-------
Process Emissions --
Chloroform process emissions originate from the purging of inert gases
from the oxychlorination vent (Vent A, Figures 6 and 7) and from the release
of gases from the column vents (Vent B, Figure 6), primarily the heads column.
Chloroform was not detected in an emissions test of a direct chlorination
vent.24
The range of emission factors for the oxychlorination vent in the air
based process was determined from chloroform emission rates and associated
EDC production rates reported by three facilities. The lowest emission
factor, 0.033 kg/Mg, was calculated from a chloroform emission rate of
2700 kg/yr25 and an associated EDC production rate of 83,000 Mg/yr. The
highest chloroform emission factor, 0.65 kg/Mg was calculated from a chloroform
27
rate of 64,400 kg/yr and an associated EDC production rate of 99,800 Mg/yr.
An intermediate value, 0.15 kg/Mg, was calculated from a chloroform emission
pp pq
rate of 7,500 kg/yr and an EDC production rate of 50,000 Mg/yr.
Data on the chloroform concentration in the oxychlorination vent emissions
from the oxygen-based process were not available; therefore, the emission
factor for this process was calculated using emission composition data from
the air-based process. It was assumed that the percentage of chloroform in
total chlorinated hydrocarbon emissions is the same for the air-based and
oxygen-based processes. However, according to composition data for
oxychlorination vent emissions for hypothetical plants of the two processes,
chlorinated hydrocarbons are a smaller component of total VOC in the oxygen-
21
based process (9.6 percent) than in the air-based process (64 percent).
Thus, the ratio of these two percentages (0.15) was used to account for the
smaller proportion of chlorinated hydrocarbons in the emissions from the
oxygen-based process.
The emission factor for the column vents (Vent B, Figure 6) was based on
a published chloroform emission factor for the heads column of 2.2 kg of
chloroform emitted per Mg EDC produced by oxychlorination. The chloroform
emission factor for the balanced process was calculated by multiplying by the
hypothetical plant EDC production by oxychlorination of 46.3 percent of total
21
EDC production.
35
-------
Many plants incinerate vent gases from the oxychlorination reactor and
column vents to reduce atmospheric emissions of volatile organics. This
includes plants using the air-based as well as the oxygen-based oxychlorination
31
processes. Thermal oxidation is estimated to reduce chloroform emissions by
98 percent or greater. Incineration destruction efficiency varies with
emission stream properties and incinerator operating parameters. The 98 percent
efficiency level is based on incinerator operation at 870ฐC and 0.75 second
23
residence time for a compound which is difficult to incinerate. The emission
reduction may be greater for longer residence times or higher operating temperature:
Storage Emissions --
The uncontrolled chloroform emission factor for the storage of waste-liquid
light ends (Vent D, Figure 6) was calculated from a VOC emission factor of
21
0.030 kg/Mg. It was assumed that the gaseous emissions from this source
TO
have the same concentration of chloroform as the light ends (10 percent).
Source Locati ons
Major EDC producers and production locations are listed in Table 8.
36
-------
TABLE 8. ETHYLENE DICHLORIDE PRODUCTION FACILITIES14'22
Manufacturer
Location
Atlantic Richfield Co.
ARCO Chem. Co., div.
Diamond Shamrock
Dow Chem. U.S.A.
E.I. duPont de Nemours & Co., Inc.
Conoco Inc., subsid.
Conoco Chems. Co. Div.
Ethyl Corp.
Chems. Group
Formosa Plastics Corp., U.S.A.
Georgia-Pacific Corp.
Chem. Div.
The BF Goodrich Co.
BF Goodrich Chem. Group
PPG Indust., Inc.
Indust. Chem. Div.
Shell Chem. Co.
Union Carbide Corp.
Ethylene Oxide Derivatives Div,
Vulcan Materials Co.
Vulcan Chems., div.
Port Arthur, TX
Deer Park, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Lake Charles, LA
Baton Rouge, LA
Pasadena, TX
Baton Rouge, LA
Point Comfort, TX
Plaquemine, LA
La Porte, TX
Calvert City, KY
Convent, LA
Lake Charles, LA
Deer Park, TX
Taft, LA
Texas City, TX
Geismar, LA
Note: This list is subject to change as market conditions change, facility
ownership changes, or plants are closed down. The reader should
verify the existence of particular facilities by consulting current
lists or the plants themselves. The level of emissions from any
given facility is a function of variables, such as throughput and
control measures, and should be determined through direct contacts
with plant personnel.
37
-------
PERCHLOROETHYLENE AND TRICHLOROETHYLENE PRODUCTION
Chloroform is formed as a byproduct during the production of
perch!oroethylene (PCE) and trichloroethylene (TCE). PCE and TCE are
produced separately or as coproducts by either chlorination or oxychlori-
nation of ethylene dichloride (EDC) or other C~ chlorinated hydrocarbons.
The relative proportions of the two products are determined by raw material
ratios and reactor conditions.
Process Descriptions
Ethylene Dichloride Chlorination Process --
The major products of the EDC Chlorination process are TCE, PCE, and
hydrogen chloride. Basic operations that may be used in the EDC Chlorination
process are shown in Figure 8.
Ethylene dichloride (Stream 1) and chlorine (Stream 2) are vaporized
and fed to the reactor. Other chlorinated C~ hydrocarbons or recycled
chlorinated hydrocarbon byproducts may also be fed to the reactor. The
Chlorination is carried out at 400ฐ to 450ฐC, slightly above atmospheric
pressure. Hydrogen chloride byproduct (Stream 3) is separated from the
chlorinated hydrocarbon mixture (Stream 4) produced in the reactor. The
chlorinated hydrocarbon mixture (Stream 4) is neutralized with sodium
33
hydroxide solution (Stream 5) and dried.
The dried crude product (Stream 7) is separated by a distillation
column into crude TCE (Stream 8) and crude PCE (Stream 9). The crude TCE
(Stream 8) is fed to two columns in series which remove light ends (Stream 10)
and heavy ends (Stream 13). TCE (Stream 12) is taken overhead from the
heavy ends column and sent to TCE storage; the heavy ends (Stream 13) and
the light ends (Stream 10) are combined, stored, and recycled.
The crude PCE (Stream 9) from the PCE/TCE separation column is sent to
the PCE column, where PCE (Stream 14) is removed as an overhead stream to
PCE storage. Bottoms from this column (Stream 15) are sent to a heavy ends
column and separated into heavy ends and tars. Heavy ends (Stream 16) are
33
stored and recycled, and tars are incinerated.
38
-------
CU
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39
-------
Ethylene Dichloride Oxychlorination Process --
The major products of the EDC oxychlorination process are TCE, PCE, and
water. The crude product contains 85 to 90 weight percent PCE plus TCE and
10 to 15 weight percent byproduct organics. Essentially all byproduct
organics are recovered during purification and are recycled to the reactor.
The process is very flexible, so that the reaction can be directed toward
the production of either PCE or TCE in varying proportions. Side reactions
produce carbon dioxide, hydrogen chloride, and several chlorinated hydrocarbons.
33
Figure 9 shows basic operations that may be used in oxychlorination.
EDC (Stream 1), chlorine or hydrogen chloride (Stream 2), and oxygen
(Stream 3) are fed in the gas phase to a fluid-bed reactor. The reactor
contains a vertical bundle of tubes with boiling liquid outside the tubes
which maintains the reaction temperature at about 425ฐC. The reactor is
operated at pressures slightly above atmospheric, and the catalyst, which
contains copper chloride, is continuously added to the tube bundle with the
crude product.
The reactor product stream (Stream 4) is fed serially to a water
cooled condenser, a refrigerated condenser, and a decanter. The noncondensed
inert gases (Stream 5), consisting of carbon dioxide, hydrogen chloride,
nitrogen, and a small amount of uncondensed chlorinated hydrocarbons, are
fed to an absorber, where hydrogen chloride is recovered by absorption in
process water to make byproduct hydrochloric acid. The remaining inert
33
gases are purged (Vent A).
In the decanter, the crude prodjct (Stream 7) is separated from the
aqueous phase and catalyst fines (Stream 8) and sent to the drying column
for removal of dissolved water by azeotropic distillation. The dried crude
product (Stream 10) is separated into crude TCE (Stream 11) and crude PCE
(Stream 12) in a PCE/TCE column. The aqueous phase from the decanter (Stream 8)
and the water from the drying column (Stream 9) are sent to waste treatment.
The crude TCE (Stream 11) is sent to the TCE column, where light ends
(Stream 13) are removed to be stored and recycled. The bottoms (Stream 14),
containing mainly TCE, are neutralized with ammonia and then dried to produce
finished TCE (Stream 15) which is sent to the TCE storage.
40
-------
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41
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The crude PCE (Stream 12) from the PCE/TCE separation column is fed to
a heavy ends removal column where PCE and lights (Stream 16) go overhead to
a PCE finishing column and the heavies (Stream 17) remaining as the bottoms
are sent to the organic recycle system. Here the organics that can be
recycled (Stream 18) are separated from tars and sent to the recycle organic
storage. The tars are incinerated. The PCE and light ends (Stream 16) from
the heavy ends column are fed to a light ends removal column. Light ends
(Stream 20) are removed overhead and are stored and recycled. The PCE
bottoms (Stream 21) are neutralized with ammonia and then dried to obtain
finished PCE (Stream 22) which is sent to the PCE storage.33
Emissions
Insufficient information is available to estimate chloroform emissions
from process vents, recycle organic storage, and process fugitive emission
sources. However, a secondary chloroform emission source has been reported
by one facility that produces perchloroethylene by EDC chlorination. This
facility removes volatile organic compounds from process wastewater with a
wastewater stripper. The uncontrolled chloroform emission factor for this
source was calculated as 3.0 kilograms/megagram (kg/Mg) of perchloroethylene
34
produced, using a production rate of 91 Mg/day and assuming 24 hours/day
operation. The facility controls emissions from the wastewater stripper
with two condensers in series, effecting a 96 percent chloroform emission
34
reduction. Thus, the controlled chloroform emission factor for the
wastewater stripper is 0.12 kg/Mg. It cannot be determined from the available
literature whether wastewater stripping is conducted at other perchloroethylene
and/or trichloroethylene production facilities.
Source Locations
Major producers of perchloroethylene and/or trichloroethylene are listed
in Table 9.
42
-------
TABLE 9. FACILITIES PRODUCING PERCHLOROETHYLENE
AND/OR TRICHLOROETHYLENE14
Chemical
produced
Company
Diamond Shamrock Corp.
Dow Chemical U.S.A.
Location
Deer Park, TX
Freeport, TX
Pittsburg, CA
Plaquemine, LA
PCEa
X
X
X
X
TCE5
X
I.E. duPont de Nemours
and Co. , Inc.
PPG Industries, Inc.
Stauffer Chemical Co.
Vulcan Materials Co.
Corpus Christi , TX
Lake Charles, LA
Louisville, KYC
Geismar, LA
Wichita, KS
X
X
X
X
X
X
PCE = perchloroethylene
TCE = trichloroethylene
cPlant has been on standby since 1981.
Note: This is a list of major facilities producing perchloroethylene
and/or trichloroethylene by any production process. Current
information on which of these facilities produce these chemicals
by ethylene dichloride chlorination or oxychlorination is not
available. This list is subject to change as market conditions
change, facility ownership changes, or plants are closed down.
The reader should verify the existence of particular facilities
by consulting current listings or the plants themselves. The
level of emissions from any given facility is a function of
variables, such as throughput and control measures, and should
be determined through direct contacts with plant personnel.
43
-------
CHLORINATION OF ORGANIC PRECURSORS IN WATER
Chloroform is produced in the aqueous reaction of chlorine with various
organic compounds in water. Potential sources of this indirect chloroform
production include the bleaching of aqueous suspensions of wood pulp with
chlorine at pulp and paper mills, i;he chlorination of industrial cooling
waters to control biofouling within heat transfer systems, and the disinfection
of municipal wastewater and drinking water supplies via chlorination.
Pulp and Paper Industry
Chloroform is produced in process water at pulp and paper mills where
wood pulp is bleached with chlorine. Chloroform is formed from the aqueous
reaction of chlorine with organic substances in the wood pulp and is released
to the air during the bleaching process, the subsequent treatment of effluent,
and after release of the treated effluent to receiving waters.
Process Description --
In the pulp and paper industry, wood and other fibrous materials such as
wastepaper are treated to produce pjlp, which can be processed to produce
paper, paperboard, or such products as rayon, cellophane, and explosives. The
production of pulp, paper, and paperboard involves several standard manufacturing
process steps as shown in Figure 10. Major steps include raw material preparation,
pulping, bleaching, and papermaking..
The major raw material in the pulp and paper industry is wood. The raw
35
material preparation step includes log washing, bark removal, and chipping.
In pulping, wood chips and other cellulosic raw materials are treated to
form pulp suitable for processing into paper or other products. There are two
primary pulping processes: mechanical pulping and chemical pulping. Chemical
pulping involves the cooking of wood chips in solutions of chemicals. Chemical
pulping processes now in use are alkaline processes such as the soda and kraft
processes, the sulfite process, and the semi-chemical process. The kraft
process is most commonly used. In mechanical pulping, wood chips are ground
mechanically to produce pulp. Where wastepaper or other secondary fibers are
used as raw materials, removal of ink, fillers, coatings, and other ncncellulosic
materials from the wastepaper (deinking) may be necessary to reclaim a useful
pulp.35
44
-------
PULP LOG
WOOD
PREPARATION
ACID SULF1TE LIQUOR
ALKALINE SULFATE LIQUOR-
(KRAFT)
NEUTRAL SULFITE LIQUOR
DEBARKED LOG
(GROUNDWOOD)
CHEMICAL
REUSE
WHITE WATER OR
FRESH WATER
WHITE WATER OR
REUSE WATER
BLEACH AND OTHER
NECESSARY CHEMICALS
FRESH WATER OR WHITE
WATER REUSE
FILLERS
DYE
SIZE
ALUM
STARCH
FRESH WATER OR
WHITE WATER REUSE
COATING CHEMICALS
WOOD
CHIPS
t
PULPING
CRUDE
PULP
EVAPORATION
(HEAT GENERATION AS
A BYPRODUCT)
KRAFT 8 NEUTRAL
SULFITE RECOVERY
r.nt\inFN<;ATP
WASHING
SCREENING
THICKENING
UNBLEACHED PULP ^ {
J l__ I
CHLOROFORM IN
BLEACHING
BLEACHING
EFFLUENT
STOCK
PREPARATION
PAPER
MACHINE
FINISHING a
CONVERTING
EFFLUENT
TREATMENT
RECEIVING
WATERS
I CHLOROFORM
EMISSIONS
FINISHED PAPER
PRODUCTS
Figure 10. Basic operations that may be used in the pulp and paper
manufacturing process.35
45
-------
Due to the presence of lignins or resins, pulp is brown or deeply colored.
Thus, it must be bleached if a white or light colored product is to be produced.
Mechanical pulp generally is bleached with hydrosulfites and peroxides while
chlorine, calcium hypochlorite, sodium hypochlorite, and chlorine dioxide are
most commonly employed in bleaching chemical pulp. Bleaching is performed in
a number of stages. Each stage consists of a reaction tower in which the pulp
is retained with the chemical agent for a given time period and then washed on
vacuum washers or diffusers before being discharged to the next stage.
High-brightness kraft pulps normally require five stages with a common sequence
being: 1) chlorination and washing, 2) alkaline extraction and washing,
3) chlorine dioxide addition and washing, 4) alkaline extraction and washing,
and 5) chlorine dioxide addition and washing. Three stages generally are used
in semi-bleached kraft operations and for the bleaching of sulfite papergrade
pulps.35
Following the bleaching process, the pulp is prepared for marketing or
converted to paper products. Pulp products include dissolving kraft and
sulfite pulps for the production of rayon, cellophane, and explosives and
kraft and sulfite pulps for paper manufacturing at nonintegrated mills. The
pulp may also be used on site to prepare a variety of products including
newsprint, tissue papers, fine papers such as printing and writing papers,
coarse papers such as packaging papers, and paperboard.
Emissions --
When chlorine or chlorine compounds are used to bleach pulp, organic
substances in the pulp are chlorinated to produce a variety of organics including
chloroform, which becomes dissolved in process water. Chloroform is released
to the atmosphere from this process water primarily during wastewater treatment.
Although some chloroform probably evaporates from process water during the
bleaching process and the transport of bleaching plant effluent to the treatment
plant, no information is available on chloroform emissions prior to wastewater
treatment.
The majority of mills treat their effluent on site. Biological treatment
systems are extensively employed at these types of mills, with aerated
stabilization the most common process used. For pulp and paper plants that do
46
-------
not have their own waste treatment facilities, the chloroform in their bleach
plant effluent will not be released to the atmosphere on site but during
transport of the effluent to and treatment at a publicly owned treatment
plant.
Some chloroform remains in the effluent after treatment, with reported
concentrations ranging from 6 to 433 micrograms/liter (ug/1). This remaining
chloroform is discharged to receiving waters, where it continues to evaporate
after mixing with natural surface waters.
Table 10 presents chloroform emission factors for eight subcategories of
pulp and paper industry products for which chlorine compounds are used in
bleaching operations: dissolving kraft pulp; market bleached kraft pulp;
bleached kraft paperboard, coarse papers, and tissue papers; soda and kraft
fine bleached papers; dissolving sulfite pulp; sulfite paper and papergrade
pulp; deink-fine papers; and deink-tissue papers. This categorization was
used by EPA in the development of effluent guidelines and is based on a
number of factors including effluent characteristics, raw materials used,
products manufactured, and production processes employed. The emission
factors were developed from chloroform mass balance calculations using measured
chloroform concentrations in the wastewater treatment system influents and
35
effluents at a number of mills.
Emission factors are presented for the calculation of chloroform emissions
at pulp and paper mill wastewater treatment facilities. For mills that do not
have their own treatment facilities, these emission factors could be used to
estimate chloroform emissions due to mill effluents at the publicly owned
treatment works to which the mills discharge their wastewaters. Emission
factors for calculating chloroform emissions after the discharge of the treated
effluent into receiving waters are also presented. These emission factors
were calculated assuming all of the chloroform released in treated effluents
will eventually evaporate. The time rate and spatial distribution of these
emissions will depend on the characteristics of the receiving waters.
Source Locations --
Table 11 presents a list of pulp and paper mills and their locations by
subcategory and includes the percentage of mills in each category that treat
effluent on site. Included are mills categorized as miscellaneous integrated
47
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-------
and miscellaneous secondary fibers at which a complex variety of pulping
processes are employed and/or a variety of products are manufactured. Processes
in which chlorine compounds are used as bleaching acents may be employed at
these mills. Once the use of these processes is identified, chloroform emissions
may be estimated by determining the quantity of each type of pulp and paper
product for which a bleaching process is used and multiplying this production
figure by the appropriate emission factor from Table 10.
Cooling Water
Process Description --
In steam electric power generators, cooling water is used to absorb heat
liberated when the steam used in the power cycle is condensed to water.
Chlorine is often added to cooling water to prevent fouling (formation of
slime-forming organisms) of heat exchanger condenser tubes, which inhibits the
y 1
39
38
heat exchange process. Chloroform is produced by the aqueous reaction of
chlorine with organic matter in the cooling water.
Two types of cooling water systems are in general use: once-through
systems and recirculating systems. In a once-through cooling water system,
the cooling water is withdrawn from the water source, passed through the
system (where it absorbs heat), and returned directly to the water source.
Any chloroform produced is discharged to water. In a recirculating cooling
water system, the cooling water is withdrawn from the water source and passed
through the condensers several times before being discharged to the receiving
water. Heat is removed from the cooling water after each pass through the
condenser. Three major methods are used for removing heat from recirculating
cooling water: cooling ponds or canals, mechanical draft evaporative cooling
towers, and natural draft evaporative cooling towers. Chloroform evaporates
to the air from these heat removal processes. The evaporation of water from a
recirculating cooling water system in cooling ponds or cooling towers results
in an increase in the dissolved solids concentration of the water remaining in
the system. Scale formation is prevented in the system by bleeding off a
portion of the cooling water (blowdown) and replacing it with fresh water
38 39
which has a lower dissolved solids concentration. '
57
-------
Emissions
Once-through cooling systems -- Once-through cooling systems are used
in approximately 60 percent of normuclear steam electric plants and in a
total of 11 nuclear power plants in the United States. The amount of
chloroform formed in once-through cooling systems can be calculated based on
the volume of cooling water used and the chloroform concentration resulting
from chlorination. Chlorination has been shown to produce 0.41 kilograms
9 39
(kg) of chloroform per 10 liters of cooling water. Assuming that all of
the chloroform in the cooling water evaporates, the chloroform emission
q
factor is 0.41 kg/10 liters of cooling water.
Recirculating cooling systems -- Chloroform production rates resulting
from chlorination in two recirculating cooling systems were measured at 2.4
. 30
and 3.6 mg chloroform per liter cooling water flow. With approximately 75
39
percent evaporating at the cooling tower , the average chloroform emission
factor for cooling towers is 2.3 kg/10 liters of cooling water. Assuming
all of the remaining chloroform discharged in cooling tower blowdown evaporates
from the receiving water, the chloroform emission factor is 0.75 kg/10
liters of cooling water.
Source Locations --
The SIC code for establishments engaged in the generation of electricity
for sale is 4911.
Drinking Water
The occurrence and formation of chloroform in finished drinking water
has been well documented. Chloroform may be present in the raw water as a
result of industrial effluents containing the chemical. In addition, chloroform
is formed from the reaction of chlorine with humic materials. Humic materials
are acidic components derived from the decomposition of organic matter.
Examples include humic acid, fulvic acid, and hymatomelanic acid. The
amount of chloroform generated in drinking water is a function of both the
amount of humic material present in the raw water and the chlorine feed.
The chlorine feed is adjusted tc maintain a fairly constant 2.0 to 2.5 ppm
chlorine residual and reflects changes in the total oxidizable dissolved
organics and the rates of various oxidation reactions. Although there is a
58
-------
higher organic content in raw water during the winter months, the more extensive
oxidation that occurs during the summer months requires a higher chlorine
feed. Thus, more chloroform is produced in drinking water during the summer
a?
-------
About 40 municipal wastewater treatment plants superchlorinate sludge.
Analyses of sludge at 2 plants have shown that superchlorination of sludge
increases the average chloroform concentration in the liquid sludge from 8
parts per billion (ppb) to 1070 ppb. Samples of sludge cake from the drying
beds at one of the plants indicated that roughly half of the chloroform
evaporated during treatment at the plant. This corresponds to an emission
factor of 580 kg/10 Mg of sludge treated by superchlorination.
60
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MISCELLANEOUS CHLOROFORM EMISSION SOURCES
Industrial Solvent Usage
As noted in a previous subsection, chloroform is widely used as a
solvent in the manufacture of Pharmaceuticals. Chloroform is also used as a
solvent in the manufacture of other specialty and small-volume chemicals.
For instance, the production of Hypalonฎ synthetic rubber is carried out in
chloroform solution. ' Hypalonฎis a chemically resistant elastomer made
49
by substituting chlorine and sulfonyl chloride groups into polyethylene.
Data are not available to estimate total chloroform solvent use in chemical
manufacture or to identify all industries where chloroform is used.
Laboratory Usage
Chloroform is currently used in hospital, industrial, government, and
university laboratories as a general reagent. Data were not available to
estimate total chloroform use in laboratories. However, laboratory use
does appear to be widespread. One university reported that in a survey on
potential carcinogens used in its 67 laboratories, chloroform was the most
51
widely used, appearing in 53 laboratories. Insufficient data are available
to develop a chloroform emission factor for laboratory usage.
Treatment, Storage and Disposal Facilities
Considerable potential exists for volatile substances, including
chloroform, to be emitted from waste treatment, storage and handling facilities,
A California study shows that significant levels of chloroform may be contained
in hazardous wastes which may be expected to volatilize within hours, days or
months after disposal by landspreading, surface impoundment or covered
landfill, respectively. Volatilization of chloroform and other substances
was confirmed in this study by significant ambient air concentrations over
52
one site. Reference 53 provides general theoretical models for estimating
volatile substance emissions from a number of generic kinds of waste handling
operations, including surface impoundments, landfills, landfarming (land
treatment) operations, wastewater treatment systems, and drum storage/handling
processes. If such a facility is known to handle chloroform, the potential
should be considered for some air emissions to occur.
61
-------
Several studies show that chloroform may be emitted from wastewater
treatment plants. In a bench scale test, the potential was demonstrated for
54
chloroform volatilization from aeration basins. In a test at a small
municipal treatment plant (handling 40% industrial and 60% municipal sewage),
chloroform emission rates from the aeration basins were measured at levels
ranging from 703 to 5756 grams/hour. Tests at a larger treatment plant
(handling about 50% industrial sewage) showed that, on an average weekday,
about 16 kilograms (kg) was present in the plant influent. Of this, about
56 percent volatilized during the activated sludge treatment process (primarily
by air stripping), resulting in weekday chloroform emissions averaging about
9.1 kg/day. Weekend chloroform emissions dropped to 6.4 kg/day on Saturdays
and 3.2 kg/day on Sundays. Too little data are available to extrapolate
these test results to other wastewater treatment plants.
62
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SECTION 5
SOURCE TEST PROCEDURES
Chloroform emissions can be measured using EPA Reference Method 23, which
was proposed in the Federal Register on June 11, I960.56 EPA Method 23 has
been validated in the laboratory for chloroform, although it has not been
CO
validated for chloroform in the field.
In Method 23, a sample of the exhaust gas to be analyzed is drawn into a
Tedlarฎ or.aluminized Mylarฎ bag as shown in Figure 11. The bag is placed
inside a rigid leak proof container and evacuated. The bag is then connected
by a Teflon* sampling line to a sampling probe (stainless steel, Pyrexฎ glass,
or Teflonฎ) at the center of the stack. Sample is drawn into the bag by
pumping air out of the rigid container.
The sample is then analyzed by gas chromatography (GC) coupled with flame
ionization detection (FID). Analysis should be conducted within 1 day of
sample collection. The recommended GC column is 3.05 m by 3.2 mm stainless
steel, filled with 20 percent SP-2100/0.1 percent Carbowax 1500 on 100/120
Supelcoport. This column normally provides an adequate resolution of halogenated
organics. (Where resolution interferences are encountered, the GC operator
should select the column best suited to the analysis.) The column temperature
should be set at 100ฐC. Zero helium or nitrogen should be used as the carrier
gas at a flow rate of approximately 20 ml/min.
The peak area corresponding to the retention time of chloroform is
measured and compared to peak areas for a set of standard gas mixtures to
determine the chloroform concentration. The range of the method is 0.1 to
200 ppm; however, the upper limit can be extended by extending the calibration
range or diluting the sample.
63
-------
FILTER
(GLASS WOOL)
PROBE
SAMPLE
LINE
STACK
WALL
SAMPLING
BAG
FLOW
METER
CHARCOAL
TUBE
RIGID
LEAKPROOF
CONTAINER
Figure 11. Method 23 sampling train.
56
64
-------
Method 23 does not apply when chloroform is contained in participate
matter. Also, in cases where chlorine and chlorine dioxide are present
in the emission stream, such as in the paper industry, aluminized Mylar
sample bags should not be used because of the reaction of these gases
with the bag surface. When chlorine and chlorine dioxide are present,
there is also the possibility that they may react with organics present
in the sample to produce additional chloroform or compounds which may
59
interfere with analysis of chloroform. To minimize such side reactions,
Method 23 requires that the sample be stored in a dark place between
collection and analysis.
65
-------
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7.
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10,
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66
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55. U.S. Environmental Protection Agency. Fate of Priority Pollutants in
Public Owned Treatment Works. EPA-440/1-82-302, Washington, DC, July 1982.
56. Method 23: Determination of Halogenated Organics from Stationary Sources.
Federal Register 45(114): 39776-39777,1980.
57. Knoll, J.E., M.A. Smith, and M.R. Midgett. Evaluation of Emission Test
Methods for Halogenated Hydrocarbons: Volume 1, CClu, C2HUC12, C2C1<,, and
C2HC13. EPA-600/4-79-025, U.S. Environmental Protection Agency, Research
Triangle Park, NC, 1979.
58. Knoll, J., U.S. Environmental Protection Agency. Personal communication
with W. Battye, GCA Corporation, September 8, 1982.
59. Elia, V.J., National Council of the Paper Industry for Air and Stream
Improvement, Inc., Corvallis, OR. Letter to T. Lahre, EPA, May 4, 1983.
70
-------
-------
APPENDIX
DERIVATION OF EMISSION FACTORS FOR CHLOROFORM PRODUCTION
This appendix presents the derivations of chloroform emission factors for
chloroform production processes that are presented in Tables 2 and 3. Emission
factors for the methanol hydrochlorination/methyl chloride chlorination
process were developed based on a hypothetical plant with a total chloromethane
production capacity of 90,000 megagrams (Mg) and a product mix of 25 percent
methyl chloride, 48 percent methylene chloride, 25 percent chloroform, and
2 percent byproduct carbon tetrachloride. Emission factors for the methane
chlorination process have been developed based on a hypothetical plant with a
total chloromethane production capacity of 200,000 Mg, and a product mix of
20 percent methyl chloride, 45 percent methylene chloride, 25 percent chloroform,
2
and 10 percent carbon tetrachloride.
The following sections describe the derivations of chloroform emission
factors for process vent emissions; in-process and product storage tank emissions;
secondary emissions from liquid, solid, and aqueous waste streams; handling
emissions from loading product chloroform; and fugitive emissions from leaks
in process valves, pumps, compressors, and pressure relief valves.
PROCESS EMISSIONS
Methanol Hydrochlorination/Methyl Chloride Chlorination
Chloroform process emissions originate from the purging of inert gases in
the condenser following the chloroform distillation column (Vent A in Figure 2).
The uncontrolled emission factor for this source was calculated from an
emission factor of 0.0056 kg chloroform per Mg of total chloromethane production
and a hypothetical plant chloroform production capacity of 25 percent of total
chloromethane production:
A-l
-------
Emission factor = Q.OQ56 kg CHC1g x total prod.
Mg total prod. 0.25 CHC13 prod.
= 0.022 kg/Mg
Methane Chlorination
Chloroform process emissions result from the venting of the inert
gases from the recycle methane stream (Vent A, Figure 3) and from the
emergency venting of the distillation area inert gases (Vent C, Figure 3).
Recycled Methane Inert Gas Purge Vent--
The uncontrolled emission factor for the recycled methane inert gas
purge vent was calculated from a chloroform emission factor of 0.0033 kg
2
per Mg total chloromethane production capacity and the hypothetical
plant's chloroform production of 25 percent of total chloromethane production.
Emission factor = 0.0033 kg CHCI? x total prod.
Mg total prod. 0.25 CHC13 prod.
= 0.013 kg/Mg
Distillation Area Emergency Inert Gas Vent--
The uncontrolled emission factor for the distillation area emergency
inert gas vent was derived from an emission factor for volatile organic
o
compounds (VOC) of 0.20 kg/Mg total chloromethane production capacity
and composition data showing chloroform to be 4.0 percent of VOC. No
information was available on the assumptions upon which the derivation
of this VOC emission factor were based. The calculation of chloroform
emissions per unit chloroform produced was made using a chloroform
production rate of 25 percent of total chloromethanes production:
Emission factor = 0.20 kg VOC x 0.040 CHCIg x total prod.
MCJ total prod. VOC 0.25 CHC13 p
= 0.032 kg/Mg
STORAGE EMISSION FACTORS
In calculating storage emission factors, all storage tanks were
I 2
assumed to be fixed roof tanks. ' Uncontrolled chloroform emission
factors for in-process and product storage for the methanol hydrochlorination
A-2
-------
process (Vents B, C, D, and E, Figure 2) and the methane chlorination
process (Vents B, D, and E, Figure 3) were calculated using emission
equations for breathing and working losses from reference 4:
LT = LB + LW
LB * 1.02 x ICT5 My (n^7-F)0.68D1.73H0.51T0.5FpCKc
Lw = 1.09 x 10~8 My PVNKpKc
where,
LT = total loss (Mg/yr)
LB = breathing loss (Mg/yr)
LW = working loss (Mg/yr)
M = molecular weight of product vapor (Ib/lb mole)
P = true vapor pressure of product (psia)
D = tank diameter (ft)
H = average vapor space height (ft): use tank specific values or an
assumed value of one-half the tank height
T = average diurnal temperature change in ฐF
F = paint factor (dimensionless); assume a value of 1 for a white tank
" in good condition
C = tank diameter factor (dimensionless):
for diameter >_ 30 feet, C = 1
for diameter< 30 feet,
C = 0.0771 D - 0.0013(D2) - 0.1334
K = product factor (dimensionless) = 1.0 for VOL
V = tank capacity (gal)
N = number of turnovers per year (dimensionless)
K = turnover factor (dimensionless):
for turnovers > 36, Kn = ^
for turnovers <_ 36, Kp = 1
For the methanol hydrochlorination/methyl chloride chlorination and
methane chlorination processes, hypothetical plant storage tank conditions
from references 1 and 2, respectively, were used for the calculations.
The tank conditions given by these references include tank volume,
number of turnovers per year, bulk liquid temperature, and an assumed
A-3
-------
diurnal temperature variation of 2!0ฐC. The diameters (D) , in feet, of the
tanks were calculated from given tank volumes (V), in gallons, with heights
(h), in feet, assumed at 8 foot intervals,5 from:
/V/7.481
D = 2 TT x h
For tanks containing mixtures, the vapor pressure of the mixture in the
tank, molecular weight of vapor, and weight percent of chloroform in
the vapor were calculated. The calculations of emission factors for all
production processes are summarized in Table A-1 . Sample calculations
are presented in their entirety for the methanol hydrochlori nation/methyl
chloride chlorination process. For the other process, storage tank
parameters and vapor composition data used in the calculations of the
emission factors listed in Table A-1 are presented in tables.
Methanol Hydrochlorination/Methyl Chloride Chlorination
Emission factors for the crude product tank, the surge tank, and
the chloroform tank were calculated using the tank parameters listed in
Table A-2.
Composition -- The composition of the mixture in the crude product
tank is based on the hypothetical plant mixture. The mole fractions of
the liquid components were derived from these weight fractions and
molecular weights. The mole fractions of the components in liquid were
then multiplied by the vapor pressures of each component to determine
component partial pressures, the sum of which is the total vapor pressure,
P. Mole fractions of the components in the vapor phase were calculated
as the ratio of component partial pressures to total vapor pressure.
The molecular weight of the vapor mixture (M ) was calculated as the sum
of the products of the component partial pressures and their molecular
weights, ignoring the molecular weight of the air. The weight percents
of components in vapor were calculated from the ratios of the product of
the mole fraction in vapor and molecular weight to the molecular weight
of the vapor mixture. These calcjlations are summarized in Table A-3.
Tank emissions -- With the parameters listed in Table A-2, total
tank losses were calculated as shown on page A-8.
A-4
-------
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A-5
-------
TABLE A-2. STORAGE TANK PARAMETERS FOR
METHANOL HYDROCHLORINATION/METHYL
CHLORIDE CHLORINATION PROCESS
Tanks
Number of tanks
Volume (V) , gal
Height (h), ft
Vapor space height (H), ft
Diameter (D) , ft
Turnovers/yr (N)
Temperature, ฐF
Vapor pressure (P), psia
Diurnal temperature change (T), ฐF
Molecular weight of vapor (M ),
Ib/lb mole v
Turnover factor (K )
Tank diameter factor (C)
Crude
1
50,000
24
12
19
6
95
9.96
22
91.0
1
0.862
Surge
1
20,000
16
8
15
6
104
6.90
22
120
1
0.731
Day
2
10,000
16
8
10
T99
104
7.09
22
119
0.317
0.508
Product
1
200,000
40
20
29
20
68
3.09
22
119
1
1
A-6
-------
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A-7
-------
L ซ (1.02 x 10"5)(91.0), _ 9^96_0>68(19)1-73(12)0-51(22)ฐ-5
= (1.02 x 10"5)(91.0)(1.66)(163)(3.55)(4.69)(0.862)
Lw = (1.09 x 10~8)(91.0)(9.96)(50,000)(6)(1)(1)
LT = LB + lw = 6.56 Mg/yr
.0), _ 9^96_^>(19)-(12)-(22)-(1)(0.862)(1)
M4.7-9.96'
5)(91
= 3.60 Mg/yr
= (1.09 x 10
= 2.96 Mg/yr
= LB + lw =
Emission factor The chloroform emission factor was calculated from
total annual tank loss, fraction of the vapor mixture that is chloroform,
and the hypothetical plant chloroform production rate of 22,500 Mg/yr:
Emission factor = (6.56 Mg/yr)(0.21)
22,500 Mg/yr
= 0.061 kg/Mg
Surge Tank --
Composition -- The calculations for the composition of the vapor of
the surge tank are presented in Table A-4.
Tank Emissions --
LR = (1.02 x 10'5)(120), _ 6^90 _ ^'^(IS)1 <73(8)ฐ-51 (22)ฐ'5(1 )(0.731 ) (1 )
_
M4.7-6.90
"5)(120)
=1.20 Mg/yr
= (1.02 x 10"5)(120)(0.92)(108)(2.89)(4.69)(0.731)
Lw = (1.09 x 10"8)(120)(6.90)(20,000)(6)(1)(1)
=1.08 Mg/yr
LT = LB + Lw =2.28 Mg/yr
Emission Factor --
Emission factor = (2.28 Mg/yr)(0.96)
22,500 Mg/yr
= O.OS7 kg/Mg
-------
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A-9
-------
Day Tanks
Tank Emissions --
LR = (1.02 x 10'5)(119), _ 7.09 x0'68^)1 -73(8)ฐ-51 (22)ฐ'5(1 ) (0.508) (1 )
B M4.7--7.09'
= (1.-02 x 10"5)(119)(0.953)(53.7}(2.89)(4.69)(0.508)
=0.43 Mg/yr
Lw = (1.09 x 10~8)(n9)(7.09)(10,OOQ)099)(0. 317)0)
=5.80 Mg/yr
LT = LB + Lw = 6.23 Mg/yr
Emission factor --
U i
Emission factor = 6.23 +1 * 2 tanks
= (1.02 x 10~5)(119)(0.407)(339)(4.61)(4.69)
22,500 Mg/yr
= 0.55 kg/Mg
Product Tank --
Tank Emissions --
LB . (,.02 x 0'
= (1.02 x
= 3.62 Mg/yr
Lw = (1.09 x 10"8)(n9)(3.09)(200,000)(20)(l)(l)
= 16.0 Mg/yr
LT = LB + Lw = 19.6 Mg/yr
Emission facto_r --
Emission factor = 19.6 Mg/yr _
22,500 Mg/yr
= 0.87 kg/Mg
Methane Chi ori nation
Emission factors for the crude product tank, two chloroform
day tanks, and the chloroform product tank were calculated using the
tank parameters listed in Table A-5. The calculations of the composition
of the vapor for the crude product tank are summarized in Table A-6.
A-10
-------
TABLE A-5. STORAGE TANK PARAMETERS FOR
METHANE CHLORINATION PROCESS
Tanks
Number of tanks
Volume (V) , gal
Height (h), ft
Vapor space height (H), ft
Diameter (D), ft
Turnovers/yr (N)
Temperature, ฐF
Vapor pressure (P), psia
Diurnal temperature change (T), ฐF
Molecular weight of vapor (M ),
Ib/lb mole v
Turnover factor (K )
Tank diameter factor (C)
Crude
1
200,000
40
20
29
6
95
9.50
22
93
1
1
Day
2
30,000
24
12
15
147
95
5.96
22
119
0.371
0.731
Product
1
400,000
48
24
38
22
68
3.09
22
119
1
1
A-11
-------
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A-12
-------
SECONDARY EMISSIONS
Methanol Hydrochlori nation/Methyl Chloride Chi on'nation
Potential sources of secondary emissions include the aqueous discharge
from the methanol hydrochlorination process stripper and the sulfuric
acid waste from the methyl chloride drying tower; however, chloroform
has not been found to be a component of the organic compounds in these
waste streams.
Methane Chlorination
Secondary emissions of chloroform can result from the handling and
disposal of process waste liquid. These liquid streams are indicated on
the process flow diagram (Source F, Figure 3) and include the waste
caustic from the scrubbers on methyl chloride and recycle methane streams
and the crude chloromethanes neutralizer and the salt solution discharge
from the crude chloromethanes dryers. The uncontrolled emission factor
for these secondary chloroform emissions was calculated using a chloroform
content of 300 parts per million reported for total wastewater discharges
averaging 68 liters per minute, the conservative assumption that 100 percent
of the chloroform will be volatilized during on-site wastewater treatment,
and the hypothetical plant chloroform production of 50,000 Mg/yr:
Emissions = 68 ฃ water 1 kg 300 kg CHC1 -, 5.26 x IP5 min
min x i water 105 kg water yr
= 10,700 kg/yr
Emission factor = 10,700 kg/yr
50,000 Mg/yr
= 0.21 kg/Mg
HANDLING EMISSIONS
The following equation from reference 6 was used to develop an
uncontrolled emission factor for loading of product chloroform. Submerged
loading of chloroform with a bulk liquid temperature of 20ฐC into clean
tank cars, trucks, and barges was assumed.
A-13
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L = 12.46
L .
2
L, = Loading loss, lb/10 gal of liquid loaded
M = Molecular weight of vapors, Ib/lb-mole = 119
P = True vapor pressure of liquid loading, psia = 3.09
T = Bulk temperature of liquid loaded (ฐR) = 528 (20ฐC)
S = A saturation factor = 0.5 for submerged file of clean tank trucks,
tank cars, and barges.
LL = 12.46 (0.5)(3. 09)019) = 4.34 1b
528 103 gal
Loading loss in lb/10 gal was converted to an emission factor in terms of
2
kg/Mg (equivalent to lb/10 Ib) by dividing by the density of chloroform
(1.49 g/ml = 12.4 Ib/gal):
Em1ssion factor - ซff
=0.35 kg/Mg
PROCESS FUGITIVE EMISSIONS
Fugitive emissions of chloroform and other volatile organics result
from leaks in process -valves, pumps, compressors, and pressure relief
valves. For both the methanol hyd^ochlorination and methane chlorination
processes, the chloroform emission rates from these sources were based on
process flow diagrams, process operation data, and fugitive source
1 2
inventories for hypothetical plants ' and EPA emission factors for process
fugitive sources.
The first step in estimating fugitive emissions of chloroform was to
list the process streams in the hypothetical plant. Their phases were
then identified from the process flow diagram and their compositions
estimated. For a reactor product stream, the composition was estimated
based on reaction completion data for the reactor and on the plant product
slate. For a stream from a distillation column or other separator, the
composition was estimated based on the composition of the input stream to
the unit, the unit description, and the general description of stream
of interest (ie. overheads, bottoms, or sidedraw).
A-14
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After the process streams were characterized, the number of valves per
stream were estimated by dividing the total number of valves at the plant
equally among the process streams. Similarly, pumps were apportioned
equally among liquid process streams, and relief valves were apportioned
equally among all reactors, columns, and other separators. The locations
of any compressors were determined from the process flow diagram.
Emissions were then calculated for pumps, compressors, valves in liquid
and gas line service, and relief valves. Emissions from flanges and drains
are minor in comparison with these sources and were, therefore neglected.
Fugitive emissions from a particular source were assumed to have the same
composition as the process fluid to which the source is exposed. For
valves in liquid service, for instance, chloroform emissions were determined
by taking the product of: (1) the total number of liquid valves in
chloroform service; (2) the average chloroform content of the streams
passing through these valves; and (3) the average fugitive emission rate per
valve per unit time as measured by EPA. Emissions from valves in gas
service, pumps, and compressors were calculated in the same manner. For
relief valves, fugitive emissions were assumed to have the composition of
the overhead stream from the reactor or column served by the relief valve.
Emissions from the various fugitive source types were summed to obtain
total process fugitive emissions of chloroform.
Because emissions from process fugitive sources do not depend on their
size, but only on their number, total process fugitive emissions are not
dependent on plant capacity. Thus, the overall emissions are expressed
in terms of kilograms per hour of operation.
Methanol Hydrochlorination/Methyl Chloride Chiorination
Hypothetical plant fugitive source inventory --
725 process valves
15 pumps (not including spares)
2 compressors
25 safety relief valves
A-15
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Process line composition--
Of the total 31 process lines, eight are in chloroform service,
from the methyl chloride chlorination reactor to chloroform storage (see
Figure A-l). Compositions were estimated as follows:
Stream number
17
18
20
24
25
26
27
28
Composition
Phase
Gas
Liquid
Liquid
Liquid
Liquid
Gas
Liquid
Liquid
CH;C1-
29
29
64
CHC1,
14
14
33
91
91
100
100
100
ecu
1.4
1.4
3
9
9
Other
55
55
Valves
725 valves
31 lines
= 23 valves per process line
Assuming 23 valves in each of the above lines, and averaging the
chloroform contents for gas and Vquid lines, total plant valve emissions
were estimated as follows:
Liquid valves
Gas valves
Component
emission factor
(kg/hr-valve) '
es 0.0071
0.0056
Valves
CHC1 K service
138
46
Avg composition
(% CHCU)
71.5
57.0
Emissions
(kg/hr)
0.70
0.14
Pumps--
15 pumps
15 liquid lines
= 1 pump per liquid process line
0.84
For one pump in each of the six liquid lines in chloroform service,
an emission factor of 0.05 kg/hr/pump, and average chloroform concentration
of 71.5 percent, pump emissions from the hypothetical plant were estimated at:
1 pumps/line x 6 lines x 0.05 kg/hr x 0.715 = 0.21 kg/hr
A-16
-------
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A-17
-------
Compressors
There are no compressors in chloroform service.
Relief valves--
25 8eco<1umns1VeS = 3 relief valves Per reactor or column
The methyl chloride reactor .and chloroform column heads will contain
chloroform at the concentrations estimated for streams 17 and 27, respectively.
With an emission factor of 0.104 kg/hr/valve, hypothetical plant emissions
were estimated as follows:
Number of
relief valves
3
3
Emisston factor
(kg/hr)7
0.104
0.104
Composition
(% CHCl.)
14
100
Emissions
(kg/hr)
0.044
0.312
CHLC1 reactor
CHCK column
0.356
Total process fugitive emissions--
Total process fugitive emissions for methanol hydrochlorination/methyl
chloride chlorination hypothetical plant:
Valves-liquid 0.70
gas 0.14
Pumps 0.21
Compressors
Relief valves 0.36
To-:al 1.41 kg/hr
A-18
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Overall efficiencies were calculated for three control options.
The first, quarterly I/M for pumps and valves has an overall efficiency
for chloroform emissions from methanol hydrochlorination/methyl chloride
chlorination of about 49 percent. Monthly I/M for pumps and valves has
an overall efficiency of about 67 percent; and the use of double mechanical
seals, application of rupture disks to relief valves, and monthly I/M
for other valves has an overall efficiency of about 77 percent.
Methane Chlorination
2
Hypothetical plant fugitive source inventory --
1,930 process valves
40 pumps (not including spares)
1 compressor
70 safety relief valves
Process line composition--
Of the total 50 process lines, about 17 are in chloroform service,
r\
from the chlorination reactor to chloroform storage (see Figure A-2).
Compositions were estimated as follows:
Composition
Stream number
4
5,8
11
10,14,16
37,38,39,40,41
44
46
47,48,48a
Valves--
Phase
Gas
Liquid
Liquid
Liquid
Liquid
Liquid
Gas
Liquid
1930 valves
55 lines
CHpCl,
28
56
45
56
56
CHCU
16
31
25
31
31
70
100
100
CCK CHL HC1
6 3 33
13
10
13
13
30
CH.Cl
12
20
- 35 valves per process line
Assuming 35 valves in each of the above lines and averaging the
chloroform contents for gas and liquid lines, total plant valve emissions
were estimated as follows:
A-19
-------
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III
fj-
in
"
a!
1-
Hl
O -
s;
flil
t/1
CO
CD
O
O
E
O
O .
>~~ l/l
-= E
U O
-------
Component Valves in
emission facto"- CHC13 Avg. composition Emissions
(kg/hr-valve)7 service (% CHCI^) (kg/hr)
Gas valves
Pumps--
s 0.0071
0.0056
526
70
47
58
1.75
0.23
1.98
35 liquid lines = ] pump per liquid process 11ne
Assuming an average of one pump for each of the 15 liquid process
lines in chloroform service, an emission factor of 0.05 kg/hr-pump
and average chloroform composition of 47 percent, pump emissions
from the model plant were estimated as follows:
1 pumps/line x 15 lines x 0.05 kg/hr x 0.47 = 0.35 kg/hr
Compressors--
There are no compressors in chloroform service.
Relief valves--
14
= 5 rel1ef va1ves Per column or reactor
A number of column and reactor overhead streams contain chloroform,
as shown below. With a relief valve emission factor of 0.104 kg/hr,7
hypothetical plant emissions were estimated as follows:
Number of Emission factor Composition Emissions
Stream relief valves (kg/hr) (% CH C1,) (kg/hr)
4
39
46
5
5
5
0.
0.
0.
104
104
104
16
31
100
0.08
0.16
0.52
0.77
Total process fugitive emission rate--
Total process fugitive emissions for methane chlorination hypothetical
plant:
A-21
-------
Valves - liquid 1.75
- gas 0.23
Pumps 0.35
Relief valves 0.76
Total 3.09 kg/hr
Controls which can be used to reduce fugitive emissions include the use
of rupture disks on relief valves, the use of pumps with double mechanical
seals, and inspection and maintenance of pumps and valves. The efficiencies
of these controls for individual components are described in the previous
section on fugitive emissions from methanol hydrochlorination/methyl
chloride chlorination.
Quarterly I/M for pumps and valves has an overall efficiency for
chloroform emissions from methane chlorination of about 49 percent.
Monthly I/M for pumps and valves has an overall efficiency of about
64 percent; and the use of double mechanical seals, application of
rupture disks to relief valves, and monthly I/M for other valves has an
overall efficiency of about 76 percent.
A-22
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REFERENCES FOR APPENDIX A
1. Hobbs, F.D. and C.W. Stuewe. Report 6: Chloromethanes by Methanol
Hydrochlorination and Methyl Chloride Chlorination Process. In: Organic
Chemical Manufacturing Volume 8: Selected Processes. EPA-450/3-80-028c,
U.S. Environmental Protection Agency, Research Triangle Park, NC,
December 1980.
2. Hobbs, F.D. and C.W. Stuewe. Report 5: Chloromethanes by Methane
Chlorination Process. In: Organic Chemical Manufacturing Volume 8:
Selected Processes. EPA-450/3-80-028C, U.S. Environmental Protection
Agency, Research Triangle Park, NC, December 1980.
3. Beale, J., Dow Chemical U.S.A., Midland, MI. Letter dated April 28, 1978,
to L. Evans, EPA concerning Dow facility at Freeport, TX.
4. U.S. Environmental Protection Agency. Storage of Organic Liquids. In:
Air Pollution Emission Factors, Third Edition - Supplement 12. AP-42,
Research Triangle Park, NC, April 1981.
5. U.S. Environmental Protection Agency. Transportation and Marketing of
Petroleum Liquids. In: Compilation of Air Pollution Emission Factors,
Third Edition - Supplement 9. AP-42, Research Triangle Park, NC,
July 1979.
6. Graf-Webster, E., Metrek Division, MITRE Corp, McLean, VA. Memo to
T. Wright, Metrek Division, MITRE Corp describing the Chemical Tank
Emission Data Base, May 1978.
7. U.S. Environmental Protection Agency. Fugitive Emission Sources of
Organic CompoundsAdditional Information on Emissions, Emission Reductions
and Costs. EPA-450/3-82-010, Research Triangle Park, NC, April 1982.
A-23
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing;
1 REPORT NO 2.
EPA-450/4-84-007c
4. TITLE AND SUBTITLE
LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF
CHLOROFORM
7 AUTHOR(S)
GCA Corporation
213 Burlington Road, Bedford, MA 01730
9 PERFORMING ORGANIZATION NAME AND ADDRESS
12. SPONSORING AGENCY NAME AND ADDRESS
Office Of Air Quality Planning And Standards
U. S. Environmental Protection Agency
MD 14
Research Triangle, NC 27711
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
March 1984
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO
10. PROGRAM ELEMENT NO.
11. CONTRACT 'GRANT NO.
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15 SUPPLEMENTARY NOTES
EPA Project Officer: Thomas F. Lahre
16. ABSTRACT
To assist groups interested in inventorying air emissions of various
potentially toxic substances, EPA is preparing a series of documents such
as this to compile available information on sources and emissions of these
substances. This document deals specifically with chloroform. Its
intended audience includes Federal, State and local air pollution personnel
and others interested in locating potential emitters of chloroform and in
making gross estimates of air emissions therefrom.
This document presents information on 1) the types of sources that
may emit chloroform, 2) process variations and release points that may be
expected within these sources, and 3) available emissions information
indicating the potential for chloroform release into the air from each
operation.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI I'Xld/Group
Chloroform
Air Emission Sources
Locating Air Emission Sources
Toxic Substances
'19 ScCoaiTY CLASS '/':.'? fieoor'
I 20 5EC'JRiT ' CLASS iTins page-
; 21 MO OF -AGES
; loo
'22 <=r)ICE
HPi For-n 2::0-: Rev. 4-77>
= REVIOOS Er;TiO^ IS OBSOLETE
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