VOLUME III
FINAL REPORT
Contract No. 68-02-1337
Task Order No. 8
GCA-TR-75-32-G (3)
ASSESSMENT OF ETHYLENE DKHIORM
AS A POTENTIAL AIR POLLUTION PROBLEM
Prepared For
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park
North Carolina 27711
January 1976
-------
GCA-TR-75-32-G(3)
ASSESSMENT OF ET1IYLENE DICIILORIDE
AS A POTENTIAL AIR POLLUTION PROBLEM
Volume III
by
Robert M. Patterson
Mark I. Bornstein
Eric Garshick
GCA CORPORATION
GCA/TECHNOLOGY DIVISION
Bedford, Massachusetts
January 1976
Contract No. 68-02-1337
Task Order No. 8
EPA Project Officer
Michael Jones
EPA Task Officer
Justice Manning
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park
North Carolina 27711
-------
This report was furnished to the U.S. Environmental Protection Agency by the
GCA Corporation, GCA/Technology Division, Bedford, Massachusetts 01730, in
fulfillment of Contract No. 68-02-1337, Task Order No. 8. The opinions,
findings, and conclusions expressed are those of the authors and not neces-
sarily those of the U.S. Environmental Protection Agency or of the cooperating'
agencies. Mention of company or product names is not to be considered as an
endorsement by the U.S. Environmental Protection Agency.
-------
ABSTRACT
This report is one of a series which assesses the potential air pollution
impacts of 14 industrial chemicals outside the work environment. Topics
covered in each assessment include physical and chemical properties,
health and welfare effects, ambient concentrations and measurement meth-
ods, emission sources, and emission controls. The chemicals investigated
in this report series are:
Acetylene
Methyl Alcohol
Ethylene Bichloride
Benzene
Acetone
Acrylonitrile
Cyclohexanone
Formaldehyde
Methyl Methacrylate
Ortho-Xylene
Maleic Anhydride
Dimethyl Terephthalate
Adipic Acid
Phthalic Anhydride.
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Volume VII
Volume VIII
Volume IX
Volume X
Volume XI
Volume XII
Volume XIII
Volume XIV
iii
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CONTENTS
Page
Abstract iii
List of Figures v
List of Tables v
Sections
I Summary and Conclusions 1
II Air Pollution Assessment Report 3
Physical and Chemical Properties 3
Health and Welfare Effects 4
Ambient Concentrations and Measurement 10
Sources of Ethylene Bichloride Emissions 12
Ethylene Bichloride Emission Control Methods 16
III References 21
Appendix
A Ethylene Bichloride Producers - 1974 24
iv
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FIGURE
_No. Page
1 Estimated Installed Cost of EDC Storage Tanks (Equip-
ment Costs Assumed to be the Same as Gasoline Storage
Tanks) 20
TABLES
No. 'Page
1 Significant Properties of EDC 3
2 Correlation of Symtoms, Exposure Time and Concentration
For Guinea Pigs Inhaling EDC 6
3 Mortality After Single Exposures to EDC 7
4 Mortality of Animals Exposed to 1500 ppm EDC 7
5 Ethylene Dichloride Consumption - 1974 13
6 Vinyl Chloride Monomer Producers Using Pyrolysis of
EDC - 1974 14
7 Ethylene Dichloride Emissions - 1974 14
8 Cost Data for Scrubbers and Condensers for Control of
EDC Emissions 17
9 Cost Data for The Control of Ethylene Dichloride by
Incineration 18
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SECTION I
SUMMARY AND CONCLUSIONS
Ethylene dichloride (EDC) is a clear, colorless oily liquid with a
pleasant chloroform-like sweet odor and taste. Industrially it is made
from ethylene by direct chlorination or by oxychlorination. EDC is used
as an industrial solvent in cleaning and extraction processes. It is
also used as a fumigant and' as a lead scavenger in gasoline. However, most
EDC produced goes into the manufacture of vinyl chloride monomer.
Data correlating acute or chronic ethylene dichloride (EDC) exposures to
human response are quite limited. Depending on the exposure time, acute
EDC poisoning may occur at high concentrations (above 3000 ppm) through
attack on the central nervous system. The current OSHA standard for
worker exposure to EDC is a time weighted average of 50 ppm for an 8-hour
work day, 40-hour work week. Chronic exposure to sufficiently high con-
centrations of EDC may cause loss of weight, drowsiness, vomiting, and
nervousness. EDC has been used as a grain and seed fumigant and does not
affect seed germination. The hydrogen-carbon bonds in EDC are reactive,
and decomposition occurs in the troposphere. Thus, it does not seem to
pose a direct threat to stratospheric ozone.
Emissions of EDC are primarily a result of EDC production, end product
manufacture, solvent usage, and bulk storage and transportation. Total
emissions of EDC are estimated to be 163 million Ib/year. EDC production
and end product manufacture are the two largest sources, accounting for
36 and 52 percent respectively of total emissions. Estimated 1974 pro-
duction was 9300 million pounds by 14 plants with about 86 percent produced
-------
in Texas and Louisiana. Production is expected to increase at 9 percent
per year through 1978. EDC is used primarily (77 percent) to manufacture
vinyl chloride monomer.
Emissions of EDC may be controlled by several methods. Currently only
scrubbers and condensers are. used to control EDC emissions from manu-
facturing processes. Incineration is a third technique; however, hydro-
chloric acid and chlorine gas are produced during incineration. Fixed
roof storage tanks can be controlled by venting to a condenser, or 'they
can be converted to a floating roof design.
Simple diffusion modeling estimates place the likely maximum 1-hour average
ambient concentration outside the work environment at about 5 ppm. The
maximum 24-hour average ambient concentration might be expected to be
about 3 ppm.
Based on the results of the health research presented in this report, and
the ambient concentration estimates, it appears that ethylene dichloride
as an air pollutant does not pose a threat to the health of the general
population. In addition, ethylene dichloride does not appear to pose
other environmental insults which would warrant further investigation or
restriction of its use at the present time. However, two actions should
be considered: (1) that concentrations be monitored in a small-scale
program around one of the larger EDC production facilities or vinyl
chloride monomer production facilities, and (2) that potential adverse
effects on the earth's ozone layer be monitored in conjunction with the
research into the effects of other halocarbons.
-------
SECTION II
AIR POLLUTION ASSESSMENT REPORT
PHYSICAL AND CHEMICAL PROPERTIES
Ethylene dichloride (EDC) is a clear, colorless oily liquid with a pleasant
chloroform-like sweet odor and taste. Industrially it is made from ethy-
lene by direct chlorination or by oxychlorination. EDC is used as an
industrial solvent in cleaning and extraction processes. It is also
used as a fumigant and as a lead scavenger in gasoline. However, most EDC
produced goes into the manufacture of vinyl chloride monomer.1 Selected
physical and chemical properties are presented in Table 1.
Table 1. SIGNIFICANT PROPERTIES OF EDC
Synonyms: 1,2 dichloroethane; sym. dichloroethane; ethylidene chloride
Chemical formula
Molecular weight
Boiling point
Melting point
Specific gravity
Vapor density
Vapor pressure
Solubility
Explosive limits
Auto ignition temperature
Flash point
At 25°C and 760 mm Hg
CH2 Cl CH2 Cl
98.97
83.5°C
o
-35.3 C
1.253 (20°/4°C)
3.34 (air = 1)
62 mm Hg at 20°C
0.9 parts/100 parts of water at 0 C soluble
in ethanol and ether
6.2 percent to 15.9 percent by volume
413°C
13°C (closed cup)
3
1 ppm vapor = 3.97 mg/m
1 mg/m-' vapor = 0.252 ppm
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HEALTH AND WELFARE EFFECTS
Effects on Man
Acute Poisoning - Reports in the literature correlating the concentration
of ethylene dichloride in air with acute human response are lacking. At
high concentrations in air, probably approaching 1000-3000 ppm based on
studies done on animals, EDC is irritating to the eyes, nose, and throat.
Two men exposed to 1200 ppm EDC vapor for 2 minutes experienced little
2
discomfort, except that the odor of EDC was extremely noticeable. Halo-
genated hydrocarbons such as EDC, upon inhalation, typically cause general
stupor, mental confusion, dizziness, nausea, vomiting, symptoms of central
3 4
nervous system depression and gastrointestinal upset. ' It is possible
to recover from such symptoms with no after effects.
Only a few fatal cases of' acute EDC poisoning have been reported. In
one case a workman repairing a vessel used to transport EDC became uncon-
scious after exposure for only a few minutes. He appeared to recover,
but several hours later lapsed into a coma and died. His skin was covered
by an oily mass due to the separation of carotene in the -skin, caused by
skin absorption of EDC. However, absorption through the skin is too
small to be significant in contributing to systemic poisoning. There
was considerable pulmonary edema, liver degeneration, renal congestion,
and meningeal hemorrhages. In a second case, two men exposed to a leaking
EDC pipe for 30 minutes died hours later with suppression of urine produc-
tion, jaundice, and circulatory failure. However, the primary target of
EDC after inhalation appears to be the central nervous system.
Oral ingestion of 1 to 2 ounces, about 845 mg/kg body weight, of EDC by
8 9
an adult male is fatal. ' Body reaction to the dose may be delayed as
much as 2 hours, with death occurring up to 22 hours later. The autopsy
report after the ingestion of 1 ounce of EDC showed hemorrhage damage
in the stomach, lungs, and brain, with acute toxic kidney degeneration
and diffuse pathological death of liver cells.
-------
Chronic Poisoning - Chronic exposure of man to EDC has not been well
documented. Two cases were reported in a cholesterol producing plant
where EDC was used as a solvent. One worker, employed for 9 weeks,
complained of weight loss, drowsiness, and nervousness. The other subject,
employed for 5 months, complained of upper-abdominal pain and tremor of
the tongue. Both complained of nausea and vomiting. -After removal from
the vapors, all symptoms disappeared.
The odor of EDC is barely detectable at 50 ppm, and is not unpleasant in
the 100 to 200 ppm range. The odor of EDC is not sharp enough to act as
a warning of dangerous chronic exposure, according to inhalation studies
done on animals. Based primarily on animal exposure data, the NIOSH
recommended standard for exposure to EDC is a 50 ppm time weighted aver-
age over an 8-hour shift. The individual may be exposed to 100 ppm for
a maximum of 10 minutes, but never above 200- ppm.
Effects on Animals
Acute Poisoning - The symptoms in animals of acute EDC exposure are
similar to human symptoms. Table 2 shows the correlation between EDC
dose and duration of exposure to symptoms produced in-guinea pigs. The
period of reco-very from semi-consciousness and unconsciousness to the
normal actions of guinea pigs varied from 15 to 60 minutes. However,
depending on the concentration and time of exposure, many of the appar-
ently recovered animals died within 8 days. The principal pathological
findings after death were congestion and edema of the lungs, and kidney
degeneration. No serious internal damage was found in guinea pigs
exposed to 60,000 ppm for 5 minutes, 17,000 ppm for 10 minutes, 4,000
ppm for 30 minutes, 2,000 ppm for 120 minutes, and 1;100 ppm for 480
minutes.
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Table 2. CORRELATION OF SYMPTOMS, EXPOSURE TIME ANDr
CONCENTRATION FOR GUINEA PIGS INHALING EDC'
Symptom
Nose and eye
irritation
Uns tcadiness
Inability to
walk
Retching
Jerky, rapid
respiration
Unconsc iousness
Concentration,
ppm '
2,000
6a
20-45
(480)
(480)
(480)
(480)
4,000-4,500
3-10
8-18
30
(360)
(360)
30-60
10,000-17,000
1-2
2-3
4-10
7-15
10-30
10-20
25,000-35,000
1-2
1-2
3-5
5-13
5-13
4-7
60,000-70,000
1
1-2
2-4
2-4 '
4-8
3-7
Time of exposure in minutes. Values in parentheses indicate the time
of exposure where the stated symptoms were not observed.
Table 3 summarizes mortality in seven species of animals due to a single
exposure to EDC. Note that in many cases death after exposure to EDC
did not occur for several days. Twenty young adult rats showed responses
to the 7-hour exposure varying from mild stupor to complete loss of
consciousness. The rats were alive at the end of the exposure period,
but all died within 48 hours. Microscopic tissue examination revealed
congestion of the viscera, particularly of the liver and spleen, fatty
degeneration of the liver, and kidney degeneration.
Exposure of dogs to 1000 ppm for 7 hours produced a clouding of the cornea
that was reversible. After repeated exposures, the dogs became resistant
to the clouding. This effect has not been demonstrated in man. Subcuta-
neous injection of EDC (1 cc/kg body weight) into rats produced an average
mortality rate of 35 percent in 24 hours, with a high incidence of fatty
12
changes in heart, liver, and kidney.
Chronic Poisoning - Table 4 summarizes the mortality rates for the
types of animals exposed to 1500 ppm EDC for 7 hours per day. After the
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Table 3. MORTALITY AFTER SINGLE EXPOSURES TO EDC
11
Animal
Exposure, 3000 ppm
Rabbits
Guinea pigs
Hogs
Cats
Raccoons
Mice
Mice
Rats
Rats
Rats
Exposure, 1500 ppm
Guinea pigs
Mice
Mice
Rats
Rnts
Number
16
14
2
3
2
22
19
20
16
15
12
20
23
20
13
Weight,
grams
3,9^0
885
27,300
3,240
146
177
257
321
170
257
Time,
hou rs
7 .
7
7
7
7
7
2
7
H
7
7
2
7
4
Mortality
Rfit io
12/16
14/14
2/2
0/3
0/2
22/22
19/19
20/20
15/16
0/15
6/12
20/20
1/23
4/20
0/13
Cumulative mortality,
days after exposure
0
0
0
0
22
0
0
0
0
4
0
0
1
7
11
0
19
19
1
1
20
0
2
2
11
13
2
20
3
4
0
2
3
12
14
5
5
1
4
4
13
6
5
15
Table 4. MORTALITY OF ANIMALS EXPOSED TO 1500 ppm EDC
11
Animal
Rats
Rabbits
Guinea pigs
Dogs
Hogs
Number
29
5
9
3
2
Weight,
grams
125
1,640
250
32,300
Mortal ity
29/29
4/5
9/9
2/3
2/2
Total deaths
Number of exposure days
1
0
1
1
0
1
2
5
1
6
0
2
3
17
1
8
0
4
26
2
9
0
5
29
4
1
6
2
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first exposure, walking became difficult, there was a loss of appetite,
and bloody crusts appeared around the nose. After three exposures the
animals lay on their sides with very shallow breathing, and moved with
difficulty. Autopsy revealed hemorrhage of the adrenal gland, hemorrhage
and congestion of the lungs, and kidney tubule degeneration.
Autopsy results for the five animal types were similar. Exposures to
lower concentrations for longer periods were also evaluated. At 1000 ppm,
repeated 7-hour exposures were rapidly fatal to guinea pigs, rats, and
mice. Dogs, cats and monkeys survived a period of 23 to 55 days. At
400 ppm and repeated 7-hour exposures, dogs remained in good health for
8 months, while rabbits were only able to survive 100 exposures. At
200 ppm, deaths still occurred among guinea pigs and rats after 126 ex-
4
posures. In another study guinea pigs and rats survived for 212 days
while being exposed to 200 ppm EDC, 7 hours-per day, 5 days per week,
but half the pigs showed histological changes.
Rats, guinea pigs, rabbits, and monkeys, exposed to a lower concentration
of 100 ppm, survived for 168 days with no ill effects. Rats, guinea
pigs, and rabbits tolerated 100 ppm for a 17-week period, with exposure
13
for 6 hours per day, 5 days per week.
The chronic toxicity of EDC in mice can be linked to its metabolic break-
down. EDC breakdown appears to involve the enzymatic removal of one its
chlorine atoms, resulting in the formation of chloroacetate. ' The
toxicity of chloroacetate has been ascribed to the lability of the chlo-
rine, by which the compound can react with the thiol groups of proteins,
disrupting normal protein function and structure.
Effects on Vegetation
EDC is widely used as a grain and seed fumigant, and thus would not
inhibit the germination of any sprayed seeds. (See below.)
8
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Other Effects
Effects of Use - In the past, EDO has been widely used as an insecticidal
fumigant, both as a pure compound and mixed with 25 percent carbon tetra-
chloride, according to a 1928 report.5 For years the Dow Chemical Company
has manufactured a series of Dowfume fumigants17 as listed below.
Weight percent
Ethylene
Fumigant
Dowfume 75
Dowfume EB-5
Dowfume EB-15
Ethylene
dichloride
70.2
29.2
19.6
Carbon
tetrachloride
29.8
63.6
60.0
Ethylene '
dibromide
--
7.2
20.4
Dowfume 75 has essentially the same acute oral and vapor toxicity as EDC.
Dowfume 75 and EB-5 are used in the control of insects in stored grain
and animal feed, while EB-15 is used as a fumigant for mill machinery.
In a recent study zero or trace amounts of EDC were found as residues in
1 8
bread made from EB-5 fumigated grain.
Effects of Decomposition - Typical chlorocarbon decomposition products
are phosgene, chlorine, and hydrogen chloride, all noxious to man. Weld-
ing tests in the presence of 500 ppm EDC produced only small amounts of
chlorine and hydrogen chloride. The possibility exists that when the
compound is burned or heated at higher concentrations, the noxious de-
19 20
composition products could be significant. '
21 22
Effects on Ozone - Evidence ' demonstrates that the photocatalyzed
removal of chlorine atoms from chlorofluorocarbons results in a catalytic
chain reaction destroying ozone in the stratosphere. However, halogenated
compounds such as EDC containing relatively reactive hydrogen-carbon
bonds are more likely to be destroyed by attack from atmospheric OH
-------
radicals before reaching the upper atmosphere. EDC does not present a
threat to the ozone layer due to a short lifetime in the atmosphere with
decomposition at lower levels.
AMBIENT CONCENTRATIONS AND MEASUREMENT
Ambient Concentration Estimates
The greatest emission source of ethylene dichloride is a vinyl chloride
manufacturing plant, located in a town of about 2000 population, with a
capacity of up to 1000 million pounds/year. Assuming a 1 percent loss
of ethylene dichloride based on vinyl chloride production, this amounts
to 10 million pounds/year of ethylene dichloride emissions. As a more
useful emission rate for ambient concentration estimation, this converts
to:
(10 x 106 Ib/yr) (453.6 B/lb) = 143<8 g/sec<
3.1536 x 107 sec/yr
Some assumptions must be made regarding this ethylene dichloride release
to the atmosphere. First of all, the emissions do not all come from one
source location, but rather from a number of locations within the plant
where ethylene dichloride vapor leaks or is vented to the atmosphere.
Thus, the emissions can be characterized as corning from an area source
which will be taken to be 100 meters on a side. Secondly, the emissions
occur at different heights, and an average emission height of 10 meters
is assumed.
Ground level concentrations can then be estimated at locations downwind
O Q
of the facility. To do this a virtual point source of emission is
assumed upwind of the facility at a distance where the initial horizontal
dispersion coefficient equals the length of a side of the area divided
by 4.3. In this case:
10
-------
ayo = 100m/4.3 = 23.3m.
Assuming neutral stability conditions (Pasquill-Gifford Stability Class D)
with overcast skies and light winds, the upwind distance of the virtual
point source is approximately 310 meters. With consideration of the
plant boundary, it is reasonable to assume that the nearest receptor loca-
tion is thus about 500 meters from the virtual point source. Finally,
taking 2 m/sec as an average wind speed, the ground level concentration
may be calculated from:
X = _JL_ e-
U7TO" a \ Z
or
143.8
(2)^(36)(18.5)
= 2.969 x 10 2 g/m3
for a 10-minute average concentration. Over a period of an hour this
becomes:
(2.969 x 10"2 g/m3) (0.72) = 2.138 x 10"2 g/m3
or 5.4 ppm 1-hour average concentration. Over a 24-hour period, the
average concentration might roughly be expected to be about 3 ppm.
Measurement Technology
Two sample collection techniques are used in air sampling for ethylene
dichloride. These are collection in aqueous pyridine solution in a
bubbler or impinger, and collection on silica gel. Analysis of samples
11
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collected by the first technique is achieved by coloritnetric methods,
whereas gas chromatography is used to analyze samples collected on
silica gel.
Using the bubbler or impinger collection method, concentrations as low
as 25 ppm may be determined from a 1-liter gas sample. The sample is
heated in a water bath followed by cooling and addition of sodium
hydroxide. Ethyl alcohol is used to dilute the sample before reading
the optical density at a wavelength of 415 my with a spectrophotqmeter.
Carbon tetrachloride, chloroform, trichloroethylene and ethylene
chlorohydrin do not interfere with the analysis but chlorine (at 3 ppm)
does interfere. This method may not be sensitive enough for measuring
atmospheric concentrations.
In the second method the sample is collected by silica gel in a narrow
glass tube. The sample is desorbed from the silica gel by heating and
passed through a gas chromatograph. Similar compounds have been mea-
24
sured by using a Celite 545 column and a flame ionization detector.
SOURCES OF ETHYLENE BICHLORIDE EMISSIONS
Ethylene Bichloride Production and Consumption
The production of ethylene dichloride (EDC) is estimated to have been
9300 million pounds in 1974 and is expected to increase at 9 percent
25
per year through 1978. Approximately 77 percent of all ethylene
dichloride produced is used to manufacture vinyl chloride monomer.
Presently, almost all production is carried on by large plants produc-
ing a balanced combination of ethylene dichloride and vinyl chloride.
The consumption of ethylene dichloride for final products and the
expected growth rate for each product are shown in Table 5.
12
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Table 5. ETHYLENE BICHLORIDE CONSUMPTION - 197426
Product
Vinyl chloride
Exports
Lead scavenger
Trichloroethylene
Perchloroethylene
Methyl chloroform
Ethyleneamines
Vinylidene chloride
Miscellaneous
Total
Millions of pounds
7,141
791
280
260
245
210
184
175
14
9,300
Expected annual
growth rate
9%
steady
decline in use
decline in use
6%
9%
7%
7%
7%
9%
Ethylene dichloride is manufactured by 10 companies at 14 locations.
About 50 percent is produced in Louisiana and 36 percent is produced in
Texas. The largest plant represents 18 percent of total EDC production
capacity. A list of EDC producers including their production capacity
and plant location, is presented in Appendix A. Because the majority of
EDC is used to produce vinyl chloride monomer, a list of vinyl chloride
monomer producers is presented in Table 6.
Ethylene Dichloride Sources and Emission Estimates
Ethylene dichloride emissions result from end product manufacturing,
ethylene dichloride production, miscellaneous solvent uses, and bulk
storage and distribution. Total emissions from all categories are esti-
mated to be 163 million pounds representing 1.8 percent of total produc-
tion (see Table 7).
13
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Table 6. VINYL CHLORIDE MONOMER PRODUCERS USING
PYROLYSIS OF EDC - 197428
Company
Location
Capacity,
million Ib/yr
Allied Chemical
American Chemical
Continental Oil
Dow Chemical
Ethyl Corporation
B.F. Goodrich
PPG Industries
Shell Chemical
Totala
Baton Rouge, La.
Long Beach, Cal.
Lake Charles, La.
Freeport, Texas
Plaquemine, La.
Oyster Creek, Texas
Baton Rouge, La.
Pasadena, Texas
Calvert City, Ky.
Lake Charles, La.
Guayanilla, P.R.
Deer Park, Texas
300
165-170
600
180
300-340
800
270
150
875-1000
300
500-575
700
5,140-5,385
An additional 525-550 million pounds are produced by
hydrochlorination of acetylene.
Table 7. ETHYLENE DICHLORIDE EMISSIONS - 1974
Source
Emissions,
million Ib/yr
End product manufacturing
Ethylene dichloride production
Solvent usage
Bulk storage and distribution
Total
85
58
14
6
163
14
-------
The major source of ethylene dichloride emissions is the manufacturing
of end products, primarily vinyl chloride. Based on a 1 percent loss,
27
emissions from this category are 85 million pounds.
The second major source is the manufacturing of ethylene dichloride. EDO
is produced chiefly by two processes, direct chlorination of ethylene and
oxychlorination as outlined below:
Direct chlorination: CH2 = CH2 + C12 + C1CH2 CH2C1
ethylene chlorine ethylene dichloride
Oxychlorination: 2 CH2 = CH2 + 0 + 4HC1 ->• 2 C1CH2 CH2C1 + 2 H20
ethylene oxygen hydrochloric ethylene water
acid dichloride
Emissions from the direct chlorination process are relatively small com-
pared to the oxychlorination process. Specifically, atmospheric pollu-
tants from the direct chlorination process are less than 1/5' of those
90
emitted by the oxychlorination method for the same quantity of product.
The main sources of emissions from the oxychlorination process are the
process vent stream and the fractionation vent stream. Estimated average
emissions from these sources are 986 Ib/hr of ethylene dichloride for a
o o
700 million Ib/yr plant. Based on these data and the 1974 production
of ethylene dichloride by the oxychlorination process (42 percent of
9300 million Ib) , emissions of EDC from this manufacturing process are
48.2 million Ib/yr. Total ethylene dichloride emissions from both manu-
facturing methods are, therefore, estimated to be 58 million Ib/yr.
The third major source of EDC emissions is the use of EDC as a solvent.
It is assumed that the total quantity of material used for this purpose
is lost to the atmosphere. Solvent usage is estimated to be 14 million
A 26
pounds »
15
-------
The last major source of emissions is the storage and distribution of
EDO. In present plants fixed roof tanks are used and are vented to the
atmosphere because the vapor pressure is low (3 psi at 100°F). It
is estimated that EDO emissions from storage and handling are 6 million
28
Ib/yr based on a 0.06 percent loss factor.
ETHYLENE BICHLORIDE EMISSION CONTROL METHODS
Emissions of EDC may be controlled by several methods. Currently only
scrubbers and condensers are used to control EDC emissions from manufac-
29
turing processes. Incineration may also be used but formation of HCl
and Cl? might create an emission problem. Fixed roof storage tanks can
be vented to a condenser or converted to a floating roof design.
Scrubbers and Condensers
Scrubbers are employed primarily to remove small amounts of HCl and in
some cases chlorine left in the noncondensed reactor effluent. A water
scrubber is able to remove most of the HCl, but dilute caustic is re-
quired to eliminate all of the chlorine from the vent gas. Depending
29
on the operating conditions some EDC may also be absorbed (39 percent).
The second control device currently being used by the industry is the
condenser. This system, unlike the aqueous scrubber, is designed pri-
marily to recover EDC. The recovery of 97.9 percent of EDC is reported
o 29
by the industry when the effluent stream is cooled to -10 F.
Cost data for both systems are presented in Table 8. While the capital
cost for condensers is almost four times higher than scrubbers, the
condenser system has a higher recovery of EDC resulting in an overall
net savings. The overall hydrocarbon control efficiency is also greater
(89.4 percent compared to 25 percent).
16
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Table 8.
COST DATA FOR SCRUBBERS AND CONDENSERS
FOR CONTROL OF EDC EMISSIONS29
Gas rate, Ib/hr
Installed cost
material and labor, $
Annual operating cost, $
Value of recovered product,
$/yr (credit)
Annual net operating cost,
$ (credit)
Overall hydrocarbon control
ef f ic iency
EDC control efficiency
Scrubber
65
12,300
3,520
1,800
1,720
25%
39%
Condenser
178
207,200
22,700
(87,400)
(64,700)
89.4%
97.9%
Costs updated to 1st quarter 1975.
Incineration
Several combustion devices have been proposed for the control of emissions
of EDC and other chlorinated compounds resulting from the manufacture of
EDC. However, none of these systems, which are mentioned below with their
related costs, are currently being used by the industry. The primary
objection to their use is the formation of HCl and Cl during combustion,
which must be scrubbed out of the effluent stream.
Table 9 presents cost data for four systems:
1. Direct fired boiler and caustic scrubber
2. Thermal incinerator and caustic scrubber
3. Thermal incinerator and waste heat boiler with a caustic scrubber
4. Flare system.
17
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a 28
Table 9. COST DATA FOR THE CONTROL OF ETHYLENE DICHLORIDE BY INCINERATION
Total flow, Ib/hr
SCFM
Total capital cost, $
Operating cost, $/yr
Steam production,
$ (savings)
Recovered EDC, $ (savings)
Net annual cost, $
Percent control of EDC
Direct fired
boiler and
caustic scrubber
78,588
17,280
1,600,000
819,000
(234,000)
-
585,000
~100%
Thermal incin-
erator and
caustic scrubber
78,588
17,280
800,000
538,000
-
-
538,000
«1007.
Thermal incin-
erator, waste heat
boiler, and caustic
scrubber
78,588
17,280
1,096,000
652,000
(234,000)
-
418,000
«1007»
Flare
system
17,588
17,280
141,000
414,000
-
-
414,000
-
oo
Costs updated to 1st quarter 1975.
-------
gtorage Tanks
Control of emissions from storage tanks would require the use of floating
roof tanks or condensers. Emissions from fixed roof tanks can readily
be vented to the condensers previously described without any significant
increase in cost. If a condenser system is not readily available, the
fixed roof tanks could be converted to floating roof tanks. A 70 percent
reduction in emissions can be achieved by conversion. Figure 1 provides
30
estimated costs of various gasoline storage tanks. These equipment cost
estimates can also be applied to EDC. As can be seen, conversion of fixed
roof to floating roof tanks by installation of internal floating covers
is more economical than the installation of new pontoon floating roof tanks,
19
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500
400
'o 300
x
O
u
o
y 200
_J
<
z
100
Totol Cosl Cono Roof Tonk Converted
with Inlernol Floating Roof
Pontoon Floating
Roof Tank
Cono Roof Tank
Internal Float Cover on Existing Cone
Roof Tank (Incremental Cost - Conversion]
50 100 150
CAPACITY, barrels x )(J3
200
Figure 1. Estimated installed cost of EDC storage tanks (equipment
costs assumed to be the same as gasoline storage tanks)
30
20
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SECTION III
REFERENCES
1. Kent, J. A. (Ed). Riegel's Handbook of Industrial Chemistry,-
Seventh Edition. New York, Van Nostrand Reinhold Company, 1974.
2, Sayers, R. R., W. P- Kant, F. A. Patty. Acute Response of Guinea
Pigs to Vapors of Some New Commercial Organic Compounds: I. Ethylene
Bichloride. Public Health Reports, U.S. Reprint No. 1949,
January 31, 1930.
3. Stevens, H. Neu otoxicity of Some Common Halogenated Hydrocarbons.
In: Laboratory Diagnosis of Diseases Caused by Toxic, Agents.
Sunderman, F. W., and F. W. Sunderman, Jr. (ed). St. Louis,
Warren H. Green, Inc., 1970. p. 193-194.
4. Irish, D. C. Halogenated Hydrocarbons. I. Aliphatic-Ethylene
Bichloride. In: Industrial Hygiene and Toxicology, Second Revised
Edition, Patty, F. A. (ed). New York, Interscience Publishers,
2:1280-84. 1962.
5. Browning, E. Toxicity and Metabolism of Industrial Solvents.
Amsterdam5 Elsevier Publishing Co., 1965. p. 247-52.
6, Brass, K. Fatal Dichloroethane Poisoning. Deut Med Worchschr. 74:
553, 1949. Cited in: Industrial Toxicology, Second Edition,
Fairhall, L. T. New York, Hafner Publishing Co., 1969. p. 213-214.
7. The Toxic Substances List 1974 Edition. U.S. Department of Health
Education and Welfare Publication No. (NIOSH) 74:134.
8. Hueper, W. C., C. Smith. Fatal Ethylene Dichloride Poisoning.
Am J M Sci. 189:778, 1935. Cited in: Ethylene Dichloride
Poisoning. McNally, W. D., Fostvedt, G. IndMed. 10:373-74, 1941.
9. Lochhead, H. B., H. P. Close. Ethylene Dichloride Plastic Cement:
A Case of Fatal Poisoning, J Amer Med Assoc. 146:1323, 1951.
21
-------
10. McNally, W. H. and G. Fostvedt. Ethylene Bichloride Poisoning.
Ind Med. 10:373-74, 1941.
11. Heppel, L. A., P- A. Neal, T. L. Ferrin, K. M. Endicott, V. T. Porter-
field. The Toxicology of 1,2-Dichloroethane (Ethylene). J Pharm
Exp Ther. 84:53-63, 1945.
12. Highman, B., L. A. Heppel, R. J. Lamprey. The Toxicology of 1,2-
Dichloroethane (Ethylene Bichloride). Arch Path. 51:346-50, 1951.
13. Hoffman, H. Th., H. Birnstiel, P. Jobst. On the Inhalation Toxicity
of 1,1- and 1,2-Dichloroethane. Arch Toxicol. 27:248-65, 1971.
14
14. Yllner, S. Metabolism of 1,2-Dichloroethane C in the Mouse.
Acta Pharmacol et Toxicol. 30:257-65, 1971.
15. Heppel, L. A., V. T. Porterfield. Enzymatic Behalogenation of Certain
Brominated and Chlorinated Compounds. J Biol Chem. 176:763-69, 1946.
14
16. Yllner, S. Metabolism of Chloroacetate-1- C in the Mouse. Acta
Pharmacol et Toxicol. 30:69-80, 1971.
17. McCollister, D. C., M. S. Hollingsworth, F. Oyen, V. K. Rowe. Com-
parative Inhalation Toxicity of Fumigant Mixtures. Arch Ind Health
13:1-7, 1956.
18. Berck, B. Fumigant Residues of Carbon Tetrachloride, Ethylene
Bichloride, and Ethylene Dibromide in Wheat, Flour, Bran, Middlings,
and Bread. J Agr Food Chem. 22:977-84, 1974.
19. Rinzema, L. C., L. G. Silverstein. Hazards from' Chlorinated Hydro-
carbon Becomposition Buring Welding. Amer Ind Hyg Assoc J. 33:
35-40, 1972.
20. Noweir, M., E. A. Pfitzer, T. F. Hatch. Becomposition of Chlorinated
Hydrocarbons: A Review. Amer Ind Hyg Assoc J. 33:454-59, 1972.
21. Scientists Betail Chlorofluorocarbon Research. Chem Eng News.
53:21-23, 1975.
22. Rowland, S. Aerosol Sprays and the Ozone Shield. New Sci. 64:717-
720, 1974. Also in: Fluorocarbons-Impact on Health and Environment.
Hearings Before the Subcommittee on Public Health and Environment
of the Committee on Interstate and Foreign Commerce, House of
Representatives, Serial No. 93-110, December 11-12, 1974, p. 22-25.
22
-------
23. Turner, D. Bruce. Workbook of Atmospheric Dispersion Estimates.
U.S. Environmental Protection Agency Report AP-26. January 1973.
24. Cropper, F. R., and S. Kaminsky. Determination of Toxic Organic
Compounds in Admixture in the Atmosphere by Gas Chromatography.
Anal Chem. 35:735, 1963.
25. Chemical Profiles. Schnell Publishing Co. 1974.
26. Chemical Economics Handbook. Stanford Research Institute-, Menlo
Park, California, 1972.
27. Survey Reports on Atmospheric Emissions from the Petrochemical
Industry. Vinyl Chloride Via EDC Pyrolysis. Volume IV.
U.S. Environmental Protection Agency. Publication No. EPA-450/3-
73-005-d. April 1974.
28. Engineering and Cost Study of Air Pollution Control for the Petro-
chemical Industry, Volume 3: Ethylene Bichloride Manufacture by
Oxychlorination. U.S. Environmental Protection Agency. Publication
No. EPA-450/3-73-006-C. November 1974.
29. Survey Reports on Atmospheric Emissions from the Petrochemical Indus-
try. Ethylene Dichloride (Direct). Volume II. U. S. Environmental
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30. Hydrocarbon Pollutant Systems Study. MSA Research Corp. NTIS Pub-
lication No. PB-219-073. October 1972.
23
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APPENDIX A
oq
ETHYLENE BICHLORIDE PRODUCERS - 1974
Total Direct OxychLori-
capacity, chlorination, nation,
million million million
Ib/yr Ib/yr Ib/yr
Allied Chemical
Corporation
American Chemical
Company
Conoco Chemicals
Diamond Shamrock
Chemical Co.
Dow Chemical
Company
Dow Chemical
Company
Ethyl Corporation
Ethyl Corporation
The B. F. Goodrich
Company
PPG Industries,
Inc.
Shell Chemical
Company
Union Carbide
Corporation
Union Carbide
Corporation
Vulcan Materials
Company
Total
Baton Rouge, La.
Long- Beach, Calif.
Lake Charles, La.
Deer Park, Texas
Freeport, Texas
Plaqueinine, La.
Baton Rouge, La.
Houston, Texas
Calvert City, Ky.
Take Charles, La.
Deer Park, Texas
Taft, La.
Texas City, Texas
Geismar, La.
645
325
968
265
1,100
1,160*
550
260
990
1,040
1,700
150
150
330
9,633
430
225
476
95 •
628
600
290
260
330
803
1,126
150
150
5,563
215
100
492
170
472
560
260
660
237
574
330
330
4,070
'Oxychlorination facility presently not in operation.
24
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