United State*
Environmental Protection
Agency
Office of
Toxic Substances
Washington DC 20460
February
EPA-560/1j-&u-Oe7
Toxic Substances
&EPA
Balance
Chloroform
Review
Copy
Level I Preliminary
-------
FINAL REPORT
LEVEL I MATERIALS BALANCE
CHLOROFORM
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF PESTICIDES AND TOXIC SUBSTANCES
EXPOSURE EVALUATION DIVISION
Task Order No. 18
Contract No. 68-01-5793
Michael A. Callahan - Project Officer
Elizabeth Bryan - Task Manager
Prepared by:
JRB ASSOCIATES, INC.
8400 Westpark Drive
McLean, Virginia 22101
Project Manager: Robert Hall
Task Leader: Kathleen Wagner
Co-Task Leader: Arlan Shochet
Contributing Writers: Hal Bryson
Gary Hunt
Submitted: February 1981
-------
TABLE OF CONTENTS
Page
EXECUTIVE SUMMARY vi
1.0 INTRODUCTION 1-1
2.0 PRODUCTION 2-1
2.1 DIRECT PRODUCTION 2-1
2.1.1 Chloroform Production by Methanol Hydro- 2-4
chlorination Followed by Methyl Chloride
Chlorination
2.1.2 Methane Chlorination Process 2-16
2.1.3 Transportation Losses 2-24
2.2 IMPORTS 2-28
2.3 STOCKPILES 2-28
2.4 INDIRECT PRODUCTION 2-28
2.4.1 Formation of Chloroform During Production 2-28
of Vinyl Chloride Monomer
2.4.2 Chlorination of Organic Precursors in Water 2-30
2.4.3 Industrial Sources 2-38
2.4.4 Combustion of Leaded Gasoline 2-39
2.4.5 Other Indirect Sources 2-40
2.5 OVERALL SUMMARY OF ENVIRONMENTAL RELEASES FROM 2-41
PRODUCTION
3.0 USES OF CHLOROFORM -3-1
3.1 CONSUMPTIVE USES 3-1
3.1.1 Chlorodifluoromethane 3-1
3.1.2 Exports 3-11
3.2 NONCONSUMPTIVE USES OF CHLOROFORM 3-11
3.2.1 Use of Chloroform in the Pharmaceutical 3-13
Industry
3.2.2 Use of Chloroform in Pesticide Production 3-13
3.2.3 Use of Chloroform as an Industrial Solvent 3-15
3.2.4 Use of Chloroform in the Textile and Dye 3-15
Industries
3.2.5 Laboratory Use and Stockpile 3-17
-------
,3.3 SECONDARY PRODUCT CONTAMINANTS 3-18
3.3.1 Releases of Chloroform Contaminant 3-18
of Methyl Chloride
3.3.2 Releases of Chloroform Contaminant of 3-20
Methylene Chloride
3.3.3 Releases of Chloroform Contaminant of 3-31
Carbon Tetrachloride
3.3.4 Releases from Perchloroethylene/Carbon Tetra- 3-39
chloride Production
3.4 SUMMARY OF ENVIRONMENTAL RELEASES FROM CHLOROFORM 3-43
USES
4.0 RELEASE SOURCE EVALUATION 4-1
4.1 DIRECT PRODUCTION 4-1
4.2 INDIRECT PRODUCTION 4-1
4.3 CHLOROFORM USES 4-4
4.3.1 CFC-22 Production 4-4
4.3.2 Other Chloroform Uses 4-4
5.0 SUMMARY OF DISPOSAL AND DESTRUCTION OF SOLID AND LIQUID 5-1
CHLOROFORM WASTES
6.0 SUMMARY OF UNCERTAINTIES 6-1
7.0 DATA GAPS 7-1
7.1 DIRECT PRODUCTION 7-1
7.2 INDIRECT PRODUCTION 7-1
7.3 USES OF CHLOROFORM 7-2
7.3.1 Manufacture of CFC-22 from Chloroform 7-2
7.3.2 Minor Uses 7-3
7.3.3 Secondary Product Contaminants 7-3
APPENDIX A A-l
APPENDIX B B-l
APPENDIX C C-l
ii
-------
LIST OF FIGURES
Figure Page
I Environmental Flow Diagram for Chloroform vii
II Environmental Materials Balance for Chloroform viii
2.1 Locations of U.S. Plants Producing Chloroform 2-2
2.2 Production of Chloroform from Methyl Chloride 2-5
Chlorination
2.3 Summary of Multimedia Releases of Chloroform from 2-15
the Methyl Chloride Chlorination Process
2.4 Production of Chloroform from Methane and Chlorine 2-17
2.5 Summary of Multimedia Releases of Chloroform from 2-25
Methane Chlorination Process
2.6 VCM Production Process 2-29
2.7 Multimedia Releases of Chloroform from Production 2-31
of VCM
3.1 U.S. Producers of Chlorodifluoromethane (CFC-22) 3-2
3.2 Multimedia Releases of Chloroform from the Use 3-12
of CFC-22
3.3 Multimedia Releases of Chloroform from Drug 3-14
Extractions
3.4 Multimedia Releases of Chloroform from Use of 3-16
Fumigant s
3.5 Multimedia Releases of Chloroform from Use^of 3-23
Paint Removers Containing Methylene Chloride
3.6 Multimedia Releases of Chloroform from Use of 3-25
Methylene Chloride in Cold Cleaning
3.7 Multimedia Releases of Chloroform from Use of 3-26
Methylene Chloride in Vapor Degreasing
3.8 Flow Diagram of Chloroform in Methylene Chloride- 3-28
Based Aerosols
3.9 Multimedia Releases of Chloroform from Use of 3-29
Aerosol Products Containing Methylene Chloride
3.10 Multimedia Releases of Chloroform from Use of 3-30
Methylene Chloride as a Blowing Agent in Urethane
Foam
3.11 Location of Chlorofluorocarbon Production Plants 3-34
3.12 Chlorofluorocarbon Production Process 3-37
iii
-------
LIST OF TABLES
Table Page
2.1 Production of Chloroform 1974 to 1978 2-1
2.2 Chloroform and Chloromethane Capacity for Seven 2-3
U.S. Plants
2.3 Sources of Fugitive Emissions and Typical Rates 2-7
of Emissions
2.4 Summary of Breathing Losses from Chloroform Storage 2-10
2.5 Summary of Estimates for Working Losses 2-12
2.6 Summary of Emission Factors for Fugitive Emissions 2-19
of Chloromethanes from Various Equipment Components
2.7 Summary of Chloroform Storage Variables and Chloro- 2-21
form Breathing and Working Losses
2.8 Summary of Environmental Releases from Chloroform 2-42
Production
3.1 1976 and 1977 Estimated Production Capacity of 3-4
Chlorinated Fluorocarbons
3.2 Annual Production of CFC-11, CFC-12, and CFC-22 3-4
3.3 Estimated 1978 Production Capacity for CFC 3-5
3.4 Releases of Chloroform Due to CFC-22 Use 3-11
3.5 Methyl Chloride Capacity in 14 U.S. Plants 3-19
3.6 Quantitative Breakdown of Methylene Chloride End 3-21
Uses and Corresponding Chloroform Contaminant
Levels
3.7 Carbon Tetrachloride Plant Production Estimates 3-32
3.8 Method I Storage, Loading, Ballasting, and Transit 3-33
Emissions
3.9 Locations and Capacities of Chlorofluorocarbon 3-35
Production Plants
3.10 United States Producers of Registered Pesticide 3-40
Products Which Contain Carbon Tetrachloride
3.11 Summary of Environmental Releases from Chloroform 3-44
End Uses
4.1 Summary of Chloroform Releases to Air and Water 4-1
from Production of Chloroform
4.2 Chloroform Concentration in Finished Drinking 4-3
Water of Various U.S. Cities
4.3 Air Emissions of Chloroform from Production of 4-4
CFC-22
IV
-------
Table Page
5.1 Solid and Liquid Chloroform-Containing Waste: 5-2
Quantities, Disposal, and Environmental Releases
6.1 Summary of Uncertainties 6-2
-------
EXECUTIVE SUMMARY
This Level I materials balance reports on emissions due to the pro-
duction and use of chloroform using 1978 for the data base. Estimates
of environmental releases were based on emission estimates in the litera-
ture, industrial contacts, and engineering judgment based on the physical
properties of chloroform. We were able to make reasonable assumptions
regarding environmental releases.
Figure I shows the overall flow of chloroform from production
through use, and the corresponding points of environmental release.
Figure II quantifies the releases of chloroform to air, water, and land,
and the quantities destroyed.
In 1978, an estimated 158,500 kkg of chloroform were produced by
two processes: methane chlorination and chlprination of methyl chloride
produced by hydrochlorination of methanol. Approximately 77 percent of
the chloroform was produced by methyl chloride chlorination, and 23 per-
cent by methane chlorination. In 1978, total chloroform production was
71 percent of capacity.
Total air emissions from process vents, storage and handling, fugi-
tive emissions, and secondary emissions were 216 kkg (or 422 kkg assum-
ing uncontrolled conditions). Other process losses were 9.5 kkg released
to water and 5.8 kkg released to land. An additional 177 kkg were lost
during transit. Total process and transit emissions amounted to 0.3 to
0.5 percent of the total chloroform produced; 16.4 kkg of chloroform
were identified as being incinerated from the methyl chloride chlorina-
tion process. The quantity of wastes incinerated from the methane
chlorination process could not be identified.
Significant indirect sources of chloroform include production of
vinyl chloride monomer; treatment of potable water, municipal waste-
water, cooling waters, pulp and paper wastes; the combustion of gaso-
line; and degradation of trichloroethylene. These indirect sources
were estimated to contribute 12,800 kkg of chloroform in 1978. Vinyl
chloride monomer production, treatment of pulp and paper, and cooling
water were the most significant indirect sources, contributing 21 per-
cent, 49 percent, and 19 percent of the total, respectively. Chloroform
releases to air from indirect production were estimated to be 9,730 kkg,
or 76 percent of the total chloroform produced indirectly. Another 620
kkg (5 percent) of chloroform were released to water, and 18 percent, or
2,290 kkg, were incinerated. The remaining 200 kkg was disposed of in
landfills.
The large environmental releases of chloroform from indirect pro-
duction are in marked contrast to the releases from direct production;
whereas direct production emitted only about 0.2 percent of the total
produced, almost all of the chloroform produced indirectly was emitted
to the environment.
vi
-------
DIRECT PRODUCTION OF CHLOROFORM
Figure I Environmental Flow Diagram for Chloroform
PAINT REMOVER
_tf 1
T| SOLVENT DECREASING )
IROSOLS |
^ URETHANE F-JAHS I
j| OTHER USES |
IMPURITY IN
METHYL CHLORIDE)
I BUTYL RUBBER
SOLVENT
TETRAMETHYL
LEAD
SILICONE
INTERMEDIATE
FLUOROCARBIW
MANUFACTURI.
)
RESINS
(TEFLON)
REFRIGER-
ANTS
-------
Produce Ion
(179,000)
Methyl Chloride
Chlorinatlon
(122,^00 kkg)
Methane
Qilorl nation
U6.1UO kkg)
Consumptive Nonconsumpclve Secondary
Usa Us* Products
(130,600) (14,600) Contaminants
9
laports
(7.670 kkg)
Iv
\f
~X
Stockpiles
(0)
t
Vinyl Chloride Monomer
(2,680 kkg)
Chlorlaacion o
Water (912
kk3)
Chlorlnaclon in MuniclpaJ
Treatment Systeas (91 kkg,
1 Chlorlnacion of Cooling
| I'ater (2,460 kkg)
P bleaching of Piper Pulp
(6,700 kkg)
Auto Exhaust**
1 Photodacorapoaltion of
| Trichloroethylana**
[other Indirect
Sources
. crc-22 ji J crc-22
Production 1 Resins
l_
CTC-22
Refrigerant
)| Exports .. _
/ ;
J
. «f Pharmaceut icals I
9| Pesticides j
Ht Laboratory Usa L «
1 * Stockpiles J
_ _ _
r
_ _ _
s
Nectiyl
Chloride
Kethylene
Chloride
Perchloro-
echylene
Carbon
Tecra-
chlorlde
Storege/Bandllm
End-Use _ _
Storaie/Handllns,
0.0014
Paint Remover
" CTT80 ~
Metal Cleaning _
Aerosols
0.305 1
Urethane Fosa
oTTso ~
Other/Exoorts
0.975 "^
.Score ge /Handling
crc-ii/cyc-12 _
Fum Irenes
Other 1.92
Stockpiles
' _
_
Deecroyed/
Retained la
Products/
Scant*
2,360
16.4
0.072
0.025
0
0
0.17
0
0
0.017
0
0.137
0.76
0
0
44
0.18
O.L2
2.6
0
;
4.2
?
0
2,290
0
0
0
0
0
0
Air
10,987 A
11,09) B
312 A*
49) B*
0
190
0.003
81 A"
116 B*
0
Meg.
?
0.0014
0.96
0.63
0.726
0.196
0.137
0.0018
0.029
0.067
1.3
1.8
0
0
570
37.8
Probably
Large
?
190
820
32
2,340
6,300
Hay b»
Lara*
May be
Large
Mater
670
7.3
0
0
0
0
0
?
0
0.192
0.105
0
0
0.027
0
0
0
0
0
0
0
46
0
Probably
Urge
?
0
92
9
120
400
0
0
Landfill
590
5.8
0
0
0
0
0
?
0
0.128
0.088
0.079
0.017
0.026
0
0
0.0006
0
0
0
0
384
0
?
t
200
0
0
0
0
0
0
Materials Balance1 Equation: A " C">croU*d B - Uncontrolled
Chloroform Produced (179,000 kkg) - Consumptive Use (130,600 kkg) * non-Consumptive Use (14,600 kkg) * Quantity Oast royed Attained
in Products (2,360 kkg) » Emissions to Air (10,900 kkg; Controlled) * Releases to Uacer
(670 kkg) * Amount Lsndfllled (590 kkg)
** Hay be large. Balance inexact due to rounding off.
Figure II, Environmental Materials Balance for Chloroform (1978)
(Units: kkg/yr)
viii
-------
The major use of chloroform is as a feedstock for the production
of chlorodifluoromethane (CFC-22). Ninety percent of the chloroform
produced domestically, or 143,000 kkg, was estimated to be used in
CFC-22 production. Air emissions have been estimated at 190 kkg, or
0.13 percent of the total chloroform consumed for this process. No
releases of chloroform to water or land were identified.
CFC-22 is used to produce refrigerants (40 percent) and CFC-22
resins (60 percent). By assuming 1 ppm of chloroform in CFC-22,
0.072 kkg of chloroform was estimated to be destroyed during CFC-22
manufacture, 0.025 kkg to be retained in refrigerants, and 0.005 kkg
to be released to air from use of refrigerants.
The remaining 10 percent of the chloroform was used nonconsump-
tively, or was stockpiled. Nonconsumptive uses include pharmaceutical
extractions, use as a fumigant, and use as a laboratory chemical.
Several literature sources suggested that chloroform is also used as
an industrial solvent, and in the textile and dye industries; however,
numerous industrial contacts made for this study indicated that use of
chloroform for these purposes is minimal, if any.
About 1,000 kkg of chloroform were used for drug extractions in
1978. This amounts to 0.6 percent of the chloroform produced. Of the
chloroform used by the pharmaceutical industry, 57 percent was emitted
to air, 5 percent was released to water, and 38 percent was landfilled.
Only 42 kkg of chloroform were used as a fumigant in 1978. The
majority of this (.90 percent) was emitted directly to air, and 10 per-
cent was retained on the grain.
The remaining 13,600 kkg of chloroform were used for laboratory
purposes, were stockpiled, or were used as an industrial solvent.
Available information was insufficient to quantify the amount of
chloroform used for each of these purposes.
The final source of chloroform releases is as a contaminant of
other chloromethanes produced concurrently with chloroform in the
methane chlorination. process and the methyl chloride chlorination
process. The total amount of chloroform present as an impurity in
carbon tetrachloride, methylene chloride, and methyl chloride was
estimated to be 54.4 kkg. Potentially significant sources of chloro-
form from the storage, handling, and use of these chloromethanes
include: 1.8 kkg to air from use of carbon tetrachloride as a fumigant;
0.96 kkg to air from the use of paint removers containing methylene
chloride; 0.73 kkg to air from the use of methylene chloride in aerosol
products; and 0.65 kkg to air from the use of methyl chloride in metal
cleaning. All other uses of chloromethanes emit less than 0.25 kkg of
chloroform.
ix
-------
1.0 INTRODUCTION
This report presents the results of a Level I Materials Balance
for Chloroform. The study has been conducted in response to a task
order from the United States Environmental Protection Agency (EPA),
Office of Pesticides and Toxic Substances (OPTS). The primary objec-
tive of the study is to determine, within the constraints of time and
information availability, the quantities of chloroform released annually
to the environment and the sources of these releases.
By definition, a Level I materials balance involves a survey of
readily available information. This information is supplied mainly
by the Management Support Division of OPTS, and is supplemented by
JEB in-house Information and information readily available by phone
calls. In a Level I study, many assumptions and estimations must be
made in accounting for all releases of the chemical to the environment.
The results of the study are based on all the assumptions presented,
and represent the best analysis of the readily available data.
1-1
-------
2.0 PRODUCTION
2.1 DIRECT PRODUCTION
There are currently five U.S. corporations producing chloroform.in
seven plant locations. The locations of these plants are shown in .
Figure 2.1. Chloroform is produced commercially by the methane chlori-
nation process or by hydrochlorination of methanol followed by methyl
chloride chlorination. In the former process, chloroform is produced
concurrently with methyl chloride, methylene chloride, and carbon
tetrachloride. In the methyl chloride process, carbon tetrachloride
is a byproduct produced in small quantities and methylene chloride is
a coproduct (Hobbs and Stuewe 1979a).
Since chloroform is produced concurrently with methyl chloride,
methylene chloride, and carbon tetrachloride, production ratios may
vary. In general, chloroform production can be increased by increasing
the chlorine/methane ratio and varying operating temperatures (Versar
1977).
In 1978, 158,500 kkg of chloroform were produced in the United
States. This represents 71 percent of the production capacity. As the
production figures in Table 2.1 Indicate, chloroform production decreased
by 14 percent in 1975, but increased by 3 percent between 1976 and 1977,
and by nearly 9 percent from 1977 to 1978.
Table 2.1 Production of Chloroform, 1974 to 1978
Year
1978
1977
1976
1975
1974
kkg
158,500
136,900
132,500
118,000
. 137,000
Source: USITC 1976, 1977a, 1977b, 1978, 1979
Table 2.2 summarizes the chloroform production capacity of the
seven U.S. plants as well as their production capacity for the other
chloromethanes. Chloroform production capacity by the methyl chloride
chlorination process accounts for 77 percent of the total capacity
while the methane chlorination process accounts for only 23 percent of
total chloroform capacity. This process is only economically competi-
tive with methyl chloride chlorination when there is a cheap source of
methane or natural gas and chlorine.
2-1
-------
1. Allied Chemical, Moundsville, WV
2. Diamond Shamrock, Belle, WV
3. Dow Chemical, Freeport, XX
4. Dow Chemical, Plaquemine, LA
5. Stauffer, Louisville, KY
6. Vulcan, Geismar, LA
7. Vulcan, Wichita, KS
Figure 2.1 Locations of U.S. Plants Producing Chloroform
Source: Hobbs and Stuewe 1979
2-2
-------
Table 2.2 Chloroform and Chloromethane Capacity for Seven U.S. Plants
Plant
Allied Chemical
(Moundsville, WV)
Diamond Shamrock
(Belle, WV)
Dow Chemical
(Freeport, TX)
Dow Chemical
(Plaquemine, LA)
Stauffer
(Louisville, KY)
Vulcan
(Geismar, LA)
Vulcan
(Wichita, KS)
TOTAL
Chloroform
Capacity
(103 kkg)
13.3
0.7
18
45
45
34
21
40.5
4.5
222.0
Methyl
Chloride
Capacity
(103 kkg)
10.5
0.5
11
32
68
7
129.0
Methylene
Chloride
Capacity
cio3 kkg>
22
1
45
91
86
27
36
45
5
358.0
Carbon
Tetrachloride
Capacity
(10 3 kkg)
4
0.2
1.5
33
4
1
1
2
1
47.7
Total
Capacity
(103 kkg)
52.2
75.5
201
203
69
58
98
756.7
Process
Methyl Chloride
Chlorination
Methane Chlorination
Methyl Chloride
Chlorination
Methane Chlorination
Methyl Chloride
Chlorination
Methyl Chloride
Chlorination
Methyl Chloride
Chlorination
Methyl Chloride
Chlorination
Methane Chlorination
NJ
OJ
Source: Hobba and Stuewe 1978, 1979a
-------
2.1.1 Chloroform Production by Methanol Hydrochlorination Followed by
Methyl Chloride Chlorination
Figure 2.2 shows a flow schematic for the hydrochlorination of
methanol followed by methyl chloride chlorination, and points where
environmental releases occur. Appendix B includes a detailed process
description. In this process, methyl chloride is produced by the
hydrochlorination of methanol. This reaction is then combined with
the continuous chlorination of methyl chloride to produce methylene
chlorine and chloroform along with carbon tetrachloride as a by-
product .
Total production capacity for plants producing chloroform by methyl
chloride chlorination in 1978 was estimated to be 172,000 kkg (Hobbs and
Stuewe 1978). No estimate was available on the quantity of chloroform
produced by this process. Since total production was 71 percent of
capacity in 1978, it was assumed that the methane chlorination process
and the methyl chloride chlorination process each produced 71 percent
of potential capacity. The amount of chloroform produced in 1978 by
methyl chloride chlorination was therefore estimated as 122,000 kkg.
This estimate is considered accurate to +10%.
The production figure of 122,000 kkg does not include chloroform
losses from production, storage, and transportation. JRB estimates
that at the most, approximately 400 kkg of chloroform are lost during
these operations, and we have therefore estimated total production at
122,400 kkg.
2.1.1.1 Air Emission
There are five sources of air emissions from the methyl chloride
chlorination process: the inert gas purge vent, the methylene chloride
and chloroform condenser vents, fugitive emissions, storage and handling
losses, and secondary emissions (see Figure 2.2).
A. Inert Gas Purge Vent
The chlorine feed to the methyl chloride chlorination reactor
contains inert gases which must be vented. However, chloroform has
not been identified as a constituent of this stream (Hobbs and Stuewe
1978).
B. Methylene Chloride and Chloroform Distillation Column Vents
Condenser vents in the distillation operation are required to
prevent pressure from building up inside the condensers during normal
operation.
Hydroscience calculated emission factors for volatile organic
compounds (VOC) for the condenser vents based on information provided
for the Vulcan Chemical plant (Hobbs and Stuewe 1978). The emission
factor for the methylene chloride condenser was estimated to be 0.019
kg of total VOC/kkg of chloromethanes and that for the chloroform
condenser was estimated to be 0.0056 kg of total VOC/kkg of chloro-
methanes. It was assumed that 30 percent of the total chloromethane
2-4
-------
HETHANOL
HCL
N3
I
Ul
-*
»
4
HCL
1
5 ">
REACTOR _ * Sj
P1
A
k
1 1 l_
WATER
r i *
r
Methylene Chloride
Condenser Vent
t
11 r
r
_j
o
LJLT^
!
,1 REACTOR
M
J '-T"J
1
:i
1
REACTOR 1 f
Hct
SOI N.
Chloroform
Condenser Vent
1*
I
r
SPENT
NaOH CAUSTIC . .
t 1 1
I
SPENT
AUSTIC
W
A
I
OKI,
2=
r
o
i
f» HCI
1 1
1 1
J REACTOR .
n ^
1 '
^J :- T
i
cc,
r
o
o
1
HEAVY
ENDS
r-1
COLUMN <- *
SPENT H
ACID 1
i
< W
A A
f.
W = Water
A = Air
METHYL CHLORIDE
to Storage
METHTLENE CHLORIDE
CHLORFORH
CARUON TETRACHLORIDE
to Storage
DOTTED ITEMS ARE OPTIONAL
Figure 2.2 Production of Chloroform from Methyl Chloride Chlorination
Source: Hobbs and Stuewe 1978
-------
product is chloroform (Hobbs and Stuewe 1978) , and that the percentage
distribution of VOC from the condenser vents was as follows (Lant 19.78)
Methylene chloride Chloroform
condenser vents condenser vents
Methylene chloride 72 . 73
Chloroform 26 26
Carbon tetrachloride 2 1
Using this information, the emission rates for chloroform are cal-
culated as follows.
[Emission factor\ /Percent chloro-\ _ Emission factor
I for total VOC J I form in VOC J ~ for chloroform
Methylene chloride condenser vent :
(0.019 kg/kkg) (0.26) = °-50 Jf chloroform/
& 5 kkg chloromethanes
Chloroform condenser vent;
/n nr.cc i /i i \ tn ICN 0.0015 kg chloroform/
(0.0056 kg/kkg) (0.26) = , , ui ^t.
& 6 kkg chloromethanes
These emission factors are based on total chloromethane production,
rather than on the production of chloroform only. Emissions associated
with production of methyl chloride, methylene chloride, and carbon
tetrachloride are presented in Section 3.3. About one-third of the
total chloromethane capacity is for chloroform (Table 2.2). The emis-
sion factor for chloroform production alone is thus assumed to be one-
third of the total VOC emissions.
/ \ / \ f -o t \ Chloroform
[Chloroform] /Combined emission] {chlorofora in | = "leased from
^produced j ^ factor J Chloromethanes/
(122, 400 0.0065 kg chloroform/ \ ,Q . _ Q 2
\ kkg / ^kkg total chloromethanes] C°'33) U.Z
No rationale was given in the Hydroscience report for the way
emission factors were determined. The estimates are assumed to be
accurate to 4v30%. This uncertainty accounts for variability in emis
sion factors at other plants besides Vulcan, and for variability in
operating conditions. When the uncertainty estimate of +10% for the
quantity of chloroform produced by methyl chloride chlorination is
taken into account, our overall uncertainty estimate for chloroform
releases is +38%.
2-6
-------
C. Fugitive Emissions
Fugitive emissions in a typical chloromethane plant result from pro-
cess fluid leaks from plant equipment including pump seals, compressor
seals, pipeline valves, and pressure relief valves.
The number of equipment components typically used in a chloro-
methane plant with a capacity of 45-180 x Kp kkg and the rates of
fugitive losses from each component are shown in Table 2.3. Controlled
emissions differ from uncontrolled emissions in that major leaks have
been repaired.
Table 2.3 Sources of Fugitive Emissions and Typical Rates of Emissions
Component
Pumps
Process valves
Relief valves
Compressors
Number of
components
30
+ 30 backup
1,000
15
2
Uncontrolled
emissions
(kg/day/unit)
1.5
0.068
1.1
3.9
Uncontrolled
emissions
(kg/day/unit)
0.16
0.006
0.1
1.0
Source: Hobbs and Stuewe 1978
By utilizing information presented in Table 2.3 plus the following
equation, total fugitive emissions (chloroform plus other constituents)
are estimated for the six plants using the methyl chloride process.
This estimated total is based on 260 days/year of operation.
/Release rate\ / , J,\ /Number of \ / , ,\ Total
\ Number of ... (Number of) .. ..
per unit . operating n . = fugitive
j I \ units \ , I \ plants / ,
per day J \ I \ days I \ / losses
For example, uncontrolled releases from pump valves equal:
(1.5 kg/day/seal) (60) (260) (6) = 140 kkg
2-7
-------
Total controlled and uncontrolled fugitive emissions are summarized
below:
Pump seals
Process valves
Pressure relief valves
Compressors
Total
Uncontrolled
emissions
(kkg)
140
110
26
12
Controlled
emissions
(kkg)
288
These estimates are considered accurate to +35% to account for varia-
tions in release rates per unit and in the number of components in
chloromethane plants.
Since detailed flow diagrams of the chloromethane plants could
not be obtained, it is not possible to calculate the percentage of
chloroform in fugitive emissions. Nevertheless, an estimate was baaed
on the volatility of feed and product compounds and the process operat-
ing conditions.
The composition of fugitive emissions is estimated to be:
Compound
HC1
Methanol
Methyl chloride
Other VOC
Mole
percent
35
25
20
20
Molecular
weight
36.0
32.0
50.5
98.9
Weight
percent
25
16
20
39
Plant capacities listed in Table 2.2 indicate that production of
chloroform, methylene chloride, and carbon tetrachloride average 32,
65, and 3 percent of the total, respectively. Assuming that fugitive
losses of chloroform included in "other VOC" are in proportion to the
total quantity of chloroform produced, the quantity of chloroform in
fugitive emissions is estimated as follows:
[Total fugitive]
I emissions /
Weight percent]
\of "other VOC"
Uncontrolled Conditions;
(288 kkg) (0.39)
Controlled Conditions:
/Weight percent
1 of chloroform
in VOC
V
(29 kkg)
(0.39)
(0.32)
(0.32)
Total Chloroform
in fugitive
emission
35.9 kkg
3.6 kkg
2-8
-------
Controlled and uncontrolled emissions are considered separately in the
overall materials balance.
Our estimate for the quantity of chlorform in fugitive emissions
under controlled conditions is considered accurate to +20%. When com-
bined with the uncertainty estimate of +35% for total fugitive emis-
sions, the overall uncertainty is +53%. Factors contributing to this
uncertainty include the variability in the age and number of process
components, which affect fugitive losses; uncertainty related to
amount of chloroform in fugitive releases; and the extent to which
fugitive emissions are controlled.
D. Storage and Handling
Storage tanks for both crude and finished chloromethanes can be a
source of evaporative losses. The American Petroleum Institute (API)
has developed an empirical formula based on field testing which corre-
lates evaporative losses with several factors related to storage, such
as tank volume, paint condition, and liquid level (USEPA 1977).
In the following section, chloroform releases from storage and
handling will be estimated using the empirical formula. Fixed roof
storage tanks are the minimum requirement for storage and it is assumed
in the calculations that follow that all tanks are fixed roof tanks.
(1) Determination of Breathing Losses
Assuming that all six plants producing chloroform by the chlorina-
tion of methyl chloride operate at about 71 percent of capacity, the
product storage requirements for chloroform will approximate the quan-
tities shown below:
Estimated Volume for
production storage
(1Q3 kkg) (103 -Q
Allied Chemical 9.4 6,270
Diamond Shamrock 12.8 8,500
Dow .Chemical 31.9 21,300
Stauffer 24.1 16,100
Vulcan (LA) 14.9 9,900
Vulcan (KS) 28.8 19,200
Total 122.0 81,300
It was assumed that the plants would maintain tanks at about 50
percent of capacity. Tank sizes and turnover rates were estimated
using data supplied by USEPA (Hobbs and Stuewe 1978) and Vulcan
(Leonard 1978) (see Appendix B). Table 2.4 shows the tank sizes and
tank turnover rates used in calculating releases from storage and
2-9
-------
Table 2.4 Summary of Breathing Losses from Chloroform Storage
Tank volume
(gallons)
7,000
16,000
50,000
100,000
461,000
(liters)
26,250
60,000
187,500
375,000
1,728,750
Number
of
tanks
12
2
6
2
2
Percent
of
capacity
50
50
50
50
50
Turnover
rates
/yr
125
125
20
20
20
Recovery
method
None
None
Refrig.
vapor
recovery
ii ii
Breathing
losses
per tank
(kkg/yr) '
0.56
1.75
4.6
3.7
13.7
Total breathing losses
(kkg/yr)a
controlled
6.8
3.5
27.5
7.3
27.3
72.4
uncontrolled
6.8
3.5
27.5
29.3
.
109.9
177.0
NJ
I
Controlled and uncontrolled emissions are considered separately in the final materials balance.
-------
handling. Using the API empirical formula (USEPA 1977), storage emis-
sions can be calculated as follows:
LB = (2.21)" 10"4M
114.7-P
i
where
0.68
D1'73 H°'51
LB = fixed roof breathing losses (Ib/day)
M = molecular weight = 119
P = true vapor pressure at bulk liquid conditions Cpsia) = 3.259
D = tank diameter; variable (see Appendix B)
H = average vapor space height, variable (see Appendix B)
T = average ambient temperature change from day to night; assume 20 F
Tp = paint factor; assume 1
C = adjustment factor for small diameter tanks - variable
Kc = crude oil factor = 1
Appendix B details calculations for breathing losses from tanks of
each size. Table 2.4 summarizes breathing losses based on the empirical
formula. It was assumed that the tanks of largest volume (375 x 10-^ and
1,729 x 10 liters) have refrigerated vapor recovery systems and that the
smaller volume tanks have no controls. Vapor recovery systems are gener-
ally 60-90 percent efficient in recovering chloromethanes. An efficiency
of 75 percent was assumed for these estimates. As shown in Table 2.4
total breathing losses from storage are estimated to be 72.4 kkg/year
with refrigerated vapor recovery systems. Without the refrigerated
vapor systems, chloroform storage losses would be 176 kkg/year, or
1.43 kg/kkg. This estimate is in reasonably good agreement with an
estimate made by Hydroscience for uncontrolled emissions from chloro-
form storage (Hobbs and Stuewe 1978). This study estimated an emission
factor of 1.7 kg/kkg for all chloromethanes. Using this estimate and
that, of 122,000 kkg of chloroform stored, total chloroform losses would
be 207 kkg/year. It is highly unlikely, however, that there are no
vapor recovery systems, at least on the larger storage tanks.
Our estimate of 72.4 kkg of controlled emission is considered
accurate to +40%, -20%. This range allows for uncertainties related
to storage conditions and the use of vapor recovery systems. When
this uncertainty estimate is combined with that of +10% for the quan-
tity of chloroform stored, the overall uncertainty is +54%, -39%.
2-11
-------
(2) Working Losses
Working losses were similarly estimated using an empirical formula
derived from API (USEPA 1977). The expression to estimate these losses
is:
-2
where
LW-2.4xlOMP KnKc
LW = fixed roof working losses (lb/10 gal)
M = molecular weight = 119
P = true vapor pressure at bulk liquid conditions
Kn = turnover factor; variable
Kc = crude oil factor = 1
3.259 psia
Appendix B details the calculations for working losses from storage
tanks assuming tank volume and turnover rates shown in Table 2.5. JRB
estimates for working losses are also summarized in Table 2.5.
Table 2.5 Summary of Estimates for Working Losses
Tank volume
(gallons)
7,000
16,000
50,000
100,000
461,000
(liters)
26,250
60,000
187,500
375,000
1,728,500
Number
of
tanks
12
2
6
2
2
Turnover
per
year
125
125
20
20
20
Working Losses
(kkg/yr)a
controlled
6.5
3.7
12.7
2.1
9.7
34.7
uncontrolled
(no vapor
recovery)
6.5
3.7
12.7
8.4
39.0
70.3
Controlled and uncontrolled conditions are considered separately in the
final materials balance.
An estimated 34.7 kkg of chloroform/year are lost during handling.
This corresponds to an emission rate of 0.28 kg/kkg. Without refrigera-
ted vapor recovery systems for the larger tank, handling emissions would
be 69.3 kkg or 0.57 kg/kkg produced. In contrast, Hydroscience estimated
controlled working losses at 0.36 kg/kkg (Hobbs and Stuewe 1978). For
this materials balance, JRB's estimate of controlled losses will be used.
This estimate is assigned an uncertainty of +30%, -0% to account for the
2-12
-------
possibility that the Hydroscience estimate is more accurate. Since the
estimated uncertainty for the quantity of chloroform in storage is +10%,
the overall uncertainty estimate is +40%, -10%.
2.1.1.2 Releases of Chloroform to Land/Secondary Emissions
Secondary VOC emissions result during handling and disposal of pro-
cess waste liquids and residues. Incineration of carbon tetrachloride
still bottoms is the major source of secondary emissions in the methyl
chloride chlorination process. The residue is produced at a rate of
1.02 kg/kkg of chloroform, and is estimated to be 18.4 percent chloro-
form by weight (Lant 1978). From these factors and the 1978 production
figure for chloroform (122,400 kkg), the total quantity of chloroform
in the carbon tetrachloride residue is estimated as 23 kkg.
No information was available on the fate of these wastes. JRB
assumed that 75 percent of the still 'bottoms are incinerated, and that
the incinerator operates at 95 percent efficiency. The quantity of
chloroform incinerated was thus estimated as 17.3 kkg. Of this amount
approximately 0.86 kkg was released to the air and 16.4 kkg were land-
filled. Presumably, the remaining still bottoms (5.8 kkg) are land-
filled. The method by which these wastes are contained is not known.
Our estimate for the quantity of chloroform in carbon tetrachloride
residues is accurate to only +25%. The estimate was based on data from
one plant only; the quantity of residue produced will undoubtedly vary
from one plant to the next. The estimates for the quantities incinera-
ted and landfilled are considered accurate to +15% and +50%, respect-
ively. When combined with the uncertainty estimate of +25% for the
total quantity of chloroform in the residue, our overall error ranges
are +39% and +72% for the quantities incinerated and landfilled,
respectively.
c
2.1.1.3 Emissions of Chloroform to Water
There are three potential sources of chloroform releases to waste-
water during chloroform production: the spent caustic water, the spent
acid waste, and the indirect contact cooling water.
A. Indirect Contact Cooling Water
Indirect contact cooling water used during production of chloro-
form may be contaminated by minor spills and leaks. One process was
reported to use 5,800 £/kkg of chloroform produced (Lant 1978). The
cooling water from one process was estimated to be contaminated with
1,000 mg of chloroform/-^ (Lant 1978). .However, comparison of emissions
from this plant and those from other plants using the methyl chloride
chlorination process showed emissions from this facility to be very
high due to the age of this plant. We assume, on an average, that
cooling water is contaminated with 100 mg of chloroform/-^. The total
2-13
-------
chloroform released from spills and leaks to cooling water can be esti-
mated as follows:
Cooli*g water/^ /Chloroform in\ Tota^
lor kk§ chloroform Cooling Water = re^ased to
chloroform/ \^ ° I \ & / cooling water
(122,400 kkg) (5,800 £/kkg) (10~7 kkg/£) = 70 kkg
It is assumed that 90 percent or 63 kkg of the chloroform is
evaporated to air and the remaining 10 percent or 7 kkg remains in the
water.
This estimate is not considered more accurate than +75%, -50%.
When combined with the uncertainty estimate of +_10% for the quantity
of chloroform produced by methyl chloride chlorination, the overall
uncertainty estimate is +90%, -56%. Releases of chloroform from spills
and leaks are intermittent and vary from one plant to the next. The
nature of this wastewater makes it difficult to.quantify chloroform
losses to cooling water.
B.. Spent Acid and Spent Caustic
Gruber and Ghassemi estimated that approximately 0.04 kg of
chloroform/kkg of total chloromethanes is released to the spent acid
and spent caustic streams. This release factor was not based on plant
data and is therefore not considered very reliable. However, in the
absence of better data, this factor is used to give an approximation
of emissions. Since the emission factor is based on total chloro-
methanes produced rather than on chloroform only, the following equa-
tion corrects for this by multiplying by the ratio of chloroform to
total chloromethanes.
/ Total \ /Emission factor\ / Percent \ Total
chloroform) I kg CHCls/kkg chloroform in = chloroform
\ produced / \ chloromethane / Whloromethanes/ released
(122,400 kkg) (0.04) (0.33) = 1.6 kkg
Because these waste streams are small, the.chloroform will be
diluted to low concentration. It is assumed that about 80 percent
or 1.3 kkg will evaporate and 20 percent or 0.3 kkg will remain in
the water. Our uncertainty estimates for the percentages released to
air and remaining in water are +_10% and +30%, respectively. Our uncer-
tainty estimate for total chloroform released to spent caustic and
spent acid wastes (1.6 kkg) is +75%. When the uncertainty of +10% for
total chloroform produced is taken into account, the overall uncertain-
ties are +110%, -100% for air and +125%, -100% for releases to water.
2.1.1.4 Summary of Environmental Releases
Figure 2.3 summarizes the multimedia releases of chloroform from
the methyl chloride chlorination process. If fugitive emissions and
2-14
-------
Incinerated
16.4 kkg
176.0 kkg (Controlled)
348.5 kkg (Uncontrolled)
Air (process losses)
Chloroform
Production by
Methyl Chloride
Chlorination
(122,400)
Water
_^ 7.3 kkg
^ 136. kkg
Air (Transportation Losses)
^ 5.8 kkg
Landfill
^122,000 kkg
Product*
*The quantity of product available will depend on the extent
fugitive, storage, and working emissions are controlled.
Although air emissions are shown for both controlled
and uncontrolled conditions, controlled conditions are
probably more representative of losses.
Figure 2.3 Summary of Multimedia Release of Chloroform from the
Methyl Chloride Chlorination Production Process
2-15
-------
storage .and working losses are assumed to be controlled, as previously
discussed, the process releases a total of 189 kkg of chloroform or
approximately 0.2 percent of the total produced. Of the chloroform
released, 93 percent is emitted to air or is evaporated from water, 4
percent is discharged to water, and 3 percent is landfilled. An addi-
tional 16.4 kkg is destroyed by incineration.
If fugitive, storage, and working emissions were not controlled,
the process would release a total of 360 kkg, with more than 96 per-
cent of the emissions going to air.
Figure 2.3 includes the transportation losses derived in Section
2.1.3.
2.1.2 Methane Chlorination Process
Chloroform is produced concurrently with methyl chloride, methylene
chloride, and carbon tetrachloride by the thermal chlorination of methane.
A detailed description of this process is presented in Appendix B. A
simple flow diagram illustrating points of environmental release is shown
in Figure 2.4.
The Dow Chemical plant at Freeport, Texas, is the only plant using
the methane chlorination process exclusively. Allied Chemical uses
chlorination of methane for about 5 percent of its total production and
the Vulcan plant at Geismar produces an estimated 10 percent of its out-
put by methane chlorination (Hobbs and Stuewe 1979a). The total chloro-
form production capacity for this process is approximately 50,200 kkg.
Production figures for 1978 were not available for the methane
chlorination process. Since total chloroform production is estimated
to operate at 71 percent of capacity, it is assumed that methane chlori-
nation and methyl chloride chlorination each operated at 71 percent
capacity in 1978. Total chloroform produced by methane chlorination is
thus estimated as 36,000 kkg, 23 percent of total chloroform production.
This estimate is considered accurate to +30%.
Estimating process emissions at about 100 kkg, total production
is assumed to be 36,100 kkg.
2.1.2.1 Air Emissions
Air emissions from the chlorination of methane come from the
following sources:
Inert gas purge vent for methane recycling
Drying bed regeneration vent
Distillation area emergency inert gas vents
Fugitive emissions
Storage and handling
Secondary emissions
2-16
-------
III III/MIL
CIILUItltlL
r
1 HE THANE
1 (TO SEHA
_
r~'
LJ
--- KtACTOK -
1 3 L.
1 s 1
~ll_
1
AND IICI
RATION)
£ "*n
to I
t- tt *>-
i/i
oa
-*-
T
i
STRIPPER
J
\
JATEI)
nc1,
SOI II
CI
\ CHLOROFORM
t. CONDENSERS
If
CIICI
3
r *
' L_
i
r
1
vj HCAC1
1
1
-MCI
1
1
Oil 1
1
1
INERT GAS
PURGE VENT '
r
I
s
c
<;iu rniiir
'laOH ACID
T T
~| :u ci
L Li
ft A CONDENSER
T tA STORAGE EMISSIONS
|i L»- HtTIIYLtNt CHLORIDE
:n ci
2 i
r- 3
» » 1 1
PENT SHtlir
AUSTIC ACID
i 4
u w
A /f^ STORAGE
STORAGE f- EMISSIONS
EMISSIONS U 1 _ «-o^c
1
CCI
r
6
LJ
1 - »- CAHUOH TCTUACIILUH I UL
TO STORAGE
1 "
II AUY
Lllll-j
hi)IIIt) 111 11$ ARC OI'TIOIIAL
Figure 2.4 Production of Chloroform from Methane and Chlorine
Source: Hobbs and Stuewe 1979a
-------
The Hydroscience report (Hobbs and Stuewe 1979a) was the only source
of data on emissions from the chlorination of methane. The emission fac-
tors in this report were based on information supplied by Dow Chemical.
A. Inert Gas Purge Vent for Methane Recycling
Inert gases enter the process with feeds to the chlorination cham-
ber, and remain with the unreacted methane throughout the methane purifi-
cation step. A portion of the recycled methane, stream is vented to pre-
vent a buildup of inert gases. It is estimated that 2.10 kg of chloro-
methanes are released per kkg of chloromethanes produced. The stream
composition indicates that the vent stream is 0.01 mole percent chloro-
form, or 0.0033 kg of chloroform/kkg of chloromethanes.
Since the emission factor is based on total chloromethanes, we have
multiplied by the fraction of chloroform in total chloromethanes produced
(about 25 percent) to determine emissions associated with chloroform pro-
duction only.
/ \ /Emission factor\ / Fraction \ . Chloroform emitted
Chloroform chloroform/ chloroform in total = from inert gas
y Pro uce I y chloromethanesy \ chloromethanes / purge vent
(36,100 kkg) (0.0033 kg/kkg) (0.25) = 0.03 kkg
The industrial source for this emission factor did not give error
bounds on this estimate. We assume the emission factor-to be accurate
to +50%, -25%. The uncertainty factors for total chloroform produced
from this process is +30%. The overall uncertainty is thus +80%, -55%.
B. Drying Bed Regeneration Vent
Chloroform has not been identified as a constituent of this stream.
C. Distillation Area Emergency Gas Vent
Venting of distillation area equipment prevents buildup of pressure
in the condensers. Emissions during emergency venting were estimated to
be 0.061 kg/kkg of chloromethanes (Hobbs and Stuewe 1979a). The compo-
sition of the uncontrolled emissions is reportedly:
Component Mole Percent
Chlorine 40
HC1 34.6
VOC 22.4
Air 3
When these constituents are expressed as percentage by weight, VOC make
up about 34 percent of the total emissions. Assuming that chloroform
comprises 25 percent of the VOC then the emission factor for the gas
vent is 0.005 kg/kkg of chloroform produced. Total releases of chloro-
form from venting of distillation area condensers are estimated from
this emission factor and chloroform production of 36,000 kkg as 0.19 kkg.
2-18
-------
Neither the method for estimating the emission factor nor the uncer-
tainty of this estimate was given. We assume the estimate to be accurate
to +50%, -25%. With an uncertainty estimate of +30% for total chloroform
produced, our overall uncertainty is +80%, -50%.
D. Fugitive Emissions
As indicated in Section 2.1.1, estimates of fugitive emissions from
process fluid leaks are based on average daily losses for controlled and
uncontrolled emissions for the petroleum refinery industry. These fugi-
tive emission factors for chloromethanes are shown in Table 2.6. The
number of process valves, compressors, and other components has been esti-
mated for a chloromethane plant with a capacity of 45-180 x 10~^ kkg
(Hobbs and Stuewe 1978). This estimate is only a rough approximation
and only accounts for fugitive losses associated with the Dow plant at
Freeport, Texas. Without detailed process descriptions, fugitive emis-
sions cannot be estimated for the Allied plant at Moundsville, West
Virginia, or the Vulcan plant at Geismar, Louisiana, since production
capacities are so small.
Table 2.6 summarizes the number of equipment components, the
average controlled and uncontrolled emissions per unit, and the total
fugitive emissions from each component. Emissions were calculated
assuming a 260 day work year, using the following equation:
[Total number \ /Average loss A /Number of\
\of components/ \^ component /day ) ywork daysy
Total fugitive
losses/components
The data presented in Table 2.6 indicate that the total uncontrolled
fugitive emissions equal 47.4 kkg/year, and total controlled fugitive emis
sions equal 5.6 kkg. These estimates are thought to be accurate to +_30%.
Table 2.6 Summary of Emission Factors for Fugitive Emissions of
Chloromethanes from Various Equipment Components
Pump seal
Compressor
Process valve
Pressure
relief valve
TOTAL
Total
no. of
units
60
2
1,000
15
Uncontrolled
losses
(kg/day/unit)
1.5
3.9
0.068
1.1
Controlled
losses
(kg/day/unit)
0.16
1.0
0.006
0.1
Total
uncontrolled
emissions4
(kkg/yr)
23.4
2.0
17.7
4.3
47.4
Total
controlled
emissions3
(kkg/yr)
2.5
0.5
1.6
0.4
5.0
aUncontrolled and controlled emission are considered separately in the over-
all materials balance.
Source: Hobbs and Stuewe 1979a
2-19
-------
Since a quantitative breakdown of the composition of gases in fugi-
tive emissions was not available, the composition was estimated based on
vapor pressure of the gases and process operating conditions. Emissions
are estimated to have the following composition:
Mole Molecular Weight
percent weight percent
Methane 30 16 2.9
Chlorine 5 70 25.4
Hydrogen chloride 30 36 13.2
Methyl chloride 20 50 18.3
Other VOC 15 103 37.4
An estimate of chloroform in other VOC was made by assuming that
this category consisted only of carbon tetrachloride, methylene
chloride, and chloroform and that the concentrations were proportional
to the quantities of each produced. The estimated percentages are:
Methylene chloride 56 percent
Chloroform 31 percent
Carbon tetrachloride 13 percent
The total quantity of chloroform in fugitive emissions is estimated
from the total fugitive emissions (47.4 kkg uncontrolled; 5.0 kkg con-
trolled), the fraction of other VOC in these emissions (0.374), and the
fraction of chloroform in other VOC (0.31). These chloroform emissions
are thus estimated as 5.5 kkg for uncontrolled conditions and 0.58 kkg
for controlled conditions. It is likely that fugitive emissions are
controlled.
The overall uncertainty for controlled emissions is +50%. This
uncertainty is attributed to the likelihood that the number of equipment
components varies from the values shown in Table 2.6, and to uncertainty
related to the composition of fugitive emissions.
E. Emissions from Storage and Handling
Emissions from storage and handling are estimated using an empiri-
cal formula developed by API which correlates evaporative losses with
several factors related to storage (USEPA 1977). It was assumed that
all tanks are of the fixed roof type and that refrigerated vapor recovery
systems are used for tanks with a volume of 375,000 liters or greater.
Efficiency of a refrigerated vapor recovery system varies from 60-90 per-
cent for chloromethanes. An efficiency of 75 percent was assumed for
these calculations.
Assumptions regarding storage tank size and factors which affect
storage emissions were based on data included in Appendix B and Table
2.7, which shows the assumed tank volumes, number of tanks, and turn-
over rates. Our estimates for breathing and working losses are also
shown in the table.
2-20
-------
Table 2.7 Summary of Chloroform Storage Variables and Chloroform Breathing and Working
Losses
Tank
volume
(gal)
300.000
16,000
7,000
TOTAL
Tank
volume
U)
1,125,000
60,000
26,250
Number
of
tanks
1
1
5
Approximate
percent
of capacity
50
50
50
Turnover
rate
20
125
125
Recovery
method
Refrigera-
ted vapor
recovery
None
None
Breathing losses
(kkg/yr)a
controlled
6.7
1.7
2.8
11.2
uncontrolled
26.7
1.7
2.8
31.2
Working losses
(kkg/yr)a
controlled
3.2
1.9
A.I
9.2
uncontrolled
12.7
1-9
4.1
18.7
Controlled and uncontrolled emissions are considered separately In the overall materials balance.
-------
Breathing losses were determined using the following equation:
10.68
LB = 2.21 x 10~4 M
D1.73 H0.51 T0.5
|14.7-p
where
LB = fixed roof working losses (Ib/day)
M = molecular weight - 119
P = true vapor pressure at bulk conditions (psia) - 3.259
D = tank diameter (see Appendix B)
H = average vapor space height (see Appendix B)
T = ambient temperature change from day to night - assume 20 F
Tp = paint factor - assume 1
C = adjustment factor for small diameter tanks - variable
Kc = crude oil factor = 1
Appendix B details the calculations for breathing losses by use of
this empirical formula. As Table 2.7 and Appendix B indicate, the total
chloroform storage losses with vapor recovery are estimated at 11,2 kkg.
This corresponds to an emission factor of 0.31 kg/kkg of chloroform pro-
duced. Without refrigerated- vapor recovery the emission factor would be
0.9 kg/kkg of chloroform. This estimate is somewhat lower than that of
1.35 kg/kkg made by Hydroscience (Hobbs and Stuewe 1979a) for uncon-
trolled fugitive losses. Although the overall materials balance con-
siders both controlled and uncontrolled emissions, the controlled condi-
tions are more likely. Our estimate of 11.2 kkg of chloroform released
during storage with vapor recovery is considered accurate to +75%, -25%.
This uncertainty takes into account the possibility that the Hydroscience
estimate is more accurate and the uncertainty related to the extent to
which vapor recovery systems are used.
F. Working Losses
Working losses were also estimated using an empirical formula
developed by API (USEPA 1977). The formula is:
LW = 2.4 x 10~2 MPKnKc
where
LW = fixed roof working losses (lb/10 gal)
M = molecular weight = 119
P = true vapor pressure at bulk liquid conditions = 3.259 psia
Kn = turnover factor - variable
Kc = crude oil factor
2-22
-------
The turnover factor is a function of the turnover rate shown in
Table 2.7. The calculations for working losses based on the empirical
formula are detailed in Appendix B. Table 2.7 summarizes working losses.
Assuming controlled conditions (i.e. vapor recovery), an estimated 9.2
kkg of chloroform were lost due to handling in 1978. This corresponds
to an emission factor of 0.26 kg/kkg. Without the use of refrigerated
vapor recovery, the emission factor would be 0.52 kg/kkg and emissions
would be about 18.7 kkg. This is significantly higher than the esti-
mate of 0.36 kg/kkg made by Hydroscience for handling emissions from
this process (Hobbs and Stuewe 1979a). The accuracy of our estimate for
controlled emissions is considered +75%, -25% to take into account the
uncertainties related to the use and efficiency of vapor recovery sys-
tems, the number of tanks, and tank turnover.
G. .Secondary Emissions
Secondary emissions result during the handling and disposal of
process liquids. Potential sources for secondary emissions include:
Incineration of carbon tetrachloride incineration bottoms
Waste caustic from scrubbers
Sulfuric acid waste from the dryer of the methyl chloride
product stream.
Quantitative estimates of these emissions could not be made.
2.1.2.2 Releases to Water
Because of similarities between the methyl chloride and the methane
chlorination processes, it is assumed that the wastewater streams in
the former process are present in the latter. These indirect streams
are contact cooling water and wastewaters containing spent caustic and
spent acid.
A. Indirect Cooling Water
Only one estimate was available on the amount of cooling water
used in chloromethane production (Lant 1978). We assume that similar
quantities, 5,800 £/kkg of chloroform, are generated in all chloro-
methane plants, although this amount is probably quite variable. We
further assume that cooling water is contaminated by spills and leaks,
producing chloroform concentrations of 100 mg/£. Contaminant levels of
1,000 mg/£ were reported for one process, but because of the age of
this plant, this value was not considered representative. For chloro-
form production of 36,000 kkg, these factors give an estimate of 21 kkg
of chloroform released to cooling water. JRB assumes that 90 percent
(18.9 kkg) of the chloroform is readily evaporated and the remaining
10 percent (2.1 kkg) is released to water. This estimate of 21 kkg is
considered accurate to +75%, -50% to account for variation in chloro-
form contaminant levels, (which have not been monitored) and in amount
of cooling water per kkg of chloroform. Since the uncertainty for the
quantity of chloroform produced is +30%, the overall uncertainty esti-
mate is +110%, -76%.
2-23
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B. Wastes Containing Spent Caustic and Spent Acid
Gruber and Ghassemi (1975) estimated release of chloroform to waste-
water from spent caustic and spent acid at 0.04 kg/kkg of total chloro-
methanes. The derivation of this release rate is not described, and it
is thought to be a rough estimate at best. Assuming that 25 percent of
the chloromethanes is chloroform, total chloroform releases to waste-
water from chloroform production can be estimated:
i_ ,,1 r \ /Emission factor\ / Fraction \ _ .
Total chloroform! | , n , , \ / ,, .. .1 Total
, , chloroform/ chloroform in =
produced / I , -, . / I .-, , / chloroform
H ' \ chloromethanes / \chloromethanesy
(36,100 kkg) (0.04 kg/kkg) (0.25) = 0.36 kkg
JRB assumed that at the dilute concentrations present in these waste
streams, 80 percent of the chloroform (0.3 kkg) will be evaporated and
20 percent (0.1 kkg) will remain in water.
Our estimates of the percentages of chloroform released to air and
water are considered accurate to +10%, -30%, respectively. Our esti-
mate of 0.36 kkg for total chloroform releases is considered accurate
to +75%. When the uncertainty of +30% for total chloroform produced is
taken into account, the overall uncertainties are +152%, -100% for air
and +150%, -100% for water.
2.1.2.4 Summary of Environmental Releases
Figure 2.5 summarizes the environmental releases of chloroform
from the methane chlorination process under both controlled and uncon-
trolled conditions. Process emissions under controlled emissions are
estimated to be. 42.6 kkg, or less than 0.2 percent of the total produc-
tion. Of the chloroform emitted, 95 percent is released directly to air
or evaporated from wastewater and the remaining 5 percent is discharged
to water. An unidentified amount is incinerated during destruction of
carbon tetrachloride still bottoms.
2.1.3 Transportation Losses
Transporting chloroform from the production sites to the end-use
sites causes losses from loading and transit. No information is
available on transportation practices. However, several reasonable
assumptions can be made to estimate these losses.
2.1.3.1 Loading Losses
Loading is the primary source of evaporative losses during trans-
portation. These losses occur when hydrocarbon vapors residing in the
empty cargo tanks are displaced to the atmosphere by liquids being
loaded. Emissions from loading can be estimated using the following
expression (USEPA 1977):
2-24
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Incinerated
40.4 kkg (Controlled)*
74.8 kkg (Uncontrolled)
Air (Process losses)
Chloroform
Production from
Methane
Chlorination
Process
(36,100 kkg)
^36,000 kkg
Water
_^2.2 kkg
(Transportation losses)
Air 41
kkg
Land
*Controlled conditions: Vapor recovery systems associated
with large storage tanks and control of fugitive emissions
by repair of major leaks. Although both controlled and
uncontrolled conditions are shown, controlled conditions
are more likely.
Figure 2.5 Summary of Multimedia Releases of Chloroform
from Methane Chlorination Process
2-25
-------
LL = 12.46
SPM
T
where
LL = Loading losses, lb/10 gal
M = Molecular weight = 119
P = True vapor pressure =3.2 psia
T = Bulk temperature liquid - assume 530 R
S = Saturation factor - assume 1.45 for tank cars
0.5 for barges
0.2 for marine vessels
The saturation factor reflects the concentration of chloroform vapor
in the tank atmosphere. It depends upon the type of loading. JRB assumes
that splash loading is used, which results in higher evaporative losses
than the alternative, submerged loading.
We also assumed that in addition to the 'chloroform exported, 20 per-
cent of the chloroform produced was transported by barge, and the remain-
der by tank trucks or cars.
Then, for tank cars:
T (12.46)(1.45)(3.2)(119)
L _ .
13.0 lb/103 gal or 1.6 kg/103 L
The quantity of chloroform loaded on tank trucks and cars is esti-
mated by subtracting the quantity exported, the quantity assumed to be
transported by barge, and the quantity produced by Allied Chemical
(which is used consumptively on-site) from the'total chloroform pro-
duced (values in kkg converted to liters by use of the density,
1.481 g/ml):
Total \
chloroform
produced I
(Exports)
/Domestically used
I chloroform
transported
by barge
Total chloroform transported
by trucks and cars
Estimated
production)
by Allied
(106 x 106 f) - [(5.3 x 106 £) + (20.0 x 106 £) + (6.3 x 106 .
74.4 x 106 L
Total chloroform losses from loading are estimated from the loss factor
and the total quantity transported as 119 kkg.
2-26
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The uncertainty of this estimate is +50%. USEPA (1977) estimates
the uncertainty at +30% when all variables in the equations are known.
Since certain assumptions were made to estimate temperature and the
saturation factor, there is added uncertainty in our estimate.
Chloroform losses from loading of barges and marine vessels can be
similarly estimated using the appropriate saturation factors of 0.5 for
barges and 0.2 for ocean vessels. Using the equation for loading losses,
the chloroform release factors are calculated as 0.5 kg/10^ L for loading
barges and 0.2 kg/10^ L for loading marine vessels. The quantities
transported by these methods were given in the above equation as
20.0 x 106 I for barges and 5.3 x 106 I for marine vessels (exports).
From these amounts and the respective loss factors, the releases are
calculated as. 10 kkg for loading barges and 1 kkg for marine vessels.
These estimates are also considered accurate to +_50%.
2.1.3.2 Transit Losses
An additional source of emissions associated with transportation is
transit losses. Small quantities of chloroform are expelled from cargo
tanks due to temperature and barometric pressure changes. Losses are
assumed to be the same from tank cars, barges, and marine vessels.
Assuming the cargo reaches the destination in about 1 week, transit
losses can be estimated using the equation:
LT = 0.1 PW
where
3
LT = Transit losses, Ib/week-10 gal
P = True vapor pressure =3.2 psia
W = Density of condensed vapor = 12.5 Ib/gal
LT = 0.1 (3.2)(12.5) = 4 lb/week-103 gal or 0.5 kg/week-103 £
Assuming that 1 week is the average transit time, the total transit
losses of chloroform are estimated as follows:
Total
quantity
produced
Productiom
it Allied I
tlelease factor!
for transit I
/Quantity\ |Loading\
lexportedJ 1 losses I
Total Chloroform Losses
from Transit
|("l06,000 x 103 £) - (6,300 x 103 £ + 5,300 x 103 I + 154 x 103 £) x
(0.5 kg/10
47 kkg
This estimate is considered accurate to +_30%, provided all ship-
ments reach their destination in about a week (USEPA 1977). Because
of the uncertainty in transit time, we estimate these emissions to be
accurate to +50%.
2-27
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Total transportation losses are equal to the sum of loading losses
from barges (10 kkg), tank cars or trucks (119 kkg), and marine vessels
(1 kkg), plus transit losses (47 kkg), or 177 kkg. The overall uncer-
tainty of this estimate is +50%.
2.2 IMPORTS
In 1978, 7,680 kkg of chloroform were imported (U.S. Bureau of
the Census 1979b). This quantity is equivalent to less than 5 percent
of the domestic production. Information was not available on quantities
imported prior to 1978 and, therefore, trends regarding chloroform
imports are not discussed.
2.3 STOCKPILES
Although no information is available on stockpiles.as a source of
chloroform, it'is not likely that any stockpiled chloroform was used
in 1978. On the contrary, it is more likely that large quantities of
domestically produced chloroform were placed in stockpiled reserves in
1978. This is discussed in Section 3.2.
2.4 INDIRECT PRODUCTION
This section discusses indirect sources of chloroform production
from both natural sources and as a byproduct in other chemical produc-
tion processes.
2.4.1 Formation of Chloroform During Production of Vinyl Chloride
Monomer
Chloroform is a byproduct of the manufacture of vinyl chloride
monomer (VCM) (McPherson et al. 1979; Shiver 1976). A balanced produc-
tion process employs oxychlorination and the direct chlorination of
ethylene to form 1,2-dichloroethane (EDC) followed by its cracking to
VCM (see Figure 2.6). The light ends from the EDC distillation column
can contain 10 percent by weight chloroform (Shiver 1976). This calcu-
lation was based on analysis of a typical VCM waste stream, and we
assume an analytical error of +5%. In 1975, production of VCM and
light ends were reported as 1,910,000 and 162,00 kkg respectively
(Shiver 1976). From these values, light ends are estimated to amount
to 0.85 percent of VCM production (Shiver 1976). The sources of these
production figures are unknown, and we assume an uncertainty of +_10%.
Using the percentage of light ends and the 1978 production figures
for VCM as reported by the International Trade Commission (USITC 1979),
3,150,000 kkg (+10%), the quantity of light ends can be estimated as
26,775 kkg (+10%). From the estimated quantity of light ends and their
reported chloroform content of 10 percent, the total amount of chloro-
form contained in the light ends is estimated as 2,680 kkg (+65%, -45%).
2.4.1.1 Air Emissions
Light ends are either incinerated, used as feedstock for other
processes, or landfilled, with the majority being incinerated (Shiver
2-28
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I
N>
Chlorine
Elhylene
Mr
or
oxygen
Vent
Vent gases
Recycle EDC
Vent
Vent
gases
Light
ends
VCM
L
Water to
steam
stripping
Recycle HCI
Tars
Figure 2.6 VCM Production Process
Source: McPherson et al. 1979
-------
1976). We assume that 90 percent (+5%) of the light ends are incinera-
ted, based on the industrial information available (Shiver 1976).
Assuming a 95 percent (+5%) emission control efficiency during incinera-
tion, which includes emissions during handling and transport of waste
ends, emissions to the atmosphere can be calculated as follows:
(\ / \ , . Estimated
1 - Efficiency j J Fraction ] / CHCL3 in \ released to
of incineration/ lincineratedl (light ends) atmosphere during
' incineration
(1 - 0.95) (0.9) - (2,680 kkg) = 120 kkg
(+246%, -100%')
The remaining 268 kkg (+148%, -72%) of the chloroform contained in"
the light ends are either landfilled or used as feedstock. We assume,
as the case with maximum releases, that all of this is landfilled. We
further assume that 25 percent (+5%) is released annually from landfill
due to damaged or rusting containers. In this case, an estimated 67
kkg of chloroform (+199%, -80%) would be released from landfills to the
atmosphere annually.
2.4.1.2 Water Emissions
The VCM production process will produce an aqueous waste from
washers and caustic scrubbers. The quantity of this waste stream and
the amount of -chloroform contained in it are unknown.
2.4.1.3 Land Emissions
We estimated that 268 kkg of chloroform contained in the light
ends are landfilled. Of this amount, 75 percent, or 200 kkg (+130%,
-71%), is estimated to remain in landfills. Material in landfills
is not considered a release to land but is considered to be in storage
until released. Figure 2.7 summarizes the multimedia releases of
chloroform from VCM production.
2.4.2 Chlorination of Organic Precursors in Water
An important source of indirect, noncommercial production of
chloroform is the aqueous reaction of chlorine with various organic
compounds in municipal drinking water supplies, municipal sewage,
industrial waste and process streams, industrial cooling water, and
most natural waters. The organic precursors to trihalomethane (THM)
formation are natural humic substances present in virtually all source
waters, rivers, lakes, reservoirs, and well water (Stevens et al. 1976).
The products of vegetative decomposition, these humic materials con-
stitute the organic coloring of natural waters; they are complex fulvic
and tannic substances generally classified as aromatic polyhydroxy-
methoxycarboxylic acids (Morris and McKay 1975) . The major mechanism
for formation of chloroform and other THM's via the chlorination of
organic matter in water supplies appears to be the classic haloform
reaction (Morris and McKay 1975) . This is commonly a base-catalyzed
series of halogenation and hydrolysis reactions between chlorine and
organics containing the acetyl group or compounds oxidizable to the
2-30
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Air
120
2412
Light Ends 2680
from VCM Production
Incineration
Air
67
268
Landfill
Figure 2.7 Multimedia Releases of Chloroform from Production of VCM
2-31
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acetyl group which occur in alkaline aqueous solution. When dispersed
in water at pH greater than 5, the chlorine is instantaneously and
completely hydrolyzed to chloride and hypochlorite (OC1 ) ions accord-
ing to the reaction:
C12 + 20H OC1 + Cl" -I- H20
When considering potential interactions with organic compounds in
water, hypochlorite is the reactive form of chlorine. In the haloform
reaction, the three hydrogens of the original compound's acetyl group
are successively replaced by chlorine (or other halogen); then the
carbon bond to the carbonyl group is split, giving rise to a haloform
and a carboxylic acid (Morris and McKay 1975). The net reactions may
be written:
CH3COR + 3 HOC1 »~ CC13COR + 3H20
CC13COR + H20 CHC13 + RCOOH
Formation of THM's via this mechanism is enhanced by increases in both
temperature and pH (Stevens et al. 1978).
Chloroform may be produced indirectly, therefore, whenever chlorine
is introduced into waters containing humic acids. It is also possible
that chlorination of other specific organic structures may contribute
significantly to chloroform formation. Potential sources of indirect
chloroform production include disinfection of municipal drinking water
supplies and sewage via chlorination, chlorination of industrial waste
streams and process streams containing precursor organics, and chlori-
nation of industrial cooling waters to control biofouling within heat
transfer systems.
2.4.2.1 Chlorination of Municipal Water Supplies
In recent years the occurrence and formation of chloroform in
potable water supplies have been investigated intensively, but no
comprehensive study has been performed to precisely quantity the
amounts of chloroform generated annually through municipal chlorination
practices.
In 1975, USEPA conducted the National Organics Reconnaissance
Survey (NORS) for halogenated organics in the drinking water of 80
U.S..cities. Results of the survey showed that untreated raw water
concentrations of chloroform were generally less than 0.1 yg/£, but
samples of finished drinking water contained concentrations of chloro-
form ranging from less than 0.2 to 311 Ug/£, with a median value of
21 vig/£ (Symons et al. 1975). In the same year, the EPA Region V
Organics Survey analyzed raw water and finished water samples collec-
ted at 83 locations throughout the Midwest. Chloroform was detected
in raw water supplies at a mean concentration of less than 1.0 Ug/£
and in finished drinking waters at concentrations ranging from less
than 1.0 to 366 Ug/£. Combining data from the Region V survey with
the NORS findings yields a median value of approximately 20 ug/£ for
2-32
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chloroform concentrations detected in treated waters (Symons 1976). The
data from these two surveys represent the analysis of 165 water samples
collected from February through April 1975. It is important to note that
80 percent of the utilities surveyed used surface water sources, although
only 20 percent of the U.S. community water utilities use surface sources
of water. Many utilities using groundwater sources do not practice
chlorination (Symons .1976)........ However, J. Carrell Morris, Professor of
Sanitary Chemistry at Harvard University, states that the 80/20 break-
down is probably accurate with respect to volumes of surface versus
groundwater (respectively) treated on a national basis (Morris 1980).
In the NORS study, the nine utilities having the highest levels
of chloroform in treated water had an average yield of chloroform equi-
valent to 2.0 percent of the total chlorine dose applied. The average
yield of chloroform at the nine highest sites in the Region V Survey
was 2.7 percent of the total chlorine dose. Symons (1976) has concluded
that high concentrations of chloroform result when surface water or
shallow groundwater with a high total organic carbon content and high
chlorine demand is dosed with sufficient chlorine to produce a high
free chlorine residual, especially if the water is somewhat basic (pH
7-10). Alan Stevens of the Water Supply Division of EPA's Municipal
Environmental Research Laboratory states that the chlorination of muni-
cipal water supplies typically yields THM concentrations of approxi-
mately 3 percent of the total chlorine applied, but that the yield
probably ranges from 0.5 to 5.0 percent depending on variations in
parameters such as pH, temperature, contact time, and concentrations of
precursor organics in the source water being chlorinated (Stevens 1980).
Representatives of the American Water Works Association (AWWA)
(DeBoer 1980), the Chlorine Institute (Doyle 1980), and recognized
experts in the field of chlorine chemistry and water treatment Robert
L. Jolley of Oak Ridge National Laboratory (Jolley 1980), James M.
Symons and Alan Stevens of EPA's Municipal Environmental Research
Lab (Symons 1980, Stevens 1980), and J. Carrell Morris, Professor of
Sanitary Chemistry at Harvard University (Morris 1980) have indi-
cated that no calculations have been performed to determine the amounts
of chloroform produced annually through municipal water chlorination
practices. Two sources in the readily available literature have esti-
mated the quantities of chloroform produced annually through water
chlorination, by use of broad assumptions. Versar, Inc. (1977) used
20 Pg/-£ as the average increase in chloroform concentration as a result
of chlorination (based on EPA's Region V Organics Survey and NORS moni-
toring data) and, assuming estimated annual noneonsumptive use of water
in the United States at 4.1 x 101 t, calculated that approximately
8,200 kkg of the compound are formed annually through water chlorination.
This figure may have an associated uncertainty range as great as +90%.
Also, "nonconsumptive" water use includes municipal wastewaters (sewage)
which are known to yield much lower amounts of chloroform than drinking
water supplies when chlorinated (Jolley 1980). Consequently, the Versar
estimate is probably too high.
2-33
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Lowenbach and Schlesinger Associates (1979) used the same basic
methodology, but assumed a 30 Ug/-£ average chloroform concentration.
They estimate that 12,000 kkg of chloroform are. discharged annually from
the chlorination of municipal drinking water. Again, the validity of
this estimate depends on the validity of their basic assumptions. A
chloroform concentration of 30 yg/£ is probably too large to use as a
national average since groundwater sources, when chlorinated, are known
to yield much smaller concentrations of chloroform than surface water
sources, and groundwater sources constitute a significant percentage of
the nation's community water supplies (Symons 1976). Therefore, the
Lowenbach and Schlesinger estimate is probably also too high.
There are two basic methods available for estimating the quantities
of chloroform produced annually during water chlorination. One method,
used by both Versar and Lowenbach and Schlesinger Associates, consists
of multiplying the volume of water chlorinated annually by the expected
concentration of chloroform in the treatment plant effluent distributed
into the municipal water system. John De Boer of AWWA states that the
average national production of water treatment plants is on the order
of 150 gallons of water per capita per day (De Boer 1980). This is
close to the figure of 148 gallons per capita per day estimated for
national water consumption in 1980 (Metcalf and Eddy, Inc. 1972). The
AWWA estimate is based on the typical output of approximately 50,000
community public water supply systems across the nation. It does not
include small-scale water supplies which may be treated at hotels,
motels, weighing stations, or other establishments not supplying water
continually. The current U.S. population is approximately 2.2 x 10°.
Therefore, the total annual national output of water treatment plants
is estimated as follows:
/Average daily per capitaA /Estimated
production of water I I U.S.
I treatment plants / \populationJ
Days per]
year
(150 gal)
(2.2 x 10°) (365)
Total annual
output
120,450 x 10
gal/year
4.56 x 1013
£/year
8
Assuming that monitoring data derived from the two 1975 surveys
are representative for chloroform concentrations in treated water through-
out the nation, then 20 yg/£ can be used as a national average for chloro-
form produced in treated municipal water supplies. The estimated total
amount of chloroform produced annually through drinking water chlorina-
tion is therefore estimated as 91.2 x 107 g or 912 kkg per year. This
figure represents an approximate upper limit on the annual production
of chloroform through drinking water chlorination, since many public
water utilities have altered their chlorination practices in recent years
to reduce THM formation in water supplies. This has been done in order
to meet the EPA drinking water limit of 100 ppb for THM's. Current
practices, include pretreatment to remove precursor organics (coagulation,
sedimentation, filtration), posttreatment to remove THM's after their
formation (carbon adsorption, aeration), or use of alternative
2-34
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disinfectants such as chlorine dioxide and ozone. The uncertainty range
associated with the value for chloroform produced through chlorination
is approximately +10%, -50%.
The second method for estimating indirect chloroform production
through water chlorination is to apply the percentage yield of chloro-
form in treated waters to the amounts of chlorine annually used at muni-
cipal water treatment plants for disinfection purposes. It has been
noted earlier that a 3 percent yield of THM's such as chloroform,
bromodichloromethane, dibromochloromethane, and bromoform is typical
based on the total chlorine dose applied to a given volume of source
water. Russell J. Foster, Commodities Specialist on chlorine with
the Bureau of Mines, has data indicating that approximately 515,000
short tons (467,000 kkg) of chlorine were consumed in "water and sani-
tary services" in 1977 (Foster 1980). Unfortunately, no breakdown is
available on the amounts used in municipal water treatment versus muni-
cipal wastewater (sewage) treatment. It is also possible that this
figure includes use of chlorine in industrial cooling water treatment.
Therefore, use of this chlorine consumption figure yields an upper
estimate (+5%, -80%) for the quantity of THM produced in 1977:
14,000 kkg.
Chloroform typically constitutes 90 percent or more of total THM
formed via chlorination of surface water supplies (Hoehn et al. 1977).
Therefore, approximately 12 ,"600 kkg of chloroform were generated in
water treatment works in 1977. Again, this number represents an esti-
mated upper limit on combined chloroform production from two sources
drinking water and wastewater chlorination and may include a third
source, cooling water chlorination.
For this materials balance, the figure derived from the first
estimation method, 912 kkg, will be used as the estimated total annual
production of chloroform through the chlorination of municipal water
supplies.
Environmental releases of chloroform produced in this manner
will occur through leaks of chloroform-contaminated water from the
municipal water distribution system (through water mains, service pipes,
and household plumbing), through domestic, commercial, industrial and
agricultural consumption of the water, and through treatment of that
portion of municipal water destined to enter the sewer system and
travel to municipal wastewater works. Chloroform is a volatile com-
pound known to evaporate quite readily from water to air. The National
Academy of Sciences (NAS 1978a,b) reports that 90 percent of chloroform
usually evaporates within an hour. The various consumptive patterns
for chloroform-contaminated municipal water tend to disperse and aerate
the liquid, and it is expected that chloroform in municipal water will
largely evaporate to the atmosphere rather than settle into waterways
or be adsorbed onto sediments. It is therefore assumed that 90 per-
cent (+5%) of the chloroform produced through chlorination of municipal
water "supplies, or 820 kkg (+45 kkg), will be released to the atmosphere.
The remaining 10 percent (+5%), or 92 kkg (+45 kkg) will remain in solu-
tion and be released to waterways as potable water is used; an unknown
portion of this amount will become bound onto soil particles or river
sediments.
2-35
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2.4.2.2 Chlorination of Municipal Sewage
Jolley (1980) has shown that disinfection of municipal sewage via
chlorination results in the formation of numerous chlorinated organic
compounds, but these do not include THM (Morris and McKay 1975).
Chlorine reacts largely with ammonia in sewage to form chloramines.
These do not react further with the organic constituents of sewage to
produce significant quantities of halogenated methanes (Hoehn et al.
1977). Because municipal sewage does not contain the high concentra-
tion of the humic precursors contained in natural source waters, and
the maintenance of a high free chlorine residual is not an important
consideration in treating wastewaters, the formation of chloroform
through sewage chlorination will be minimal (Jolley 1980).
Nevertheless, monitoring data from a typical sewage treatment
plant show an increase of 2 to 3 Ug/£ in chloroform concentrations
detected in chlorinated effluent compared to the levels found in untrea-
ted influent (NAS 1978a,b). In general, about 60 to 80 percent of the
per capita consumption of water, or 100 gallons per capita per day
(assuming 70 percent), will become sewage (Metcalf and Eddy 1972). All
of this water is assumed to be chlorinated before discharge from the
wastewater treatment plant (the second chlorination of this water, which
was chlorinated before use). Assuming an upper limit of 3.0 yg/£ increase
in chloroform after chlorination, then the estimated total amount of
chloroform produced annually through wastewater treatment is calculated:
/Increase in \ /Average \ f \ / \ Total annual
.Jays l , . _,
I chloroform 1
after
\ chlorination /
volume
of sewage
\generatedy
U.S.
population
/
I _ production of
p I chloroform through
J ^» » I _ ^ A* A _ 4_ _" _ ._ ^ _ __
/
wastewater treatment
\
(3.0 x 106 g/£) (379 £/capita-day) (2.2 x 108) (365) = 91 kkg/year
This figure represents a gross approximation of the annual production
of chloroform in wastewater treatment, with an estimated uncertainty
of +5.0%.
Treated wastewater effluents in which chloroform has been formed
are generally discharged directly to natural waterways, although in
some instances (particularly in the western United States) the effluent
may be used in crop irrigation systems. In either case, chloroform
present in sewage effluent will be released primarily to the atmosphere
as it volatilizes from water to air. Again, it is assumed that 90 per-
cent (+5%), or 82 kkg (+56 kkg) of the chloroform produced through
sewage chlorination will be released to the atmosphere. The remaining
10 percent (+5%) or 9 kkg (+4 kkg) of chloroform constitutes a release
to water; some unknown portion of this amount may become bound onto
soil and sediments.
2.4.2.3 Chlorination of Cooling Waters
Chlorine is the principal biocide used for antifoulant treatment
of cooling systems in electric power-generating plants (Jolley et al.
1978). The chlorination of waters to prevent intake screen and
2-36
-------
condenser fouling in both once-through and closed-cycle (cooling tower)
systems results in the formation of THM compounds including chloroform
(Jolley et al. 1978). No laboratory or field studies have been per-
formed to determine the expected yields of THM from cooling water
chlorination. However, Jolley (1978) has estimated total annual
chloroform production based on a study of three power plant cooling
systems (two cooling towers, one once-through) used in Tennessee.
Based on a Federal Power Commission (FPC) estimate of total United
States electric power production (340,000 MW in 1977), Jolley projects
that 100 to 200 tons of chloroform (90-180 kkg) are produced each year
through the chlorination of cooling waters at electric power plants.
Jolley notes that this estimate is probably too low because the three
cooling systems he studied are not representative of typical power
plant operations.
Another estimate for chloroform production in cooling waters can
be derived assuming that the yield of THM through cooling water
chlorination is equivalent to 3 percent of the total applied chlorine
dose as was the case for waters chlorinated in municipal water treat-
ment plants. This approximation is based on the likelihood that source
waters used for cooling purposes contain the same types and concentra-
tions of THM precursors (humic acids) as do source waters used for
municipal drinking water supplies. The total amount of chlorine applied
annually to cooling waters at electric power plants has been estimated
at 50,000 to 100,000 tons, 100,000 tons, and 100,000 to 200,000 tons by
three different sources in recent years (Hamilton 1978). Hamilton
'points out that these widely varying estimates are based on projected
usage; he presents figures derived from FPC records which show that
the total amount of chlorine applied annually to cooling waters at
steam electric plants averaged approximately 26,000 tons (23,600 kkg)
from 1969 through 1974. This total does not include chlorine applied
as calcium or sodium hypochlorite, and has undoubtedly increased since
1974 with several new fossil and nuclear power plants coming onstream.
For the purposes of this materials balance, it is assumed that 100,000
tons (approximately 91,000 kkg) of chlorine were applied to power plant
cooling waters in 1977. Assuming a 3 percent yield of THM, of which
chloroform constitutes 90 percent, then the estimated amount of chloro-
form produced in this manner in 1977 is calculated to be 2,400 kkg.
This estimate has a probable uncertainty range of +20%, -50%.
It is likely that approximately 95 percent (+5%) of this total, or
2,340 kkg (+120 kkg), will evaporate to the atmosphere through cooling
tower stacks, or as cooling tower "blowdown" or once-through system
waters are discharged to receiving waters. This total also includes
an unknown portion of the chloroform which will evaporate from recy-
cled cooling water within the power plant. The remaining 120 kkg
(+120 kkg) of chloroform (5 percent of the total) will remain in spent
cooling waters released directly to natural waterways.
Cooling towers and once-through cooling systems are also used
to remove heat from many other industrial processes or from large
pieces of machinery that generate substantial quantities of waste
heat, such as commercial air conditioning plants (Stratton and Lee
2-37
-------
1975). However, no information on these specific industries or the quan-
tities of chlorine they use in treating cooling waters was presented in
t.he readily available literature.
2.4.3 Industrial Sources
2.4.3.1 Pulp and Paper Industry
The pulp and paper industry is recognized as a significant source
of chloroform releases to the environment (NAS 1978a,b). The chlorine
bleaching of wood pulp fiber in the production of white paper may yield
major quantities of chloroform. Monitoring of paper mill effluents
discharged to the Mobile River in Alabama revealed chloroform concen-
trations of 270 to 1,700 yg/£ (NAS 1978a,b).
Lowenbach and Schlesinger Associates (1979) estimate that 1.4 kkg
of chloroform are discharged annually to surface waters in paper mill
effluents. This calculation assumes an average chloroform concentra-
tion of 1,000 yg/£ and a total annual industry discharge of 1.4 million
kkg. However, chloroform releases from this source were calculated
to be as high as 300,000 kkg annually, assuming a 6 percent conversion
of total chlorine used to chloroform produced in the bleaching process
(Lowenbach and Schlesinger Associates 1979).
Because of the high concentration of humic precursors in wood pulp,
J. Carrell Morris of Harvard University has estimated the chlorine-to-
chloroform conversion efficiency to be approximately 50 percent greater
than that expected from the chlorination of municipal source waters
(3 percent), or 4.5 percent (Morris 1980). The total quantity of
chlorine used in the paper products industry in 1977 is reported to be
1.38 million tons, or 1.25 million kkg (Foster 1980). It is assumed
that this quantity was consumed entirely in the bleaching of wood pulp
and, further, that
-------
average chloroform production to this figure yields an estimate of
14.8 x 106 Ib/year or 6,700 kkg/year for the total quantity of chloro-
form generated annually through the bleaching of wood pulp at paper
mills. For this materials balance, this figure will be used as the
estimated total quantity of chloroform produced annually from pulp
bleaching operations.
The NCASI study found that, on the average, there was a 94 percent
reduction in chloroform as the mill effluent passed through treatment
(aerated lagoons) before discharge to natural waterways. This reduc-
tion is due largely to vaporization of chloroform from solution to the
atmosphere (NCASI 1977). Hence, of the 6,700 kkg of chloroform pro-
duced annually through pulp bleaching, about 94 percent (+5%), or
6,300 kkg (+330 kkg), will vaporize to the atmosphere as paper mill
effluents are treated. The remaining 400 kkg (+330 kkg) of chloroform
will remain in treated effluents discharged to surface waters. The
average concentration of chloroform detected in treated effluents
from the mills surveyed by NCASI was 100 ppb (Blosser 1980).
2.4.3.2 Other Sources
Other possible industrial sources of indirect chloroform production
include effluents from chlorinated "rubber manufacturing and the chlori-
nation of wastewaters from the textile industry, the food processing
industry (e.g., fruit and vegetable washing and canning), and breweries
(USGAO 1977). Estimates of indirect chloroform production from only
one of these industries are found in the readily available literature.
Lowenbach and Schlesinger Associates (1979) estimate chloroform dis-
charge to the environment from chlorinated rubber manufacturing to be
on the order of 20 kkg per year. This calculation is based on several
general assumptions and undoubtedly has a great degree of uncertainty
associated with it. However, JRB has no additional data upon which to
base a separate calculation of such releases.
2.4.4 Combustion of Leaded Gasoline
Analysis of undiluted samples of automobile exhaust has shown
the presence of ppb levels of chloroform resulting from the combustion
of leaded gasoline (Harsch et al. 1977). Samples of exhaust from a
1975 Pinto equipped with a catalytic converter and operated on non-
leaded gasoline contained much lower levels of chloroform less than
100 ppt (by volume) than did exhaust gases from a 1972 Rambler
running on leaded gasoline (6-7 ppb). Harsch suggests that the com-
bustion of leaded gasoline may contribute significantly to elevated
levels of chloroform that have been detected in samples of urban air
in the State of Washington. The precise mechanism for chloroform
formation due to gasoline combustion is not reported in the litera-
ture, nor are the estimated total quantities of chloroform produced
in this manner. It has been suggested that the use of chlorinated
compounds as gasoline additives (e.g., ethylene dichloride) is the
source of chloroform detected in auto exhaust (Lowenbach and
Schlesinger Associates 1979).
2-39
-------
A reasonably good estimate of annual chloroform releases from auto
exhausts cannot be made because of inadequate data. However, JRB has
made the following rough estimate of releases of chloroform from com-
bustion of gasoline. In 1977, an estimated 9.56 x 10^ kkg of ethylene
dichloride were used as a lead scavenger compound added to leaded gaso-
line to provide cleaner burning of anti-knock compounds in the engine
(JRB Associates 1979). Assuming that combustion of this compound in
leaded gasoline is the sole source of chloroform detected in automobile
exhaust, and that typical yields of chloroform from this source are as
great as 1 percent of the ethylene dichloride combusted, then the amount
of chloroform indirectly produced through the combustion of leaded gaso-
line in 1977 is calculated to be 956 kkg. This quantity represents an
environmental release of chloroform to the atmosphere.
The accuracy of this estimate depends upon the validity of the
assumption that ethylene dichloride is the source of chloroform detec-
ted in automobile exhaust. A 1 percent yield of chloroform from the
degradation of ethylene dichloride during gasoline combustion is
probably too high an estimate; consequently, 956 kkg is thought to
represent an upper limit on the amount of chloroform so produced.
The uncertainty range for this estimate is +5%, -90%.
2.4.5 Other Indirect Sources
Other possible sources of indirect chloroform production include
the thermal decomposition of plastics and foams, atmospheric degrada-
tion of tri- and tetrachloroethylene, combustion of tobacco products
treated with chlorinated pesticides, biological production in red
marine algae, and the reaction of chlorinated pollutants with humic
substances in natural waters. The quantitative contribution of chloro-
form from these sources cannot be evaluated without further basic
research into these areas (NAS 1978a,b).
The pyrolysis of rigid urethane foams at 500 C has been reported
to yield chloroform as a volatile degradation product (NAS 1978a,b).
However, the thermal decomposition of plastics is not considered a
significant source of chloroform in the environment (Lowenbach and
Schlesinger Associates 1979).
Halogenated ethylenes are subject to attack in the atmosphere by
hydroxyl radicals to yield dichloroacetyl chloride, photolysis of
which leads to formation of chloroform and phosgene. Conditions simu-
lating tropospheric irradiation of trichloroethylene have lead to
efficient production of chloroform in laboratory studies (Lowenbach
and Schlesinger Associates 1979). Photochemical conversion of tri-
chloroethylene in the troposphere may therefore represent a signifi-
cant source of indirect chloroform production, especially since
atmospheric releases of trichloroethylene have been estimated to be
on the order of hundreds of thousands of kkg annually. Estimates of
such releases, however, vary by a factor of 700 percent. Farmer et
al. (1979) have estimated the total releases of trichloroethylene to
the atmosphere to be approximately 90,000 kkg in 1977. Assuming a
0.5 percent conversion efficiency to chloroform in the troposphere,
then 450 kkg of chloroform were produced via this mechanism in 1977.
2-40
-------
This figure represents a very crude estimate, with an associated
uncertainty range as great as +700%, -90%. Photooxidation of tetra-
chloroethylene appears to be a less directly source of atmospheric
chloroform (Lowenbach and Schlesinger Associates 1979).
A 1972 study of cigarette smoke detected chloroform that was
derived from tobacco fumigated with p,p'-DDT. This pesticide fumigant
is no longer used in the United States (NAS 1978a,b). Cigarette smoke
is considered an insignificant source of chloroform production.
The National Academy of Sciences (NAS 1978a,b) cites biological
production in species of red marine algae as another natural source of
chloroform; however, no data are available for use in estimating such
production. It is also possible that chlorine derived from pesticides
and herbicides in agricultural runoff and various industrial discharges
reacts with humic percursors in natural waters to produce significant
quantities of chloroform. More basic research and monitoring data are
required before such indirect sources of chloroform production can be
accurately evaluated.
2.5 OVERALL SUMMARY OF ENVIRONMENTAL RELEASES FROM PRODUCTION
Table 2.8 summarizes our estimates for the quantities of chloro-
form produced and the environmental releases from each production
source. The data indicate that indirect production is the major route
for environmental release. The pulp and paper industry contributes
nearly 54 percent of the total chloroform emitted- to air, and releases
from cooling water account for another 19 percent. In contrast, even
if direct production releases are uncontrolled, these processes release
only 4.1 percent of the chloroform emitted. A similar situation is
observed for releases to water; the pulp and paper industries release
nearly 63 percent of the total, and cooling waters release another 19
percent. In contrast, direct production processes release only about
2 percent of the total chloroform emitted to water.
2-41
-------
Table 2.8 Summary of Environmental Releases from Chloroform Production
Process
Methyl chloride
chlorinat ion
Methane
chlorinat ion
Transportation
VCM
Municipal
water supply
Municipal
wastewater
Cooling water
Pulp and paper
Leaded gasoline
Tr ic hloroe thy lene
TOTAL
Total
chloroform
produced
(kkg)
122 ,400
36,100
177
2,680
912
91
2,460
6,700
965
450
173,400
To air
(kkg)
176b
347b
40. 4a
74. 8b
177
187
820
82
2,340
6,300
965
450
11,500*
11,700
(% of
total)
1.5
0.4
1.5
1.6
7.1
0.7
20.3
54.6
8.4
3.9
To water
(kkg)
7.3
2.2
0
1.6
92.0
9.0
120.0
400.0
0
0
632
(% of
total)
1.2
0.4
0
0.3
14.6
0.1
19
63.2
0
0
To landfill
(kkg)
5.8
0
0
200
0
0
0
0
0
0
206
(% of
total)
3
0
0
97
0
0
0
0
0
0
Incinerated
(kkg)
16.4
?
0
2,290
0
0
0
0
0
0
2,307
(% of
total)
1
?
0
99
0
0
0
0
0
0
a = controlled case
b = uncontrolled case
-------
3.0 USES OF CHLOROFORM
3.1 CONSUMPTIVE USES
Chloroform is used consumptively in the production of chlorodifluoro-
methane. This process accounts for 90 percent of the total domestic
chloroform production. Exports, which are considered a consumptive use,
amounted to 5 percent of 1978 chloroform production. The remaining 5
percent is used nonconsumptively, and is discussed in Section 3.2.
3.1.1 Chlorodifluoromethane
3.1.1.1 Production of Chlorodifluoromethane
Chloroform is used primarily as feedstock for the production 'of the
chlorinated fluorocarbon (CFC) chlorodifluoromethane (CHC1F2)> commonly
known as CFC-22. (The du Pont product is called F-22 after the trade name
Freon.) There are five domestic producers of CFC's: du Pont, Allied
Chemical, Kaiser Aluminum and Chemical, Pennwalt, and Racon. The loca-
tions of U.S. plants producing CFC-22 are shown on the map in Figure 3.1.
Of the 158,500 kkg of chloroform domestically produced, 80-90
percent is used to manufacture CFC-22. Wolf (1979) estimates 90 per-
cent of 1977 production was used for this purpose. EPA's product data
report on organic chemical producers estimated that 90 percent of 1978
production was used for CFC-22 manufacture (Radian Corp. 1979). .This
value was also reported by Dow (Farber 1980), Allied Chemical (Boberg
1980), and Chemical Marketing Reporter (1979). However, reported CFC-
22 production figures for 1978 indicate' that only 81 percent of the
chloroform produced was required for this purpose (USITC 1979).
Mannsville (1978a) also estimated that 80 percent of chloroform pro-
duction was used for this purpose in 1978. However, as discussed in
Section 3.2, many former nonconsumptive uses of chloroform have been
discontinued; one manufacturer, Allied Chemical, reports that products
formulated with chloroform are no longer in the market. Because noncon-
sumptive usage has apparently declined in recent years, JRB.will use the
higher of the available estimates (90 percent or 142.7 x 10 kkg) for
consumptive usage of chloroform in the manufacture of CFC-22.
Process block diagrams for the production of CFC-22 are shown in
Appendix C. The processes used by du Pont (Smith 1978b) and Allied
(Hobbs and Stuewe 1978), although similar, differ at stages which the
coproduct dichlorofluoromethane (CFC-23) is separated from CFC-22.
In du Font's process, CFC-23 is distilled from CFC-22 and each gas is
cleaned separately. Allied inverts these steps by cleaning the com-
bined product gases prior to distillation. The process used by du
Pont also vents noneondensables from both CFC-22 and CFC-23 to the
atmosphere while Allied's process recycles the CFC-22 noncondensables
back into the process. The major difference related specifically to
chloroform is the presence of a condenser unit on the chloroform
storage tank at du Pont. This unit is lacking at Allied. The rates
of chloroform loss to the atmosphere are 0.036 percent at du Pont
3-1
-------
1. Allied Chemical, El Segundo. CA.
2. E. I. du Pont, Louisville, KY.
3. Kaiser Aluminum and Chemical, Cramercy, LA.
4. Pennwalt Corp., Calverc Clcy, KY.
S. Racon, Inc., Wichita, KA.
Figure 3.1 U.S. Producers of Chlorodifluoromethane (CFC-22)
-------
(Smith 1978b) and 0.26 percent at Allied (Boberg 1980, Pitts 1978).
No specific data are available on the processes employed at Penwalt,
Racon, or Kaiser.
Production capacity for CFC-22 apart from other CFC's is not
available. Because of the similarity in the processes used to produce
CFC-22 from chloroform and CFC-11/12 from carbon tetrachloride, many
of the production facilities are flexible. They may be used to pro-
duce either of these chlorofluorocarbons as needed. The production
capacity for CFC-22 must be derived from data on total production
capacity. Total CFC capacity must first be reduced by that used for
CFC-113/114. The remaining capacity is for CFC-11 (CC13F), CFC-12
(CC12F2), and CFC-22. Judgments on the relative production of these
chlorofluorocarbons are used to apportion the remaining capacity to
the specific products.
3
Total production capacity was estimated at 650 x 10 kkg for 1976
(Burt 1980). Due to the mandated reductions in fluorocarbon propellant
use, Allied, du Pont, and Pennwalt have reduced capacity. Union Car-
bide exited from production, but still resells CFC products (Mannsville
1978b). These reductions apparently did not affect CFC-113/114, since
production figures for 1976-1978 for miscellaneous fluorocarbons did
not change appreciably (USITC 1977b, 1978, 1979). Wolf (1979) estima-
ted total CFC capacity and a breakdown by specific products and manu-
facturers for 1977. These data are shown in Table 3.1. According to
Wolf (1979) and Burt (1980), 45.4 x 103 kkg of CFC-113/114 are pro-
duced by du Pont, and Allied's capacity is half that much. Du Font's
total CFC-22 capacity is reported to be 54.5 x 103 kkg (Wolf 1979).
The capacity apportionment of CFC-22 for Pennwalt and Kaiser was esti-
mated to be 25 percent and that for Racon, 50 percent.
JRB believes the ratio of CFC-22 to CFC-11/12 in the product
mix of flexible plants has been understated. Table 3.2 gives USITC
production figures for CFC-11, CFC-12, and CFC-22 for 1975-1978.
Although total production has been decreasing, that of CFC-22 has
been increasing. JRB estimates that both dedicated and flexible
capacity are 413 x 103 kkg for CFC-11, CFC-12, and CFC-22 and that
CFC-22 accounts for 28 percent of production. In our calculations,
we have assigned 30 percent of the capacity to CFC-22. This appor-
tionment is shown in Table 3.3.
3.1.1.2 Environmental Releases of Chloroform During the Production
of CFC-22
Releases of chloroform during the production of CFC-22 are from
chloroform storage, fugitive process emissions, and controlled process
emissions from condenser vents, catalyst disposal, and gas scrubbers.
The amount of chloroform available for each process is the apportioned
amount reduced by storage losses. The resultant chloroform is conver-
ted to CFC-22 and CFC-23 and process losses are then computed.
Air emissions from the production processes for CFC-22 are esti-
mated to be 150 kkg +20%. There are no 'quantifiable releases of
chloroform to water or land from fluorocarbon manufacture.
3-3
-------
Table 3.1 1976 and 1977 Estimated Production Capacity of Chlorinated
Fluorocarbons (1C)3 kkg)
du Pont
Allied
Pennwalt
Kaiser
Racon
Union Carbide
TOTAL
Total
1976a
315.5
140.7
52.2
36.3
15.9
90.8
651.4
CFC Capa-
city 1977
(est.)b
272.4
108.9
27.2
36.3
22.7
467.5
CFC-113/114
1977 (est.)
45.4'
22.7
68.1
CFC-11/12
1977 (est.)
172.5
66.7
20.4
27.2
11.3
298.1
CFC-22
1977 (est.)
54.5
19.5
6.8
9.1
11.4
101.3
a
Burt 1980
bWolf 1979
Table 3.2 Annual Production of CFC-11, CFC-12, CFC-22 (10 kkg)
CFC-11
CFC-12
CFC-22
TOTAL
1975
122.58
178.42
59.93
360.93
1976
116.22.
178.42
77.18
371.82
1977
96.47
162.67
81.45
340.59
1978
87.94
148.50
91.98
328.42
Source: USITC 1977a,b, 1978, 1979
3-4
-------
Table 3.3 Estimated 1978 Production Capacity for CFC (103 kkg)
OJ
Cn
DuPont
Allied
Pennwalt
Kaiser
Racon
TOTAL
Total }
Capacity '
272.4
122.6
27.2
36.3
22.7
481.2
CFC-113/114(a)
45.4
22.7
_ _
68.1
CFC-ll/12(b)
159.0
69.9
19.0
25.4
15.9
289.2
CFC-2200
68.0
30.0
8.2
10.9
6.8
123.9
Percent
of CFC-22
Capacity
54.9
24.2
6.6
8.8
5.5
100.0
Source: (a) Wolf 1979
(b) JRB Estimate
-------
A. Process Which Condenses Vapors from Chloroform Storage
According to the quantities derived in the previous section, the
process used by du Pont accounts for 55 percent of CFC-22 production
and is assumed to consume 55 percent, or 78.5 x 1(P kkg, of chloroform.
Smith (1978b) reported the vent stream exits from the condenser
on the chloroform storage tank at a rate of 0.165 kkg/100 kkg and con-
tains 6.26 percent chloroform by volume. This calculation was based
on vapor pressure data at a temperature of -5°C. On a weight basis,
this vent stream contains 22.5 percent chloroform calculated as
follows:
(Volume % CHC13) (Vapor Density CHC13) = Weight
Afolume 7,\ /Vapor Density\/Volume\ /Vapor Density\ %
^ CHC13 J [ CHC13 j \^% Air ) ^ Air J CHC13
(6.26% x 4.36 g/l) = 22 5
(6.26% x 4.36 g/£) + (93.74% x 1.02 g/£)
The chloroform releases from storage are then given by:
/ CHC13 \ . / CHC13 \ CHC13
I used in J (Loss rate) I concentration = releases
Iproduction / \in vent streamy from storage
(78.5 x 103 kkg) (0.165 x 10~2 kkg/kkg) (.225) = 29.1 kkg
The loss rate and stream composition are each assumed to be accurate to
+10%.
Production of CFC-22 (with small amounts of CFC-23) is equal to
the net chloroform usage multiplied by the ratio of the molecular
weight of CFC-22 to that of chloroform.
) CFC-22
(78,500 kkg - 29 kkg) (86.45/119.39) = 56.8 x 103 kkg
No data were available on fugitive emissions from CFC-22 manufacture.
However, an emission rate of 1.46 percent has been estimated for CFC-11/12
(Smith 1978a) and since the process for CFC-22 is similar to that for
CFC-11/12, the same emission factor will be used. In addition, CFC-11/12
are reported to contain less than 2 ppm carbon tetrachloride (NAS 1978a,b)
and therefore, JRB has assumed a 1 ppm level for residual chloroform in
CFC-22. Fugitive emissions from the production of 56,800 kkg of CFC-22
would then be 0.83 kkg. The fact that fugitive emissions were stated
for CFG 11/12 (Smith 1978a) and not for CFC-22 (Smith 1978b), could indi-
cate that emissions of CFC-22 are quite low. Bearing this in mind, JRB
views the 0.83 kg value as an upper limit, and JRB estimates the uncer-
tainty as -50%.
3-6
-------
Following the fluorination reaction, the product gas stream goes to
a distillation column where CFC-23. is separated from CFC-22. Each gas is
alkali-scrubbed prior to collection, and there is a vent to the atmosphere
at the end of each stream. No data were available on the rate of CFC-23
production for the du Pont process. We have Allied Chemical's values of
9.6 x 10-3 kkg/kgg of CFC-22 for a production rate of 22.7 kkg/day; at
18.2 kkg/day, CFC-23 is produced at a rate of 8.9 x 10~3 kkg/kkg (Hobbs
and Stuewe 1978) . For purposes of this study, we will use the upper
value and assume an uncertainty of +20%.
The quantities of CFC-22 and CFC-23 produced can be computed from
the production ratio of CFC-23/CFC-22 and the ratio of, fluorocarbon
formed per unit weight of chloroform. The later values are given by
molecular weight ratios.
/ \ / \ / \ /CFC-22/21\ / \
/ CFC-22 \/MW CHC13 \ I CFC-22 \[ A L. \ f MW CHCli \ CHC13
I produced! I MW CFC-22 )+ produced) I pr°^^lonJ I MW'CFC-23J " consumed
/I 1 Q ^Q\ _"} / 1 1 Q TQ\ ' T
(CFC-22) f i6'mll\ + (CFC-22) (9.6 x 10 J) F^f] - 78.5 x 10J kkg
Using this equation, the quantity of CFC-22 produced is calculated as
56.2 x 103 kkg. The amount of chloroform required to produce this quan-
tity of CFC-22 is calculated as follows:
/ CFC-22 \ / MW CHC13 \ __, . .
, , ^T ~c.o oo = CHCli required
Iproduced/ I MW CFC-22y J ^
3 11Q T.Q 3
(56.2 x 10J) I ir/fll = 77-6 x 10 kki
-
The amount of chloroform available for conversion to CFC-23 is the total
chloroform available minus that used for CFC-22, or 0.9 x 103 kkg. The
CFC-23 equivalent is:
(available = CFC-23 Produced
\for CF
(0.9 x 103 kkg) hj = 550 kkg
Smith (1978b) estimates the vent stream from the CFC-23 condensa-
tion process to contain 85 percent CFC-23 by weight. The flow rate is
estimated at 0.3 kg/100 kg of CFC-23 produced. Assuming that the CFC-23
contains 1 ppm chloroform, the air emissions are calculated as follows:
product ion\ /Emission^ f CFC-23 \ . , ... _ Air emissions
I of CFC-23 I \ rate / ^concentration) W^'^-**' of chloroform
(550 kkg) (0.3 xlO-2) (.85)
3-7
-------
The air emissions from the CFC-22 condenser vent can be computed similarly
from an emission generation factor of 0,19 kkg/100 kkg of CFC-22 and 70
percent CFC-22 content in the vent stream:
/Production \ /Emission\ CFC-22 \ lo/ri7r , nn
^ of CFC-22 J ^ rate J Concentration ) (CHCl3/CFC-22) = sions of
(56.2 x 103 kkg) (.19 x 10-2) (0.70) (lO*6) -
The catalyst used for liquid phase fluorination of either carbon
tetrachloride or chloroform is a mixture of antimony chlorides and tri-
chlorofluorome thane (CC13F) (Gruber 1977) . A typical composition is 60-
70 percent CC13F with the remainder being SbCls and SbCls in a 10:1 ratio.
A 1-kg catalyst charge is equivalent to 1 kg of product per hour (Gruber
1977) . Approximately twice a year the spent catalyst containing about 10
percent feedstock is replaced (Gruber 1977). Smith (1978b) reports that
du Pont ships the spent material from the plant for catalyst regeneration.
The specific process is unknown, but two potential processes have been
identified by EPA (Gruber 1977). In one, the spent catalyst is dechlori-
nated. The other process is a series of distillations in which CFC's,
feedstock, and SbCls are recovered and the tars generated by the distil-
lation of SbCls are sent to a landfill.
According to Gruber (1977), a quantity of catalyst equal to 0.02
percent of. the CFG production requires regeneration annually. The
quantity of chloroform in the catalyst is calculated as follows:
/Fraction of\ / CHC13 \ CHC13
(Total CFG produced) f spent fraction in = in
\ catalyst / I catalyst J catalyst
(56.2 x 103 kkg + 0.55 kkg) (0.02 x 10~4) (0.1) = 11.35 kg
If 10 percent of the chloroform in the catalyst was released as air
emissions, the quantity would be 1.14 kg.
Smith (1978b) also reports that wastewater from the scrubber at
du Pont is treated with lime and settled prior to disposal in an open
ditch that directs effluents to a plant water treatment facility.
du Pont contends the organic content of the waste stream is negligible.
This, in fact, may be true. For the similar CFC-11/12 process (Smith
1978a) , the presence of some organic components was reported, but that
of the feedstock carbon tetrachloride was not. It may be that levels
of carbon tetrachloride are too low to be detected or that analysis for
feedstock components was not performed. Since the CFC-11/12 production
process, similar to that for CFC-22, is not reported to produce an
appreciable amount of carbon tetrachloride in this wastewater stream,
JRB assumed that the chloroform content in the analogous waste stream
for CFC-22 production is also low (1 ppm) . Because of the assumption
and lack of available data on the solubility of chloroform in salt
solutions, JRB has made no estimate of water-borne releases of chloro-
form. This information may be obtainable in a Level II effort.
3-8
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B. Process in which Vapors from Chloroform Storage Are Not Condensed
The remaining 45 percent of the chloroform.used for CFC-22 manufac-
ture (64.2 x 103 kkg) is assumed to be made by the process used by Allied
Chemical. This process recycles noncondensables rather than venting them
and there is apparently no condenser on the chloroform storage tank
(Pitts 1978). A loss rate of 2.54 kg/kkg has been reported (Pitts 1979b).
Losses from storage may be calculated as 160 kkg. The uncertainty in
this calculation is estimated to be +25%.
Fugitive emissions are assumed to be 1.46 percent with a residual
chloroform concentration of 1 ppm, as was the case with the du Pont
process.
/MM CFC-22^ ,_ . . ^ , /CHC13 Con-\
(w CHC13 J (Emission rate) ^centrationj -
Fugitive emissions
(64,200 - 160 kkg) (86.48/119.39) (1.46 x 10"2 kkg/kkg) (10~6)
0.67 kg
As previously stated, the uncertainty in the fugitive emission value is
estimated to be -50%.
The relative production rates of CFC-23 to CFC-22 have been esti-
mated at 9.6 x 10~3 kkg/kkg at 22.7 x 103 kkg/day and 8.9 x 10~3 kkg/
kkg at 18.2 kkg/day (Pitts 1978). JRB estimates the uncertainty to be
+20% at the higher production rate.
(
CFC-22 \ (MW CHC1? \ / CFC-22 W^f 22 I P* CHCl3 1 = CHCl3
Iproduced) \MW CFC-22 j \producedj\ ;.,',. J \ MW CFC-23/ consumed
fCFC ,2) - + (CFC-22) (9 6 x 10') ' = x
(CFC-22) I 86.48 I + <-CFC ^ ^y-b x iu M 70.03 1 kkg
3
The quantity of CFC-22 produced is 45.9 x 10 kkg, which consumes
63.3 x 10^ kkg of chloroform. The remaining chloroform, 0.8 x 103 kkg,
is converted to 470 kkg of CFC-23.
Allied reports their current practice is to landfill spent cata-
lyst (Pitts 1978). Assuming that catalyst usage is 0.02 percent.of CFC
produced, and that the chloroform level is 10 percent, 9.3 kg of
chloroform are landfilled annually. At a 10 percent leakage rate,
0.9 kg would be released as air emissions.
The total chloroform release due to CFC-22 manufacture is the sum
of the individual releases and losses.
3-9
-------
du Pont process storage loss 29.1 kkg
du Pont process fugitive emissions -I- 0.00083
du Pont process condenser vent emissions -I- 0.0000764
du Pont process catalyst regeneration + 0.01135
Allied.process storage loss 4- 160
Allied process fugitive emissions 4- 0.00067
Allied process catalyst disposal 4- 0.0009
Total chloroform releases 190 kkg
3.1.1.3 Environmental Releases of Chloroform During the Use of CFC-22
One available reference that discussed chloromethane impurities
in CFC's indicated that residual carbon tetrachloride in CFC-11/12 was
less than 2 ppm (NAS 1978a,b). Since the production process for CFC-22
is similar to that for CFC-11/12, JRB has assigned a value of 1 ppm for
residual chloroform in CFC-22 for the purposes of this study. Even
this level may be high. According to industry sources, chloroform
'content in CFC used as refrigerant must be extremely low due to the
possible corrosion potential from traces of water and chloroform 3
(Boberg 1980, Evers 1980). The total CFC-22 production is 102 x 10
kkg. At an estimated chloroform concentration of 1 ppm, there would
be 102 kg of residual chloroform in CFC-22.
CFC-22 is used as a chemical intermediate in the production of a
variety of fluorocarbons such as Halon fire extinguishants and Teflon
PFTE. According to Boberg (1980), any residual chloroform present
will be reacted along with the CFC-22. Estimated use of CFC-22 for
refrigerants was 80 percent in 1973 (Council on Environmental Quality
1975), 55 percent in 1974 (Lowenheim and Koran 1975), and 30 percent
in 1978 (Radian Corp. 1979). For purposes of this balance, we will use
40 percent for refrigerant/air conditioner use and 60 percent for fluoro-
carbon products. The following assumptions are made about refrigerant
usage (Evers 1980):
Ten percent is used in hermetically sealed refrigeration systems,
of which 10 percent are discarded. Of the discarded systems,
10 percent leak.
Twenty-five percent is used in hermetically sealed air condi-
tioners, of which 2 percent leak during repair.
Ten percent is used in charged refrigeration systems, with a
1 percent loss during charging, and a 5 percent loss during
repair.
Fifty-five percent is used in charged air conditioning systems,
including autos. There is a 1 percent loss during charging,
and a 20 percent loss due to leaks.
3-10
-------
Using these assumptions, our estimates for releases of chloroform from
the end uses of CFC-22 are shown in Table 3.4. Figure 3.2 is a diagram
of multimedia releases of chloroform from CFC-22 use. Total losses of
5.2 kg could be understated by as much as 150 percent depending on use
patterns and frequency of repair.
Table 3.4 Release of Chloroform Due to CFC-22 Use
Use
Sealed
refrigerator3
Sealed air
conditioner3
Charged
refrigerator3
Charged air
conditioner3
Fluorocarbon
precursor
TOTAL
Percentage
of use
4
10
4
22
60
100
CHC13
content
(kg)
4.1
10.2
4.1
22.4
61.2
102.0
Destroyed
61.2
61.2
Loss
rate0
l%b
2%
6%
21%
Loss
(kg)
0.04
0.20
0.25
4.7
.5.19
Use pattern based on Council on Environmental Quality 1975.
10 percent of the 10 percent discarded refrigerators leak.
CBased on Evers 1980.
3.1.2 Exports
In 1978, the United States exported 7,900 kkg of chloroform (U.S.
Bureau of Census 1979a). This is approximately 5 percent of the total
chloroform produced. This amount was a 13 percent reduction from exports
in 1977. Information was not available on exports prior to 1977 and
therefore trends cannot be discussed.
3.2 NONCONSUMPTIVE USES OF CHLOROFORM
In 1978 approximately 15,600 kkg of chloroform were used for non-
consumptive purposes or were stockpiled. Nonconsumptive uses of
chloroform reported in the literature include use in extraction, in
Pharmaceuticals as a solvent, in lacquers and floor polishes as a sol-
vent, in artificial silk manufacture, as an intermediate for pesticides
and dyes, and as a fumigant ingredient (Radian Corp. 1979, Sittig 1979,
Kirk-Othmer 1970). Several industrial and government contacts were made
to determine the extent to which chloroform is currently being used.
3-11
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0.061 kkg
Destroyed During
Fluorocarbon
Manufacture
0.102 kkg
Chloroform in"
CFC-22
L I
0.005 kkg
Emitted
to Air
CFC-22 Use
60% Fluorocarbon
40% Refrigerant
and
Air Conditioners
0 kkg
Release to Water
0 kkg
Release to Land
0.036 kkg
Retained in Products
Figure 3.2 Multimedia Releases of Chloroform from the Use of CFC-22
3-12
-------
The discussion that follows indicates that many of the uses cited in the
literature no longer apply to chloroform. Where chloroform was identi-
fied, as still in use, the quantities are generally small.
3.2.1 Use of Chloroform in the Pharmaceutical Industry
Several sources identified the pharmaceutical industry as a major
use of chloroform. The FDA indicated, however, that since chloroform
was banned as an active and inactive ingredient in drugs and toiletries
in 1976, its use has decreased markedly and is currently limited to
extraction procedures (DeGuano 1980). A representative of Squibb indi-
cated that chloroform may also be used as a wetting agent, although
Squibb does not use the solvent at all (Schwadron 1980). No literature
was found on use of chloroform as a wetting agent. Shering-Plough
indicated that methylene chloride and, to a much lesser extent, chloro-
form are the major halogenated solvents used in extraction procedures
(Henley 1979).
In 1975, the pharmaceutical industry purchased approximately
1,100 kkg of chloroform for the preparation of ethical drugs (derived
from USEPA 1978a). Although the ban on the use of chloroform as an
active or inactive ingredient was not yet in effect, none of the chloro-
form purchased was used as a drug ingredient. It is reasonable to assume
that the chloroform was being used for extractions and that the ban did
not significantly affect the purchase of chloroform. We have assumed
that 1,000 kkg were purchased in 1978 for drug extractions.
The estimates for the disposition of chloroform waste, listed
below and shown in Figure 3.3, are based on information supplied by
the Pharmaceutical Manufacturers Association (USEPA 1978c).
Air emissions 570 kkg
Sewer 46 kkg
Contract hauled ' 350 kkg
(assumed landfilled)
Disposed in landfill 34 kkg
or deepwell
No uncertainty estimates were available for the quantity of chloro-
form purchased or for the amounts disposed by each method. We have
assumed that the estimate of 1,000 kkg used in extractions is accurate
to +20%, and that quantities disposed of by various methods are accurate
to +35%.
3.2.2 Use of Chloroform in Pesticide Production
The use of chloroform in the production or formulation of pesti-
cides is limited. Chloroform has not been identified as an intermediate
in the production of any pesticides (Melnikov 1971, USEPA 1972, SRI 1976,
Parsons 1977). However, chloroform's anesthetic and toxic properties
are useful in improving the effectiveness of fumigant mixtures (NAS
1978a,b), and chloroform has been registered with the EPA for use as a
3-13
-------
570 kkg
Air
Chloroform
1,000 kkg
Pharmaceutical
Extractions
46 kkg
384 kkg
Water
Landfill
Figure 3.3 Multimedia Releases of Chloroform from Drug Extractions
3-14
-------
commodity fumigant (USEPA 1972). This includes application of fumigants
for the protection of harvested crops and food products in storage, and
prevention of insect, rodent and other vermin infestation in mills,
warehouses, grain elevators, railcars, shipholds, and other storage
areas. The use of chloroform in fumigants was reported to be 35 kkg in
1976 (Versar 1977). This value is based on an aggregate of data submit-
ted by several companies to the EPA Office of Pesticides. We assigned
an uncertainty of +10% to this value to account for possible variability
or unreported usage of chloroform in fumigants.
To project consumption to 1978 we assumed that usage of chloroform
in fumigants increased 10 percent (+1%) annually, which is the general
trend for other major fumigants (SRI 1976). The amount of chloroform
used in fumigants in 1978 was estimated as 42 kkg.
Estimates from the grain industry indicate that the amount of
stockpiled fumigant is 10 percent (+1%) of the total amount consumed.
Assuming that this estimate will apply to fumigants containing chloro-
form, then the amount stockpiled in 1978 is 4.2 kkg (+24%, -21%). The
remaining 37.8 kkg (+11%) were applied to grain.
Air emissions of chloroform will occur when the fumigated grain is
exposed to the atmosphere. Grain storage areas are vented to allow
shifting the grain for refumigation due to moisture accumulation or
infestations. Emissions will also occur when grain is removed from
storage areas for loading and transit. We assume that all of the applied
chloroform is emitted to the atmosphere.
Figure 3.4 shows the multimedia releases of chloroform that is
used in fumigants.
3.2.3 Use of Chloroform as an Industrial Solvent
The use of chloroform as an industrial solvent appears to be
decreasing rapidly, primarily due to restrictions imposed by OSHA guide-
lines (Davenport 1980).. The declining use of chloroform was verified by
several contacts. Textile Chemical Company, a large mid-Atlantic
regional distributor, reported that only two 200-liter drums were sold
during 1978, a decrease of about 90 percent from previous periods
(Davenport 1980). Ashland Chemical (1980), a national supplier spe-
cializing in industrial solvents, reported that they purchase small drum
quantities on an intermittent basis. Eastman Organic Chemicals (.1980)
reported no sales other than those to laboratories. Johnson's Wax (1980)
indicated chloroform is not used in any of their formulations nor is
chloroform used as a solvent in paints and coatings. The U.S. Consumer
Product Safety Commission confirmed that chloroform has minimal use as
a solvent in consumer products (Simpson 1980).
3.2.4 Use of Chloroform in the Textile and Dye Industries
Although several literature sources identified chloroform as being
used in the textile and dye industries, JRB has found, through numerous
contacts, that this use is extremely limited. Only seven of 418
respondents to an Effluent Guidelines questionnaire for these industries
3-15
-------
Air
37.8 kkg
Chloroform
42 kkg
Fumigants
Water
0 kkg
Stockpiled
4.2 kkg
0 kkg
Land
Figure 3.4 Multimedia Releases of Chloroform from the Use of Fumigants
3-16
-------
were known or suspected of using chloroform (Buzzell 1980). These sur-
vey results support our conclusion that chloroform has limited use in
these industries.
One industry source (Bochner 1980) mentioned that chloroform might
be used as a solvent for the alkylation of quaternary dyes, but stated
that any specifics would be proprietary information. JRB has been
unable to confirm this usage. A study by Mbnsanto Research Corpora-
tion reported finding chloroform in the raw waste of 12 to 29. textile
plants (USEPA 1978a). The levels of chloroform ranged from 5 to 500
yg/£. The origin of the chloroform could not be determined (Samfield
1980). Sources knowledgeable about the textile and dye industry were
contacted, but little additional information was obtained. West Point
Pepperill indicated no known use other than two government-required
quality control tests (Robert 1980). Hydroscience (Earnhardt 1980)
and Sverdrup Corporation (Buzzell 1980) both report no known use in
the textile industry. According to Moser (1980), an extension spe-
cialist in dye chemistry at North Carolina State University, the use
of chloroform as a solvent for dyes is expensive. Perchloroethylene
would be a preferred solvent. Neither he nor any other staff members
contacted by Livingood (1980) at N.C. State could identify any chloro-
form uses in the textile industry.
3.2.5 Laboratory Use and Stockpile
Chloroform is currently being used in hospital, industrial, and
R&D laboratories. Major laboratory uses include spectrophotometric
work, density determination's., and solvent uses (Eastman Organic Chemi-
cals 1980). Several distributors, including J.T. Baker, Mallincrodt,
and Eastman Organic Chemicals, were contacted to obtain quantitative
information on chloroform used for laboratory purposes, but this infor-
mation is considered proprietary.
JRB has estimated an upper limit on the quantity of chloroform
used for laboratory purposes or stockpiled in 1978. This quantity is
estimated as follows:
Sources (kkg)
CHC13 produced 158,500
Imports 7,670
165,670
Known distribution (kkg)
Losses during production 248 (controlled conditions)
Transportation losses 177
CFC-22 production 142,700
Exports 7,900
Used for pharmaceuticals 1,000
Used for fumigants 42
152,067
3-17
-------
Quantity
(Sources) - (Known distribution) = unaccounted
for
(165,670) - (152,067) - 13,600
The 13,600 kkg unaccounted for was estimated to be the upper limit on
the quantity used for laboratory purposes or stockpiled. Small quan-
tities may also be used for other miscellaneous uses such as in the
textile industry.
3.3 SECONDARY PRODUCT CONTAMINANTS
As indicated in Section 2.1, chloroform is produced concurrently
with methyl chloride, methylene chloride, and carbon tetrachloride in
the methane chlorination process; and with methylene chloride and by-
product carbon tetrachloride by the further chlorination of methyl
chloride.
These products are subsequently separated by distillation but remain
contaminated with chloroform at low concentrations.
3.3.1 Releases of Chloroform Contaminant of Methyl Chloride
Methyl chloride is produced by the catalytic chlorination of methane
or hydrochlorination of methanol. The latter reaction,
HC1 + CH3OH - H20 + CH-jCl
yields only methyl chloride whereas direct chlorination of methane yields
all of the chloromethanes:
CH4 + C12 - »- CH-jCl + CH2C12 + CHC13 + CCl^ + HC1
The methane chlorination process results in low levels of product
contamination. Chloroform levels in methyl chloride produced from this
process are on the order of 5-10 ppm (Boberg 1980) .
Table 3.5 shows that of the 14 plants producing methyl chloride,
only the Dow plant in Freeport, Texas, uses the methane chlorination
process exclusively; Allied Chemical and the Vulcan plant in Wichita,
Kansas, use this process for a small percent of their total production
(Hobbs and Stuewe 1979a) . The production capacity for methyl chloride
in the methane chlorination process is 32,500 kkg. JRB estimates that
production by this process is, at most, 70 percent of capacity, or
22,800 kkg.
Assuming chloroform contaminant levels of 7.5 ppm, total chloro-
form content of methyl chloride is estimated as 170 kg. This estimate
is considered accurate to +75% to allow for uncertainties related to
chloroform contaminant levels and the quantity of methyl chloride
produced by the methane chlorination process.
3-18
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Table 3.5 Methyl Chloride Capacity in 14 U.S. Plants
Plant
1977
Capacity
(103 kkg)
Process
Allied Chemical,
.Moundsville, WV
Continental, Westlake, LA
Diamond Shamrock, Belle, WV
Dow, Freeport, TX
Dow, Plaquemine, LA
Dow Corning, Garronton, KY
Dow Corning, Midland, MI
du Pont, Niagara Falls, NY
Ethyl Corp., Baton Rouge, LA
General Electric, Waterford, NY
Stauffer, Louisville, KY
Union Carbide, Institute, KY
Vulcan, Geismar, LA
Vulcan, Wichita, KS
Total
11"
45
lla
32a
68a
9
7
36a
45
23
7a
23
b
b
Methanol hydrochlorination
and methane chlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methane chlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
Methanol hydrochlorination
317
(a) Production varies with amount of methyl chloride separated as
product and amount used for additional chlorination.
(b) All production used for methylene chloride and chloroform.
Source: Hobbs and Stuewe 1979a
3-19
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There are no losses of chloroform resulting from the storage of
methyl chloride at the production sites since methyl chloride is stored
under pressure.
i
The major chemical uses of methyl chloride are in the production
of tetramethyl lead, silicones, and methyl arsenate herbicides (Radian
Corp. 1979). It appears that methanol derived methyl chloride is used
in these applications and chloroform contamination would not be expected.
Dow Corning, General Electric, and Ethyl Corporation probably use methyl
chloride directly. Vulcan uses all of their production as feedstock
for methylene chloride and chloroform. One nonchemical use of methyl
chloride from the methane chlorination process is as a catalyst carrier
at low temperatures in the production of butyl rubber (Mannsville 1978b).
No specific process or consumption information could be obtained regarding
this use,
3.3.2 Releases of Chloroform Contaminant of Methylene Chloride
Methylene chloride is produced concurrently with chloroform by the
chlorination of methane, by hydrochlorination of methane, or by hydro-
chlorination of methanol followed by methyl chloride chlorination. The
processes are discussed in Section 2.1.
Table 3.6 summarizes the quantities of methylene chloride utilized
for various end uses in 1977 and the quantities of chloroform contaminant
derived by assuming an impurity concentration of 15-20 ppm (Boberg 1980).
The total chloroform contaminant is 4.28 kkg. The accuracy of the con-
taminant level is estimated at +30%.
3.3.2.1 Releases of Chloroform During Storage and Handling of Methylene
Chloride
Releases of chloroform can occur during the storage and handling of
methylene chloride. To estimate these emissions, we have used the emis-
sion factors derived in Section 2.1. Storage conditions for methylene
chloride and chloroform are not expected to be significantly different,
and these emission factors are considered to be accurate with an uncer-
tainty range of +25%. The emission factor for storage is 0.59 kg/kkg,
which gives an estimated chloroform release of 2.5 kg.
This overall estimate for chloroform released during storage is
considered accurate to +60%, -50% to allow for the uncertainties
related to storage conditions for methylene chloride, chloroform con-
taminant levels in methylene chloride, and the emission factor estima-
ted in Section 2.1.
For working losses, the estimated emission factor is 0.33 kg/kkg.
The corresponding estimate for chloroform emission during handling is
1.4 kg. This estimate is considered accurate to +40%. As was the
case for breathing losses, there are uncertainties related to storage
conditions, chloroform contaminant levels, and the emission factor.
3-20
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Table 3.6 Quantitative Breakdown of Methylene Chloride End Uses and Corresponding
Chloroform Contaminant Levels
CO
I
to
End Uses
Paint remover
Metal degreasing
Aerosol propellant
Blowing agent
Exports
Other
Total
Methylene
chloride3
(kkg)
73,000
49,000
46,000
20,000
44,000
12,000 f"
Chloroform
contaminant ,
based on 15 ppm
(kg)
1,095
735
690
300
660
180
3,660
Chloroform
contaminant
. based on 20 ppm
(kg)
1,460
980
920
400
880
240
4,880
Chloroform
contaminant
average, 17.5 ppm
(kg)
1,280
860
805
350
770
210
4,275
1977 estimates (SRI 1979)
-------
3.3.2.2 Releases of Chloroform from Methylene Chloride-Based Paint
Removers
Thirty percent of the methylene chloride produced in 1977 was used
in paint removers (SRI 1979). For an average chloroform contaminant
concentration of 17.5.ppm, the quantity of chloroform in these paint
removers is estimated in Table 3.6 as 1.28 kkg. This estimate is
considered accurate to +20% due to uncertainties related to the amount
of paint removers containing methlylene chloride and chloroform con-
taminant levels in these products.
Multimedia environmental releases of chloroform from paint removers
depend upon the method of application and the type of product. Paint
removers range In viscosity from liquids to semigels and may be applied
by dip, spray, or brush methods. Frequently the solvent and softened
paint-film mixtures are rinsed off the surface with water. Although
most of the solvent evaporates, there are losses to water and land from
the use and disposal of these products. Because of its high volatility,
JRB estimates that 75 percent of the solvent is emitted directly to air,
15 percent is disposed of in water as used solvent, and 10 percent is
disposed osf to land, mostly as residue in used containers. Based on
these assumptions, losses of chloroform from use of thes.e paint removers
are estimated as 960 kg to air, 192 kg to water, and 128 kg to land.
Our percentage estimates for chloroform disposal are considered
accurate to +15% for land and water and +5% for air. When combined
with our uncertainty estimate of +20% for total chloroform released
from these products, our overall uncertainty esimates for releases to
air, water, and land are +25%, +30%, and +34%, respectively.
Figure 3.5 summarizes the multimedia environmental releases of
chloroform from use of these products.
3.3.2.3 Releases of Chloroform from Use of Methylene Chloride in
Metal Degreasing
Halogenated solvents are used widely in the metal cleaning industry
because of their high solvency power and nonflammable nature. Approxi-
mately 49,000 kkg of methylene chloride were used in metal cleaning in
1977 (SRI 1979). The quantity of chloroform released from the use of
methylene chloride in metal cleaning was estimated in Table 3.6 as
860 kg.
There are varying estimates in the literature on the percentage
of methylene chloride used for cold cleaning versus vapor degreasing.
A survey conducted by Dow suggested that 54 percent was used for vapor
degreasing and 46 percent for cold cleaning (Dow Chemical Co. 1976).
The Office of Air Quality Planning and Standards claims that the break-
down is 23 percent for vapor degreasing and 77 percent for cold cleaning
(Bellinger and Schumaker 1977). Since the Dow estimates were based on
an industrial survey, these results are considered more reliable.
3-22
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Air
t
960 kkg
Chloroform
1,280 kkg
Paint
Removers
128 kkg
t
Landfill
192 kkg
Water
Figure 3.5 Multimedia Releases of Chloroform from Use of Paint
Removers Containing Methylene Chloride
3-23
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Based on the Dow survey, multimedia releases of chloroform from the
use of methylene chloride are estimated as follows:
L ^ \ /Total chloroform\ /Percent methylene\ Chloroform
Percent of I f 1 \ I ,. ., . J = released to
, released from chloride for I n
release I 1 I \ / individual
y \ metal cleaning / wapor degreasing/
' / * media
Emissions to air: 80% x 860 kg x 0.54 = 372 kg
Incinerated: 2% x 860 kg x 0.54 = 9 kg
Discharged: 10% x 860 kg x 0.54 = 46 kg
Landfilled: 8% x 860 kg x 0.54 = 37 kg
Total = 464 kg
Cold Cleaning
Emissions to air: 70% x 860 kg x 0.46 = 278 kg
Incinerated: 2% x 860 kg x 0.46 = 8 kg
Discharged: 15% x 860 kg x 0.46 = 59 kg
Landfilled: 13% x 860 kg x 0.46 = 51 kg
Total = 396 kg
Combined Emissions (Cold Cleaning and Vapor Degreasing)
Emissions to air: 650 kg
Incinerated: 17 kg
Discharged: 105 kg
Landfilled: 88 kg
Figures 3.6 and 3.7 summarize the environmental releases of chloro-
form from use of methylene chloride by the metal cleaning industry.
The estimate of 860 kg of chloroform released from the combined use
of methylene chloride in vapor degreasing and cold cleaning is considered
accurate to +20%. The factors contributing to our error range include
the uncertainties for the quantity of methylene chloride used in metal
cleaning and the contaminant levels. Our estimates for the percentage
releases are thought to be accurate to +10% for air and incineration,
and +30% for water and land. Using these individual uncertainties our
overall uncertainty estimates for air, water, land, and incineration are
+32%, +48%, +46%, and +29%, respectively.
3.3.2.4 Releases of Chloroform from Use of Methylene Chloride in
Aerosols
In 1977, 46,000 kkg of methylene chloride were used in aerosol
products. As estimated in Table 3.6, these products contained 17.5 ppm
or 805 kg of chloroform. We estimate the accuracy of this number at
+30% to allow for uncertainties related to the amount of methylene
chloride used in aerosols and the chloroform concentration.
3-24
-------
Incinerated Air
t t
8 kg
278 kg
Chloroform
397 kg
Cold
Cleaning
Discharged
59 kg
51 kg
Landfilled
Figure 3.6 Multimedia Releases of Chloroform from Use of Methylene
Chloride in Cold Cleaning
3-25
-------
Incinerated Air
19 kg I 372 kg
Chloroform
464 kg
Vapor
Degreasing
37 kg
Water
46 kg
Landfill
Figure 3.7 Multimedia Releases of Chloroform from Use of Methylene
Chloride in Vapor Degreasing
3-26
-------
A quantitative breakdown of chloroform releases from various types
of aerosol products for automotive and household use, etc. can be esti-
mated from the number of aerosol cans in each product category (Kirk-
Othmer 1970, USCPSC 1979). Figure 3.8 shows the percentage and total
quantity of chloroform released from each product category.
Multimedia releases of chloroform were estimated by assuming that
2 to 3 percent is emitted to air during formulation of aerosols, 10
percent of the chloroform in aerosol products is landfilled as residual
in used cans, and the remaining chloroform is emitted during use. An
estimated 20 kg were emitted to air during production; of the remaining
785 kg, 79 kg were disposed to land and 706 kg were emitted to air during
use. JRB's percentage estimates are believed accurate to within +5% for
air and +25% for land. When combined with an estimated uncertainty of
+20% for the amount of chloroform in these aerosol products, our overall
uncertainties for air and land emissions are +25% and +43%, respectively.
Figure 3.9 summarizes the total releases of chloroform from the use of
aerosol products containing methylene chloride.
3.3.2.5 Releases of Chloroform from Methylene Chlorine-Based Blowing
Agents for Urethane Foam
In 1977, 20,000 kkg of methylene chloride were used in urethane
foam blowing (SRI 1979). At a. chloroform contaminant level of 17.5 ppm,
the quantity of chloroform released from the manufacture and use of ure-
thane foam is estimated as 350 kg (Table 3.6).
In calculating environmental releases of chloroform from urethane
foam, it is assumed that 2 percent of the chloroform impurites (7 kg)
are released to air during the manufacturing process. It is further
assumed that urethane foams are used in open and closed systems in
approximately equal portions (Council on Environmental Quality 1975).
Virtually 100 percent of the chloroform present in open systems (172 kg)
will be released to air. Losses of chloroform from the use of urethane
foam in closed systems will be negligible except for an assumed 10
percent of the products in which leaks occur. This will result in 17.2
kg of chloroform being released to the air. It is also assumed that an
additional 10 percent of these systems containing 17.2 kg of chloroform
are discarded in landfills and the remaining 80 percent which contain
an estimated 137 kg of chloroform are contained in products in use.
These releases are summarized in Figure 3.10.
The estimate of 350 kg of chloroform contaminant in methylene
chloride used as a foam blowing agent is considered accurate to +20%
to account for uncertainty regarding the chloroform levels in methylene
chloride and the quantity of methylene chloride used for this purpose.
Our estimates for the percentages released to air, to land, and
retained in closed systems are considered accurate to +20%, +30%, and
+30%, respectively. The overall uncertainty estimates for quantities
of chloroform are +39% for air, +47% for land, and +47% for products.
3-27
-------
LO
I
NJ
oo
20 kg to air
during production
\
805 kg
785 kg
Chloroform In methylene
chloride-based aerosol
products
27%
212 kg
Household products
4%
31kg 7
13%
Automotive products
102 kg
Coatings and finishes
51%
400 kg7
5%
Personal care products
39 kg
Pesticide products
(under CPSC jurisdiction)
(under FDA jurisdiction)
(under EPA jurisdiction)
Figure 3.8 Flow Diagram of Chloroform in Methylene Chloride-Based Aerosols
-------
Air
726 kg
Chloro-
form 805 kg,
Aerosols
Landfill
79 kg
Figure 3.9 Multimedia Releases of Chloroform from Use of Aerosol
Products Containing Methylene Chloride
3-29
-------
Air 196 kg
Chloroform
350 kg_
Urethane
Foam
Blowing
Agent .
137 kg
»End Use
Products
17.2 kg
"^Landfill
Figure 3.10 Multimedia Releases of Chloroform from Use of Methylene
Chloride as a Blowing Agent in Urethane Foam
3-30
-------
3.3.2.6 Releases of Chloroform from Miscellaneous Use of Methylene
Chloride
Approximately 210 kg of chloroform (+20%) were released from miscel-
laneous uses of methylene chloride in 1978. These uses included traffic
paints, cesspool cleaners, adhesives, extraction of spices, beer hops,
and coffee, plastics processing, and others. No estimate could be made
on the chloroform releases from specific end uses. It can be assumed,
however, that approximately 70-80 percent is emitted directly to air
(147-168 kg), 10-15 percent is landfilled (21-32 kg), and 10-15 percent
is discharged to water or groundwater (21-32 kg). Since the miscellaneous
uses have not been differentiated, our estimates for multimedia releases
are not considered more accurate than +85%.
3.3.3 Releases of Chloroform Contaminant of Carbon Tetrachloride
3.3.3.1 Handling, Storage, and Transportation Emissions
Technical grade carbon tetrachloride can contain up to 150 ppm
chloroform (Kirk-Othmer 1978). To account for possible analytic error
associated with this value, we assigned a confidence limit of +_10%.
Carbon tetrachloride is produced by 13 plants owned by eight chemical
corporations (see Table 3.7). These plants produced 334,000 kkg (+10%)
of carbon tetrachloride in 1978 (USITC 1979). Assuming that all of
this carbon tetrachloride contained 150 ppm chloroform, the amount of
chloroform contained in the carbon tetrachloride is estimated as 50 kkg
(+10%, -20%).
Atmospheric emissions of carbon tetrachloride during storage,
loading, ballasting, and transit are summarized in Table 3.8 (Rams et al.
1979). These emissions total 191 kkg. These calculations are based on
information in AP-42 (USEPA 1977). The total has an estimated uncer-
tainty of +25%. The emissions of chloroform associated with this car-
bon tetrachloride are estimated as 0.029 kkg (+41%, -34%).
3.3.3.2 Production of CFC-11 and CFC-12 from Carbon Tetrachloride
Production of CFC-11 (CC^F) and CFC-12 (CC12F2) accounts for over
87 percent of the industrial utilization of carbon tetrachloride (CC14).
There are currently five producers of chlorofluorocarbons in the United
States. Their production capacities and plant locations are shown in
Figure 3.11 and Table 3.9, respectively. In 1978, 148,000 kkg (+10%)
of CFC-12 and 88,000 kkg (+10%) of CFC-11 were produced in the United
States (USITC 1979). This represents a 9 percent reduction in chloro-
fluorocarbon production from 1977. This trend is believed to have con-
tinued, resulting in a 25 percent recuction in CFC-11 production and a
14 percent decrease in CFC-12 production for 1979 (see Table 3.2).
This decrease in production is a result of EPA regulations which banned
the use of chlorofluorocarbons as aerosol propellants as of December 15,
1978 (Federal Register 1978). Use of chlorofluorocarbons as aerosol
propellants previously accounted for about 50 percent of the CFC-11 and
CFC-12 marketed (Kirk-Othmer 1978, Mannsville Chemical Products 1978a).
Currently, CFC-11 and CFC-12 are used as refrigerants, foam blowing
agents, and solvents. Unless there is a ban on all chlorofluorocarbon
3-31
-------
Table 3.7 Carbon Tetrachloride Plant Production Estimates
Plant
Allied, WV
Diamond, WV
Dow Chemical,
TX
Dow Chemical,
CA
Diamond, WV
du Pont, TX
FMC, WV
Inland, PR
Stauffer, AL
Stauffer, KY
Stauffer, NY
Vulcan, LA
Vulcan, KS
TOTAL
1978 capacity
millions
of pounds
8
11
135
80
125
500
300
N/A
200
35
150
90
60
1,694
Fraction of total
industrial output
(%)
0.47
0.65
8.0
4.7
7.4
30
18
-
12
2.1
9.9
5.3
3.5
101
Estimated 1978
production
(kkg/yr)
1,555
2,151
26,473
15,553
24,488
99,273
59,563
-
39,709
6,949
29,451
17,538
11,582
334,285
Process type
Hydrocarbon chloronolysis
carbon disulfide
Methane chlorination
Hydrocarbon chloronolysis
methane chlorination
Hydrocarbon chloronolysis
methane chlorination
Hydrocarbon chloronolysis
Hydrocarbon chloronolysis
Carbon disulfide
-
Carbon disulfide
Hydrocarbon chloronolysis
methane chlorination
Carbon disulfide
Hydrocarbon chloronolysis
Hydrocarbon chloronolysis
methane chlorination
10
I
U)
NJ
Due to rounding, percents did not total 100, nor did estimated 1973 production match the reported
334,319 kkg (USITC 1979).
Source: Rams et al. 1979
-------
Table 3.8 Method I Storage, Loading, Ballasting, and Transit Emissions
Plant
Allied
uv
Diamond
UV
Dow
TX
Dow
CA
Dow
LA
Du Pont
TX
FMC
WV
Storage
Production
Capacity Breathing Working
1.708 .026 .67
4,818 .072 1.9
26,486 .40 10
15,942 .24 6.2
24.509 .37 9.6
95.681 1.4 17
59.416 .89 23
Loading Ballaatlng Tranalt
Tank cars/ Ocean Ocean Tank Cara/ Ocean
Truck* Tankera Bargea Bargea Tankera -Bargea Bargea Truck* Tankera Bargea
.22 .059 .0037 ~
.63 .17 .010
.69 .41 .91 .32 .34 .011 .5} .69
3.3 .062 .11 .048 .041 .055 .083 . 083
3.2 85 .053
2.5 1.5 3.3 1.1 1.2 .041 2.0 2. 5
_ . _ _. ,,o - _
Bargea
.044
.13
.64
.62
Inland __^
Scauf fer
AL
Scauf fer
KV
Stauf fer
tit
Vulcan
LA
Vulcan
KS
TOTALS
39,666 .59 li
7,045 .11 2.7
29.451 .44 11
17.589 .26 6.9
11,988 .18 4.7
314.319 5.0 129
2.1 2.2 .034
.55 .3* .0091
.77 .52 .91 .40 .34 .013 .69 .69
2.3 . .61 .038
3.1 .052
31 2.S 2.5 5.0 1.9 1.9 .12 3.3 4.0
1.7
.26
.46
3.9
I
OJ
CO
-------
COMPANY
Allied Chemical Corporation
Specialty Chemicals
Division
E.I. du Pont de Nemour and
Company, Inc.
Freon Products Division
Essex Chemical Corporation
Racon Inc.
Kaiser Aluminum and
Chemical Corporation
Kaiser Chemicals Division
Pennwalt Corporation
Inorganic Chemicals Division
LOCATION
1. Baton Rouge, Louisiana
2. Danville, Illinois
3. Elyabech,cNew Jersey
4. El Segundo, California
5. Antioch, California
6. Corpus Christi, Texas
7. Deepwater, New Jersey
8. Louisville, Kentucky
9. Montague, Michigan
10. Wichita, Kansas
11. Cramercy, Louisianna
12. Calvert City, Kentucky
Figure 3.11 Locations of Chlorofluorcarbon Production Plants
3^34
-------
Table 3.9 Locations and Capacities of Chlorofluorocarbon Production Plants
OJ
I
Company
Allied Chemical Corporation
Specialty Chemicals
Division
E.I. du Pont de Nemours and
Company, Inc.
Freon" Products Division
Essex Chemical Corporation
Racon Inc.
Kaiser Aluminum and
Chemical Corporation
Kaiser Chemicals Division
Penwalt Corporation
Inorganic Chemicals Division
Location
Baton Rouge, Louisiana
Danville, Illinois
Elyabech, New Jersey .
El Segundo, California
Antioch, California
Corpus Christ!, Texas
Deepwater, New Jersey
Louisville, Kentucky
Montague, Michigan
Wichita, Kansas
Gramercy, Louisiana
Calvert City, Kentucky
TOTAL
Annual
Capacity (kkg)
1.8144 x 105
2.268 x 105
.20412 x 105
.29484 x 105
.36288 x 105
4.944 x 105
% of Annual
Capacity
36.7%
45.9%
: 4.1%
6.0%
7.3%
-------
usage, production of CFC-11 and CFC-12 should stabilize at the 1979 pro-
duction level'and thereafter increase at a 5 percent annual rate (Manns-
ville Chemical Products 1978a, SRI 1979, Wolf 1979).
The production of CFC-11 and CFC-12 accounted for 293,000 kkg (+10%)
of carbon tetrachloride in 1978 (Rams et al. 1979). Assuming that the
carbon tetrachloride contained the maximum reported concentration of
chloroform, 150 ppm (+10%), 44 kkg (+20%, -18%) of chloroform were
present.
CFC-11 and CFC-12 are produced in an integrated facility using a
liquid phase catalytic reaction of anhydrous hydrogen fluoride, carbon
tetrachloride, and chlorine, A typical process diagram, based on pro-
cesses utilized by Allied Chemical Corporation and E. I. du Pont de
Nemours and Company, is shown in Figure 3.12. Possible primary sources
of emissions from this process include storage of raw materials, the
vent on the hydrogen chloride recovery column, and vents on the dis-
tillation column. Secondary emissions can result from the disposal of
waste hydrogen chloride, spent alumina, waste sulfuric acid, waste
sodium chloride, spent catalyst and from releases occuring during
usage of the contaminated finished product.
During the production process, chloroform can react with hydrogen
fluoride, producing CFC-22. The amount of chloroform consumed during
the production process is unknown, but we assume that all the chloro-
form not emitted during production was consumed.
A. Air Emissions
The amount of carbon tetrachloride released during storage depends
on the type of storage tanks used, the storage conditions, and the
type of emission control system. Allied Chemical estimated breathing
and working losses from the fixed roof tank at their production facility,
with no emission control devices, at 0.00035 kkg/kkg of product (Pitts
1978). E. I. du Pont (Smith 1978b) calculated storage tank losses for
carbon tetrachloride to be 0.002 kkg/kkg of product. These estimates
were made using procedures outlined in the Compilation of Air Pollu-
tant Emission Factors, AP-42 (EPA 1977, Pitts 1979a). To account for
assumptions utilized in AP-42, the uncertainty associated with these
emission factors is +25%.
Assuming that emissions from the Allied Chemical plant are typical
of the industry and that the chloroform level in the feedstock is
150 ppm, releases of chloroform to the atmosphere from manufacture of
236,000 kkg of CFC-11/12 can be calculated as 0.012 kkg (+58%, -38%).
B. Process Emissions
Emissions of carbon tetrachloride during chlorofluorocarbon pro-
duction and from waste streams originating from the production process
can occur from various point and nonpoint sources. These sources
include landfilling of spent antimony chloride catalyst, which contains
10 percent carbon tetrachloride; byproduct hydrogen chloride, anhydrous
3-36
-------
STORAGE
LO
I
CO
Figure 3.12
Chlorofluorpcarbon Production Process
Source: Pitts 1979b
-------
hydrogen chloride recovery column vent; distillation column vents, the
caustic scrubber, sulfuric acid and alumina dryers; and fugitive emis-
sions. A study of emissions of carbon tetrachloride from the chloro-
fluorocarbon production process estimated atmospheric emissions of 367
kkg (+30%) (Rams et al. 1979). Assuming 150 ppm chloroform in the car-
bon tetrachloride, emissions contain an estimated 0.055 kkg (+44%, -64%).
C. Emissions from Contaminated Finished Products
Levels of carbon tetrachloride in fluorocarbons were estimated by
industry to be below 2 ppm (NAS 1978a,b).. From this value, the amount
of carbon tetrachloride in products has been estimated as 0.47 kkg
(+30%), and the amount of chloroform as 7.1 x 10~5 kkg (+41%, -63%).
We assume that all of this chloroform would be released to the atmosphere.
Total emissions of chloroform to the atmosphere from the produc-
tion of CFC-11 and CFC-12 are 0.067 kkg (+46%, -40%).
D. Water Emissions
Carbon tetrachloride is contained in the aqueous waste streams from
the caustic scrubber and the H2S04 dryer (streams 7 and 8 in Figure 3-12).
We assume that due to limited solubility of carbon tetrachloride in water
only'residual traces would be left after biological treatment of these
waste streams.
Another source of carbon tetrachloride in wastewater is through
leakage or disposal into the plant sewage system. The amount of emis-
sions from these sources is unknown, but we assume them to be small.
Thus, the total amount of chloroform emitted in waste streams from
these production sources is believed to be small.
E. Land Emissions
It has been estimated that 3.9 kkg (+75%) of carbon tetrachloride
are in spent catalyst from fluorocarbon production, which is landfilled
(Rams et al. 1979). The amount, of chloroform in the landfilled cata-
lyst is estimated as 0.0006 kkg (+89%, -22%).
3.3.3.3 Use of Carbon Tetrachloride in Fumigants
Carbon tetrachloride is used in the formulation of pesticides
applied as fumigants for nonagricultural purposes. These uses include
application of fumigants to protect harvested crops and products in
storage, and prevention of insect, rodent, and other vermin infestation
in mills, warehouses, grain elevators, railcars, ship holds, and other
storage areas (SRI 1976).
Carbon tetrachloride is effective in grain disinfestation when long
exposure is possible. Due to its excellent penetration and diffusion
capabilities, it is a preferred fumigant for use under a wide range of
conditions. In liquid form, it is poured or pumped into storage areas.
It vaporizes upon contact within 'the first few feet of grain, and pene-
trates through the bulk of the stored grain. Applications are generally
performed a short time after the grain is harvested and stored, and may
be repeated as the grain is packaged and transported for use.
3-38
-------
Grain fumigants, including carbon tetrachloride, constitute the
major type of pesticide used for nonagricultural applications. There
are currently 119 pesticide products registered for manufacture in the
United States which contain carbon tetrachloride. These products, pri-
marily grain and spot fumigants, are manufactured by a total of 55 com-
panies, listed in Table 3.10. These production sites are clustered in
several centers: the New York-New Jersey area, the Baltimore-Washington
area, West Virginia, the Cleveland-Detroit area, the Chicago area,
St. Louis-Kansas City area, New Orleans-Alabama area, the Houston area,
Los Angeles area, and the San Francisco Bay area.
In 1978, 13,300 kkg (+40%) of carbon tetrachloride were used in
the production of fumigants. Of this amount, 1,200 kkg (+35%) were
stockpiled (Rams et al. 1979). Because of the nature of the fumiga-
tion process, all of the carbon tetrachloride used in fumigants, or a
total of 12,100 kkg (+40%), was emitted to the atmosphere during appli-
cation. The amount of chloroform emitted to the atmosphere from the
use of carbon tetrachloride in fumigants is estimated as 1.8 kkg
(+40%, -40%); the amount of chloroform in the stockpiled fumigants is
estimated as 0.18 kkg (+50%, -39%).
3.3.3.4 Minor Uses of Carbon Tetrachloride
Carbon tetrachloride has many nonconsumptive industrial uses
(Rams et al. 1979). These include laboratory uses, metal cleaning, use
in the production of paints, adhesives, textiles, embalming supplies,
Pharmaceuticals, plastics, rubber, chlorinated paraffins, and various
other miscellaneous uses. Emissions of carbon tetrachloride to the
atmosphere from these uses amounted to 11,800 kkg (+95%) in 1978 (Rams .
et al. 1979). The amount of chloroform in these emissions is estimated
as 1.8 kkg (+111%, -96%).
Of the amount of carbon tetrachloride used in embalming supplies,
831 kkg (+95%) are contained in caskets. The amount of chloroform
in this embalming fluid, which is assumed to be in temporary storage,
is estimated as 0.12 kkg (+125%, -95%).
3.3.3.5 Stockpiled Carbon Tetrachloride -
It has been reported that 17,100 kkg (+95%) of carbon tetrachloride
were stockpiled in 1979 (Rams et al. 1979). The amount of chloroform in
the stockpiled carbon tetrachloride is estimated as 2.6 kkg (+111%, -96%)
We assume that none of the stockpiled carbon tetrachloride is emitted
to the atmopshere because it is stored in sealed drums and tanks.
3.3.4 Releases from Perchloroethylene/Carbon Tetrachloride Production
Perchloroethylene is formed by the chlorination of hydrocarbons at
or near pyrolytic conditions. Production of perchloroethylene and car-
bon tetrachloride from the chlorination of hydrocarbons has been esti-
mated at 318,800 kkg (Farmer et al. 1980, Rams et al. 1979). The
hydrocarbon feed to the process can be any of several hydrocarbons or
a mixture of hydrocarbons. One source of the mixed hydrocarbon feed-
stock is distillate residue from chloromethane processes. This
3-39
-------
Table 3.10 United States Producers of Registered Pesticide Products
which Contain Carbon Tetrachloride
Agway, Inc.
Atomic Chemical Co.
Bartels & Shores Chemical Co.
Big F Insecticides, Inc.
Brayton Chems, Inc.
Cardinal Chemical Co.
Chemi Sol Chemical & Sales Co.
Colorado International Corp.
Coyne Chemical Co.
Dettelbach Chemicals Co.
Diamond Shamrock Agricultural Chemicals
Douglas Chemical Co.
Dow Chemicals, U.S.A.
Farmland Industries, Inc.
Ferguson Fumigants
FMC
Grain Conditioners, Inc.
Hill Manufacturing Co.
Hockwald Chem. (Division of Oxford Chem.)
Huge Company,. Inc.
Syracuse, New York
Spokane, Washington
Greenwood, Mississippi
Memphis, Tennessee
W. Burlington, Iowa
San Francisco, California
Hutchinson, Kansas
Lakewood, Colorado
Los Angeles, California
Atlanta, Georgia
Newark, New Jersey
Des Moines, Iowa
Green Bayou, Texas
Baltimore, Maryland
Liberty, Missouri
Midland, Mississippi
Freeport, Texas
Pittsburg, California
Kansas City, Missouri
Hazlewood, Missouri
Middleport, New York
Baltimore, Maryland
New Orleans, Louisiana
Atlanta, Georgia
Brisbane, California
St. Louis, Missouri
3-40
-------
Table 3.10 United States Producers of Registered Pesticide Products
Which Contain Carbon Tetrachloride (Continued)
Industrial Fumlgant Co.
J-Chem
Knox Chemicals Co.
Leitte, E.H.. Co.
Lester Labs, Inc.
Levensons, Inc.
Lystad, Inc.
UFA Oil Co.
Momar, Inc.
Morgro Chemical & Energy Corp.
Oxford Chemicals
Parsons Chemicals
Patterson Chemical Company, Inc.
PBI-Gordon Corp.
Quinn Drug & Chemicals
Research Products Co.
Riverdale Chemicals Co.
Selig Chemical Industries
Southland Pearson & Co.
Southwestern Grain Supply Co.
Staffel Company
Stephenson Chemicals Co., Inc.
Olathe, Kansas
Houston, Texas
St. Louis, Missouri
Lake Elmo St. Paul, Minnesota
Atlanta, Georgia
Omaha, Nebraska
Grand Forks, North Dakota
Shenandoah, Iowa
Atlanta, Georgia
Salt Lake City, Utah
Atlanta, Georgia
Grand Lodge, Mississippi
Kansas City, Missouri
Kansas City, Kansas
Kansas City, Missouri
Salinas, Kansas
Chicago Heights, Illinois
Atlanta, Georgia
Mobile, Alabama
Amarillo, Texas
San Antonio, Texas
College Park, Georgia
3-41
-------
Table 3.10 United States Producers of Registered Pesticide Products
Which Contain Carbon Tetrachloride (Continued)
Stauffer Chemicals Co.
Techne Corp.
Thompson-Hayward Chemicals
Universal Corporaters, Inc.
Vulcan Materials Co.
Warren-Douglas Chemical Co., Inc.
Weevil-Cide Co.
Weil Chemical Co.
West Chemicals Products, Inc.
Wood Folk Chem Works, Inc.
Zep Manufacturing Corp.
Perry, Ohio
Mt. Pleasant, Tennessee
Henderson, Nevada
Ardsley, New York
Kansas City, Missouri
Kansas City, Kansas
Minneapolis, Minnesota
Wichita, Kansas
Omaha, Nebraska
Salina, Kansas
Memphis, Tennessee
Long Island, New York
Ft. Valley, Georgia
Atlanta, Georgia
3-42
-------
particular feedstock contains chloroform, which may be released 'to the
air with vented emissions from the hydrocarbon .storage tanks. Chloro-
form was found at 0.037 mole percent (less than 0.1 percent by weight)
in the combined emissions from hydrocarbon storage and hex wastes from
perchloroethylene distillation. An emission factor of 5.6 x 10~3 kkg/kkg
of capacity was estimated (Hobbs and Stuewe 1979b). This emission factor
represents an upper limit, since many producers do not store hydrocarbon
wastes for feed.
An upper limit estimate of chloroform releases was determined by
multiplying the emissions factor by the percent of chloroform in the
emission stream to obtain an emission factor for chloroform alone, and
then multiplying this product by the quantity of perchloroethylene and
carbon tetrachloride produced by this production process.
Emission rate \ /_, , - \ / Production of \ Total
, j . \ /Chloroforml / ... _, .. , \ ,- -
from hydrocarbon -, -, perchloroethylene + j = chloroform
' l leV6J- / \ CCU / released
storage J ^ J \
(5.6 x 10"3 kkg/kkg) (0.001) (318,800 kkg) = 1.8 kg/yr
t
This estimate is not considered more accurate than +60%, -80%
because of uncertainty related to the frequency with which hydrocarbon
waste contaminated with chloroform is used as feedstock.
3.4 SUMMARY OF ENVIRONMENTAL RELEASES FROM CHLOROFORM USES
The major environmental release of chloroform resulting from its
industrial use is that associated with pharmaceutical extraction. This
source accounted for 1,000 kkg or 73 percent of chloroform released to
the environment in 1978. Most of this, 570 kkg, was released to the
atmosphere. The amount of chloroform used in laboratories is unknown
but we estimate it to be large because of chloroform's excellent solvent
properties. The releases from laboratory uses could also be large
because of the uncontrolled conditions under which chloroform is used.
The remaining releases of chloroform associated with its industrial use
are small and account for about 23% of the total releases.
Table 3.11 summarizes the releases of chloroform associated with
its use.
3-43
-------
Table 3.11 Summary of Environmental Releases from Chloroform End-Uses
(kkg)
Use
CFC-22 production
CFC-22 refrigerant
Pharmaceutical extractions
Fumigants
Laboratory Uses
Contamination of methyl
chloride
Contamination of methylene
chloride
- storage
- paint remover
- metal cleaning
- aerosols
- urethane foam
- other
Contamination of
perchloroethylene
Contamination of car-
bon tetrachloride
- storage
- CFC-ll/CFC-12
- fumigants
- other
Quantity
released
(kkg)
190
0.005
1,000
37.8
Potentially
large
0.0014
1.28
0.843
0.805
0.213
0.21
?
0.029
0.0676
1.8
1.8
Quantity released to
Air
190
0.005
570
37.8
?
7
0.0014
0.96
0.65
0.726
0.196
0.157
0.0018
0.029
0.067
1.8
1.8
Land
0
384
0
?
9
0.128
0.088
0.079
0.017
0.026
0.00058
Water
0
46
0
?
?
0.192
0.105
0
0
0.027
3-44
-------
4.0 RELEASE SOURCE EVALUATION
The objective of this chapter is to pinpoint specific geographic
areas and specific processes or operations where significant environ-
mental releases of chloroform may occur.
4.1 DIRECT PRODUCTION
There are five domestic producers of chloroform with plants at
seven sites. Chloroform emissions are low, amounting to only about
0.2 percent of the total chloroform produced. Nevertheless, releases
to air and water may be locally significant, particularly from fugitive
emissions and storage and handling losses. Table 4.1 summarizes air
emissions and water emissions for the seven plants producing chloroform.
It is important to note that, in the absence of other information,
emissions were estimated using the same emission rate for all plants
and with the assumption that production was 71 percent of capacity at
each plant. Consequently, actual emissions may vary significantly from
those shown in Table 4.1. Based on these emission estimates, the Gulf
Coast, with producers located in Freeport, Texas; Plaquemine, Texas;
and Geismer, Louisiana; is the most significant area for environmental
releases from chloroform production.
Table 4.1 Summary of Chloroform Releases to Air and Water from
Production of Chloroform (assuming controlled conditions)
Producer
Allied Chemical
Diamond Shamrock
Dow Chemical
Dow. Chemical
Stauffer
Vulcan
Vulcan
Production
site
Mound sville, WV
Belle, WV
Freeport, TX
Plaquemine, TX
Louisville, KY
Geismer, LA
Wichita, KS
Percent
of
total
6.3
8.1
20.3
20.3
15.3
9.4
20.3
Releases
to air
(kkg)
13.6
17.5
43.9
43.9
33.1
20.3
43.9
Releases
to water
(103 kkg)
0.6
0.8 .
1.9
1.9
1.9
0.9
1.9
4.2 INDIRECT PRODUCTION
Environmental releases of chloroform will occur as water is dis-
tributed and used in municipalities which directly chlorinate their
water supplies (especially surface water sources) without treating to
remove trihalomethanes before distribution. Public water utilities
4-1
-------
which draw their supplies from source waters contaminated with chlori-
nated organics run an even greater risk of subsequent chloroform for-
mation.
The 1975 NORS study (Symons et al. 1975) identified 37 cities of
various population sizes whose treated water contained chloroform at
concentrations greater than 30 yg/£. Table 4.2 lists these cities
in the survey whose drinking water contains high levels of chlorofrom
and major population centers whose drinking water contains at least
30 yg/£ of chloroform. In a more recent study, treated water drawn
from the Occoquan Reservoir in Northern Virginia contained levels of
chloroform ranging from 24 to 409 yg/£ (Hoehn et al. 1977). These
monitoring data, however, are not up to date, and do not reflect
changes in treatment strategies that municipalities may have adopted
in order to lower trihalomethane levels in their drinking waters.
For example, Cincinnati stopped the practice of prechlorinating
source water (from the heavily industrialized Ohio River) in late
1975. Chloroform levels in finished water subsequently fell from
300 ppb to 20-50 ppb (Dallaire 1977). It is not known to what extent
other municipalities with high levels of chloroform in finished waters
have altered their treatment strategies, or how effective these changes
have been. The use of ozone as an alternative disinfectant in water
treatment may, in fact, enhance trihalomethane formation when practiced
in conjunction with postchlorination (Riley et al. 1978).
Steam electric power plants (nuclear and fossil fuel) are poten-
tial "hot spots" for chloroform releases when large quantities of
once-through cooling waters and cooling tower waters are chlorinated
to control biofouling. The quantities of chloroform produced and
released from this source depend on the organic content of cooling
waters, the doses of chlorine applied, the length of contact time,
and the quantities of spent cooling water discharged annually.
Paper mills are a key source of chloroform releases; pulp
bleaching effluents contain high concentrations (up to ^2.0 ppm) of
chloroform (NAS 1978a,b). Aerated lagoons may act to protect surface
waters from substantial chloroform contamination, but significant
quantities of chloroform may be released to air due to pulp bleaching
operations. Information regarding specific locations of paper mills,
the extent of pulp bleaching at these mills, the types of pulp bleached
and bleaching processes employed, the quantities of effluents dis-
charged annually, and the use of aerated lagoons to treat these
effluents is necessary in order to identify the mills that are sources
of major chloroform releases.
Gasoline combustion is reported to be a source of atmospheric
chloroform releases. In a study of exhaust gases from two cars
(Harsch et al. 1977) , much higher chloroform concentrations were
found in exhaust from a car running on unleaded gasoline (6-7 ppb)
than leaded gasoline (< 100 ppt). Since only two cars were tested,
more research is necessary to assess the significance of this source
of indirect chloroform production, particularly in urban areas with
high concentrations of gasoline-powered, vehicles.
4-2
-------
Table 4.2 Chloroform Concentration in Finished
Drinking Water of Various- U.S. Cities
City
San Juan, PR
Philadelphia, PA
Washington, DC
Baltimore, MD
Annandale, VA
Wheeling, WV
Miami, FL
Atlanta, GA
Charleston, SC
Cincinnati, OH
St. Paul, MN
Columbus, OH
Piqua, OH
Youngstown, OH
Houma, LA
Davenport , IA
Topeka, KS
Cape Girardeau, MO
St. Louis, MO
Huron, SD
Dos Palos, CA
Los Angeles, CA
San Diego, CA
San Francisco, CA
Ilwaco, WA
Chloroform
concentration
47
86
41
32
67
72
311
36
195
45
44
134
131
80
134
88
88
116
55
309
61
32
52
41
167
Source: Symons et al. 1975
4-3
-------
4.3 CHLOROFORM USES
4.3.1 CFC-22 Production
Chloroform releases from storage at the five CFC-22 production
sites comprise the major source of potential environmental problems
associated with the use of chloroform. As calculated in Section 3.1.1,
total air emissions amount to 190 kkg (+20%), and would be distributed
according to each producer's market share. This apportionment is
detailed in Table 4.3, and the five release sites were shown on the
map in Figure 3.1.
Table 4.3 Air Emissions of Chloroform from the Production of CFC-22
Location
El Segundo, CA
Louisville, KY
Gramercy, LA
Calvert City, KY
Witchita, KS
Producer
Allied Chemical
E . I . duPont
Kaiser Aluminum & Chemical
Pennwalt Corporation
Racon , Inc .
Quantity
(kkg)
81.7
38
30.4
22.8
17.1
190.0
% of
total
43
20
16
12
9
100
4.3.2 Other Chloroform Uses
Although approximately 14,640 kkg of chloroform were available for
miscellaneous uses, only 7 percent of this total could be accounted for.
Most of the 13,600 kkg unaccounted for is probably used in laboratories
or is stockpiled. There are no known areas of concentrated emissions
from miscellaneous uses.
Releases of chloroform as a contaminant in other chloromethanes
(methyl chloride, methylene chloride, and carbon tetrachloride) are
also not significant for any geographic areas. These products are
contaminated with chloroform at low levels, and their uses are geo-
graphically dispersed.
4-4
-------
5.0 SUMMARY OF DISPOSAL AND DESTRUCTION OF SOLID
AND LIQUID CHLOROFORM WASTES .
This chapter summarizes the Information on the quantities of
chloroform-containing solid and liquid wastes destroyed and disposed of
during the production and uses of chloroform. Table 5.1 summarizes this
information.
The amount of chloroform present in the heavy-end waste stream of
the methanol hydrochlorination followed by methyl chloride chlorination
process is 23.1 kkg. Assuming that the incinerator used in the destruc-
tion of heavy-end waste achieves a 95 percent efficiency, the quantity of
chloroform released to air from incineration of this heavy-end waste is
0.87 kkg. Of the heavy-end waste stream, 5.8 kkg is landfilled. Because
of the lack of information on the types of containment procedures used,
the amount of chloroform released from the landfills is unknown and
assumed to be minimal.
The quantity of chloroform present in the solid wastes from the
CFC-22 production process, pharmaceutical extractions', and contaminants
in methylene chloride and carbon tetrachloride amounted to only about
34 kkg. The majority of this solid waste is from use of chloroform in
pharmaceutical extractions. Most of this quantity is disposed of in
landfills.
5-1
-------
Table 5.1 Solid and Liquid Chloroform-Containing Waste: Quantities, Disposal, and Environmental Releases
Type of waste produced
Methanol hydrochlorination followed
by methyl chloride chlorination
CFC-22 catalyst disposal
Pharmaceutical extractions
Contaminant of methylene chloride
- Paint removers
- Metal cleaning
- Aerosol products
- Foam blowing agent
- Miscellaneous uses
Contaminant of carbon tetrachloride
- Spent catalyst from CFC-11 and
CFC-21 production
- Embalming supplies
Destroyed by
Solid waste incineration
(kkg) , (kkg)
23.1 16.4
0.9
34 ?
0.128
0.105 0.017
0.079
0.017
0.026
0.00058
0.12
Released
to air from
incineration Landfilled
(kkg) (kkg)
0.86 5.8
? 34
0.128
0.00085 0.088
0.079
0.017
0.026
. 0.00058
0.12
Ul
I
ho
-------
6.0 SUMMARY OF UNCERTAINTIES
Table 6.1 lists the estimates for environmental releases of methyl
chloroform by process and media of release along with the corresponding
uncertainty estimate for each value. The rationale for assigning a
specific uncertainty to each number is discussed in detail in Chapters
2 and 3. Our recommendations for "fine tuning" the materials balance
to reduce the uncertainty of these estimates are discussed in Chapter 7.
6-1
-------
Table 6.1 Summary of Uncertainties
Source
Production:
Methanol hydro -
chlorination
followed by
methyl chloride
chlorination
Description
Total chloroform produced
Total chloroform released from methylene
chloride and chloroform distillation column
vent
Total controlled fugitive losses of chloro-
form
Breathing losses of chloroform (controlled
conditions)
Working losses of chloroform (controlled
conditions)
Chloroform in carbon tetrachloride residue
Chloroform landfilled in still bottoms
Chloroform incinerated with still bottoms
Secondary emissions to air from incineration
of carbon tetrachloride residue
Releases of chloroform to cooling water
Releases of chloroform to water in spent
caustic and acid wastes
Chloroform evaporated from spent caustic
and acid wastes
Chloroform remaining in water from spent
caustic and acid wastes
Quantity
(kkg)*
122..400
0.26
3.6
72.4
34.7
23.0
5.8
16.4
0.86
70
1.6
1.3
0.3
Individual
uncertainty
(percent)
-
+30
+20
+40/-20
+70/-20
-
+50
+15
+15
+75/-50
+75
-
-
Overall
uncertainty
(percent)
+10
+38
+53
+54 /-39
+80/-30
+25
+72
+39
+39
+90/-56
-
+110/-100
+12 5 /- 100
*kkg unless otherwise noted
-------
Table 6.1 Summary of Uncertainties (continued)
Source
Production:
Methane chlori-
nation process
Transportation
Losses
Description
Total chloroform produced
Releases of chloroform from recycled methane
inert gas purge vent
Releases of chloroform from distillation area
emergency gas vent
Total controlled fugitive losses of chloro-
form
Breathing losses of chloroform (controlled
conditions)
Working losses of chloroform (controlled
conditions)
Release of chloroform to cooling water
Release of chloroform to spent acid and spent
caustic wastes
Chloroform evaporated from spent caustic and
spent acid
Chloroform remaining in water
Total chloroform released from transpor-
tation
Quantity
(kkg)*
36,100
0.03
0.19
0.6
11.2
9.2
21
0.4
0.3
0.1
177
Individual
uncertainty
(percent)
+50/-25
+50/-25
+20
-
-
+75/-50
±75
+10
+30
Overall
uncertainty
(percent)
+30
+80/-55
+80/-55
+50
+75/-2S
+7S/-25
+110/-76
+152/-100
+150/-100
+50
-------
Table 6.1 Summary of Uncertainties (continued)
Source
Chlorination of
Municipal Water
Supply
Chlorination of
Municipal Sewage
Chlorination of
Cooling Water at
Power Plants
Bleaching of
Paper Pulp
Combustion of EDC
in Leaded Gaso-
line
Tropo spheric
Ph o tode c omp o s i-
tion of Tri-
chloroethylene
Description
Total chloroform produced
Evaporation of chloroform to air from use of
potable water
Release of chloroform to natural waterways
Total chloroform produced
Chloroform released to air
Chloroform released to water
Total chloroform produced
Chloroform released to. air
Chloroform discharged to surface water
Total chloroform produced
Total chloroform produced and released to air
Total chloroform produced
Quantity
(kkg)*
912
820
92
91
82
9
2,460
2,340
120
6,700
965
450
Individual
uncertainty
(percent)
+5
+50
+6
+50
+5
+100
-
-
-
Overall
uncertainty
(percent)
+10/-50
+15/-55
+60/-100
+50
+56"
+100
+20/-50
+25/-5S
+12 O/- 100
+50
+5/-90
+700/-90
-------
Table 6.1 Summary of Uncertainties (continued)
Source
Du Pont Process
for CFC-22
Manufacture
Allied Chemical
Process for
CFC-22 Manu-
facture
CFC-22 Usage
Pharmaceutical
Extractions
Description
Condenser vent emission rate (kkg/kkg)
Chloroform concentration in vent stream
(volume %)
Fugitive emissions (kg)
Production rate of CFC-23 (kkg/kkg)
CFC-23 condenser vent emissions
CFC-22 condenser vent emissions
Emissions due to catalyst regeneration
Chloroform emissions from storage
Fugitive emissions
Production rate of CFC-23 (kkg/kkg)
Catalyst disposal
Total air emissions from CFC-22 manufacture
Chloroform content of CFC-22
Air emissions
Total chloroform used in extractions
Chloroform released to air
Chloroform landfilled
IV .
Chloroform released to water
Quantity
(kkg)*
0.165
6.26
0.83
9.6 x 10~3
1.4 x 10~6
75 x 10~6
1.14
120
0.67
9.6 x 10~3
0.9
190
1 ppm
0.005
1,000
570
384
46
Individual
uncertainty
(percent)
+10
+10
+50
+20
-
ND
+25
+50
+20
ND
+25/-50
Overall
uncertainty
(percent)
+20
+150/-100
+20
+35
+35
+35
ND - not determined
-------
Table 6.1 Summary of Uncertainties (continued)
Source
Fumigants
Laboratory Use/
Stockpiles
Contaminant of
Methyl Chloride
Contaminant of
Methylene
Chloride
Description
Amount of chloroform used in fumigants
Amount of chloroform in stockpiled fumigants
Amount of chloroform emitted to the atmo-
sphere
Total quantity of chloroform used in labora-
tories and stockpiled
Total chloroform in methyl chloride
Total chloroform in methylene chloride
Releases of chloroform from storage of
methylene chloride
Releases of chloroform from handling of
methylene chloride
Releases of chloroform from use of methylene
chloride-based paint removers
- emissions to air
- emissions to water
- emissions to land
Quantity
(kkg)*
42
4.2
37.8
13,600
0.17
A. '2 7
2.5
1.280
0.960
0.192
0.128
Individual
uncertainty
(percent)
may be large
+75
+30
+20
+15
+15
+15
Overall
uncertainty
(percent)
+12 /-ll
+24/-21
+11
may be large
+33
+34
-------
Table 6.1 Summary of Uncertainties (continued)
Source
Chloroform
Contained in Car-
bon Tetrachlo-
ride - CFC-12 and
CFC-11 Production
Description
Production of CFC-12
Production of CFC-11
Amount of CCl^ used in the production of
CFC-11 and CFC-12
Amount of CHC13 in CC1,
Amount of CHC1- in the CCl^ utilized in the
production of CFC-11 and CFC-12
Allied Chemical Corporation estimated
breathing and working losses
E. I. DuPont de Nemours and Company storage
losses
Estimated emissions of CHClg from the stor-
age of CC14
Estimated amount of CHCls emitted to the
atmosphere during the production process
CC1, in finished product
CHC1- in finished product
Total atmosphere emissions
CC1, in spent catalyst
CHC1- in catalyst landfilled
Quantity
(kkg)*
148,000
8,000
293,000
15 0 ppm
44
0.00035
0.0002
0.012
0.055
0.47
7.1 x 10~5
0.067
3.9
0.00058
Individual
uncertainty
(percent)
Overall
uncertainty
(percent)
+10
+10
+10
+10
+20/-18
+25
+25
+58/-3S
+44/-64
+30
+41/-63
+46/-40
+75
+S9/-22
CTv
I
-J
-------
Table 6.1 Summary of Uncertainties (continued)
Source
CCl^ in Fumigants
Minor Uses of
CC1A
Stockpiled CCl^
Perchloro-
ethylene
Description
CCl^ used in fumigants
CCl^ in fumigants stockpiled
CCl4 emitted to atmosphere during fumigant
use
CHC13 emitted to atmosphere during CC1A
fumigant use
CHC13 in stockpiled CC14 fumigants
Emission of CC14 to the atmosphere
CHCl^ emitted from minor uses
CC14 used in embalming supplies
CHC13 in embalming supplies
CCl^ stockpiled
CHC13 in CC14 stockpiled
Total chloroform emitted from hydrocarbon
feed
Quantity
(kkg)*
13,300
1,200
12,100
1.8
0,18
11,800
1.8
831
0.12
17,100
2.6
1.8
Individual
uncertainty
(percent)
Overall
uncertainty
(percent)
+40
+35
+40
+40
+39/-50
+95
+111/-96
+95
+125/-95
+95
+111/-96
+60/-80
oo
-------
7.0 DATA GAPS
In preparing the Level I materials balance for chloroform, JRB
found numerous data gaps which prevented an accurate assessment of
chloroform release patterns and quantities. Some of this information
is available in the literature, but could not be obtained within the
time frame or scope of the study. Other data gaps require detailed
monitoring data, input from industrial sources, and/or plant visits.
7.1 BISECT PRODUCTION
Our estimates for chloroform releases to air from direct produc-
tion processes were based largely on emission factors derived from
information supplied by one plant for each production process. It was
necessary to assume that 'all five plants producing chloroform by
chlorination of methanol had the same operating conditions and con-
trols. Furthermore, the emission factors were taken from a secondary
source since the primary plant data.were not available; the. method used
to determine these emission factors is not known. The primary sources
for the plant data are available at the Emission Standards and
Engineering Division of the Office of Air Quality Planning and Stand-
ards. These sources could not be obtained within the time frame of
the study. Ideally, air .emission factors should be determined from
actual monitoring data. In the absence of monitoring data, estimates
should be obtained from more than one plant.
No reliable Information was available on the releases of chloro-
form to water (cooling water, spent caustic, and spent acid). Esti-
mates were made using the available information, but the reliability
of these estimates is low. Again, monitoring data or, at a minimum,
estimates from producers should be obtained.
Finally, no information was available on the quantity of carbon
tetrachloride still bottoms produced in the methane chlorination
process. Carbon tetrachloride is produced by the methane chlorination
process and the still bottoms contain small quantities of chloroform.
It is claimed these wastes are incinerated, but it would be useful to
determine secondary air emissions from the incineration of still
bottoms.
7.2 INDIRECT PRODUCTION
In order to derive more accurate estimates for the quantities of
chloroform produced annually through chlorination of municipal drink-
ing water supplies and sewage effluents, it is necessary to have plant-
specific data for representative municipal waterworks throughout the
nation. Information on specific treatment schemes employed by these
public utilities, such as chlorine doses applied daily (if, in fact,
chlorination is practiced), any pretreatment methods which may be used
to reduce the concentration of trihalomethane precursors in water, the
nature of source waters (i.e., surface versus ground), pH and tempera-
ture of treated waters, and the amount of water or wastewater handled
7-1
-------
daily would enable a much, more accurate quantification of nationwide
chloroform production from these sources. Also, regular monitoring
of trihalomethane concentrations in treated water and sewage would
reveal "hot spots" of chloroform production and subsequent environmen-
tal releases. Chloroform production will vary based on the amounts of
organic precursors in source waters, seasonal variations in the chlorine
demand of treated waters, and the specifics of the treatment process
employed. A national survey of public water utilities and a nationwide
monitoring effort of the type performed by EPA in 1975 (i.e., NOR.S) are
two possible means of obtaining data required In order to derive valid
and accurate estimates of indirect chloroform production via municipal
chlorination practices. The same suggestions would apply for deriving
information on the industrial sources Cbleaching of paper pulp, cooling
water' chlorination) of indirect chloroform formation, and estimates of
the amounts produced by these sources.
The chlorination of other industrial effluents which contain high
concentrations of THM precursors may be a significant source of indirect
chlorform releases. Sources of such releases include the textile
industry and food processing operations; there may be many other indus-
tries which chlorinate wastewaters and, therefore, contribute to chloro-
form formation. However, none of these are identified in the available
literature. Monitoring for chloroform in untreated waste streams and
chlorinated effluents from such industries will identify those plants
which are indirectly producing and subsequently releasing major quan-
tities of chloroform.
The combustion of leaded gasoline has also been cited as a poten-
tially significant source of chloroform in the environment, based
mainly on a single monitoring study performed in 1977 in which exhaust
from only two automobiles was analyzed. Using such limited data
for a nationwide estimate of chloroform by combustion of leaded gaso-
line leads to a high uncertainty. Additional monitoring data and
research into the sources of chlorine in gasoline and the mechanism
of chloroform formation are needed before the extent of chloroform
production through gasoline combustion can be accurately assessed.
7.3 USES OF CHLOROFORM
Information provided on the use patterns of chloroform was
sketchy, and several estimates were made in order to quantify these
uses.
7.3.1 Manufacture of CFC-22 from Chloroform
A major data gap identified in this study was the discrepancy
in the percentage of chloroform produced which is used as feedstock
for CFC-22 manufacture. According to Dow (Farber 1980) and estimates
supplied by Wolf (1979), Radian Corp. (1979), and Boberg (1980), 90
percent of the 1978 chloroform production was used for CFC-22 manu-
facture. The production figures supplied by USITC (1979) and an
estimate fay Mannsville (1978a) suggest that only about 81 percent of
the chloroform is used for CFC-22 production. This is a point which
needs to be clarified, since it is not clear what fraction of the
7-2
-------
chloroform produced is used for miscellaneous end uses or exported. For
this balance we used Dow's estimate that 90 percent of the chloroform
is used for CFC-22.
In the production of CFC-22 from chloroform, the product gases are
cleaned by alkali scrubbing. No data detailing chloroform content of
the waste streams from this process were available. Specific details
of du Font's catalyst regeneration, ratio of CFC-23 to CFC-22 produc-
tion, and an estimate of fugitive emissions were not available. Simi-
lar details were also not available for the process used by Allied
Chemical, and no information about the processes used by Pennwalt,
Kaiser, or Racon was obtained.
One of the more important pieces of data lacking for this report
is the level of chloroform impurity in CFC-22 product. One industry
source indicated that the level was low, but that CFC-22 was not
analyzed for traces of chloroform (Boberg 1980).
7.3.2 Minor Uses
As discussed in Section 3.2, numerous companies, government
agencies, and chemical distributors were contacted in an effort to
quantify chloroform used as a fumigant, a solvent, a laboratory chemi-
cal, and in the pharmaceutical, textile, and dye industries. The con-
sensus among contacts was that the use of chloroform in textile and
dyes and as an industrial solvent is extremely limited. The total
production figure for chloroform, minus the fraction used for CFC-22,
is the upper bound for the estimate of chloroform going to minor uses
(13,600 kkg). If further research indicates that the fraction going
to these uses is greater than the 10 percent estimated in this report,
closer examination of the minor use of chloroform may be warranted.
7.3.3 Secondary Product Contaminants
Industry estimates were available for chloroform contaminant
levels in methyl chloride, methylene chloride, and carbon tetra-
chloride. Environmental releases of chloroform from use of these
chloromethanes are believed to be comparatively small. Better esti-
mates of these releases are not warranted.
7-3
-------
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communication in January 1980 to K. Wagner, JRB.
Barnhardt E 1980. Hydroscience Corporation, Knoxville, TN. Personal
communication in January 1980 to A. Shochet, JRB.
Blosser RO 1980. Technical Director, National Council of the Paper
Industry for Air and Stream Improvement, Inc., New York, NY.
Personal communication in January 1980 to H. Bryson, JRB.
Boberg R 1980. Allied Chemical Company, Morristown, NJ. Personal
communication in January 1980 to A. Shochet, JRB.
Bochner B 1980. Atlantic Chemical Corporation, Nutley, NJ. Personal
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DeGuano Dr 1980. Bureau of Drugs, Food and Drug Administration,
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-------
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-------
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-------
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-------
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-------
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-------
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-------
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-------
APPENDIX A
PHYSICAL AND CHEMICAL PROPERTIES OF CHLOROFORM
-------
I. PHYSICAL AND CHEMICAL PROPERTIES
Chemical Abstracts serial number
Synonyms
Molecular formula
Molecular weight
Boiling point
Melting point
i
Vapor pressure
Optical rotation
Specific gravity
Solubility
Explosive limit
Flash point
Vapor density
Conversion factors (25°C; 760 mm Hg)
000067663
Trichloromethane
Trichloroform
Methenyl trichloride
Formyl trichloride
Methyl trichloride
CHC13
119.38
61.3°C, 142.3°F (760 mm Hg)
-63.2°C, -81.7°F
100 mm Hg (10.4°C)
200 mm Hg (25°C)
.k
n^° 1.4476
1.48069 (25°C),
(water = 1.000 at 4°C)
1.0 g/100 ml H20 at 15°C
1 ml in 200 ml H2O (258C) ;
soluble in ethanol, ethyl ether,
benzene, acetone, and carbon di-
sulfide
None
None
4.0 g/liter (25°C; 760 mm Hg)
1 mg/liter =205 ppm
1 mg/cu m = 0.205 ppm
1 ppm = 4.89 mg/cu m
Source: NCI 1977
A-l
-------
APPENDIX B
PRODUCTION PROCESS DESCRIPTION
AND
RELATED EMISSION CALCULATION
-------
PROCESS DESCRIPTIONS
In the United States th« main processes of producing chloronethanes consist of
ethanol hydrochlorination followed by further chlorination of the methyl chloride
produced. As of Hay 1977 about 90% of methyl chloride, 75% of methylene chloride,
and 77% of chloroform capacities in the United States were based on these processes.
Soae carbon tetrachloride is formed as a by-product in the chlorination of methyl
chloride but is not generally directly purified into product by domestic producers.
The unpurified carbon tetrachloride is either sold as is or is used in-house as
feed to carbon tetrachlorideperchloroethylene producing facilities.
HETHANOL HYDROCHLORINATION AND METHYL CHLORIDE CHLORINATION PROCESSES
Basic Process
Although some domestic producers manufacture methyl chloride exclusively by
hydrochlorination of raethanol, it is common practice to combine this reaction
with the continuous chlorination of methyl chloride to produce methylene chloride
and chloroform, along with carbon tetrachloride in small amounts as a by-product.
These two processes are discussed as an integral process for the purpose of this
report.
Methyl chloride is produced by the reaction
CH3OH + HCl > CH3C1 + H20
(Hethanol) (Hydrogen (Methyl (Water)
Chloride) Chloride)
Methylene chloride, chloroform, and by-product carbon tetrachloride are then
produced from methyl chloride by the reactions
CHjCl + C12 > CH2C12 * HC1
(Methyl (Chlorine) (Methylene (Hydrogen
Chloride) Chloride) Chloride)
Source: Reprinted from Hobbs and Stuewe 1978,
Hobbs and Stuewe 1979a
B-l
-------
CH2C12 » C12 » CHC13 + HC1
(Methylene (Chlorine) (Chloroform) (Hydrogen
Chloride) Chloride)
CHC13 + C12 > CC14 » HC1
(Chloroform) (Chlorine) (Carbon (Hydrogen
Tetrachloride) Chloride)
A typical continuous-process flow diagram for the basic process is shown in
Fig. B-l
Hethanol is hydrochlorinated by feeding equimolar proportions of vaporized methanol
(Stream 1) and hydrogen chloride (Stream 2) at 180200°C to the hydrochlorination
reactor. The reactor is packed with any one of a number of catalysts, including
alumina gel, cuprous or zinc chloride on activated carbon or pumice, or phosphoric
acid on activated carbon. The reactor is maintaned at a temperature of about
350°C. The reaction is exothermic. Hethanol conversion of 95% is typical.
The reactor exit gases (Stream 3) enter the quench tower, where unreacted hydrogen
chloride and methanol are removed by water scrubbing. The discharge from the
quench tower (Stream 4) is stripped of virtually all dissolved methyl chloride
and most of the methanol, both of which are recycled to the hydrochlorination
reactor (Stream 5). The remaining aqueous solution from the stripper (Stream 6)
consists of dilute hydrochloric acid, which is used in-house or is sent to waste-
water treatment.
Methyl chloride from the quench tower (Stream 7) is fed to the drying tower,
where concentrated sulfuric acid removes residual water. The dilute sulfuric
acid effluent (Stream 8) is sold or is reprocessed on-site.
A portion of the dried methyl chloride (Stream 9) is compressed, cooled, and
liquefied as product. The rest of the dried methyl chloride (Stream 10) is fed
to the chlorination reactor. The methyl chloride and chlorine (Stream 11) are
mixed in the reaction chamber to form methylene chloride and chloroform, along
with hydrogen chloride and a small amount of carbon tetrachloride. The reactions
are exothermic.
B-2
-------
W
POC.TOA
Figure B.I Process Diagram for Production of Chloroform by Methanol Hydrochlorination
Followed by Methyl Chloride Chlorination
Source: Hobbs and Stuewe 1978
-------
Hydrogen chloride is itripped from the condensed crude product and is recycled to
the methanol hydrochlorination reactor (Stream 12). The amounts of individual
products (methyl chloride, methylene chloride, chloroform, and by-product carbon .
tetrachloride) determine whether sufficient hydrogen chloride by-product will be
available for operation of the reactor. The crude methylene chloride, chloro-
form, and carbon tetrachloride from the stripper (Stream 13) are transferred to a
storage tank, which feeds to the methylene chloride distillation column. The
methylene chloride product from this distillation (Stream 14) is fed to a day
tank, where inhibitors are added as stabilizers, and is then sent to methylene
chloride storage and loading. Bottoms .from methylene chloride distillation
(Stream 15) go to the chloroform distillation column. The chloroform product
(Stream 16) is also taken to a day tank where inhibitors are added for control of
hydrochloric acid, and then sent on to storage and loading. Bottoms from chloro-
form distillation (Stream 17) consist of crude carbon tetrachloride, which is
stored for subsequent transfer to a separate carbon tetrachlorideperchloroethylene
process or is sold.
Process emissions originate at the vents used for purging inert gases from the
condensers associated with methyl chloride product recovery (Vent A), with dis-
tillation of methylene chloride (Vent B), and with distillation of chloroform
(Vent C), as shown in Fig. B-l.. Fugitive-emissions occur when leaks develop in
valves, pumps, seals, or other equipment. Corrosion caused by the hydrogen
chloride and chlorine in the process can result in leaks, which hinder control of
fugitive emissions.
Emissions result from the- storage of feed material, intermediates, products, and
by-products and from handling of the products.
Two potential sources of secondary emissions (K on Fig. B-l ) are aqueous wastes
from the methyl chloride stripper and waste sulfuric acid from the methyl chloride
drying tower.
B-4
-------
Methane Chlorination Process
Methane can be chlorinated thermally, photochemically, or catalytically, with
thermal chlorination being the most important method.1 Methyl chloride, methylene
chloride, chloroform, and carbon tetrachloride are produced in this process by
the following reactions:
CS4
(methane)
C12
(chlorine)
CH3C1 -t- HC1
(methyl chloride) (hydrogen chloride)
CH3C1
(methyl chloride)
C12
(chlorine)
> CH2C12 » HC1
(methylene chloride) (hydrogen chloride)
CH2C12 +
(oethylene chloride)
CHC13 + HC1
(chloroform) (hydrogen chloride)
» CC1« f HC1
(carbon tetrachloride) (hydrogen chloride)
A typical continuous process flow diagram for the basic process is shown in
Fig. B-2.
Methane (Stream 1) is mixed with chlorine (Stream 2); then the mixture is pre-
heated before it is fed to the chlorination reactor, which is operated at a
temperature of about 400°C1 and a pressure of about 200,000 Pa.2 Nearly 100%
chlorine conversion and 65% methane conversion are typical with product yields
of about 58.5% methyl chloride. 29.3% methylene chloride, 9.7% chloroform and
2.3% carbon tetrachloride.3 (Methyl chloride can be recycled to the reactor
after separation to enhance yields of the other chloromethanes.) Gases exiting
the reactor (Stream 3) are partly condensed and then scrubbed with chilled chloro-
"ethanes from the process to absorb most of the chloromethanes from unreacted
aethane and by-product hydrogen chloride. The unreacted methane and by-product
hyrogen chloride from the absorber (Streaa 4) are fed serially to a hydrogen
chloride absorber, caustic scrubber, and drying column, with the purified methane
(Stream S) being recycled to the chlorination reactor.
Source: Reprinted from Hobbs and Stuewe 1979a
B-5
-------
C ***«*. t**».nte
Cl«.CA.Ut -Uj»m»*»* ttxU~»<
»"» 1 ***»
...~.,k
<
L C
*>*
^
If
'V
^
W
.^jdj
>'£>~l
p i
r
j
*
-k>
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^
^
i
n
tr*
^
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.ca CO
PBCCUCT
P«>O
-------
Condensed material fro* the separator and liquid effluent from the absorber are
eoaklned (Stream 6) and fed to a stripper. Overheads from the stripper, which
include hydrogen chloride, methyl chloride, and some of the higher boiling chloro-
nethanes (Stream 7), are fed to a water scrubber, where most of the hydrogen
chloride is removed as weak hydrochloric acid (Stream 3). The overheads are then
scrubbed with dilute sodium hydroxide solution to remove residual hydrogen chloride.
Water is then removed from the crude chloromethanes in a drying column.
The crude' chloromethanes from the drying column (Stream 9) are compressed, condensed,
and fed to a methyl chloride distillation column. Methyl chloride from the distil-
lation column can be recycled back to the chlorination reactor (Stream 10) or be
condensed and then transferred to storage and loading as product (Stream 11).
Crude methylene chloride, chloroform, and carbon tetrachloride from the stripper
(Stream 12) are neutralized, dried, and combined with bottoms from the methyl
chloride distillation column (Stream 13) in a crude storage tank. The crude
chloromethanes (Stream 14) pass to a methylene chloride distillation column.
Hethylene chloride from the overheads (Stream IS) is condensed and fed to day
storage tanks, where inhibitors may be added for stabilization. Product methylene
chloride is transferred to product storage and loading. Bottoms from the methylene
chloride distillation column (Stream 16) are fed to a chloroform distillation
column, with chloroform overheads (Stream 17) being condensed and fed to day
storage tanks, where inhibitors may be added for stabilization. Product chloro-
form is transferred to storage and loading. Bottoms from the chloroform distil-
lation column (Stream 18) are fed to a carbon tetrachloride distillation column,
with carbon tetrachloride overheads (Stream 19) being condensed and fed to day
storage tanks, where inhibitors may be added for stabilization. Product carbon
tetrachloride is transferred to storage and loading. Bottoms from the carbon
tetrachloride distillation column are incinerated.
Vented gases from the four distillation columns could be recycled to the absorber,
as is indicated in Fig. B-2 ,
Process emissions from the model plant result from venting of the inert gases
from the recycle methane stream (Vent A, Fig. B-2 , from regeneration of the
methane recycle stream drying bed (Vent B, Fig. B-2 , and from emergency vent-
ing of the distillation-area inert gases (Vent C,)
B-7
-------
Fugitive emissions can occur when leaks deveiop in valves, pump seals, and other
equipment. Corrosion caused by the hydrogen chloride and chlorine in the procesi
can result in leaks that hinder control of fugitive emissions.
Emissions result from the storage of intermediates and products and from the
handling of products.
Potential sources of secondary emissions (K on Fig. B-2 .) are aqueous discharge*
from the three caustic scrubbers, the sulfuric acid drying column, and the dryer.
Another potential source is the incineration of heavies from carbon tetrachloride
distillation.
B-8
-------
APPENDIX B
Breathing Losses of Chloroform from the Methyl Chloride Chlorination Process
Calculations for estimation of breathing losses from fixed storage
'tanks are detailed below based on an empirical formula developed by API
which relates losses to several variables related to storage (USEPA 1977).
Table 2.4 shows assumptions which were made regarding storage. Section
2.1.2.1 further discusses the assumptions used in making these estimates.
~0.68
LB = 2.21 x 10"4m
14.7-P
1.73 ..0.51 ^0.5 ,
x D x H x T TpcKc
where LB = fixed roof breathing losses (Ib/day)
m = molecular weight = 119
P = true vapor pressure at bulk liquid conditions (psia) = 3.259
D = tank diameter; variable (Table 2.4)
H = average vapor space height; variable (Table 2.4)
T = average ambient temperature change from day to night
Tp = paint factor; assume 1
c = adjustment factor for small diameter tanks; variable
Kc = crude oil factor = 1
7.000 gallon (26.250 £) (12 tanks)
0. 68 177 C1 c
x 101*'-* x 6.5i51 x 20'5 x 1 x 0.51 x 1
[3.259
14.7-3.259
*-
LB = 2.21 x 10-4(119)
= 0.0263 x 0.0263 x 0.280'68 x 101'73 x 6.5°*51 x 20°*5 x 1 x 0.51 x 1
= 0.0263 x 0.42 x 53.7 x 2.5 x 4.47 x 0.51 x 1
=3.4 Ib/day
3.4 Ib/day x 0.454 kg/lb x 12 tanks x 365 days = 6.8 kkg
16.000 gallon (60.000 -0 (2 tanks)
LB = 2.21 x 10-4(119) (0.28)0.68 x 15!.73 x 6.5°-51 x 20°-5 x 1 x .75 x 1
= 0.0263 x 0.42 x 108 x 216 x 4.5 x 1 x .75 x .1 = 10.5 Ib/day
0.5 Ib/day x 0.454 kg/lb x 2 tanks x 365 days =3.5 kkg'
B-9
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50.000 gallon (185.000 £) (6 tanks)
LB = 2.21 x 10-4(119) (0.28)0-68 x 221'73 x 10°»51 x 20°-5 x 1 x .83 x 1
= 0.0263 x 0.42 x 210 x 3.2 x 4.5 x 1 x .83 x 1 = 27.7 Ib/day
27.7 Ib/day x 0.454 kg/lb x 6 tanks x 365 days =27.5 kkg
100,000 gallons (375.000 £)
LB = 2.21 x 10-4(119) (0.28)0-68 x 331-73 x 17-51 x 20-5 x 1 x 1 x 1
= 0.0263 x .42x423.7x4.2x4.5xlxlx 1
=88.4 Ib/day
88.4 Ib/day x 0.454 kg/lb x 2 tanks x 365 days = 29.3 kkg
Assuming refrigerated vapor recovery of 75 percent efficiency, then actual
chloroform emissions from these tanks are:
0.293 kkg x 0.25 - 7.3 kkg
461.000 gallons (1.720,000 I) (2 tanks)
LB = 2.21 x 10-4(119) (0.28)0'68 x 701'73 x 17.5-51 x 20-5 x 1 x 1 x 1
= 0.0263 x 0.42 x 1,556 x 4.3 x 4.47 x 1 x 1 x 1
= 330 Ib/day
330 Ib/day x 0.454 kg/lb x 2 tanks x 365 days = 109 kkg
Again, assuming 75 percent recovery by refrigerated vapor condensation, then:
(Total emissions) = (Total uncontrolled emissions) x (percent unrecovered)
109 kkg x 0.25 = 27.3 kkg
Working Losses of Chloroform from Methyl Chloride Chlorination Process
Calculations for working losses from fixed roof storage, are detailed
below, using the assumptions shown in Table 2.5 and the following empirical
formula (USEPA 1977):
B-10
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LW - 2.4 x 1CT2 MPKnKc
where LW = fixed roof working losses (lb/103 gal)
M = molecular weight = 119
P = true vapor pressure (psia) = 3.259
Kn = turnover factor - variable
Kc = crude oil factor = 1
7.000 gallon tanks (26,250 £) (12 tanks)
LW = 2.4 x ID"2 x MPKnKc
.024 x 119 x 3.259 x 0.44 x 1 = 4.1 lb/103 gal
Storage requires eight 7,000 gallon (26,250 £) tanks of which all are 50
percent full. Turnover in these tanks occurs 125 times/yr. Therefore,
annual throughput is estimated as follows:
(No. of tanks) x (Tank volume) x (percent capacity) x (No. of turnovers) =
volume throughput
8 tanks x 7,000 gallons x 50 percent capacity x 125 turnovers = 3,500 x 103
gallons
4.1 lb/103 gallons x 3,500 x 103 gallons = 14.4 x 103 Ib
14.4 x 103 Ib x 454 x 10~6 kkg/lb = 6.5 kkg
16,000 gallons (60.000 £) (2 tanks)
LW = 2.4 x 10~2 MPKnKc
.024 lb/103 gal x 110 Ib/lb mole x 3.259 x .44 x 1 = 4.1 lb/103 gal
2 tanks x 16,000 gallons x 50 percent x 125 turnovers = 2,000 x 103 gal
throughput
4.1 lb/103 gallon x 2,000 x 10^ gallons = 8.2 x 103 Ib
8.2 x 103 Ib x 454 x 10'6 kkg/lb = 3.7 kkg
B-ll
-------
50.000 gallons (187.500 -£) (6 tanks)
IW - 2.4 x 10~2 MPKnKc
.024 lb/103 gal x 119 Ib/lb mole x 3.259 x 1 x 1 = 9.3 lb/103 gal
6 tanks x 50,000 gallons x 50 percent x 20 turnovers = 3,000 x 103 gal
throughput
9.3 lb/103 gal x 3,000 x 103 gal = 27.9 x 103 Ib
27.9 x 103 Ib x 454 x 10~6 kkg/lb = 12.7 kkg
100.000 gallons (375.000 £) (2 tanks)
LW = 2.4 x 10~2 MPKnKc
.024 lb/103 gal x 110 Ib/mole x 3.259 x 1 x 1 = 9.3 lb/10S gal
2 tanks x 100,000 gallons x 50 percent x 20 turnovers = 2,000 x 103 gal
throughput
9.3 lb/103 gal x 2,000 x 103 gal = 18.6 x 103 Ib
18.6 x 103 Ib x 454 x 10~6 kkg/lb = 8.4 kkg
Assuming refrigerated vapor recovery at 75 percent efficiency, emissions
are:
8.4 kkg x 0.25 - 2.1 kkg
461.000 gallons (1,728.750 £) (2 tanks)
LW = 2.4 x 10~2 MPKnKc
.024 x 110 x 3.259 x 1 x 1 = 9.3 Ib x 103 gal
2 tanks x 460,000 gallons x 50 percent capacity x 20 turnovers = 9,220 x
103 gal thoughput
9.3 lb/103 gallon x 9,220 x 103 gal = 85.7 x 103 Ib
85.7 x 103 Ib x 454 x 10~6 kkg/lb = 38.9 kkg
B-12
-------
Assuming refrigerated vapor recovery at 75 percent efficiency, then actual
emissions are:
38.9 kkg x 0.25 = 9.7 kkg
Breathing Losses of Chloroform from the Methane Chlorination Process
Breathing losses from the storage of chloroform are calculated below
using the assumptions shown in Table 2.7 and the following empirical
formula:
LB = 2.21 x 10~4 m
0.68
x D1'73 x H°'51 x T°'5 TpCKc
14.7-P
where LB = fixed roof working losses (Ib/day)
m = molecular weight =119
P = true vapor pressure at bulk conditions (psia) = 3.259
D = tank diameter
H = average vapor space height
T = ambient temperature change from day to night - assume 20°
Tp = paint factor; assume 1
C = adjustment factor for small diameter tanks - variable
Kc = crude oil factor = 1
w
10.68
LB = 2.21 x 10~4 (119)
3.259
14.7-3.259|
x D1'73 x H°'51 x T°-5 x TpCKc
7.000 gallons (26.250 l)_ (5 tanks)
0.0263 x 0.280'68 x 101-73 x 0.65°-51 x 20°-5 x 1 x .51 x 1
0.0263 x .42 x 53.7 x 2.5 x 4.47 x 1 x 0.51 x 1 = 3.4 Ib/day
3.4 Ib/day x 454 x 10~6 kkg/lb x 5 tanks x 365 days = 2.8 kkg
16,000 gallons (60,000 I) (1 tank)
0.0263 x 0.280'68 x 151'73 x 6.5°'51 x 20°'5 x 1 x .75 x 1
0.0263 x 0.42 x 108 x 2.6 x 4.5 x 1 x .75 x 1 = 10.5 Ib/day
10.5 Ib/day x 454 x 10~6 kkg/lb x 1 tank x 365 days =1.7 kkg
B-13
-------
300.000 gallons (1.125.000 I) (1 tank)
n «r,ro ~00-68 e,1.73 . ,0Q.51 on0.5 . , .
0.0253 x 28 x51 x!2 x20 xlxlxl
0.0253 x .42 x 900 x 3.6 x 4.5 x 1 x 1 x 1 = 161 Ib/day
161 Ib/day x 454 x 10~6 kkg/lb x 365 days = 26.7 kkg
Assuming refrigerated vapor recovery at 75 percent efficiency, then
(chloroform releases from the 1.1 x 10° £ tank) = (total emission) x
(percent not recovered)
26.7 kkg x 0.25 = 6.7 kkg
Total breathing emissions from storage =2.8 kkg +1.7 kkg +6.7 kkg = 11.2 kkg
Working Losses of Chloroform from^Methane Chlorination Process
Working losses are estimated using the following empirical formula:
LW = 2.4 x 10~2 MPKnKc
where LW = fixed roof working losses (lb/10-^ gal)
M = molecular weight = 119
P = true vapor pressure at bulk liquid conditions = 3.259
Kn = turnover factor - variable
Kc = crude oil factor
7.000 gallon tanks (26.250 I) (5 tanks)
LW = 2.4 x 10~2 x 119 x 3.259 x 0.44 x 1 = 4.1 lb/103 gal
Storage requires five 7,000 gallon tanks which are 50 percent full. Turn-
over in these tanks is 125 times/yr. Therefore, annual throughput is esti-
mated as follows:
(Number of tanks) x (tank volume) x (percent capacity) x (number of turn-
overs) = volume throughput
B-14
-------
5 tanks x 7,000 gallons x 50 percent capacity x 1.25 turnovers = 2,220 x
10 gallons
4.1 lb/103 gallons x 2,200 x 103 gallons = 9 x 103 Ib
9 x 103 Ib x 454 x 10~6 kkg/lb = 4.1 kkg
i
16.000 gallon tanks (60.000 -0 (.1 tank)
0.024 lb/103 gal x 110 Ib/lb mole x 3.259 x .44 x 1 = 4.1 lb/103 gal
16,000 gallons x 1 tank x 50 percent capacity x 125 turnovers = 1,000 x 103
gal throughput
4.1 lb/103 gallons x 1,000 x 103 gallons = 4.1 x 103 Ib
4.1 x 103 Ib x 454 x 10'6 kkg/lb = 1.9 kkg
300.000 gallon tanks (1,125,000 1} (1 tank)
.024 lb/103 gal x 110 Ib/lb mole x 3.259 x 1 x 1 = 9.3 lb/10^ gal
300,000 gallons x 1 x 50 percent capacity x 20 turnovers = 3,000 x 103 gal
throughput
9.3 lb/103 gal x 3,000 x 103 gal = 27.9 x 10^ Ib
27.9 x 103 Ib x 454 x 10~6 kkg/lb =12.7 kkg
Again, assuming 75 percent vapor recovery, then, chloroform emissions from
the 300,000 gallon tank:
12.7 kkg x .25 = 3.2 kkg
Total working losses:
(4.1 kkg) + (1.9 kkg) + (3.2 kkg) = 9.2 kkg
B-15
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APPENDIX C
PROCESS DIAGRAMS FOR
CFC-22 PRODUCTION
-------
CATALYST
TO
DISPOSAL
FC-23
PRODUCT
DISPOSAL
DISPOSAL
Figure C-l Allied Chemical Process for CFC-22 Production
Source: Pitts 1978
-------
VENT TO
ATMOSPHERE
BY PRODUCT: HCL
BY PRODUCT! FC-23
CHCLj
PRODUCT: fo2?
HF
O
N>
-» VENT
TO
ATMO -
SPHERE
SPENT CATALYST
TO VENDER FOR
RECOVERY
WATER
SCRUBBER
>
/
FLASH
TANK
^
/
LIME
TREATMENT
TANK
*
>,
ALKALI
SCRUBBER
^
/
FLASH
TANK
,
,
LIQUID
WASTE
T
LIQUID WASTE
VENT TO
ATMOSPHERE
Figure C-2 Du Pont Process for CFC-22 Production
Source: Smith 1978b
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