont facility located a Deepwater/Pennsville, New Jersey
Latituded 39ฐ 41' 24" N - Longitude3 75ฐ 30' 28" W
Emission IDb
P-25
P-31
P-62
P-63
P-68
P-69
P-71
P-72
P-73
P-74
P-75
P-80
P-81-1
P-81-2
P-81-3
P-87-4
P-88
P-89-1
P-89-2
P-89-3
P-89-4
P-89-5
P-90-1
P-90-2
P-90-3
ELC
TOTAL
Estimated
Emissions
(kg/yr)
54
3,100
211,000
72,000
73
6,100
27
82
27
45
140
140
27
27
27
27
18
2,000
2,000
2,000
2,000
2,000
2,000
2,000
2,000
29.600
339Mg/yr
a. Letter from MP Polakavic, N.J. EPD, to G Hume, OAQPS, EPA. May 25, 1988.
Computer Printout (dated May 24, 1988) for Ethyl Chloride Emissions
from Du Pont's Chamber Works Facility.
,b. P-process emission, EL-equipment leak.
c. U.S. Environmental Protection Agency, Fugitive Emission Sources of Organic
Compounds-Additional Information on Emissions, Emissions Reductions, and
Costs. EPA-450/3-82-010. Research Triangle Park, NC. April 1982. p.1-6,
5-4
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b.1.2.3 Ethylene Pi chloride
Ethyl chloride is a reaction by-product of ethylene dichloride
(EDC) production. The two main processes for EDC production are chlori-
nation of ethylene and oxychlorination of ethylene. These processes can
yield other chlorinated compounds such as 1,1,2-trichloroethane,
perchloroehtylene, pentachloroethane, and others.? Ethyl chloride is a by- .
product of both of these processes. It is probably present due to the
equilibrium position of the EDC reactions at the specific process conditions.
An unusual amount of ethyl chloride emissions data was available due
to recent .data collection and analysis for EDC emissions. Site specific
data was used as much as possible. Detailed dispersion modeling parameters
can be found in the appendicies.
To estimate ethyl chloride emissions from EDC production, a ratio of
ethyl chloride to EDC was developed. This ratio was applied to estimates
of EDC emissions from process vents. This ratio was also applied to
equ-ipment leaks. For some facilities equipment counts for EDC were available.
These were developed into equipment leak estimates by using synthetic
Organic manufacturing industry (SOCMI) average values.3 For facilities
without equipment counts, values for fugitive emissions of EDC were available
and served as the basis for ethyl chloride equipment leak estimates.
Table 5.1-4 lists emission estimates for specific facilities. Specific
calculations and devivations are given in the appendicies.
5-6
-------
5.1.2.2 Ethyl cellulose and Ethylhydroxyethyleellulose. Due to the
lack of available information on domestic production of these cellulose
ethers and the few (2) production facilities in the U.S., process emissions
were not estimated for this source category. However, equipment leak
emission estimates were made using unadjusted, average SOCMI unit emission
factors for the Model A type facility.^ These values, along with the
combined capacity for production, are listed in Table 5.1-3. Calcula-
tions follow in Appendix 8.8.
Table 5.1-3 Ethyl Cellulose: Estimated EtCl Equipment Leak Emissions
Company/
Site
Domestic*
Consumption
(106lbs/yr)
Fugitive Emissions
Estimate (Mg/yr)t
Dow
Midland, Mi.
30
Hercules, Inc.
Hopewe11, Va.
.30
Totals
60 Mg/yr
* Cellulose Ethers, Chemical Economics Handbook, SRI International, Menlo Park,
CA, December 1984, p.581.5022X.
t obtained using SOCMI Model A emission factors
5-5
-------
TABLE 5.1-4 Ethyl Chloride Emissions from EDC Production
Company Name/
Plant Location/
Emission Source
U.S. Industrial.
Chemicals
Port Arthur, TX
process
equipment leaks
BF Goodrich
Calvert City, KY
process
process
equipment leaks
BF Goodrich
LaPorte, TX
process
process
equipment leaks
Borden
Geismar, LA
process
equipment leaks
Diamond Shamrock
Convent, LA
process
equipment leaks
Diamond Shamrock
Pasadena, TX
process
equipment leaks
North Latitude
(deg min s)
29 51 56
37 02 50
29 46 00
30 12 20
30 03 44
29 43 00
West Longitude
(deg min s)
93 59 49
88 19 20
95 05 00
91 01 08
90 49 55
95 07 00
EtCl
emission
rate
(kg/yr)
22
10,700
1,040
1,040
36,900
585
585
36,900
21,000
62,400
22
62,400
21,000
36,900
5-7
-------
TABLE 5.1-4 Ethyl Chloride Emissions from EDC Production (cont.)
Company Name/
Plant Location/
Emission Source
Dow Chemical
Freeport, TX
process
equipment leaks
Dow Chemical
Oyster Creek, TX
process
process
process
equipment leaks
Dow Chemical
Plaquemine I, LA
process
process
equipment leaks
Dow Chemical
Plaquemine II, LA
process
process
equipment leaks
Formosa
Baton Rouge, LA
process
equipment leaks
North Latitude
(deg min s)
28 57 39
28 58 00
30 19 46
30 19 46
30 30 00
West Longitude
(deg min s)
95 19 24
95 21 00
91 14 21
91 14 21
91 11 00
EtC2
emission
rate
(kg/yr)
22
7,850
15,100
15,100
15,100
51,400
430
431
145,000
1985
1985
41,500
18960U
53,300
5-8
-------
TABLE 5.1-4 Ethyl Chloride Emission from EDC Production (cont.)
Company Name/
PI ant Location/
Emission Source
Fo rmos a
Point Comfort, TX
p rocess
process
equipment leaks
Georgi a Gulf
PIaquemi ne, LA
process
process
equipment leaks
01 i n Corporation
Lake Charles, LA
process
equipment leaks
PPG Industries
Lake Charles,. LA
process
process
equipment leaks
Shel 1 Chemical
De er Pa rk, TX
process
process
equipment leaks
Vista
Westlake, LA
process
process
equipment leaks
Vulcan Chemicals
Geismar, LA
process
process
equipment leaks
North Latitude
(deg mi n s )
28 41 04
30 16 30
30 14 00
30 13 27
29 43 04
30 15 04
30 11 30
West Longitude
(deg min s )
96 32 12
. 91 10 30
93 16 00.
93 16 59
95 07 53
93 17 00
90 58 27
EtCl
emission
rate
(kg/yr)
198
199
39,000
5,950
5,950
81,500
22
16,700
3,680
3,680
23,-000
54
54
53,000
10
11
70,400
25
26
19,200
Total
982 Mg/yr
*Latitudes and longitudes are from Table 1. In: Dispersion Modeling Parameters
for Ethylene Di chloride - EDC Case 1 in Memorandum from Marjorie Putnam, Midwest
Research Institute, to Dave Beck, ESD, U.S. EPA, April 23, 1986. Estimates of
Ethylene Di chloride Emissions from Production Facilities and HEM Inputs. References
and other values are specified in Appencix G.
5-9
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5.1.2.4 Polystyrene Foam Blowing
Ethyl chloride has only been used for foam blowing for a few years.
It was chosen subsequent to extensive research for a blowing agent with
the necessary characteristics.^ Only one company is known to use ehtyl
chloride in their polystyrene foam blowing process.1J> This company
operates foam blowing units at six domestic facilities.
Ethyl chloride is a physical blowing agent. It does not react to
form a gas; it vaporizes. Ethyl chloride can be emitted from process
vents, equipment leaks, and during storage of the foam product. The
largest quantities of emissions occur during storage.
Emission estimates for this category were based upon testimony given
to the Illinois Pollution Control Board1^ and conversations with industry
personnel. 1^ป16,17 y\ summary of the emissions is given in table 5.1-5.
Calculation and more background data may be found in the appendicies.
5.2 Other Sources of" Emissions
In addition to those from synthetic organic chemical manufacturing,
ethyl chloride emissions have been detected from non-industrial sources.
It was identified, along with other volatile organic compounds, at a
hazardous waste site in New Jersey.11 Although not a target compound, it
was identified at one site 25-bO percent of the time, by mass spectrometry,
Five locations were tested for VOC: two on-site, one bordering, two away
from the site. One on-site test location contained leachate pools, while
the border location was near a residential area.
5-10
-------
Findings from another investigation show ethyl chloride vapors to
result from the thermal oxidative degradation of coal mine combustion
products.12 Those included in the study were products of PVC and .neoprene
compositions, urethane rigid foams, and creosote (a coal tar distillate)
treated pine.
Although ethyl chloride is available for use as a topical anesthetic
in spray cannisters, data on emissions from this source were not available.
5-11
-------
TABLE 5.1-5 - Ethyl Chloride Emissions from Polystyrene Foam Blowing3
Location'3
City, State
Allyn's Poing/
GalesFerry, CT
Da It on, GAd
Ironton, OH
Ooliet, lie
Pevely/
Riverside, MO
To ranee, CA
Total
Longitude
Latitude
(ฐ ' "N)(ฐ ' "W)
41 26 29/72 04 58
34 46 06/84 57 42
38 31 00/82 40 00
41 31 36/88 04 48
39 10 06/94 36 12
33 51 02/118 19 49
Type ofc
Emission
P
F
S
P
F .
S
P
F
S
P
F
S
P
F
S
P
F
S
Estimated
Ethyl
' Chloride
Emissions
(mg/yr)
50
20
84
70
20
120
70
20
120
71
20
120
110
20
180
' 20 . .
20
36
1170
a. All facilities are owned and operated by Dow Chemical U.S.A.
b. Telecon. Warila, B. Dow Chemical, with Hume, G. EPA, March 29, 1988.
Ethyl Chloride Emissions from Foam Blowing.
c. P - process emission, F - equipment leaks
S = storage emissions
d. The Joliet emission estimates are based upon testimonies by DOW
personnel for the Illinois Pollution Control Board Springfield,
Illinois on February 10, 1987.
5-12
-------
5.3 SHORT-TERM
Although attempts were made to secure such information, data on
short-term emissions were not available at the time of this writing.
Short term emissions are also refered to as acute releases. These
emissions are those which significantly exceed the annual average
for a specific time period, such as one hour.
5-13
-------
5.4 REFERENCES
1. Data from Emissions Inventory, Texas Air Control Board, Austin, Texas,
September 1986.
2. SRI International, Chemical Economics Handbook. Menlo Park, California.
February 1988. p.646.5030 B
3. U.S. Environmental Protection Agency, Fugitive Emission Sources of
Organic Compounds - Additional Information on Emissions, Emission Reductions,
and Costs. EPA - 450/3-82-U10. Research Triangle Park, North Carolina.
April 1982. p.1-6, 2-70.
4. Letter from MP Polakovic, N.J. EPD, to 6 Hume, OAQPS, EPA. May 25,
1988. Computer Printout (dated May 24, 1988) for Ethyl Chloride Emissions
from Du Pont's Chamber Works Facility.
5. Khan, Z.S., T.W. Hughes, Source Assessment: Chlorinated Hydrocarbon
Manufacture, Office of Energy, Minerals and Industry, U. S. Environmental
Protection Agency, Research Triangle Park, NC, August 1979,
EPA 600/2-79-019, p.66.
6. Pervier, J.W., R.C. Bailey, et al., Survey Reports on Atmospheric
Emissions for the Petrochemical Industry: Vol II, Office of Air and Water
Programs, Office of Air Quality Planning and Standards, U. S. Environmental
Protection Agency, Research Triangle Park, N.C. April 1974, EPA-450/3-73-005b',
Table EDC-III.
7. SRI International, Chemical Economics Handbook. Menlo Park, California.
September 1985. p. 651.5032 A.B.
8. Putnam, M., Estimates of Ethylene Dichloride Emissions from
Production facilities and HEM Input, Office of Air Quality Planning and
Standards, U. S. Environmental Protection Agency, Research Triangle Park,
NC, April 23, 1986.
9. Direct communication with Leslie B. Evans, EPA. June 23, 1988.
Complexity of ethyl chloride production and tetraethyl lead production
processes.
10. LaRegina, J., J. Bozzelli, et al, Volatile Organic Compounds at
Hazardous waste Sites and a Sanitary Landfill in New Jersey, Environmental
Progress, Vol 5, No. 1, February 1986, pp.18-27.
5-14
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6. REPORTS AND EXPERIMENTAL FINDINGS
6.1 AMBIENT AIR
Two reports were sponsored by the Agency in 1983 to measure and assess
hazardous organic chemicals in the ambient atmosphere. The first of these
reports measured atmospheric concentrations, variabilities, and mean diurnal
behavior of 44 chemicals, including ethyl chloride. On-site field collection
programs, based on single site studies of 9-11 days duration each, were
conducted in 10 U.S. cities. Measurements were collected around-the-clock.
It was theorized that the daily loss rate, i.e.. percentage loss due to chemical
reaction in the atmosphere, was low (3.3 percent) for ethyl chloride becouse
it is relatively unreactive. The hydroxyl radical (OH) reaction rate
constant was given as 0.39xlO~12 cm3 molec-^s"1 at 300K.1
The average ethyl chloride concentrations at most sites was 0.1 ppb
or less. The exception was Houston whose average and maximum
levels were 0.23 and 1.3 ppb, respectively. The maximum concentrations at
the other sites did not exceed 0.32 ppb. Background concentrations of
ethyl chloride (at 40ฐN'latitude) were also reported and lie in'the range
of-10-15 ppt.1 ' .
In a follow-up report, data were collected on 151 chemicals from a
variety of sources between 1970 and 1980. The data were classified
according to. data quality, and then analyzed to assess their reliability
and usefulness in concentration trend analysis. For the hazardous organic
chemicals of this study, relatively little information was available with
which health assessments or trend analysis could have been confidently
made. Most data were limited to a few geographic regions and had been
collected during the daylight hours of warmer months.2
The same study group investigated concentrations of ethyl chloride
over the eastern Pacific Ocean (1981). Within 0-40ฐN latitude over the
northern and southern hemispheres, weighted average.concentrations (ppt)
were 19 and <5, respectively. Ethyl chloride was not detectable south of
10ฐN. The global average was reported at 10 ppt.3
6-1
-------
6.2 EXPOSURE DATA
6.2.1 Standards
The exposure levels of ethyl chloride adopted by the U.S. Occupational
Safety and Health Administration (USHA) and the American Conference of
Governmental Industrial Hygienists (ACGIH) are provided in Table 6.2-1.
Table 6.2-1 Ethyl Chloride Exposure Limits
OSHA
Standard
PELt
ACGIH
Guideline Standard
TLVฎ*
1UOO ppm
26UO mg/m3
1000 ppm
2600 mg/m3
All figures are for an 8-hour time weighted average (TWA)
t Permissible Exposure Limit
* Threshold-Limit Value
6.2.2 Survey Report
An industrial- hygiene survey was conducted at a tetraethyl lead
facility (Ethyl Corporation, Pasadena,Texas) in April of 1980 sponsored
by the U.S. National Institute for Occupational Safety and Health (NIOSH).4
Personal and area samples were collected for TEL and ethyl chloride, as
well as for three other pollutants. The ethyl chloride personal samples
averaged 0.425 mg/m3, well below the 2600 mg/m3 OSHA and ACGIH levels.
Samples were collected for 6-8 hours per shift using two charcoal tubes
in series followed by MDA Accuhaler (Model 808) low flow pumps. A modified
NIOSH Method S-lOb was employed to analyze the samples. Statistics were
generated by job title, but were not fully descriptive of the exposure
data.
6-2
-------
6.3 AQUEOUS EMISSIONS
A February 1979 report investigated the presence of organic compounds
in industrial effluent discharges.^ Samples taken from 63 effluent and
22 intake waters from a wide range of chemical manufacturers, were precon-
centrated for four-part organics analysis: volatile organics by helium-gas
stripping and semivolatile organics by extraction with methylene chloride,
resulting in separate neutral, acidic and basic fractions. A total of
570 compounds were tentatively identified. The identifications were labeled
"tentative" because they were limited by "purity" of sample component mass
spectrum and data base accessibility of individual compound spectra. Of
the 63 samples, ethyl chloride was identified once at a concentration
between 10-100 ug/1 and twice at levels <10 ug/1.5
The evaporative half-life of ethyl chloride in water was experimentally
found to be 23.1 min.6 Half-lives of 0.50 and 16.7 mins were also reported.7
With a partition coefficient of 0.46, and the above reported half-lives, it
is possible that ethyl chloride evaporates relatively quickly from an aqueous
environment, leaving very small, if any, concentrations in effluent waters..
6-3
-------
REFERENCES
1. Singh, H. B., L.J. Salas, et al, Measurements of Hazardous O.ryanic
Chemicals in the Ambient Atmosphere, Office of Research and Development,
U. S. Environmental Protection Agency, Research Triangle Park, NC,
EPA-6UO/3-83-U02, January 1983. p. 48.
Brodzinsky, R., H.B. Singh, Volatile Organic Chemicals in the Atmosphere:
Assessment of Available Data, Office of Research and Development, U. S.
2.
an
Environmental Protection Agency,
EPA-6UO/3-83-U27A, April 1983.
Research Triangle Park, NC,
3. Singh, H.B., L.J. Salas, et al.
in the Air and Oceanic environment,
No. 6, 1983.
Selected Man-made Halogenated Chemicals
Journal of Geophysical Research, Vol 88,
4. Ringenburg, V.L., Survey Report of Ethyl Corporation, Pasadena, Texas,
April 7-10, 1980, National Institute for Occupational Safety and Health,
May 4, 1983.
5. Perry, D.L., C.C. Chuany, et al, Identification of Organic compounds
in Industrial Effluent Discharges, Office of Toxic Substances, U. S.
Environmental Protection Agency, Washington, D.C., February 1979,
EPA-600/4-79-016, p.43.
6. Oil ling, W.L., Interphase Transfer Processes. II. Evaporative
Rates of Chloro-Methanes, Ethanes, Ethylenes, Propanes, and Propylenes
from Dilute Aqueous Solutions. Comparisons with Theoretical Predictions,
Environmental Science and Technology, Vol III, No. 4, April 1977, pp.405-
409. ' '
7. Dilling, W;L., Atmospheric Environment, Environmental Risk Analysis
for Chemicals, R.A. Conway, editor, Van Nostrand Reinhold, New York, NY,
1982, p.173.
6-4
-------
7. UNCERTAINTIES AND FUTURE WORK
The emission estimates calculated in this assessment are annual
approximations. Site-specific information is usually not available.
These estimates were based upon the most appropriate of the available
data and conservative assumptions. A conservative assumption results in
higher emission and concentration estimates in the ambient air.
7-1
-------
-------
APPENDICES
A. ฃthyl Chloride Synonyms
B. Ethyl Chloride Imports and Exports
C. Ethyl Chloride Production
D. Tetraethyl Lead (TEL) Production
E. Ethyl cellulose (EC) Production
F. Polystyrene Foam Bl cwing
G. Ethylene Bichloride (EDC) Production
H. Human Exposure Model (HEM) Inputs
8-1
-------
-------
A. CAS No. 75-00-3
Chloroethane
Monochloroethane
Chlorethyl
Ether Hydrochloric
Ether Muriatic
Ether Chloratus
Aethylis Chloridum
Kelene
Chelene
The Merck Index 10th edition, p. 548
A-l
-------
-------
APPENDIX B. ETHYL CHLORIDE IMPORTS AND EXPORTS
ETHYL CHLORIDE IMPORTS
Yearly figures,are given below:
Imports
Year
1964
1966
1967
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
10ฐ Ibs
1.91
1.27
2.32
1.10
2.14
1.10
2.36
0.66
2.78
4.92
0.22
1.32
2.89
3.47
2797.81
11079.39
. 5121.54
Mg
0.86
0.58
1.05
0.50
0.97
0.50
1.07
0.30
1.26
2.13
0.10
0.60
1.31
1.57
1269.08
5025.58
. 2323.12
1964-79 - All imports from Federal Republic of Germany (FRG)
1980 - All imports from Canada
1981 - 99 percent of-imports from Canada; 1 percent FRG and Switzerland
Chemical Economics Handbook, Ethyl Chloride: Salient Statistics, SRI
International, Men! o Park, California, 1983, p.646.5030E.
B-l
-------
E ETHYL CHLORIDE EXPORTS
Year
106 Ibs
Exports
103 Mg
103 dollars
1978
1979
1980
1981
1982
28.15
28.04
26.18
26.87
26.46
12.77
12.72
11.88
12.19
12.00
4.46
4.94
5.51
5.82
5.44
1981 - 86 percent of exports received by Mexico.
1982 - 94 percent of exports received by Mexico.
Chemical Economics Handbook, Ethyl Chloride: Salient Statistics, SRI
International, MenloPark, California, 1983, p.646.5030E-F.
B-2
-------
APPENDIX C. ETHYL CHLORIDE PRODUCTION
Production Estimates:
1984 total capacity = 460 million Ibs.
1984 total production = 290 million Ibs.
1984 production'factor = production _ 0.63
capacity
1985 total capacity = 460 million Ibs.
1985 total production = 170 million Ibs.
1985 production factor = 0.37
1986 total capacity = 470 million Ibs.
1986 total production = 157 million Ibs
1986 estimated production factor = 0.33
1987 total capacity = 395 million Ibs.
1987 estimated production = 164 million Ibs.
1987 estimated production factor, = 0.42'
Annual Chaage in Production:
1980-81 = -18%
1981-82 = +5%
1982-83 = -17%
1983-84 = +4%
1984-85 = -41%
Estimated 1986-87 = +5%
C-l
-------
Calculation of Emission Factor from Production:
Process: Hydrochlorinatio.n of Ethylene
Two process vents, each with 34818 kg ethyl chloride emissions per year
Basis: Process vent emission rates* Ethyl Corporation
Pasadena, Texas
Two process vents, each with 34818 kg ethyl chloride emissions
1986 capicity = 160 million IDS.
*Data from Texas Air Control Board .Emission Inventory, September 1986
Since production figures were not available at specific sites, the
process emission factor was based on the 1986 emission data and capacity
for Ethyl Corporation at Pasadena, Texas. Process emissions are a function
of throughput, so an underlying assumption used here is that all facilities
operated at the same product!on/capacity rate as Ethyl Corporation
Industry-wide, this rate was 0.33 in 1986.
Capacity = 160 x 105 1 b/yr x 0.4536 kg/.lb = 72.6 x 105 kg/yr.
= 72.6 Gg/yr.
Emission Factor
total emissions = 2 x 34818 kg/yr = 950 kh/Gg
capacity 72.6 Gg/yr
s 480 kg/Gg at each of two process vents.
A specific value for process emission velocity for hydrochlorination
of ethylene was not available. Because of this, a value which was considered
to be in a reasonable range (2500-3000 fpm) was chosen.^ The calculation for
converting to metric units is given below.
2500 feet | 1 min
mi n I 60 sec
1 meter = 13 meters/sec
3.281
C-2
-------
Calculation of Emission Factor from Production (Continued):
It was assumed that, like the Ethyl Corporation facility, each facility
would have two process vents emitting equal quantities. Two of the facilities
do not manufacture ethyl chloride by hydrochlon"nation of ethylene. However,
no specific process values or emission factors were available to quantify
ethyl chloride emissions from other processes. Therefore, it was assumed
that the process emissions and equipment leaks would be the same as for the
hydrochlorination process.
C-3
-------
Table C-l Ethyl Chloride Emissions from Ethyl Chloride Production3
Company/
Location
Dow Chemical U.S.A.
Freeport, TX
E.I. du Pont de
Nemours & Co. , Inc.
Deepwater, NJ
Ethyl Corporation
Pasadena, TX
PPG Industries
Lake Charles, LA
1
Process Sources'3
PI
P2
EL
PI
P2
EL
PI
P2
EL
. PI
P2
EL
Capacity0
(Gg/yr)
4.54
45.4
72.6
56.7
Emi ssion
Factor5
(kg/vent/Gg
capicity)
480
480
480
480
480
480
---.
480
480
Emi ssions
(Mg/yr)
2.18
2.18
29.6
21.8
21.8
29.6
34.8
34.8
29.6
27.2
27.2
29.6
TOTALS
179
960 kg/Gg
290.4
a. Process is assumed to be hydrochlorination of ethylene. This process is
actually in use only at the Ethyl and PPG facilities. References indicate
that Dow capacity is a by-product of vinyl chloride production or a product
of direct reduction of vinyl chloride. Du Pont capacity is a by-product
of Freonฎ manufacture and actual production is well below stated capacity.
b. Process vents are assumed to emit equal proportions of total process
emissions.
c. SRI International, Chemical Economics Handbook, February 1988. p.646.5030 B
C-4
-------
Equipment counts and other equipment leak data were not available
for the ethyl chloride production.process. A model plant was the basis
of the equipment leak estimate. To determine the most appropriate model
plant, the number of pumps in the process were estimated and compared
with the number of pumps in the three models. Model Plant A has eight
pumps in light liquid service and seven pumps in heavy liquid service;
Model B has thirty and thirty; Model C has ninety-two and ninety-three,
respectively. ^
The number of pumps in the ethyl chloride production process (hydro
chlorination of ethylene) was estimated after a review of a flow diagram
and a process description.3 Al lowances were made for industry norms for
equipment redundancy. A total of sixteen pumps, ten in light liquid
service and six in heavy liquid service, were estimated.4 This estimate
indicated that Model Plant A was most appropriate.
'Since the main product of this process is ethyl chloride, it.was :
assumed that 100 percent of the emitted VOC was ethyl chloride. The
equipment leak estimate for these plants totalled 29.6 Mg/yr.
Not all four of the production facilities use ehtylene hydro-
chlorination to produce ethyl chloride. Two of the facilities obtain
ethyl chloride as a by-product from other processes. The hydrochlorination
process is thought to be more complex than the ethyl chloride separation
units of the other processes. Therefore, the Model Plant A is an appropriate
model for all four production plants.
C-5
-------
Calculation of Emission Factor For Equipment Leaks
Table C-2 Equipment Leak Factors and Equipment Leaks
Number of
Sources* for
Model
Pump Seals
Light liq.
Heavy liq.
Va 1 ves
Gas
Light liq.
Heavy liq.
Sa f ety/ r el i ef valves
Gas
Open-ended lines
Compressor Seals
Sampling connections
Flanges
TOTAL
Unit A
8*
7
99
131
132
3
104
1
7
600
Emission Factor
(kg/hr/source)
(kg/m/source)
0.0494
0.0214
0.0056
0.0071
0.00023
0.1040
0.0017
0.228
0.0150
0.00083
Emi ssion
Rate
(kg/hr)
(kg/m)
.395
.150
.554
.930
.030
.312
.177
.228
.105
.498
3.38
Ann Emissions**
(kg/yr)
(kg/yr)
3462
1312
4857
8148
266.0
2733
1549
1997
919.8
4362
29600 kg/yr
* Environmental Protection Agency Fugitive Emission Sources of Organic
Compounds- Additional Information on Emissions, Emission Reductions, and Costs.
EPA-450/3-82-010, Research Triangle Park, North Carolina, April 1982.
p.1-6, 2-70.
**Hours of operation assumed to be 8760/yr., i.e., continuous operation assumed.
Transportation and Storage Emissions:
Due to the volatility of ethyl chloride, it is usually stored in
pressurized tanks. Data have indicated that no emissions result from such
storage methods.5 Transporation losses are expected to occur only during
connection and disconnection for actual transfer. They are expected to be
minimal. Actual data are unavailable.
C-6
-------
American Conference of Governmental Industrial Hygienists, Industrial
Ventilation: A Manual of Recommended Practice, 14th ed. AC6IH.
Lansing, Michigan, 1977. p. 6-23.
2. Environmental Protection Agency, Fugitive Emission Sources of
Organic Compounds-Additional Information on Emissions, Emission
Reductions, and Costs. EPA-450/3-92-010. Research Triangle Park,
NC, April 1982. p. 1-6.
3. Environmental Protection Agency, Draft Report: Ethyl Chloride
Prelimiary Source Assessment. April 25, 1988. p.2-1, 2-3, 2-4.
4. Direct communication with Leslie.B. Evans, EPA. June 23, 1988.
Complexity of ethyl chloride production and tetraethyl leak
production processes.
5. Data reported from Emi ssions Inventory: Rhone-Poulenc, Inc. (Freeport, TX),
Texas Air Control Board, Austin, TX, September 1986.
C-7
-------
-------
APPENDIX D. TETRAETHYL LEAD (TEL) PRODUCTION
Table D-l. Annual TEL Production
Year
Annual Production3
Annual Consumption9
TEL
(10 IDS)
Other Lead
Alkylsb
(10 IDS)
Alky Is
(10 IDS)
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986
555
485
371
325
281
302
353
464
315
364
327
328
412
325
275
224
299
460
506
504
670
763
455
353
553
463
433
192
132
130
106
107
624
657
688
688
655
670
659
578
520
557
528
496
421
248
196
204
161
146
61
31
SRI International, Chemical Economics Handbook,
Menlo Park, California, September 1986. p. 543.7051 S,U.
Includes tetramethyl lead (TML), tetramethyethyl leads, organolead
compounds (1972), and mixed lead alkyl compounds (1973^1975).
D-l
-------
Tetraethyl lead is produced domestically at one site. The
production unit is owned and operated by DuPont at their Deepwater/
Pennsville, New Jersey facility.
The emissions data which were obtained from the New Jersey Department of
Environmental Protection included emission rates and stream characteristics
for process emissions.l This date also contained a value for the radius
of the emission area.
The number of process emission points (see Table 1) might be taken as
an indication of a complex process. In fact, these emissions are probably
not emitted exclusively from the TEL production unit. Ethyl chloride is
produced at this Du Pont facility. It is likely that it is used in other
processes. The ethyl chloride process emissions given are the facility
wide totals. 'Which emissions come specifically from the TEL production
unit is not known. The conservative assumption that was used was that
all of the process vents are from the TEL production unit.
Equipment counts and other equipment leak data were not available
for the tetraethyl lead production process. A model plant was the basis
of the equipment leak estimate. To determine the most appropriate model
plant, the number of pumps in the process were estimated and compared
with the number of punps in the three models. Model Plant A has eight
pumps in light liquid service and seven pumps in heavy liquid service;
Model B has thirty and thirty; Model C has ninety-two and ninety-three,
respectively.2
D-2
-------
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The number of pumps in the tetraethyl lead production process was
estimated after a review of a flow diagram.and a process description.3
Allowances were made for industry norms for equipment redundancy.
Seven pumps, each with a back-up pump, were estimated for a total of
fourteen pumps in the TEL production.4 This estimate indicated that
Model Plant A was the most appropriate model.
Since ethyl chloride is a major component of the process, and because
stream composition data were not available, it was assumed that 100 percent
of the emitted VOC was ethyl chloride. The equipment leak estimate
at the facility totalled 29.6 Mg/yr. See Appendix C, table C-2 for more
details on this model facility calculations.
, The necessary parameters for the human exposure model (HEM) are
given in Table D-2.
D-4
-------
1. Letter from MP Polakovic, N.J. EPD, to G Hume, OAQPS, EPA.
May 25, 1988. Computer Printout (dated May 24,1988) for
Ethyl Chloride Emissions from Du Pont's Chamber Works Facility.
2. U.S. Environmental Protection Agency, Fugitive Emission Sources
of Organic Compounds-Additional Information on Emissions,
Emission Reductions, and Costs. EPA-450/3-82-010. Research Triangle
Park, NC. April 1982. p. 1-6.
3. Environmental Protection Agency, Draft Report: Ethyl Chloride
Prelimnary Source Assessment. April 25, 1988. p. 3-1 through 3-5.
4. Direct communication with Leslie B. Evans, EPA. June 23, 1988.
Complexity of ethyl chloride production and tetraethyl lead
production processes.
D-5
-------
-------
APPENDIX E. ETHYLCELLULOSE (EC) PRODUCTION
Domestic Consumption of Ethyl Cellulose (EC)
and ฃthylhydroxyethyl cellulose (EHEC)
Year
Millions of pounds
1965
8
1969
9
1973
7
1976
7
Chemical Economics Handbook, Cellulose Ethers, SRI International, Menlo Park,
California, November 1977, p.584-5022J.
E-l
-------
Due to lack of process information on ethyl cellulose and ethyl
hydroxy ethyl cellulose manufacture, process emissions were not estimated.
Equipment leaks were estimated using SOCMI average emission factors for
Model Unit A.
The procedure used for estimation of equipment leaks is identical to
to that for ethyl chloride production facilities. For more information on
this calculation see Appendix C, Table C-2.
Company/ location
Dow Chemical Co.
Midland, Michigan
Hercules, Inc.
TOTAL
Fugitive Emissions
(Mg/yr)
29.6
29.6
59.2
E-2
-------
APPENDIX F. POLYSTYRENE FOAM BLOWING
.Ethyl chloride is used as a foam blowing agent by one .company at
six domestic sites. All of the information regarding this use has come
from testimonies of company personnel for the Illinois Pollution Control
Board1 and from direct contact with company personnel.2ป3ป4
The testimonies given were related to (I) "generic rules" regarding
emission standards of organic materials and (2) emissions of ethyl
chloride at the Joliet, Illinois facility.
The three main emission types were identified as:
1) Emissions during outdoor storage of the polystyrene
foam product - 137 tons/yr of ethyl chloride.
2) Equipment leaks - 22 tons/yr of ethyl chloride.
3) Process emissions - 78 tons/yr of ethyl chloride.
Equipment leaks are primarily a function of the amount and types
of equipment involved in a process. Because the same company, operates
all of these facilities and because site specific equipment counts were
unavailable, it was assumed that similar process equipment is used at
all sites. Based upon the Joliet data, 20 Mg/yr of ethyl chloride are
emitted through equipment leaks.
22 tons 12000 Ibs |0.4536 Mg
1000 1 bs
ton
= 20 Mg/yr
To assist in estimating storage and process emissions at the other
facilities, company personnel estimated emissions at each site relative
to the emissions at Joliet. This information can be found in Table F-l.
F-l
-------
Table F-l - Ethyl Chloride Emissions from Styrofoamฎ Production3
Lo cati onb
Ci ty , St ate
Al lyn's Point/
GalesFerry, CT
Dalton, 6A
Ironton, OH
Joliet, ILe
Pe vely/
Riverside, MO
Torrance, CA
Longitude/
Latitue
(OI"N)(01"W)
41 26 29/72 04 58
34 46 06/84 57 42 .
.38 31 00/82 40 00
41 31 36/88 04 48
39 10 06/94 36 12
.
33 51 02/118 19 49
Process & Storage0
Bui ssions
(% relative to
Joliet facility)
70
100
100
150
30
Type of
Emi ssiond
P
EL
S
P
EL
S
P
EL
S
P
EL
S
P
EL
S
P
EL
S
Estimated
Ethyl
Chloride
Emissions
(Mg/yr)
50
20
84
70
20
120
70
20
120
70
20
120
110
20
180
20
20
36
Total
1170
a. Styrofoam is a registered trade mark of a Dow Chemical U.S.A. polystyrene foam
product.
b. Telecon. Warila, B. Dow Chemical, with Hume, 6. EPA, March 29, 1988. Ethyl
Chloride Emissions from Foam Blowing.
c. ibid. Estimates are given relative to those from the Joliet, IL facility.
d. P = process emission, EL = equipment leaks, S = storage emissions.
e. The Joliet emission estimates are based upon testimonies by Dow Chemical U.S.A.
personnel (R.S. Thompson, Kyung W. Suh, Steve West, Patrick F. Carrera), for
the Illinois Pollution Control Board in Springfield, Illinois on February 10,
1987.
F-2
-------
Table F-2. Emission Stream Characteristics
Type of
Emi ssion
Process'3
Fugitive
St orage
Release
Height
(m)
10
1
3
Stack
Di ameter
(m)
1.1
--
--
Exit
Velocity
(m/s)
14
.01
.01
Exit
Temperature
(K)
300
300
300
Release
Area
Gn2)
21000ฐ
Du raationZ
(hrs)
C
C
C
a. C = continuous (8,760 hours)
,b. Telcon. Warila, B. Dow Chemical U.S.A. with Hume, G., EPA, March 29, 1988.
Ethyl Chloride Emissions from foam blowing.
c. Based upon testimonies by Dow personnel for the Illinois Pollution Control
Board, February 10, 1987.
F-3
-------
1. Testimonies of R.S. "Thompson, Kyung W. Sun, Steve West, and Patrick
F. Carrera, Dow Chemical U.S.A., before the Illinois Pol.lution
Control Board, Springfield, IL on February 10, 1987.
2. Telecon. Steve Rose, Dow Chemical U.S.A. with Gretchen Hume, EPA,
September 18, 1987. Ethyl Chloride Use in Polystyrene Form Blowing.
3. Telecon. Steve Rose, Dow Chemical U.S.A. with Gretchen Hume, EPA.
March 28, 1988. Ethyl Chloride for Foam Blowing.
4. Telecon. Bob Warila, Dow Chemical U.S.A. with Gretchen Hume, EPA.
March 29, 1988. Ethyl Chloride Emissions from Foam Blowing.
F-4
-------
APPENDIX G. ETHYLENE OICHLORIDE (EDC) PRODUCTION
The predominant processes for domestic ethylene dichloride (EDC)
production are chlorination of ethylene and oxychlorination of ethylene.
EDC emissions have been evaluated recently by the EPA.10 This evaluation
made much more data than usual available for this preliminary evaluation
of ethyl chloride emissions. How the EDC data and other data were used
to evaluate ethyl chloride emissions is detailed in this appendix.
The first step in making use of the EDC data was to determine an
ethyl chloride: EDC ratio. The process emissions and equipment leaks of
EDC were then evaluated and multiplied by the ratio. This resulted in
emission estimates for ethyl chloride.
The ethyl chloride dispersion modeling parameters are assembled in
table 6.4-1, toward the end of this appendix. The eighteen domestic EDC
production facilities emit an estimated 982 Mg/yr of ethyl chloride.
6-1
-------
G.I Calculation of Ratio of Ethyl Chloride to Ethylene Di chloride
The ratio of ethyl chloride (EtC) to ethylene dichloride (EDC) was
based on composition data for uncontrolled emissions from oxychlorination
and direct chlorination process vents.1 These data were combined because
information specifying the process or processes currently in use at all
facilities was not available. The EtCl: EDC ratio was used for both
process emissions and equipment leaks because no information concerning
composition of equipment leaks at EDC production facilities was found.
Of ten facilities reporting compositions, one facility did not report
a composition estimate for either EtCl or EDC. Data from that facility
could not be used. The remaining nine data sets had values for E+C1 or
VOC and EDC.
Of these data sets (see Table 3)-, one facility reported composition
in percent. Molecular weights were used to convert the mole percent to
weight fractions (see Figure.1). The remaining eight data sets were
reported in weight percents or pounds per hour which could both be .converted
directly to weight fractions.
6-2
-------
TABLE G.l-1 COMPOSITIONS REPORTED FROM PROCESS VENTS FOR EDC PRODUCTION
Facility A B . CD E F 6 H.I
Units (wt %) Qb/hr) (wt %) (16/hr) (wt %) (wt %) (mole %) (Ib/hr) Qb/hr)
Component
EDC
Ethyl
Choride
Ethyl ene
Other. VOC
3.03 414 0.75 130 5 4.6
0.92 489 1.00 0.59 5 2.1
117 0.02 119 44 0.8
6.53 60 0.23 0.75 --- 2.6
1.7
74.4 200
0.01
3.3 183.1 318
0.02 2.45 68
1. U.S. Environmental Protection Agency, Report 1: Ethylene Dichloride in:
Organic Chemical Manufacturing; Volumes. Selected Processes, EPA-450/3-80-
028c. December 1980. p. F-4,5.
G-3
-------
Component
EDC
EtCl
Molecular Weight
98.96
64.52
0.01 mole EtC
64.52 g EtCl = 0.6452 g EtC
0.6452 g EtCl
168.23 g EDC
mole
= 0.0038 weight fraction EtC:EDC
Figure G-l. Converting Mole Percent to Height Fraction
All of the data sets used had estimates for EDC. Seven of the eight
had estimates for EtCl but, two data sets were missing values for EtCl.
Both of these sets did have values the component "other VOC",, For these
two sets, the ratio of EtCl to EDC was obtained"through ratios of these
components to volatile organic compounds (VOC). For simplicity, it was
assumed that VOC would be comprised of the chemicals: ethyl chloride,
ethylene, and other VOC where these data were available. The ratio for
ethyl chloride to VOC was based upon the composition data in six data
sets. The seventh data set, given in mole percent, could not be used
because the molecular weight for the category "other VOC" was unknown.
G-4
-------
Facility
Units
Component
ethyl chloride
VOC
EtCl
VOC"
Table G.l-2 Ratio of Etc to VOC
A B C . D E F
Qb/hr) (wt%) Qb/hr) (wt%) (wt%)
0.92 489 1.00 0.59 5
7.45 666 1.25 120.34 49
21
5*.5
0.123 0.734 0.800 0.0049 0.102 0.382 0.358+0.341
The ratio of ethyl chloride to VOC was multiplied by the weight
fraction of VOC to ethylene dichloride to determine an E+CI to EDC weight
fraction for the two incomplete data sets.
Example for facility H -
0.358 EtCl | 2.45 (Ib/hr) VOC
l unit VUG. |74.4 (I b/h r) EDC
= 0.0118 EtCl/unit EDC
Figure G-2 - Obtaining the EtCl to EDC ratio via the EtCl to VOC and
VOC to EDC ratios.
G-5
-------
The weight fractions of EtCl to EDC were determined for all nine
facilities. Tire average EtCl:EDC ratio was 0.490 with a standard
deviation of 0.538.
Table G. 1-3 Ratios of EtCl to EDC (wt. fraction: 1)
facility -ABCD'EF G H.I avg^td dev.
EtCl:EDC 0.304 1.18 1.33 0.005 1.00 0.457 0.0038 0.0118 0.122 0.490 _+ 0.538
This value was based upon process vent compositions. As indicated by
the large standard deviation, the ratio varied greatly among the different
facilities. Details were not available of how these original composition
values (see Table D.l-1) were obtained (i.e. whether they were obtained
through stack testing, mass balances, engineering judgement, etc.) It
was decided that using the average ratio for all facilities would yield
the best overall estimates. .
6-6
-------
G.2 Ethyl Chloride Emissions from Process Vents at Ethylene Di chloride
Production Facilities
The only data .avalilable for process emissions from ethyl dichloride
(EDC) production facilities was generally specific to EDC emissions.
Since specific ethyl chloride (EtCl) data were not available, it was
assumed that ethyl chloride would be emitted at a rate proportional to
the EDC rate from the same process points as the EDC, i.e. the same
vents, stacks, etc.
The following sections detail the calculations for EDC process
emissions. These emission estimates were based upon data from responses
to 114 questionnaires.2,3,4,5,6,7,8 A 114 questionnaire is a request for
emission information which is sent to a company by the U.S. EPA. The .
authority to obtain the information is provided by section 114 of the
Cl ean Ai r Act. .
Site specific information was not available for all EDC production
facilities. However, from those that were provided, emission estimates
had been made for all facilities for the EDC project.9
6-7
-------
G.2.1 EtCl Process Emission Rates
The process emission rates of EtCl for all facilities were based
upon summaries of EDC process emissions (see table G.2-1). EDC emissions
from all process vents were totaled and multiplied by the EtCl:EDC ratio.
The EtCl total was then divided by the number of process vents. In some
cases, it was assumed that two process vents were present. Two was the
average number of process vents per facility recorded on the EDC emission
summary. The following section details the other emission stream char-
acteristics, such as temperature and release height.
For facilities with .more than one process vent listed it was necessary
to assume an equal emission rate from all vents. The assumption was made
because it was not possible to.cornel ate the specific stream characteristics
with the appropriate emission rates.
G-8
-------
Table G.2-1 Total EOC and EtCI emissions from process vents
Location
Port Arthur, TX
Calvert City, KY
LaPorte, TX
Geismar, LA
Convent, LA
Pasadena, TX
Free port, TX
Oyster Creek, TX
Plaquemine I, LA
PI aquemi ne II, LA
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
Lake Charles, LA
Lake Charles, LA
Deer Park, TX
Westlake, LA
Geismar, LA
estimated
EDC
emissions9
(kg/yr)
45
4247
2390
42925
45
42925
45
92405
1757
8110
38000
810
24280
45
15030
220
42.54
105
273,430
estimated
EtCI
emissions'3
(kg/yr)
22
2080
1170
21000
22
21000
22
45300
861
3970
18600
397
11900
22
7360
108
21
51
133,900 '
__
number of
process
vents
for EDC
emissions3
1
7
3
1
1
1
1
3
2
1
1
2
3
1
4
2
8
2
44. .
2..4ฑ2.1
Company
U.S. Industrial Chemicals
BF Goodrich
BF Goodrich
Bo rden
Diamond Shamrock
Di amond Sh amrock
Dow Chemical
Dow Chemical
Dow Chemical
Dow Chemical
Fo rmos a
Fo rmosa
Georgia Gulf
01 i n Co rp
PPG Industries
Shell Chemical
Vista
Vul can Chemicals
total
avgj.std.dev..
a. Values obtained from Memorandum, M.. Putnam, Midwest Research Institute
to D. Beck, OAQPS, EPA, Estimates of Dichloride Emissions from Production
Facilities and HEM Inputs. April 23, 1986.p.5-ll
b. Weight fraction EtC:EDC = 0.49:1.0 (see section G.I)
G-9
-------
G.2.2. EtCl Process Emission Stream Characteristics
The values for the stream characteristics, such as stack height and
vent diameter, were based either on non-confidential responses to 114.
questionnaires or on the EDC memorandum (references 2-9). These
non-confidential data were compiled to obtain average values. Average or
typical values from the EDC emission memorandum were also used. Table
G.2-2 lists the values which were obtained from 114 responses and the
average values which were derived from them. When data necessary to
determine velocity of the process stream were not available, the value
7.9 m/s was used. This value was taken from the EDC memorandum.9
G-10
-------
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G.3 Ethyl Chloride Emissions from Equipment Leaks at Ethylene
Dichloride Production Units.
The ethyl chloride equipment leak emissions were based upon site
specific equipment counts or ethylene dichlorice (EDC) fugitive emission
estimates. The equipment counts were given in' responses to 114
questionnaires. The 114 equipment counts were analyzed to develop weighted
total, or 1UO percent EDC equivalent, equipment counts for each site.
The counts were multiplied by average synthetic organic chemical manufacturing
industry (SOCMI) emission factors and prorated with the EtCl:EDC weight
fraction.
Where site specific equipment counts were unavailable, estimates for
fugitive EDC emissions were prorated using the EtCl:EDC weight fraction.
As noted previously, this weight fraction was based upon composition
data for process vents. It is not known how equipment leak composition
might differ from process vent composition.
The1 stream characteristics for equipment leaks are default values.-
An exception to this is that source area was known for some facilities.
The methods of calculation and references for all values are given
in the following sections.
G -12
-------
G.3.1 Ethyl Chloride Equipment Leak Rates
In the 114 responses used for these calculations, component counts
were broken down into categories of EDC weight percent for the emission
stream. The six weight percent categories are given in table G.3-1. For
four of the weight percent categories, it was assumed that the midpoint
of the percent range was the best estimate of the actual percent for all
components in that range. For the lowest (<5%) and the highest (>99%)
composition streams, the upper bound, being the conservative estimate,
was used.
Table G.3-1 Representative Weight Percent
Weight Percent
Category
(*)
<5
5-10
11-25
26-75
76-99
>99
Midpoint or
Assigned Value
5
. 7.5
18
50.5
87.5
100
Mass (Weight)
Fraction
0.05
0,075
0.18
0.505
0.875
1.00
G-13
-------
To simplify the necessary calculations, the number of components in
each category and the representative weight percent of that category were
combined to give a single number of each type of component. This number
was a value equivalent to assuming all components were in 100 percent EDC
service. In other words, the equipment counts for the six categories
were condensed to a single equivalent equipment count. The components of
the equivalent equipment count were all assumed to be in use only for EDC.
Figure G.3-1 gives a generalized mathematical expression for the procedure
that was used to obtain the total EDC emissions for each of the 11 facilities
with equipment counts. The step which is mentioned above, which simplified
the calculation by means of the 100 percent EDC equivalent equipment
counts, occurs in the separation of the summations.
T=
j=l
. li
6 .
n 6
H
1=1
.
(j)
j= number of component types (i.e. pumps, valves, etc.)
z(j)= emission factor for total organics, specific for each
component type, (k.g/hr/ source).
i= number of ranges or values for the mass .fraction of the
chemical of concern, x, of total organics
x(i)=mass fraction of chemical of concern (kg x/kg z)
q(iปj)= number of components of type j which contain mass fraction
x(i) of chemical of concern.
T- total emissions of x from process unit (kg/hr)
Figure G.3-1 Summations for process unit emissions of an Organic
Species.
G-14
-------
The inner summation in figure 6.3-1 is what has previously been
refered to as the equivalent equipment count. The simplified example
below demonstrates how the equations in figure G.3-1 were used.
6-15
-------
Example - Obtaining an Equivalent Equipment Count Facility with the
following equipment count for EDC:
Table 6.3-2 Simplified Version of a 114 Equipment Count
weight percent of EDC-
valves
5-10%
11-25%
26-75%
76-99%
>99%
vapor service
liquid service
1
0
0
2
5
0
0
0
0
2
0
1
From the ranges for weight percent-
.05, x(2)=.075, x(3)=.18, x(4)=.505, x(5)=.875, x(6)=1.00
From table 6.3-2
q(l,l)=l, q(2,l)=0, q(3,l)=5, . q(6,l)=0
q(l,2)=0, q(2,2)=2,...q(6,2)=l
Equivalent 100 percent EDC equipment count-
6
for vapor service valves = .05(1)+.075(0)+.18(5)+0+0+0
= 0.95
for liquid service valves = .05(0)+.075(2)+0+0.875(2)+1.00(1)
= 2.90
For this example, the following approximations of organic emission
factors are used:
valves in vapor service = 0.006 kg/hr/s ounce
valves in liquid service = 0.004 kg/hr/source
That is, z(l) = 0.006, z( 2) = 0.004
2 6 .
Total emissions of EDC= > z (j) ^ x(i)q(ij)
j-1 1-1
.006(0.95)+.004(2.90)
= 0.0173 kg/hr
G-16
-------
The equivalent equipment counts which were obtained for
facilities with 114 responses are given in table 6^3-3. The
for each component, which was obtained from the eleven data sets,
given in the table.
the eleven
average value
is also
Using the same methodology as illustrated in the example, the total
emissions of EDC were estimated for the facilities given in table 6.3-5.
The second column in this table shows the estimated emissions of EtCl,
these values were obtained by multiplying the EDC estimate by the EtCl:EOC
ratio. In order to obtain an annual emission estimate, it was assumed
that each facility operates continuously, i.e. 8760 hours per year.
Average values for EDC and EtCl emissions were determined based upon
the 114 equipment counts. Although they might have been, these averages
were not used for the facilities with unknown equipment counts. EDC
fugitive estimates from the EDC project were believed to give a better
basis for EtCl emissions than the use of average values would. However,
the averages are included in the table for comparison purposes.
Another way to estimate equipment leaks at facilities with out
equipment counts would have been to use the model plant approach. The
averages could have been compared with values for a model SOCMI facility.10
(This comparison was made and the average counts fit best with the model
B facility). Then the equipment count for the model facility could have
been used for the unknown counts.
Again, the EDC fugitive calculations developed for the EDC project,
were thought to give the best basis for calculating EtCl equipment leaks.
Table G.3-6 lists the EDC estimates and the EtCl. estimates which were
derived for the seven EDC production facilities without site specific.
equipment counts.
G-17
-------
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footnotes for Table G.3-3 (cont.)
b. Original equipment counts were given in the following 114 responses:
114 responses -
1. Letter from JW Chapein, Arco, to J Farmer, OAQPS, EPA,
dated March 29, 1984.
2. Letter from S Arnold, Dow Chemical, to 0 Farmer, OAQPS, EPA
dated April 25, 1984.
3. Letter from C McAulliffe, Formosa Plastics Corp., to J Farmer,
OAQPS, EPA, dated March 28, 1984
4. Letter from LE Kerr, 01 in Corp., to J Farmer, OAQPS, ESA,
dated July 23, 1984.
5. Report for Site Visit to Shell Chemical Company, Deer Park,
TX, April 2, 1984, from JR Butler, Midwest Research Institute
to DA Beck, OAQPS, EPA.
6. Letter form RA Conrad, Conoco Chemicals, to J Farmer, OAQPS,
EPA, dated May 15,. 1984. .
7. Letter from CV Gordon, Vulcan Chemicals, to J Farmer, OAQPS,
EPA, dated May 7, 1984.
G - 19
-------
The component categories in the 114 responses (e.g., five pumps,
three valves) were the same as the component categories of the average
synthetic organic chemical manufacturing industry (SOCMI) emission factors
for equipment leaks. However, the phase and composition of the process
streams are unknown.
Table G.3-4 shows the original emission factorslO and how they were
combined with the 114 equipment counts.
Table G.3-4 Average SOCMI Emission Factors and Modifications
Component
Average SOCMI
factors3
(kg/hr/source)
Pump Seals:
light liquid .0494
heavy liquid .0-214
Compressor Seals ' .228
Flanges .00083
Valves:
gas .0056
light liquid .0071
heavy liquid .00023
Safety Relief Valves-gas .104
Sampling Connections .0150
Open-Ended Lines .0017
Value used for EDCb
(kg/hr/source)
..0354
ii
.228
.00083
.0056
.0037
.104
.0150
.0017
G-20
-------
Table G.3-5 Estimated Equipment Leaks based on 114 Data3-
Company,
Location
U.S. Industrial Chemicals
Port Arthur, TX
Dow Chemical
Freeport, TX
Dow Chemical
Oyster Creek, TX
Dow Chemical
PI aquemi ne I , LA
Dow Ch emi cal
PI aquemi ne 1 1, LA
Formosa PI astics
Baton Rouge, LA
Formosa PI astics
Point Comfort, TX
01 in
Lake Charles, LA
Shell
Deer Park, TX
Vi sta
Westlake, LA
Vulcan
Geismar, LA
Total
avg +_ std. dev.
estimated estimated annual
EDC equipment EtCl equipment EtCl
eak emissions b leak emissions0 equipment leaksu
fkg/hM (kq/hr) (Mg/yr )
2.5 1.2 11.
1.8 0.90 7.8
12 5.9 51
34 17 150
9.7 4.7 42
12 6.1 53
9.1 4.5 39
. . 3.9 1.9 17 ..
12 6.0 53
16 8.0 70
4.5 2.2 19
118 58.4 508
11+9.0 5.3+4.4 46^39
a. All numbers have been rounded to two significant figures.
b. Values based upon 114 responses and average SOCMI factors.
See references 2-10 and previous sections of this appecdix.
c. (EDC emissions) x EtCl: EDC weight ratio (0.49:1.0)
d. 8760 hours of annual operation assumed -for all facilities
G-21
-------
Table G.3-6 Estimated Equipment Leaks Based on EDC Fugitive Emissions3
estimated
EDC equipment
estimated
EtCl equipment
Company
Location
BF Goodrich
Calvert City, KY
BF Goodrich
LaPorte, TX
Bo r den
Geismar, LA
Diamond Shamrock
Convent, LA
Diamond Shamrock
Pasadena, TX
Georgia Gulf
PI aquemine, LA
PPG Industries
Lake Charles, LA
Total
leak emissions13
(Mg/yr )
75
75
130
130
75
170
47
702
leak emissions0
(Mg/yr)
37
37
62
62
37
'82
23
340
a. All values are rounded to two significant figures.
b. Memorandum from M Putnam, Midwest Research Institute, to Dave Beck
OAQPS,EPA. Estimates of Ethylene Dichloride Emissions from
Production Facilities and HEM inputs. April 23, 1986.p.5-11
c. (EDC emissions) x E+C1:EDC weight ratio (0.49:1.0)
G-22
-------
G.3.2 EtCl Equipment Leak Stream Characteristics
Most of the stream characteristics for ethyl chloride equipment-
leaks are standard default values. These default values are: emission
relelse height, 3.0 m; emission velocity, 0.01 m/s; and temperature,
293 K.
Some site specific values for the area were given in the 114 responses
Other v^ues were given in the EDC memorandum. For those facilities for
wMch neither of these values was given' the ^^ ฐf ,the-^UeS th
fVom thTlU responses was used. Table G.3.7 lists the facilities, the
release area, and the reference for the release area.
G-23
-------
'Table 6.3.7
r.nmpanv. Location
U.S. Industrial Chemicals
Port Arthur, TX
BF Goodrich
Calvert City, KY
LaPorte, TX
Bordon
Geismar, LA
Diamond Shamrock
Convent, LA
Pasadena, TX
Dow Chemical
Freeport, TX
Oyster Creek, TX
Plaquemine I, LA
Plaquemine II, LA
Formosa
Baton Rouge, LA
Point Comfort, TX
Georgia Gulf
Plaquemine, LA
Olin , , .
Lake Charles, LA
PPG Industries
Lake Charles, LA
Shell Chemical
Deer Park, TX
Vista
West lake, LA
Vulcan
** * .._. ** I A
Equipment Leak Release Area
release area (mz)_
36,000
36,000
36,000
142,516
36,000
142,516
36,000
36,000
23,000
126,994
25,0b3
1,300,000
36,000
930
36,000
142,516
36,000
5,600
. reference
114 average3
114 average3
114 average3
EDC memorandum13
114 average3
EDC memorandum
114 average3
114 average3
114 response0
EDC memorandum0
EDC memorandum ^
EDC memorandum
114 average3
114 responsed
114 average3
EDC memorandum"3
114 average3
114 response8
G - 24
-------
Footnotes for Table 6.3-7
a. The average value from the non confidential 114 responses was
used when no other value was available. See table G.2-2.
b. Memorandum fromM. Putnam, Midwest Research Institute, to
D. Beck, OAQPS, EPA. Estimates of Ethyl en e Di chloride Emissions
from Production Facilities and HEM Inputs. April 23, 1986.
p. 5-11.
c. Letter from S. Arnold, Dow Chemical, to 0. Farmer, OAQPS, U.S.
EPA, dated April 25, 1984.
d. Letter from L.E. Kerr, 01 in Corp. to J. Farmer, OAQPS, U.S. EPA
dated July 23, 1984.
e. Letter fromC.V. 6ordon, Vulcan Chemicals to J. Farmer, OAQPS,
U.S. EPA dated May 7, 1984.
6-25
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TABLE G.4.-2 REFERENCES FOR ETHYL CHLORIDE DISPERSION MODELING PARAMETERS
Emissions
Company/ Process Stream
Plant Location Rate Characteristics
U.S. Industrial
Chemicals
Port Arthur, TX
8F Goodrich
Calvert City, KY
LaPorte, TX
Borden
Geismar, LA
Diamond Shamrock
Convent, LA
Pasadena, TX
Dow Chemical
Freeport, TX
Oyster Creek, TX
Plaquemine I, LA
Plaqueraine II, L
Formosa
Baton Rouge, LA
Poi'nt Comfort, T
Georgia Gulf
Plaquemine, LA
Olin
Lake Charles, LA
PPG Industries
Lake Charles,- LA
Shell Chemical
Deer Park, TX
Vista
West lake, LA
Vulcan Chemicals
Geismar, LA
C
C
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Bl
Bavg
Bavg
D
Bavg
D
B2
B2
B2
D
D
D
Bavg
Bavg
Bavg
B5
B6
B7
Equipment
Leaks Stream
Rate Characteristics Exceptions
'Al
C
C
C
C
C
A2
A2
A2
A2
A3
A3
C
A4
C
A5
A6
A7
. D
D
D
D
D
0
D
D
D
D
D
D
D
D
D
D
area-Bavy
area-Bavg, p.vel-
area-Bavg
area-Bavg
area-Bavg
area-Bavg
area-Bavg
area-Bavg
p.temp-B3
area-Bavg
area-Bavg
area-Bavg
area-Bavg
area-B7, p.vel-D
G - 31
-------
(cont.)
Footnotes for table 6.4-Z Details of calulations are given in previous
sections of Appendix G.
'-swi-^KrwSS&ssrsSStr'
,^.,;^A Reuort for Site Visit to. Shell Chemical Company, Deer Park, TX
on April 2, 1984 from J.R. Butler, MRI, to D.A. Beck, OAQPS,
U.S. E.P.A.
6 Letter from R.A. Conrad, Conoco Chemicals Company to J. 'Farmer,
OAQPS, U.S. E.P.A. dated May 15, 1984.
7 Letter from C.V. Gordon, Vulcan Chemicals to J. Farmer,
OAQPS, U.S. E.P.A. dated May 7, 1984.
-
above in footnote A.
G - 32
-------
c -
Bavg - The data available from the 114 questionnaires were compiled
to obtain average values for certain stream characteristics. The
averages which were used in the table,.are listed below. . The standard
deviation for each average is also listed to indicate the variation
in the available data.
number.'of process vents = 2.2 _+ 1.9
source area (m2) = 36,400 +. 51,800
stack height (m) = 18.5 +. 10.2
stack diameter (m) = 0.58 _+ 0.27
process vent emission temperature (ฐC) = 29.6 +_24.2
The emission rates for all process vents and the equipment leaks for
facilities which did not receive 114 questionnaires were calculated
based upon 1) ethyl ene dichloride emission rates as given in Memorandum
from M Putnam, Midwest Research Institute, to D. Beck, OAQPS, E.P.A. .
Estimates of Ethylene Bichloride Emissions from Production Facilities
and HEM Inputs. April 23, 1986. p. 5-11. and 2) the E+C1:EDC ratio (see
reference in A). The EDC process emissions were calculated and
then multiplied by the EtclrEDC ratio.
The total EtCl process emissions were
then divided by the number of process vents.
Total EDC (kg/yr) x EtCl (kg) = EtCl (kg/yr)
EDC (kg)
D - Default values and stream characteristics from EDC production analysis.
The values, as given in the EDC memorandum (referenced in C above) were:
equi pment
leaks
St ack/
vent
height
Cm)
3.0
Stack/
vent
diameter
60
Emission
velocity
(m/s)-
0.01
Temperature
(K)
293
When data necessary to determine velocity of the process stream were
not available, the value 7.9 m/s was used. This value was also from
the EDC memorandum.
G-33
-------
Appendix 6 References
1. U.S. Environmental Protection Agency, Report'l: Ethylene Dichloride
In: Organic Chemical Manufacturing, Volume 8. Selected Processes,
EPA-450/3-80-028C. December 1980. p. F-4,5.
2. Letter from J.W. Chupein,Arco, to J. Farmer, Office of Air Quality
Planning and Standards, U.S. EPA, dated March 29, 1984.
3. Letter from S. Arnold, Dow Chemical, to J. Farmer, OAQPS, U.S. EPA
dated April 25, 1984.
4. Letter from C. McAulliffe, Formosa Plastics Corp., to J. Farmer,
OAQPS, U.S. EPA dated March 25, 1984.
5. Letter from L.E. Kerr, 01 in Corp. to J. Farmer, OAQPS, U.S. EPA
dated July 23, 1984.
6. Report for Site Visit to Shell Chemical Company, Deer Park, TX on
April 2, 1984 from J.R. Butler, MR I, to D.A. Beck, OAQPS, U.S. EPA.
7. Letter from R.A. Conrad, Conoco Chemicals Company to J. Farmer,
OAQPS, U.S. EPA dated May 7, 1984.
8. Letter from C;V. Gordon, Vulcan Chemicals to J. Farmer, OAQPS, U.S.
EPA dated May 7, 1984.
9. Memorandum from M. Putnam,. Midwest .Research Institute, to D. Beck,
OAQPS, .U.S. EPA. Estimates of Ethylene Dichloride Emissions from
Production Facilities and HEM Inputs. April 23, 1986. p. 5-11.
10. U.S. Environmental Protection Agency, Fugitive Emission Sources of
Organic Compounds - Additional Information on Emissions, Emission
Reductions, and Costs, EPA 450/3-82-010, Research Triangle Park, NC,
April 1982. p. 1-6, 2-70.
G-34
-------
APPENDIX H. HUMAN.EXPOSURE MODEL (HEM) INPUTS
The human exposure model. (HEM) is'a screening model which is used in
the risk assessment process. The model combines emission estimates, health
assessment, and census data to indicate the relative risk to the public
from emissions of a chemical.
The input parameters necessary for the dispersion model are listed
in Tables H.2-1 through H.2-5. Information on the bases and estimation
of these values is given in the main text and the other appendices of
this document.
H.I. Default Parameters
Process specific data for emissions are rarely available. Because
of this, defult input parameters frequently must be used for dispersion
modeling. Some of these default parameters have to do with the location
of point sources. If the specific latitude and longitude of a process
facility are not available, the latitude and" longitude of the city in the
facility's address are used. Unless other information is available,
facilities are assumed to be located in rural, rather than urban, areas.
The rural designation means that a less turbulent air flow pattern will
be used in the dispersion model.
Frequently used default parameters for equipment leaks are given in
Table H.l-1.
Table H.l-1 - Equipment Leak Default Parameters
Stack/ vent
height
(meters)
Emi ssion
velocity
(M/s)
Emi ssion
temp.
(K)
0.01
298
H-l
-------
Because process emission data are rarely available, it is frequent,y
neces ary to L. assumptions or use defau,t values for the,, a
palters also. An ambient temperature, H, the range of ZW-30ซMป
frequently assumed unless other information is ava,lable.
"*" 0 . of the necessary parameters is the emission steam ,. oc, y.
velocity used for ethyl chloride production is given in Appendix t. Un t
colverlns for a reasonable range of process emission velocity are g,ven
below.
Process Velocity Emissions:
Basis:
Reasonable velocity range - 2,500 - 3,000 fpm from:
American Conference of Governmental Industrial Hygiemsts,
industrial Ventilation: A Manual of Recommended Practice,
14th Ed. ACGIH. Lansing Michigan. 1977. p.6-23.
2.500 ft x l.min x 1 meter = 12.7 meter/s
m1ri 60 sec 3,281-ft . . . . . .
3.000 ft x 1 min x 1 meter =15.2 meter/s
min 60 sec 3.281 ft
H 9 HEM Input Tables
T e val es in these tables are estimates based upon readi,y availb e
^formation. IThey should oniy be used while ,eeping in mind the uncert^ ties
and limitations associated with the calculation of these estate Sight
into these limitations may be gained by familiarity ซith the ,ndustnes
the processes, and the various methods of estimation wh,ch were used to
obtain the values.
H-2
-------
Because process emission data are rarely available, it is frequently
necessary to make assumptions or use default values for those emission
parameters also. An ambient temperature, in the range of 293-300K is
frequently assumed unless other information is available.
One of the necessary parameters is the emission steam velocity. The
velocity used for ethyl chloride production is given in Appendix C. Unit
conversions for a reasonable range of process emission velocities are given
below.
Process Velocity Emissions:
Basis: Reasonable velocity range = 2,500 - 3,000 fpm from:
American Conference of Governmental Industrial Hygienists,
Industrial Ventilation: A Manual of Recommended Practice,
14th Ed. ACGIH. Lansing Michigan. 1977. p.6-23.
2,500 ft x 1 min x 1 meter = 12,7 rfieter/s
min 60 sec .3,281 ft '
3,000 ft x 1 min x 1 meter =15.2 meter/s
min 60 sec 3.281 ft
H.2. HEM Input Tables
The values in these tables are estimates based upon readily availble
information. IThey should only be used while keeping in mind the uncertainties
and limitations associated with the calculation of these estimates. Insight
into these limitations may be gained by familiarity with the industries,
the processes, and the various methods of estimation which were used to
obtain the values.
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